U.S. patent application number 14/124253 was filed with the patent office on 2014-04-24 for materials for battery electrolytes and methods for use.
This patent application is currently assigned to Asahi Kasei Kabushiki Kaisha. The applicant listed for this patent is Vinay Bhat, Gang Cheng, Steven Kaye, Bin Li, Risa Olugbile, Jen Hsien Yang. Invention is credited to Vinay Bhat, Gang Cheng, Steven Kaye, Bin Li, Risa Olugbile, Jen Hsien Yang.
Application Number | 20140113186 14/124253 |
Document ID | / |
Family ID | 47114477 |
Filed Date | 2014-04-24 |
United States Patent
Application |
20140113186 |
Kind Code |
A1 |
Bhat; Vinay ; et
al. |
April 24, 2014 |
Materials for Battery Electrolytes and Methods for Use
Abstract
Described herein are materials for use in electrolytes that
provide a number of desirable characteristics when implemented
within batteries, such as high stability during battery cycling up
to high temperatures high voltages, high discharge capacity, high
coulombic efficiency, and excellent retention of discharge capacity
and coulombic efficiency over several cycles of charging and
discharging. In some embodiments, a high voltage electrolyte
includes a base electrolyte and a set of additive compounds, which
impart these desirable performance characteristics.
Inventors: |
Bhat; Vinay; (San Diego,
CA) ; Cheng; Gang; (San Diego, CA) ; Kaye;
Steven; (San Diego, CA) ; Li; Bin; (San Diego,
CA) ; Olugbile; Risa; (San Diego, CA) ; Yang;
Jen Hsien; (San Diego, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Bhat; Vinay
Cheng; Gang
Kaye; Steven
Li; Bin
Olugbile; Risa
Yang; Jen Hsien |
San Diego
San Diego
San Diego
San Diego
San Diego
San Diego |
CA
CA
CA
CA
CA
CA |
US
US
US
US
US
US |
|
|
Assignee: |
; Asahi Kasei Kabushiki
Kaisha
Osaka
JP
|
Family ID: |
47114477 |
Appl. No.: |
14/124253 |
Filed: |
June 7, 2012 |
PCT Filed: |
June 7, 2012 |
PCT NO: |
PCT/US2012/041352 |
371 Date: |
December 6, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
13459702 |
Apr 30, 2012 |
|
|
|
14124253 |
|
|
|
|
61495318 |
Jun 9, 2011 |
|
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|
61543262 |
Oct 4, 2011 |
|
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|
61597509 |
Feb 10, 2012 |
|
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Current U.S.
Class: |
429/188 ;
29/623.2 |
Current CPC
Class: |
C07F 9/095 20130101;
H01M 10/052 20130101; H01M 2300/0025 20130101; Y02T 10/70 20130101;
C07F 9/1415 20130101; H01M 10/0567 20130101; Y10T 29/4911 20150115;
C07F 9/098 20130101; Y02E 60/10 20130101; H01M 10/0525 20130101;
C07F 7/0834 20130101 |
Class at
Publication: |
429/188 ;
29/623.2 |
International
Class: |
H01M 10/0567 20060101
H01M010/0567; H01M 10/0525 20060101 H01M010/0525 |
Claims
1. A battery comprising: an anode comprising an anode active
material characterized by a first specific capacity; a cathode
comprising a cathode active material characterized by a second
specific capacity, wherein the first specific capacity and the
second specific capacity are matched such that the battery is
characterized by a rated charge voltage greater than about 4.2 V;
and an electrolyte comprising a lithium salt, a non-aqueous
solvent, and a compound represented by the formula (I):
##STR00017## wherein R.sub.1, R.sub.2, and R.sub.3 are
independently selected from the group consisting of substituted and
unsubstituted C.sub.1-C.sub.20 alkyl groups, substituted and
unsubstituted C.sub.1-C.sub.20 alkenyl groups, substituted and
unsubstituted C.sub.1-C.sub.20 alkynyl groups, and substituted and
unsubstituted C.sub.5-C.sub.20 aryl groups; X is nitrogen or
oxygen; and Y is selected from the group consisting of hydride
groups, halo groups, hydroxy groups, thio groups, alkyl groups,
alkenyl groups, alkynyl groups, aryl groups, iminyl groups, alkoxy
groups, alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy
groups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,
alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio
groups, alkenylthio groups, alkynylthio groups, arylthio groups,
cyano groups, N-substituted amino groups, alkylcarbonylamino
groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonyl amino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups, and
N-substituted arylcarbonylamino groups, boron-containing groups,
aluminum-containing groups, silicon-containing groups,
phosphorus-containing groups, and sulfur-containing groups.
2. The battery of claim 1 wherein the cathode active material is
characterized by a specific capacity of at least about 10 mAh/(g of
active material) upon discharge at a current of about 0.01 C over a
voltage range of about 4.9 V to about 4.2 V.
3. The battery of claim 1 wherein the cathode active material is
characterized by a specific capacity of at least about 40 mAh/(g of
active material) upon discharge at a current of about 0.01 C over a
voltage range of about 4.9 V to about 4.2 V.
4. The battery of claim 1 wherein the cathode active material is
characterized by a specific capacity of at least about 100 mAh/(g
of active material) upon discharge at a current of about 0.01 C
over a voltage range of about 4.9 V to about 4.2 V.
5. The battery of claim 1 wherein the battery has a coulombic
efficiency at 100 cycles from an initial cycle of at least about
90%.
6. The battery of claim 1 wherein the battery has a coulombic
efficiency at 100 cycles from an initial cycle of at least about
90% when the battery is operated in an environment at a temperature
of greater than about 50 degrees C.
7. The battery of claim 1 wherein the battery has a coulombic
efficiency at 100 cycles from an initial cycle of at least about
90% when the battery is at a temperature of about 50 degrees C.
8. The battery of claim 1 wherein the cathode active material
comprises a material selected from the group consisting of nickel,
manganese, and cobalt.
9. The battery of claim 1 wherein the cathode active material
comprises a spinel structure lithium metal oxide, a layered
structure lithium metal oxide, or a lithium-rich layered structured
lithium metal oxide.
10. The battery of claim 1 wherein the cathode active material
comprises a lithium metal phosphate.
11. An electrolyte solution for a high voltage battery, comprising:
a lithium salt; a non-aqueous solvent; and a compound represented
by the formula (I): ##STR00018## wherein R.sub.1, R.sub.2, and
R.sub.3 are independently selected from the group consisting of
substituted and unsubstituted C.sub.1-C.sub.20 alkyl groups,
substituted and unsubstituted C.sub.1-C.sub.20 alkenyl groups,
substituted and unsubstituted C.sub.1-C.sub.20 alkynyl groups, and
substituted and unsubstituted C.sub.5-C.sub.20 aryl groups; X is
nitrogen or oxygen; and Y is selected from the group consisting of
hydride groups, halo groups, hydroxy groups, thio groups, alkyl
groups, alkenyl groups, alkynyl groups, aryl groups, iminyl groups,
alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy groups,
carboxy groups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,
alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio
groups, alkenylthio groups, alkynylthio groups, arylthio groups,
cyano groups, N-substituted amino groups, alkylcarbonylamino
groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonyl amino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups, and
N-substituted arylcarbonylamino groups, boron-containing groups,
aluminum-containing groups, silicon-containing groups,
phosphorus-containing groups, and sulfur-containing groups; wherein
the electrolyte solution is characterized by electrochemical
stability in a high voltage battery at voltages above about 4.2
V.
12. The electrolyte solution of claim 1 wherein the solution is
further characterized by electrochemical stability when the battery
is operated in an environment at a temperature at about 50 degrees
C.
13. The electrolyte solution of claim 1 wherein the solution is
further characterized by electrochemical stability when the battery
is at a temperature at about 50 degrees C.
14. The electrolyte solution of claim 1 wherein the solution is
characterized by electrochemical stability in a high voltage
battery at voltages above about 4.5 V.
15. The electrolyte solution of claim 1 wherein the solution is
characterized by electrochemical stability in a high voltage
battery at voltages above about 5.0 V.
16. A method of making a high voltage battery, comprising:
providing an electrolyte solution comprising: a lithium salt, a
non-aqueous solvent, and a compound represented by the formula (I):
##STR00019## wherein R.sub.1, R.sub.2, and R.sub.3 are
independently selected from the group consisting of substituted and
unsubstituted C.sub.1-C.sub.20 alkyl groups, substituted and
unsubstituted C.sub.1-C.sub.20 alkenyl groups, substituted and
unsubstituted C.sub.1-C.sub.20 alkynyl groups, and substituted and
unsubstituted C.sub.5-C.sub.20 aryl groups; X is nitrogen or
oxygen; and Y is selected from the group consisting of hydride
groups, halo groups, hydroxy groups, thio groups, alkyl groups,
alkenyl groups, alkynyl groups, aryl groups, iminyl groups, alkoxy
groups, alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy
groups, alkylcarbonyloxy groups, alkenylcarbonyloxy groups,
alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio
groups, alkenylthio groups, alkynylthio groups, arylthio groups,
cyano groups, N-substituted amino groups, alkylcarbonylamino
groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonyl amino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups, and
N-substituted arylcarbonylamino groups, boron-containing groups,
aluminum-containing groups, silicon-containing groups,
phosphorus-containing groups, and sulfur-containing groups;
providing an anode comprising an anode active material
characterized by a first specific capacity; providing a cathode
comprising a cathode active material characterized by a second
specific capacity, wherein the first specific capacity and the
second specific capacity are matched such that the battery is
characterized by a rated charge voltage greater than about 4.2 V;
assembling the anode and cathode and optionally a separator into an
electrochemical cell; adding the electrolyte solution to the cell;
and sealing the cell to form the high voltage battery.
17. The method of claim 16 wherein the cathode active material is
characterized by a specific capacity of at least about 10 mAh/(g of
active material) upon discharge at a current of about 0.01 C over a
voltage range of about 4.9 V to about 4.2 V.
18. The method of claim 16 wherein the cathode active material
comprises a material selected from the group consisting of nickel,
manganese, and cobalt.
19. The method of claim 16 wherein the cathode active material
comprises a spinel structure lithium metal oxide, a layered
structure lithium metal oxide, or a lithium-rich layered structured
lithium metal oxide.
20. The method of claim 16 wherein the cathode active material
comprises a lithium metal phosphate.
Description
[0001] This application claims priority to and the benefit of each
of the following applications: U.S. Provisional Application No.
61/495,318 filed Jun. 9, 2011 entitled "Battery Electrolytes for
High Voltage Cathode Materials"; U.S. Provisional Application No.
61/543,262 filed Oct. 4, 2011 entitled "Battery Electrolytes for
High Voltage Cathode Materials"; U.S. Provisional Application No.
61/597,509 filed Feb. 10, 2012 entitled "Battery Electrolytes for
High Voltage Cathode Materials"; and U.S. application Ser. No.
13/459,702 filed Apr. 30, 2012 entitled "Materials for Battery
Electrolytes and Methods for Use"; each of which applications is
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The invention relates generally to battery electrolytes.
More particularly, the invention relates to battery electrolytes to
improve stability of batteries, such as one or more of high voltage
stability, thermal stability, electrochemical stability, and
chemical stability.
[0003] An electrolyte serves to transportions and prevent
electrical contact between electrodes in a battery. Organic
carbonate-based electrolytes are most commonly used in lithium-ion
("Li-ion") batteries, and, more recently, efforts have been made to
develop new classes of electrolytes based on sulfones, silanes, and
nitriles. Unfortunately, these conventional electrolytes typically
cannot be operated at high voltages, since they are unstable above
4.5 V or other high voltages. At high voltages, conventional
electrolytes can decompose, for example, by catalytic oxidation in
the presence of cathode materials, to produce undesirable products
that affect both the performance and safety of a battery.
[0004] In the case of Li-ion batteries, cobalt and
nickel-containing phosphates, fluorophosphates, fluorosulphates,
spinels, and silicates have been reported to have higher energy
densities than LiFePO.sub.4, LiMn.sub.2O.sub.4, and other commonly
used cathode materials. However, these cathode materials also have
redox potentials greater than 4.5 V, allowing for operation of the
battery at higher voltages but also possibly causing severe
electrolyte decomposition in the battery. In order to use a cathode
material to deliver a higher energy density at a higher voltage
platform, the hurdle of electrolyte decomposition should be
addressed at least up to, or above, a redox potential of the
cathode material.
[0005] Another problem with both organic carbonate-based
electrolytes and other classes of electrolytes is chemical
stability at elevated temperatures. Even at low voltages, elevated
temperatures can cause conventional electrolytes to decompose, for
example, by catalytic oxidation in the presence of cathode
materials, to produce undesirable products that affect both
performance and safety of a battery.
[0006] It is against this background that a need arose to develop
the electrolytes and related methods and systems described herein.
Certain embodiments of the inventions disclosed herein address
these and other challenges.
BRIEF SUMMARY
[0007] Certain embodiments of the invention are directed to an
electrolyte and an electrolyte solution for a high voltage battery.
The electrolyte includes a lithium salt, a non-aqueous solvent, and
a compound represented by the formula (I):
##STR00001##
wherein R.sub.1, R.sub.2, and R.sub.3 are independently selected
from the group consisting of substituted and unsubstituted
C.sub.1-C.sub.20 alkyl groups, substituted and unsubstituted
C.sub.1-C.sub.20 alkenyl groups, substituted and unsubstituted
C.sub.1-C.sub.20 alkynyl groups, and substituted and unsubstituted
C.sub.5-C.sub.20 aryl groups; X is nitrogen or oxygen; and Y is
selected from the group consisting of hydride groups, halo groups,
hydroxy groups, thio groups, alkyl groups, alkenyl groups, alkynyl
groups, aryl groups, iminyl groups, alkoxy groups, alkenoxy groups,
alkynoxy groups, aryloxy groups, carboxy groups, alkylcarbonyloxy
groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonyl amino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups, boron-containing groups, aluminum-containing groups,
silicon-containing groups, phosphorus-containing groups, and
sulfur-containing groups. In certain embodiments, the electrolyte
solution is characterized by electrochemical stability in a high
voltage battery at voltages above about 4.2 V. In certain
embodiments, the electrolyte solution is characterized by
electrochemical stability when the battery is operated in an
environment at high temperatures.
[0008] Certain embodiments of the invention are directed to a
battery including an anode having an anode active material
characterized by a first specific capacity, a cathode having a
cathode active material characterized by a second specific capacity
and an electrolyte comprising a lithium salt, a non-aqueous
solvent, and a compound represented by the formula (I) above. The
first specific capacity and the second specific capacity are
matched such that the battery is characterized by a rated charge
voltage greater than about 4.2V. In certain embodiments, the
battery includes a cathode active material that is characterized by
a specific capacity of at least about 10 mAh/(g of active material)
upon discharge at a current of about 0.01 C over a voltage range of
about 4.9 V to about 4.2 V. In certain embodiments, the battery has
a coulombic efficiency at 100 cycles from an initial cycle of at
least about 90% when the battery is operated in an environment at a
temperature of about 50 degrees Celsius.
[0009] Other embodiments of the invention are directed to methods
of forming, conditioning, and operating a battery including such
high voltage and high temperature electrolyte solutions. For
example, methods of operating or using a battery can include
providing the battery, and cycling such battery to supply power for
consumer electronics, portable electronics, hybrid vehicles,
electrical vehicles, power tools, power grid, military
applications, and aerospace applications. For example, methods of
forming a battery can include providing an anode, providing a
cathode, and providing an electrolyte solution facilitating the
flow of current between the anode and the cathode. The electrolyte
can include an electrolyte solution of certain embodiments of the
invention. The methods of forming the battery can also include
converting a stabilizing additive compound of the electrolyte into
a derivative thereof.
[0010] Other aspects and embodiments of the invention are also
contemplated. The foregoing summary and the following detailed
description are not meant to restrict the invention to any
particular embodiment but are merely meant to describe some
embodiments of the invention.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0011] FIG. 1 illustrates a Li-ion battery implemented in
accordance with an embodiment of the invention.
[0012] FIG. 2 illustrates the operation of a Li-ion battery and a
graphical representation of an illustrative non-limiting mechanism
of action of an electrolyte including an additive compound,
according to an embodiment of the invention.
[0013] FIG. 3A compares capacity retention with and without a
stabilizing additive over several cycles, and FIG. 3B compares
coulombic efficiency with and without the stabilizing additive over
several cycles, according to an embodiment of the invention.
[0014] FIG. 4 compares capacity retention with and without a
stabilizing additive over several cycles at 25.degree. C.,
according to an embodiment of the invention.
[0015] FIG. 5 superimposes results of measurements of capacity
retention at 50.degree. C. onto FIG. 4, according to an embodiment
of the invention.
[0016] FIG. 6 is a plot of capacity retention at the 50th cycle as
a function of concentration of a stabilizing additive, according to
an embodiment of the invention.
[0017] FIG. 7 is a plot of coulombic efficiency at the 50.sup.th
cycle as a function of concentration of a stabilizing additive,
according to an embodiment of the invention.
[0018] FIG. 8 sets forth superimposed cyclic voltammograms for the
1.sup.st cycle through the 3.sup.rd cycle. according to an
embodiment of the invention.
[0019] FIG. 9 sets forth superimposed cyclic voltammograms for the
4.sup.th cycle through the 6.sup.th cycle, according to an
embodiment of the invention.
[0020] FIG. 10 compares capacity retention with and without a
stabilizing additive over several cycles after aging, according to
an embodiment of the invention.
[0021] FIG. 11 compares capacity retention with and without a
stabilizing additive over several cycles at 50.degree. C. for a
LiMn.sub.1.5Ni.sub.0.5O.sub.4 cathode material, according to an
embodiment of the invention.
[0022] FIG. 12 compares capacity retention with and without a
stabilizing additive over several cycles at 50.degree. C. for a
LiMn.sub.2O.sub.4 cathode material, according to an embodiment of
the invention.
[0023] FIG. 13 sets forth open circuit voltage measurements at
50.degree. C., according to an embodiment of the invention.
[0024] FIG. 14 sets forth residual current measurements at a
constant voltage at 50.degree. C., according to an embodiment of
the invention.
[0025] FIG. 15 compares capacity retention with and without a
stabilizing additive over several cycles, according to an
embodiment of the invention.
[0026] FIG. 16 compares capacity retention with stabilizing
additives including silicon and stabilizing additives lacking
silicon, according to an embodiment of the invention.
[0027] FIG. 17 compares specific capacity upon discharge at the
50.sup.th cycle for battery cells including various
silicon-containing stabilizing additives, according to an
embodiment of the invention.
[0028] FIG. 18 compares capacity retention of silicon-containing
stabilizing additives over several cycles, according to an
embodiment of the invention.
[0029] FIG. 19 compares specific capacity upon discharge at the
100.sup.th cycle with and without silicon-containing stabilizing
additives in conventional electrolytes, according to an embodiment
of the invention.
[0030] FIG. 20 compares specific capacity upon discharge at
different temperatures with and without a silicon-containing
stabilizing additive, according to an embodiment of the
invention.
[0031] FIG. 21 compares capacity retention at the 25.sup.th cycle
with and without a silicon-containing stabilizing additive for
various cathode materials, according to an embodiment of the
invention.
[0032] FIG. 22 sets forth residual current measurements for battery
cells held at about 4.5V, about 4.9V, and about 5.1V for about 10
hours at 50 degrees C., according to an embodiment of the
invention.
[0033] FIG. 23 compares coulombic efficiency with and without a
stabilizing additive over several cycles for a
LiMn.sub.1.5Ni.sub.0.5O.sub.4 cathode material, according to an
embodiment of the invention.
[0034] FIG. 24 compares specific capacity upon discharge with and
without a stabilizing additive over several cycles after storage at
50 degrees C. for 8 days for a doped LiCoPO.sub.4 cathode material,
according to an embodiment of the invention.
[0035] FIG. 25 compares capacity retention with and without a
stabilizing additive at different charging and discharging rates,
according to an embodiment of the invention.
[0036] FIG. 26 compares capacity retention with and without a
stabilizing additive at room temperature for a
LiMn.sub.1.5Ni.sub.0.5O.sub.4 cathode material, according to an
embodiment of the invention.
[0037] FIG. 27 sets forth voltage profiles at the 1.sup.st and
100.sup.th cycles during charging with and without a stabilizing
additive, according to an embodiment of the invention.
[0038] FIG. 28 sets forth voltage profiles at the 3.sup.rd cycle
during discharging with and without a stabilizing additive,
according to an embodiment of the invention.
[0039] FIG. 29 compares coulombic efficiency of battery cells with
and without stabilizing additives at the first cycle.
[0040] FIG. 30 compares capacity retention of the battery cells
with and without stabilizing additives over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle, according to an
embodiment of the invention.
[0041] FIG. 31 compares capacity retention of the battery cells
with and without stabilizing additives over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle, according to an
embodiment of the invention.
[0042] FIG. 32 compares coulombic efficiency of the battery cells
with and without stabilizing additives at the first cycle,
according to an embodiment of the invention.
[0043] FIG. 33 compares capacity retention of the battery cells
with and without stabilizing additives over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle, according to an
embodiment of the invention.
[0044] FIG. 34 compares coulombic efficiency of the battery cells
with and without stabilizing additives at the first cycle,
according to an embodiment of the invention.
[0045] FIG. 35 compares coulombic efficiency of the battery cells
with and without stabilizing additives at the first cycle,
according to an embodiment of the invention.
[0046] FIGS. 36 through 43 compare capacity retention of the
battery cells with and without stabilizing additives over several
cycles, expressed in terms of a percentage of an initial specific
capacity upon discharge retained at a particular cycle, according
to an embodiment of the invention.
[0047] FIG. 44 compares energy efficiency of the battery cells with
and without stabilizing additives over several cycles, according to
an embodiment of the invention.
[0048] FIG. 45 and FIG. 46 compare capacity retention of the
battery cells with and without stabilizing additives over several
cycles, expressed in terms of a percentage of an initial specific
capacity upon discharge retained at a particular cycle, according
to an embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0049] The following definitions apply to some of the aspects
described with respect to some embodiments of the invention. These
definitions may likewise be expanded upon herein. Each term is
further explained and exemplified throughout the description,
figures, and examples. Any interpretation of the terms in this
description should take into account the full description, figures,
and examples presented herein.
[0050] As used herein, the singular terms "a," "an," and "the"
include the plural referents unless the context clearly dictates
otherwise. Thus, for example, reference to an object can include
multiple objects unless the context clearly dictates otherwise.
[0051] As used herein, the term "set" refers to a collection of one
or more objects. Thus, for example, a set of objects can include a
single object or multiple objects. Objects of a set also can be
referred to as members of the set. Objects of a set can be the same
or different. In some instances, objects of a set can share one or
more common characteristics.
[0052] As used herein, the terms "substantially" and "substantial"
refer to a considerable degree or extent. When used in conjunction
with an event or circumstance, the terms can refer to instances in
which the event or circumstance occurs precisely as well as
instances in which the event or circumstance occurs to a close
approximation, such as accounting for typical tolerance levels or
variability of the embodiments described herein.
[0053] As used herein, the term "sub-micron range" refers to a
general range of dimensions less than about 1 .mu.m or less than
about 1,000 nm, such as less than about 999 nm, less than about 900
nm, less than about 800 nm, less than about 700 nm, less than about
600 nm, less than about 500 nm, less than about 400 nm, less than
about 300 nm, or less than about 200 nm, and down to about 1 nm or
less. In some instances, the term can refer to a particular
sub-range within the general range, such as from about 1 nm to
about 100 nm, from about 100 nm to about 200 nm, from about 200 nm
to about 300 nm, from about 300 nm to about 400 nm, from about 400
nm to about 500 nm, from about 500 nm to about 600 nm, from about
600 nm to about 700 nm, from about 700 nm to about 800 nm, from
about 800 nm to about 900 nm, or from about 900 nm to about 999
nm.
[0054] As used herein, the term "main group element" refers to a
chemical element in any of Group IA (or Group 1), Group IIA (or
Group 2), Group IIIA (or Group 13), Group IVA (or Group 14), Group
VA (or Group 15), Group VIA (or Group 16), Group VIIA (or Group
17), and Group VIIIA (or Group 18). A main group element is also
sometimes referred to as a s-block element or a p-block
element.
[0055] As used herein, the term "transition metal" refers to a
chemical element in any of Group IVB (or Group 4), Group VB (or
Group 5), Group VIB (or Group 6), Group VIIB (or Group 7), Group
VIIIB (or Groups 8, 9, and 10), Group IB (or Group 11), and Group
IIB (or Group 12). A transition metal is also sometimes referred to
as a d-block element.
[0056] As used herein, the term "rare earth element" refers to any
of Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,
and Lu.
[0057] As used herein, the term "halogen" refers to any of F, Cl,
Br, I, and At.
[0058] As used herein, the term "chalcogen" refers to any of O, S,
Se, Te, and Po.
[0059] As used herein, the term "heteroatom" refers to any atom
that is not a carbon atom or a hydrogen atom. Examples of
heteroatoms include atoms of halogens, chalcogens, Group IIIA (or
Group 13) elements, Group IVA (or Group 14) elements other than
carbon, and Group VA (or Group 15) elements.
[0060] As used herein, the term "alkane" refers to a saturated
hydrocarbon, including the more specific definitions of "alkane"
herein. For certain embodiments, an alkane can include from 1 to
100 carbon atoms. The term "lower alkane" refers to an alkane that
includes from 1 to 20 carbon atoms, such as from 1 to 10 carbon
atoms, while the term "upper alkane" refers to an alkane that
includes more than 20 carbon atoms, such as from 21 to 100 carbon
atoms. The term "branched alkane" refers to an alkane that includes
one or more branches, while the term "unbranched alkane" refers to
an alkane that is straight-chained. The term "cycloalkane" refers
to an alkane that includes one or more ring structures. The term
"heteroalkane" refers to an alkane that has one or more of its
carbon atoms replaced by one or more heteroatoms, such as N, Si, S,
O, F, and P. The term "substituted alkane" refers to an alkane that
has one or more of its hydrogen atoms replaced by one or more
substituent groups, such as halo groups, while the term
"unsubstituted alkane" refers to an alkane that lacks such
substituent groups. Combinations of the above terms can be used to
refer to an alkane having a combination of characteristics. For
example, the term "branched lower alkane" can be used to refer to
an alkane that includes from 1 to 20 carbon atoms and one or more
branches. Examples of alkanes include methane, ethane, propane,
cyclopropane, butane, 2-methylpropane, cyclobutane, and charged,
hetero, or substituted forms thereof.
[0061] As used herein, the term "alkyl group" refers to a
monovalent form of an alkane, including the more specific
definitions of "alkyl" herein. For example, an alkyl group can be
envisioned as an alkane with one of its hydrogen atoms removed to
allow bonding to another group. The term "lower alkyl group" refers
to a monovalent form of a lower alkane, while the term "upper alkyl
group" refers to a monovalent form of an upper alkane. The term
"branched alkyl group" refers to a monovalent form of a branched
alkane, while the term "unbranched alkyl group" refers to a
monovalent form of an unbranched alkane. The term "cycloalkyl
group" refers to a monovalent form of a cycloalkane, and the term
"heteroalkyl group" refers to a monovalent form of a heteroalkane.
The term "substituted alkyl group" refers to a monovalent form of a
substituted alkane, while the term "unsubstituted alkyl group"
refers to a monovalent form of an unsubstituted alkane. Examples of
alkyl groups include methyl, ethyl, n-propyl, isopropyl,
cyclopropyl, butyl, isobutyl, t-butyl, cyclobutyl, and charged,
hetero, or substituted forms thereof.
[0062] As used herein, the term "alkylene group" refers to a
bivalent form of an alkane, including the more specific definitions
of "alkylene group" herein. For example, an alkylene group can be
envisioned as an alkane with two of its hydrogen atoms removed to
allow bonding to one or more additional groups. The term "lower
alkylene group" refers to a bivalent form of a lower alkane, while
the term "upper alkylene group" refers to a bivalent form of an
upper alkane. The term "branched alkylene group" refers to a
bivalent form of a branched alkane, while the term "unbranched
alkylene group" refers to a bivalent form of an unbranched alkane.
The term "cycloalkylene group" refers to a bivalent form of a
cycloalkane, and the term "heteroalkylene group" refers to a
bivalent form of a heteroalkane. The term "substituted alkylene
group" refers to a bivalent form of a substituted alkane, while the
term "unsubstituted alkylene group" refers to a bivalent form of an
unsubstituted alkane. Examples of alkylene groups include
methylene, ethylene, propylene, 2-methylpropylene, and charged,
hetero, or substituted forms thereof.
[0063] As used herein, the term "alkene" refers to an unsaturated
hydrocarbon that includes one or more carbon-carbon double bonds,
including the more specific definitions of "alkene" herein. For
certain embodiments, an alkene can include from 2 to 100 carbon
atoms. The term "lower alkene" refers to an alkene that includes
from 2 to 20 carbon atoms, such as from 2 to 10 carbon atoms, while
the term "upper alkene" refers to an alkene that includes more than
20 carbon atoms, such as from 21 to 100 carbon atoms. The term
"cycloalkene" refers to an alkene that includes one or more ring
structures. The term "heteroalkene" refers to an alkene that has
one or more of its carbon atoms replaced by one or more
heteroatoms, such as N, Si, S, O, F, and P. The term "substituted
alkene" refers to an alkene that has one or more of its hydrogen
atoms replaced by one or more substituent groups, such as halo
groups, while the term "unsubstituted alkene" refers to an alkene
that lacks such substituent groups. Combinations of the above terms
can be used to refer to an alkene having a combination of
characteristics. For example, the term "substituted lower alkene"
can be used to refer to an alkene that includes from 1 to 20 carbon
atoms and one or more substituent groups. Examples of alkenes
include ethene, propene, cyclopropene, 1-butene, trans-2 butene,
cis-2-butene, 1,3-butadiene, 2-methylpropene, cyclobutene, and
charged, hetero, or substituted forms thereof.
[0064] As used herein, the term "alkenyl group" refers to a
monovalent form of an alkene, including the more specific
definitions of "alkenyl group" herein. For example, an alkenyl
group can be envisioned as an alkene with one of its hydrogen atoms
removed to allow bonding to another group. The term "lower alkenyl
group" refers to a monovalent form of a lower alkene, while the
term "upper alkenyl group" refers to a monovalent form of an upper
alkene. The term "cycloalkenyl group" refers to a monovalent form
of a cycloalkene, and the term "heteroalkenyl group" refers to a
monovalent form of a heteroalkene. The term "substituted alkenyl
group" refers to a monovalent form of a substituted alkene, while
the term "unsubstituted alkenyl group" refers to a monovalent form
of an unsubstituted alkene. Examples of alkenyl groups include
ethenyl, 2-propenyl (i.e., allyl), isopropenyl, cyclopropenyl,
butenyl, isobutenyl, t-butenyl, cyclobutenyl, and charged, hetero,
or substituted forms thereof.
[0065] As used herein, the term "alkenylene group" refers to a
bivalent form of an alkene, including the more specific definitions
of "alkenylene group" herein. For example, an alkenylene group can
be envisioned as an alkene with two of its hydrogen atoms removed
to allow bonding to one or more additional groups. The term "lower
alkenylene group" refers to a bivalent form of a lower alkene,
while the term "upper alkenylene group" refers to a bivalent form
of an upper alkene. The term "cycloalkenylene group" refers to a
bivalent form of a cycloalkene, and the term "heteroalkenylene
group" refers to a bivalent form of a heteroalkene. The term
"substituted alkenylene group" refers to a bivalent form of a
substituted alkene, while the term "unsubstituted alkenylene group"
refers to a bivalent form of an unsubstituted alkene. Examples of
alkenyl groups include ethenylene, propenylene,
2-methylpropenylene, and charged, hetero, or substituted forms
thereof.
[0066] As used herein, the term "alkyne" refers to an unsaturated
hydrocarbon that includes one or more carbon-carbon triple bonds,
including the more specific definitions of "alkyne" herein. In some
embodiments, an alkyne can also include one or more carbon-carbon
double bonds. For certain embodiments, an alkyne can include from 2
to 100 carbon atoms. The term "lower alkyne" refers to an alkyne
that includes from 2 to 20 carbon atoms, such as from 2 to 10
carbon atoms, while the term "upper alkyne" refers to an alkyne
that includes more than 20 carbon atoms, such as from 21 to 100
carbon atoms. The term "cycloalkyne" refers to an alkyne that
includes one or more ring structures. The term "heteroalkyne"
refers to an alkyne that has one or more of its carbon atoms
replaced by one or more heteroatoms, such as N, Si, S, O, F, and P.
The term "substituted alkyne" refers to an alkyne that has one or
more of its hydrogen atoms replaced by one or more substituent
groups, such as halo groups, while the term "unsubstituted alkyne"
refers to an alkyne that lacks such substituent groups.
Combinations of the above terms can be used to refer to an alkyne
having a combination of characteristics. For example, the term
"substituted lower alkyne" can be used to refer to an alkyne that
includes from 1 to 20 carbon atoms and one or more substituent
groups. Examples of alkynes include ethyne (i.e., acetylene),
propyne, 1-butyne, 1-buten-3-yne, 1-pentyne, 2-pentyne,
3-penten-1-yne, 1-penten-4-yne, 3-methyl-1-butyne, and charged,
hetero, or substituted forms thereof.
[0067] As used herein, the term "alkynyl group" refers to a
monovalent form of an alkyne, including the more specific
definitions of "alkynyl group" herein. For example, an alkynyl
group can be envisioned as an alkyne with one of its hydrogen atoms
removed to allow bonding to another group. The term "lower alkynyl
group" refers to a monovalent form of a lower alkyne, while the
term "upper alkynyl group" refers to a monovalent form of an upper
alkyne. The term "cycloalkynyl group" refers to a monovalent form
of a cycloalkyne, and the term "heteroalkynyl group" refers to a
monovalent form of a heteroalkyne. The term "substituted alkynyl
group" refers to a monovalent form of a substituted alkyne, while
the term "unsubstituted alkynyl group" refers to a monovalent form
of an unsubstituted alkyne. Examples of alkynyl groups include
ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, t-butynyl, and
charged, hetero, or substituted forms thereof.
[0068] As used herein, the term "alkynylene group" refers to a
bivalent form of an alkyne, including the more specific definitions
of "alkynylene group" herein. For example, an alkynylene group can
be envisioned as an alkyne with two of its hydrogen atoms removed
to allow bonding to one or more additional groups of a molecule.
The term "lower alkynylene group" refers to a bivalent form of a
lower alkyne, while the term "upper alkynylene group" refers to a
bivalent form of an upper alkyne. The term "cycloalkynylene group"
refers to a bivalent form of a cycloalkyne, and the term
"heteroalkynylene group" refers to a bivalent form of a
heteroalkyne. The term "substituted alkynylene group" refers to a
bivalent form of a substituted alkyne, while the term
"unsubstituted alkynylene group" refers to a bivalent form of an
unsubstituted alkyne. Examples of alkynylene groups include
ethynylene, propynylene, 1-butynylene, 1-buten-3-ynylene, and
charged, hetero, or substituted forms thereof.
[0069] As used herein, the term "arene" refers to an aromatic
hydrocarbon, including the more specific definitions of "arene"
herein. For certain embodiments, an arene can include from 5 to 100
carbon atoms. The term "lower arene" refers to an arene that
includes from 5 to 20 carbon atoms, such as from 5 to 14 carbon
atoms, while the term "upper arene" refers to an arene that
includes more than 20 carbon atoms, such as from 21 to 100 carbon
atoms. The term "monocyclic arene" refers to an arene that includes
a single aromatic ring structure, while the term "polycyclic arene"
refers to an arene that includes more than one aromatic ring
structure, such as two or more aromatic ring structures that are
bonded via a carbon-carbon bond or that are fused together. The
term "heteroarene" refers to an arene that has one or more of its
carbon atoms replaced by one or more heteroatoms, such as N, Si, S,
O, F, and P. The term "substituted arene" refers to an arene that
has one or more of its hydrogen atoms replaced by one or more
substituent groups, such as alkyl groups, alkenyl groups, alkynyl
groups, halo groups, hydroxy groups, alkoxy groups, alkenoxy
groups, alkynoxy groups, aryloxy groups, carboxy groups, cyano
groups, nitro groups, amino groups, N-substituted amino groups,
silyl groups, and siloxy groups, while the term "unsubstituted
arene" refers to an arene that lacks such substituent groups.
Combinations of the above terms can be used to refer to an arene
having a combination of characteristics. For example, the term
"monocyclic lower alkene" can be used to refer to an arene that
includes from 5 to 20 carbon atoms and a single aromatic ring
structure. Examples of arenes include benzene, biphenyl,
naphthalene, anthracene, pyridine, pyridazine, pyrimidine,
pyrazine, quinoline, isoquinoline, and charged, hetero, or
substituted forms thereof.
[0070] As used herein, the term "aryl group" refers to a monovalent
form of an arene, including the more specific definitions of "aryl
group" herein. For example, an aryl group can be envisioned as an
arene with one of its hydrogen atoms removed to allow bonding to
another group. The term "lower aryl group" refers to a monovalent
form of a lower arene, while the term "upper aryl group" refers to
a monovalent form of an upper arene. The term "monocyclic aryl
group" refers to a monovalent form of a monocyclic arene, while the
term "polycyclic aryl group" refers to a monovalent form of a
polycyclic arene. The term "heteroaryl group" refers to a
monovalent form of a heteroarene. The term "substituted aryl group"
refers to a monovalent form of a substituted arene, while the term
"unsubstituted arene group" refers to a monovalent form of an
unsubstituted arene. Examples of aryl groups include phenyl,
biphenylyl, naphthyl, pyridinyl, pyridazinyl, pyrimidinyl,
pyrazinyl, quinolyl, isoquinolyl, and charged, hetero, or
substituted forms thereof.
[0071] As used herein, the term "imine" refers to an organic
compound that includes one or more carbon-nitrogen double bonds,
including the more specific definitions of "imine" herein. For
certain embodiments, an imine can include from 1 to 100 carbon
atoms. The term "lower imine" refers to an imine that includes from
1 to 20 carbon atoms, such as from 1 to 10 carbon atoms, while the
term "upper imine" refers to an imine that includes more than 20
carbon atoms, such as from 21 to 100 carbon atoms. The term
"cycloimine" refers to an imine that includes one or more ring
structures. The term "heteroimine" refers to an imine that has one
or more of its carbon atoms replaced by one or more heteroatoms,
such as N, Si, S, O, F, and P. The term "substituted imine" refers
to an imine that has one or more of its hydrogen atoms replaced by
one or more substituent groups, such as halo groups, while the term
"unsubstituted imine" refers to an imine that lacks such
substituent groups. Combinations of the above terms can be used to
refer to an imine having a combination of characteristics. For
example, the term "substituted lower imine" can be used to refer to
an imine that includes from 1 to 20 carbon atoms and one or more
substituent groups. Examples of imines include
R.sub.1CH.dbd.NR.sub.2, where R.sub.1 and R.sub.2 are independently
selected from hydride groups, alkyl groups, alkenyl groups, and
alkynyl groups.
[0072] As used herein, the term "iminyl group" refers to a
monovalent form of an imine, including the more specific
definitions of "iminyl" herein. For example, an iminyl group can be
envisioned as an imine with one of its hydrogen atoms removed to
allow bonding to another group. The term "lower iminyl group"
refers to a monovalent form of a lower imine, while the term "upper
iminyl group" refers to a monovalent form of an upper imine. The
term "cycloiminyl group" refers to a monovalent form of a
cycloimine, and the term "heteroiminyl group" refers to a
monovalent form of a heteroimine. The term "substituted iminyl
group" refers to a monovalent form of a substituted imine, while
the term "unsubstituted iminyl group" refers to a monovalent form
of an unsubstituted imine. Examples of iminyl groups include
--R.sub.1CH.dbd.NR.sub.2, R.sub.3CH.dbd.NR.sub.4--,
--CH.dbd.NR.sub.5, and R.sub.6CH.dbd.N--, where R.sub.1 and R.sub.4
are independently selected from alkylene groups, alkenylene groups,
and alkynylene groups, and R.sub.2, R.sub.3, R.sub.5, and R.sub.6
are independently selected from hydride groups, alkyl groups,
alkenyl groups, and alkynyl groups.
[0073] As used herein, the term "alcohol" refers to an organic
compound that includes one or more hydroxy groups. For certain
embodiments, an alcohol can also be referred to as a substituted
hydrocarbon, such as a substituted arene that has one or more of
its hydrogen atoms replaced by one or more hydroxy groups. Examples
of alcohols include ROH, where R is selected from alkyl groups,
alkenyl groups, alkynyl groups, and aryl groups.
[0074] As used herein, the term "ketone" refers to a molecule that
includes one or more groups of the form: --CO--. Examples of
ketones include R.sub.1--CO--R.sub.2, where R.sub.1 and R.sub.2 are
independently selected from alkyl groups, alkenyl groups, alkynyl
groups, and aryl groups, and R.sub.3--CO--R.sub.4--CO--R.sub.5,
where R.sub.3 and R.sub.5 are independently selected from alkyl
groups, alkenyl groups, alkynyl groups, and aryl groups, and
R.sub.4 is selected from alkylene groups, alkenylene groups, and
alkynylene groups.
[0075] As used herein, the term "carboxylic acid" refers to an
organic compound that includes one or more carboxy groups. For
certain embodiments, a carboxylic acid can also be referred to as a
substituted hydrocarbon, such as a substituted arene that has one
or more of its hydrogen atoms replaced by one or more carboxy
groups. Examples of carboxylic acids include RCOOH, where R is
selected from alkyl groups, alkenyl groups, alkynyl groups, and
aryl groups.
[0076] As used herein, the term "hydride group" refers to --H.
[0077] As used herein, the term "halo group" refers to --X, where X
is a halogen. Examples of halo groups include fluoro, chloro,
bromo, and iodo.
[0078] As used herein, the term "hydroxy group" refers to --OH.
[0079] As used herein, the term "alkoxy group" refers to --OR,
where R is an alkyl group.
[0080] As used herein, the term "alkenoxy group" refers to --OR,
where R is an alkenyl group.
[0081] As used herein, the term "alkynoxy group" refers to --OR,
where R is an alkynyl group.
[0082] As used herein, the term "aryloxy group" refers to --OR,
where R is an aryl group.
[0083] As used herein, the term "carboxy group" refers to
--COOH.
[0084] As used herein, the term "alkylcarbonyloxy group" refers to
RCOO--, where R is an alkyl group.
[0085] As used herein, the term "alkenylcarbonyloxy group" refers
to RCOO--, where R is an alkenyl group.
[0086] As used herein, the term "alkynylcarbonyloxy group" refers
to RCOO--, where R is an alkynyl group.
[0087] As used herein, the term "arylcarbonyloxy group" refers to
RCOO--, where R is an aryl group.
[0088] As used herein, the term "thio group" refers to --SH.
[0089] As used herein, the term "alkylthio group" refers to --SR,
where R is an alkyl group.
[0090] As used herein, the term "alkenylthio group" refers to --SR,
where R is an alkenyl group.
[0091] As used herein, the term "alkynylthio group" refers to --SR,
where R is an alkynyl group.
[0092] As used herein, the term "arylthio group" refers to --SR,
where R is an aryl group.
[0093] As used herein, the term "cyano group" refers to --CN.
[0094] As used herein, the term "nitro group" refers to
--NO.sub.2.
[0095] As used herein, the term "amino group" refers to
--NH.sub.2.
[0096] As used herein, the term "N-substituted amino group" refers
to an amino group that has one or more of its hydrogen atoms
replaced by one or more substituent groups. Examples of
N-substituted amino groups include --NR.sub.1R.sub.2, where R.sub.1
and R.sub.2 are independently selected from hydride groups, alkyl
groups, alkenyl groups, alkynyl groups, and aryl groups, and at
least one of R.sub.1 and R.sub.2 is not a hydride group.
[0097] As used herein, the term "alkylcarbonylamino group" refers
to --NHCOR, where R is an alkyl group.
[0098] As used herein, the term "N-substituted alkylcarbonylamino
group" refers to an alkylcarbonylamino group that has its hydrogen
atom replaced by a substituent group. Examples of N-substituted
alkylcarbonylamino groups include --NR.sub.1COR.sub.2, where
R.sub.1 is selected from alkyl groups, alkenyl groups, alkynyl
groups, and aryl groups, and R.sub.2 is an alkyl group.
[0099] As used herein, the term "alkenylcarbonylamino group" refers
to --NHCOR, where R is an alkenyl group.
[0100] As used herein, the term "N-substituted alkenylcarbonylamino
group" refers to an alkenylcarbonylamino group that has its
hydrogen atom replaced by a substituent group. Examples of
N-substituted alkenylcarbonylamino groups include
--NR.sub.1COR.sub.2, where R.sub.1 is selected from alkyl groups,
alkenyl groups, alkynyl groups, and aryl groups, and R.sub.2 is an
alkenyl group.
[0101] As used herein, the term "alkynylcarbonylamino group" refers
to --NHCOR, where R is an alkynyl group.
[0102] As used herein, the term "N-substituted alkynylcarbonylamino
group" refers to an alkynylcarbonylamino group that has its
hydrogen atom replaced by a substituent group. Examples of
N-substituted alkynylcarbonylamino groups include
--NR.sub.1COR.sub.2, where R.sub.1 is selected from alkyl groups,
alkenyl groups, alkynyl groups, and aryl groups, and R.sub.2 is an
alkynyl group.
[0103] As used herein, the term "arylcarbonylamino group" refers to
--NHCOR, where R is an aryl group.
[0104] As used herein, the term "N-substituted arylcarbonylamino
group" refers to an arylcarbonylamino group that has its hydrogen
atom replaced by a substituent group. Examples of N-substituted
arylcarbonylamino groups include --NR.sub.1COR.sub.2, where R.sub.1
is selected from alkyl groups, alkenyl groups, alkynyl groups, and
aryl groups, and R.sub.2 is an aryl group.
[0105] As used herein, the term "silyl group" refers to
--SiR.sub.1R.sub.2R.sub.3, where R.sub.1, R.sub.2, and R.sub.3 are
independently selected from, for example, hydride groups, alkyl
groups, alkenyl groups, alkynyl groups, and aryl groups.
[0106] As used herein, the term "siloxy group" refers to
--OSiR.sub.1R.sub.2R.sub.3, where R.sub.1, R.sub.2, and R.sub.3 are
independently selected from, for example, hydride groups, alkyl
groups, alkenyl groups, alkynyl groups, and aryl groups.
[0107] As used herein, the term "ether linkage" refers to
--O--.
[0108] As used herein, the term "specific capacity" refers to the
amount (e.g., total or maximum amount) of electrons or lithium ions
a material is able to hold (or discharge) per unit mass and can be
expressed in units of mAh/g. In certain aspects and embodiments,
specific capacity can be measured in a constant current discharge
(or charge) analysis which includes discharge (or charge) at a
defined rate over a defined voltage range against a defined
counterelectrode. For example, specific capacity can be measured
upon discharge at a rate of about 0.05 C (e.g., about 7.5 mA/g)
from 4.95 V to 2.0 V versus a Li/Li.sup.+ counterelectrode. Other
discharge rates and other voltage ranges also can be used, such as
a rate of about 0.1 C (e.g., about 15 mA/g), or about 0.5 C (e.g.,
about 75 mA/g), or about 1.0 C (e.g., about 150 mA/g).
[0109] As used herein, a rate "C" refers to either (depending on
context) the discharge current as a fraction or multiple relative
to a "1 C" current value under which a battery (in a substantially
fully charged state) would substantially fully discharge in one
hour, or the charge current as a fraction or multiple relative to a
"1 C" current value under which the battery (in a substantially
fully discharged state) would substantially fully charge in one
hour.
[0110] As used herein, the terms "cycle" or "cycling" refer to
complementary discharging and charging processes.
[0111] As used herein, the term "rated charge voltage" refers to an
upper end of a voltage range during operation of a battery, such as
a maximum voltage during charging, discharging, and/or cycling of
the battery. In some aspects and some embodiments, a rated charge
voltage refers to a maximum voltage upon charging a battery from a
substantially fully discharged state through its (maximum) specific
capacity at an initial cycle, such as the 1.sup.st cycle, the
2.sup.nd cycle, or the 3.sup.rd cycle. In some aspects and some
embodiments, a rated charge voltage refers to a maximum voltage
during operation of a battery to substantially maintain one or more
of its performance characteristics, such as one or more of
coulombic efficiency, retention of specific capacity, retention of
energy density, and rate capability.
[0112] As used herein, the term "rated cut-off voltage" refers to a
lower end of a voltage range during operation of a battery, such as
a minimum voltage during charging, discharging, and/or cycling of
the battery. In some aspects and some embodiments, a rated cut-off
voltage refers to a minimum voltage upon discharging a battery from
a substantially fully charged state through its (maximum) specific
capacity at an initial cycle, such as the 1.sup.st cycle, the
2.sup.nd cycle, or the 3.sup.rd cycle, and, in such aspects and
embodiments, a rated cut-off voltage also can be referred as a
rated discharge voltage. In some aspects and some embodiments, a
rated cut-off voltage refers to a minimum voltage during operation
of a battery to substantially maintain one or more of its
performance characteristics, such as one or more of coulombic
efficiency, retention of specific capacity, retention of energy
density, and rate capability.
[0113] As used herein, the "maximum voltage" refers to the voltage
at which both the anode and the cathode are fully charged. In an
electrochemical cell, each electrode may have a given specific
capacity and one of the electrodes will be the limiting electrode
such that one electrode will be fully charged and the other will be
as fully charged as it can be for that specific pairing of
electrodes. The process of matching the specific capacities of the
electrodes to achieve the desired capacity of the electrochemical
cell is "capacity matching."
[0114] To the extent certain battery characteristics can vary with
temperature, such characteristics are specified at room temperature
(25.degree. C.), unless the context clearly dictates otherwise.
[0115] Certain embodiments of the invention relate to electrolyte
solutions that provide a number of desirable characteristics when
implemented within batteries, such as high stability during battery
cycling to high voltages at or above 4.2 V, high specific capacity
upon charge or discharge, high coulombic efficiency, excellent
retention of specific capacity and energy density over several
cycles of charging and discharging, high rate capability, reduced
electrolyte decomposition, reduced resistance and its build-up
during cycling, and improved calendar life. The electrolyte
solutions provide these performance characteristics over a wide
range of operational temperatures, encompassing about -40.degree.
C. or less and up to about 60.degree. C., up to about 80.degree.
C., or more. In some embodiments, these performance characteristics
can at least partially derive from the presence of a set of
additives or compounds, which can impart high voltage and high
temperature stability to an electrolyte while retaining or
improving battery performance.
[0116] For example, in terms of their stability, electrolytes that
include compounds according to some embodiments of the invention
can undergo little or no decomposition (beyond any initial
decomposition related to film formation at battery electrodes or as
part of initial cycling) when batteries incorporating the
electrolytes are cycled at least up to a redox potential of a high
voltage cathode material, such as at least about 4.2 V or about 4.5
V and up to about 4.95 V, up to about 5 V, up to about 5.5 V, up to
about 6 V or more, as measured relative to a lithium metal anode
(Li/Li.sup.+ anode). These voltages may vary for other
counterelectrodes, but the improved performance is retained
according to some embodiments. Such reduction in electrolyte
decomposition, in turn, yields one or more of the following
benefits: (1) mitigation against loss of electrolyte; (2)
mitigation against the production of undesirable by-products that
can affect battery performance; (3) mitigation against the
production of gaseous by-products that can affect battery safety;
and (4) reduced resistance and its build-up during cycling.
[0117] Also, batteries incorporating the electrolyte solutions
including compounds according to certain embodiments can exhibit
high coulombic efficiency, as expressed in terms of a ratio of a
specific capacity upon discharge to a specific capacity upon charge
for a given cycle. As measured upon cycling at a rate of 1 C (or
another reference rate higher or lower than 1 C, such as 0.1 C,
0.05 C, 0.5 C, 5 C, or 10 C), batteries incorporating the improved
electrolytes can have a coulombic efficiency at the 1.sup.st cycle
(or another initial cycle, such as the 2.sup.nd cycle, the 3.sup.rd
cycle, the 4.sup.th cycle, the 5.sup.th cycle, the 6.sup.th cycle,
the 7.sup.th cycle, the 8.sup.th cycle, the 9.sup.th cycle, or the
10.sup.th cycle) or an average coulombic efficiency over an initial
set of cycles, such as cycles 1 through 3, cycles 1 through 5,
cycles 3 through 10, cycles 5 through 10, or cycles 5 through 15,
that is at least about 60%, such as at least about 70%, at least
about 80%, at least about 90%, or at least about 95%, and up to
about 97%, up to about 98%, up to about 99%, up to about 99.8%, up
to about 99.9%, up to about 99.99%, up to about 99.999%, or more.
Stated in another way, and as measured upon cycling at a
substantially constant current of 150 mA/g (or another reference
current higher or lower than 150 mA/g, such as 15 mA/g, 7.5 mA/g,
75 mA/g, 750 mA/g, or 1,500 mA/g), batteries incorporating the
electrolyte solutions including compounds of certain embodiments
can have a coulombic efficiency at the 1.sup.st cycle (or another
initial cycle, such as the 2.sup.nd cycle, the 3.sup.rd cycle, the
4.sup.th cycle, the 5th cycle, the 6.sup.th cycle, the 7.sup.th
cycle, the 8.sup.th cycle, the 9.sup.th cycle, or the 10.sup.th
cycle) or an average coulombic efficiency over an initial set of
cycles, such as cycles 1 through 3, cycles 1 through 5, cycles 3
through 10, cycles 5 through 10, or cycles 5 through 15, that is at
least about 60%, such as at least about 70%, at least about 80%, at
least about 90%, or at least about 95%, and up to about 97%, up to
about 98%, up to about 99%, up to about 99.8%, up to about 99.9%,
up to about 99.99%, up to about 99.999%, or more. The stated values
for current can be per unit mass of a cathode active material, and
can be expressed in units of mA/(g of the cathode active
material).
[0118] In addition, batteries incorporating the electrolyte
solutions including compounds of certain embodiments can exhibit
excellent capacity retention defined in terms of a specific
capacity (both upon charge and upon discharge) over several
charging and discharging cycles, such that, after 100 cycles, after
200 cycles, after 300 cycles, after 400 cycles, after 500 cycles,
after 600 cycles, after 1,000 cycles, or even after 5,000 cycles
from an initial cycle, at least about 50%, at least about 60%, at
least about 70%, at least about 75%, at least about 80%, or at
least about 85%, and up to about 90%, up to about 95%, up to about
98%, or more of an initial or maximum specific capacity at the
1.sup.st cycle (or another initial cycle, such as the 2.sup.nd
cycle, the 3.sup.rd cycle, the 4.sup.th cycle, the 5.sup.th cycle,
the 6.sup.th cycle, the 7.sup.th cycle, the 8.sup.th cycle, the
9.sup.th cycle, or the 10.sup.th cycle) is retained, as measured
upon cycling at a rate of 1 C (or another reference rate higher or
lower than 1 C, such as 0.1 C, 0.05 C, 0.5 C, 5 C, or 10 C) or upon
cycling at a substantially constant current of 150 mA/g (or another
reference current higher or lower than 150 mA/g, such as 15 mA/g,
7.5 mA/g, 75 mA/g, 750 mA/g, or 1,500 mA/g). The stated values for
current can be per unit mass of a cathode active material, and can
be expressed in units of mA/(g of the cathode active material).
[0119] In addition, batteries incorporating the electrolyte
solutions including compounds of certain embodiments can exhibit
excellent efficiency retention defined in terms of a coulombic
efficiency over several charging and discharging cycles, such that,
after 100 cycles, after 200 cycles, after 300 cycles, after 400
cycles, after 500 cycles, after 600 cycles, after 1,000 cycles, or
even after 5,000 cycles from an initial cycle, at least about 70%,
at least about 80%, at least about 90%, or at least about 95%, and
up to about 97%, up to about 98%, up to about 99%, up to about
99.9%, or more of an initial or maximum coulombic efficiency at the
1.sup.st cycle (or another initial cycle, such as the 2.sup.nd
cycle, the 3.sup.rd cycle, the 4th cycle, the 5.sup.th cycle, the
6.sup.th cycle, the 7.sup.th cycle, the 8.sup.th cycle, the
9.sup.th cycle, or the 10.sup.th cycle) is retained, as measured
upon cycling at a rate of 1 C (or another reference rate higher or
lower than 1 C, such as 0.1 C, 0.05 C, 0.5 C, 5 C, or 10 C) or upon
cycling at a substantially constant current of 150 mA/g (or another
reference current higher or lower than 150 mA/g, such as 15 mA/g,
7.5 mA/g, 75 mA/g, 750 mA/g, or 1,500 mA/g). The stated values for
current can be per unit mass of a cathode active material, and can
be expressed in units of mA/(g of the cathode active material).
[0120] In terms of rate capability or power performance, batteries
incorporating the electrolyte solutions including compounds of
certain embodiments can exhibit excellent rate capability defined
in terms of retention of specific capacity (both upon charge and
upon discharge) when charged, discharged, or cycled at higher
rates, such that, as measured at a high rate of 1 C (or another
high rate that is n times a reference, low rate, with n>1 such
as n=5, n=10, n=20, or n=100), at least about 60%, at least about
70%, at least about 75%, at least about 80%, at least about 85%, at
least about 90%, or at least about 95%, and up to about 99%, up to
about 99.5%, up to about 99.9%, or more of a low rate or maximum
specific capacity at a rate of 0.05 C (or another reference rate
higher or lower than 0.05 C, such as 0.1 C) is retained. Stated in
another way, batteries incorporating the electrolyte solutions
including compounds of certain embodiments can exhibit excellent
retention of specific capacity (both upon charge and upon
discharge) when charged, discharged, or cycled at higher currents,
such that, as measured at a substantially constant current of 150
mA/g (or another current that is n times a reference current, with
n>1 such as n=5, n=10, n=20, or n=100), at least about 60%, at
least about 70%, at least about 75%, at least about 80%, at least
about 85%, at least about 90%, or at least about 95%, and up to
about 99%, up to about 99.5%, up to about 99.9%, or more of a low
rate or maximum specific capacity at a substantially constant
current of 7.5 mA/g (or another reference current higher or lower
than 7.5 mA/g, such as 15 mA/g) is retained. The stated values for
current can be per unit mass of a cathode active material, and can
be expressed in units of mA/(g of the cathode active material).
[0121] Likewise, batteries incorporating the electrolyte solutions
including compounds of certain embodiments can exhibit excellent
rate capability defined in terms of retention of energy density
when cycled at higher rates, such that, as measured at a rate of 1
C (or another rate that is n times a reference rate, with n>1
such as n=5, n=10, n=20, or n=100), at least about 60%, at least
about 70%, at least about 75%, at least about 80%, at least about
85%, at least about 90%, or at least about 95%, and up to about
99%, up to about 99.5%, up to about 99.9%, or more of a low rate or
maximum coulombic efficiency at a rate of 0.05 C (or another
reference rate higher or lower than 0.05 C, such as 0.1 C) is
retained. Stated in another way, batteries incorporating the
electrolyte solutions including compounds of certain embodiments
can exhibit excellent retention of energy density when cycled at
higher currents, such that, as measured at a substantially constant
current of 150 mA/g (or another current that is n times a reference
current, with n>1 such as n=5, n=10, n=20, or n=100), at least
about 60%, at least about 70%, at least about 75%, at least about
80%, at least about 85%, at least about 90%, or at least about 95%,
and up to about 99%, up to about 99.5%, up to about 99.9%, or more
of a low rate or maximum coulombic efficiency at a substantially
constant current of 7.5 mA/g (or another reference current higher
or lower than 7.5 mA/g, such as 15 mA/g) is retained. The stated
values for current can be per unit mass of a cathode active
material, and can be expressed in units of mA/(g of the cathode
active material).
[0122] In addition, batteries incorporating the electrolyte
solutions including compounds of certain embodiments can have a
reduced resistance and a reduced resistance build-up during
cycling. Such reduced resistance, in turn, yields one or more of
the following benefits: (1) efficient removal of Li ions from
electrodes; (2) higher specific capacity and higher energy density;
(3) reduced hysteresis in a voltage profile between charging and
discharging; and (4) mitigation against temperature increase during
cycling.
[0123] Advantageously, the electrolyte solutions including
compounds of certain embodiments can provide these performance
characteristics over a wide range of operational temperatures, such
as when batteries incorporating the electrolyte solutions including
compounds of certain embodiments are charged, discharged, or cycled
from about -40.degree. C. to about 80.degree. C., from about
-40.degree. C. to about 60.degree. C., from about -40.degree. C. to
about 25.degree. C., from about -40.degree. C. to about 0.degree.
C., from about 0.degree. C. to about 60.degree. C., from about
0.degree. C. to about 25.degree. C., from about 25.degree. C. to
about 60.degree. C., or other ranges encompassing temperatures
greater than or below 25.degree. C. The improved electrolytes also
can provide these performance characteristics over a wide range of
operational voltages between a rated cut-off voltage and a rated
charge voltage, such as when the batteries are charged, discharged,
or cycled between voltage ranges encompassing about 2 V to about
4.2 V, about 2 V to about 4.3 V, about 2 V to about 4.5 V, about 2
V to about 4.6 V, about 2 V to about 4.7 V, about 2 V to about 4.95
V, about 3 V to about 4.2 V, about 3 V to about 4.3 V, about 3 V to
about 4.5 V, about 3 V to about 4.6 V, about 3 V to about 4.7 V,
about 3 V to about 4.9 V, about 2 V to about 6 V, about 3 V to
about 6 V, about 4.2 V to about 6 V, about 4.5 V to about 6 V,
about 2 V to about 5.5 V, about 3 V to about 5.5 V, about 4.5 V to
about 5.5 V, about 2 V to about 5 V, about 3 V to about 5 V, about
4.5 V to about 5 V, or about 5 V to about 6 V, as measured relative
to a lithium metal anode (Li/Li.sup.+ anode). Stated in another
way, the batteries incorporating the electrolyte solutions
including compounds of certain embodiments have a rated charge
voltage of at least about 4.2 V, at least about 4.3 V, at least
about 4.5 V, at least about 4.6 V, at least about 4.7 V, or at
least about 5 V, and up to about 5.5 V, up to about 6 V or more, as
measured relative to anodes included within the batteries and upon
charging at a rate of 1 C (or another reference rate higher or
lower than 1 C, such as 0.1 C, 0.05 C, 0.5 C, 5 C, or 10 C) or upon
charging at a substantially constant current of 150 mA/g (or
another reference current higher or lower than 150 mA/g, such as 15
mA/g, 7.5 mA/g, 75 mA/g, 750 mA/g, or 1,500 mA/g). The batteries
can be charged to the rated charge voltage while substantially
retaining the performance characteristics specified above, such as
in terms of coulombic efficiency, retention of specific capacity,
retention of coulombic efficiency, and rate capability.
[0124] A high voltage electrolyte according to some embodiments of
the invention can be formed with reference to the formula:
base electrolyte+stabilizing compound(s).fwdarw.high voltage
electrolyte (1)
[0125] A high temperature electrolyte according to some embodiments
of the invention can be formed with reference to the formula:
base electrolyte+stabilizing compound(s).fwdarw.high temperature
electrolyte (2)
[0126] In formulas (1) and (2), the base electrolyte can include a
set of solvents and a set of salts, such as a set of Li-containing
salts in the case of Li-ion batteries. Examples of suitable
solvents include nonaqueous electrolyte solvents for use in Li-ion
batteries, including carbonates, such as ethylene carbonate,
dimethyl carbonate, ethyl methyl carbonate, propylene carbonate,
methyl propyl carbonate, and diethyl carbonate; sulfones; silanes;
nitriles; esters; ethers; and combinations thereof. Additional
examples of suitable solvents include those discussed in Xu et al.,
"Sulfone-based Electrolytes for Lithium-Ion Batteries," Journal of
the Electrochemical Society, 149 (7) A920-A926 (2002); and Nagahama
et al., "High Voltage Performances of Li.sub.2NiPO.sub.4F Cathode
with Dinitrile-Based Electrolytes," Journal of the Electrochemical
Society, 157 (6) A748-A752 (2010); the disclosures of which are
incorporated herein by reference in their entirety. Examples of
suitable salts include Li-containing salts for use in Li-ion
batteries, such as lithium hexafluorophosphate ("LiPF.sub.6"),
lithium perchlorate ("LiClO.sub.4"), lithium tetrafluoroborate
("LiBF.sub.4"), lithium trifluoromethane sulfonate
("LiCF.sub.3SO.sub.3"), lithium bis(trifluoromethane sulfonyl)
imide ("LiN(CF.sub.3SO.sub.2).sub.2"), lithium bis(perfluoroethyl
sulfonyl) imide ("LiN(CF.sub.3CF.sub.2SO.sub.2).sub.2"), lithium
bis(oxalato)borate ("LiB(C.sub.2O.sub.4).sub.2"), lithium difluoro
oxalato borate ("LiF.sub.2BC.sub.2O.sub.4"), and combinations
thereof. Other suitable solvents and salts can be used to yield
high voltage and high temperature electrolytes having low
electronic conductivity, high Li ion solubility, low viscosity,
high thermal stability, and other desirable characteristics.
[0127] In formulas (1) and (2), the stabilizing compound(s) is a
set of additives that can correspond to a single additive, a pair
of different additives, or a combination of three or more different
additives. Examples of suitable stabilizing additives include
silicon-containing compounds, such as silanes, siloxanes, and other
organosilicon compounds including a SiX.sub.4 moiety or a SiR.sub.3
moiety. One or more of the stabilizing additives described herein
can be used in combination with one or more conventional additives
to impart improved performance characteristics.
[0128] Examples of suitable silicon-containing compounds include
silanes represented with reference to the formula:
##STR00002##
[0129] In formula (3), X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be the same or different, and, in some embodiments, at least one of
X.sub.1, X.sub.2, X.sub.3, and X.sub.4 is an organic group
including from 1 to 20 carbon atoms. For other embodiments, at
least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 is an organic
group including more than 20 carbon atoms. X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can be independently selected from, for
example, hydride group, halo groups, hydroxy group, thio group,
alkyl groups, alkenyl groups, alkynyl groups, aryl groups, iminyl
groups, alkoxy groups, alkenoxy groups, alkynoxy groups, aryloxy
groups, carboxy groups, alkylcarbonyloxy groups, alkenylcarbonyloxy
groups, alkynylcarbonyloxy groups, arylcarbonyloxy groups,
alkylthio groups, alkenylthio groups, alkynylthio groups, arylthio
groups, cyano groups, N-substituted amino groups,
alkylcarbonylamino groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonylamino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups,
N-substituted arylcarbonylamino groups, boron-containing groups,
aluminum-containing groups, silicon-containing groups (e.g., silyl
groups and siloxy groups), phosphorus-containing groups, and
sulfur-containing groups.
[0130] Examples of suitable silane compounds include, but are not
limited to: 1,2-Bis(chlorodimethylsilyl)ethane,
Bis(trimethylsilylmethyl)sulfide, Tetrakis(trimethylsilyl)silane,
Tetraethylsilane, 4-(Trimethylsilyl)-3-butyn-2-one,
Trivinylmethylsilane, Dimethyldichlorosilane, Hexamethyldisilane,
Tris(trimethylsilyl)silane, Vinyl(trifluoromethyl)dimethylsilane,
Tetravinylsilane, 1,3-Bis[(trimethylsilyl)ethynyl]benzene,
1,2-Bis(methyldifluorosilyl)ethane,
2,2-Bis-(trimethylsilyl)dithiane, Phenyltrimethoxysilane,
Pentafluorophenyltriethoxysilane, and combinations thereof.
[0131] According to certain embodiments, suitable
silicon-containing compounds according to formula (3) include
compounds where at least one of X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 includes a nitrogen atom or group. X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can be the same or different, and, in some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including from 1 to 20 carbon atoms. For other
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including more than 20 carbon atoms. In some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
includes an ether linkage, and, in other embodiments, at least one
of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 includes a silicon atom
or another heteroatom. X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, N-substituted arylcarbonylamino groups,
and heterocycle groups.
[0132] In certain preferred embodiments, X.sub.1, X.sub.2, and
X.sub.3 are alkyl groups, and in particular methyl groups. In
certain preferred embodiments where each of X.sub.1, X.sub.2, and
X.sub.3 are methyl groups, these silicon-containing compounds are
referred to as NTMS compounds after the silicon-nitrogen bond ("N")
and the trimethylsilyl ("TMS") provided by each of X.sub.1,
X.sub.2, and X.sub.3 being methyl groups. As described in more
detail below, NTMS compounds exhibit desirable properties as
additives according to certain embodiments of the invention.
[0133] Examples of suitable NTMS compounds include, but are not
limited to: Bis(trimethylsilyl)carbodiimide, Trimethylsilylazide,
Bis(trimethylsilyl)urea, N,O
-Bis(trimethylsilyl)trifluoroacetamide,
N,O-Bis(trimethylsilyl)acetamide,
(N,N-Dimethylamino)triethylsilane, Methylsilatrane, Trimethylsilyl
isocyanate, Tetraisocyanatosilane, 1-Trimethylsilyl-1,2,4-triazole,
2-(Trimethylsilyl)thiazole, Heptamethyldisilazane, and combinations
thereof.
[0134] According to certain embodiments, suitable
silicon-containing compounds according to formula (3) include
compounds where at least one of X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 includes a carbon atom or group. X.sub.1, X.sub.2, X.sub.3,
and X.sub.4 can be the same or different, and, in some embodiments,
at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 is an
organic group including from 1 to 20 carbon atoms. For other
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including more than 20 carbon atoms. In some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
includes an ether linkage, and, in other embodiments, at least one
of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 includes a silicon atom
or another heteroatom. X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, N-substituted arylcarbonylamino groups,
and heterocycle groups.
[0135] In certain preferred embodiments, X.sub.1, X.sub.2, and
X.sub.3 are alkyl groups, and in particular methyl groups. In
certain preferred embodiments where each of X.sub.1, X.sub.2, and
X.sub.3 are methyl groups, these silicon-containing compounds are
referred to as CTMS compounds after the silicon-carbon bond ("C")
and the trimethylsilyl ("TMS") provided by each of X.sub.1,
X.sub.2, and X.sub.3 being methyl groups. As described in more
detail below, CTMS compounds exhibit desirable properties as
additives according to certain embodiments of the invention.
[0136] Examples of suitable CTMS compounds include, but are not
limited to: 2-(Trimethylsilyl)thiazole,
Bis(trimethylsilylmethyl)sulfide,
1,3-Bis[(trimethylsilyl)ethynyl]benzene,
4-(Trimethylsilyl)-3-butyn-2-one, 2,2-Bis-(trimethylsilyl)dithiane,
and combinations thereof.
[0137] According to certain embodiments, suitable
silicon-containing compounds according to formula (3) include
compounds where at least one of X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 includes a fluorine atom or group. X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can be the same or different, and, in some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including from 1 to 20 carbon atoms. For other
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including more than 20 carbon atoms. In some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
includes an ether linkage, and, in other embodiments, at least one
of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 includes a silicon atom
or another heteroatom. X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, N-substituted arylcarbonylamino groups,
and heterocycle groups.
[0138] Examples of compounds according to certain embodiments of
the invention in which X.sub.4 includes a fluorine atom or group
include, but are not limited to:
Tridecafluoro-1,2,2-tetrahydrooctyl)triethoxysilane,
1h,1h,2h,2h-Perfluorooctyltriethoxysilane,
(Pentafluorophenyl)triethoxysilane.
Bis(1h,1h,2h,2h-perfluorooctyltetramethyldisiloxane,
1,3-Bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,
1,2-Bis(methyldifluorosilyl)ethane,
1-3-Bis(trifluoropropyl)tetramethyldisiloxane,
Vinyl(trifluoromethyl)dimethylsilane, and combinations thereof.
[0139] In certain preferred embodiments, X.sub.1, X.sub.2, and
X.sub.3 are alkyl groups, and in particular methyl groups. In such
preferred embodiments where each of R.sub.1, R.sub.2, and R.sub.3
are methyl groups, these silicon-containing compounds are referred
to as trimethylsilyl ("TMS") compounds provided by each of X.sub.1,
X.sub.2, and X.sub.3 being methyl groups. TMS compounds that also
contain a fluorine atom or group can exhibit desirable properties
as additives according to certain embodiments of the invention.
[0140] Examples of suitable TMS compounds which also contain a
fluorine atom or group include, but are not limited to:
Trimethylsilyl trifluoroacetate,
N,O-Bis(trimethylsilyl)trifluoroacetamide, and combinations
thereof.
[0141] According to certain embodiments, suitable
silicon-containing compounds according to formula (3) include
compounds where at least one of X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 includes an aromatic ring. X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 can be the same or different, and, in some embodiments, at
least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 is an organic
group including from 1 to 20 carbon atoms. For other embodiments,
at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 is an
organic group including more than 20 carbon atoms. In some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
includes an ether linkage, and, in other embodiments, at least one
of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 includes a silicon atom
or another heteroatom. X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, N-substituted arylcarbonylamino groups,
and heterocycle groups.
[0142] Examples of compounds according to certain embodiments of
the invention in which X.sub.4 includes an aromatic ring include,
but are not limited to: 1,3-Bis[(trimethylsilyl)ethynyl]benzene,
Phenyltrimethoxysilane, Pentafluorophenyltriethoxysilane, and
combinations thereof.
[0143] According to certain embodiments, suitable
silicon-containing compounds according to formula (3) include
compounds where at least one of X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 includes one or more unsaturated bond. X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can be the same or different, and, in some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including from 1 to 20 carbon atoms. For other
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including more than 20 carbon atoms. In some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
includes an ether linkage, and, in other embodiments, at least one
of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 includes a silicon atom
or another heteroatom. X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, N-substituted arylcarbonylamino groups,
and heterocycle groups.
[0144] Examples of compounds according to certain embodiments of
the invention in which X.sub.4 includes one or more unsaturated
bond include, but are not limited to:
Bis(trimethylsilyl)carbodiimide, Tris(trimethylsilyloxy)ethylene,
Isopropenoxytrimethylsilane, 4-(Trimethylsilyl)-3-butyn-2-one,
Trivinylmethylsilane, Trivinylmethoxysilane,
Vinyl(trifluoromethyl)dimethylsilane, Bis(trimethylsilyl)itaconate,
Hexavinyldisiloxane, Trivinylethoxysilane,
Allyltris(trimethoxysilyloxy)silane,
1,3-Bis[(trimethylsilyl)ethynyl]benzene, Phenyltrimethoxysilane,
Pentafluorophenyltriethoxysilane, and combinations thereof.
[0145] According to certain embodiments, suitable
silicon-containing compounds according to formula (3) include
compounds where at least one of X.sub.1, X.sub.2, X.sub.3, and
X.sub.4 includes an oxygen atom or group. X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can be the same or different, and, in some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including from 1 to 20 carbon atoms. For other
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
is an organic group including more than 20 carbon atoms. In some
embodiments, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
includes an ether linkage, and, in other embodiments, at least one
of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 includes a silicon atom
or another heteroatom. X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, N-substituted arylcarbonylamino groups,
and heterocycle groups.
[0146] Examples of compounds according to certain embodiments of
the invention in which X.sub.4 includes an oxygen atom or group
include, but are not limited to:
1,3-Bis(trimethylsiloxy)-1,3-dimethyldisiloxane,
Tris(trimethylsilyl)phosphate, Decamethyltetrasiloxane,
(Tridecafluoro-1,1,2,2-tetrahydrooctyl)triethoxysilane,
Trimethylsilyl trifluoroacetate, Tris(trimethylsilyloxy)silane,
Silicon tetraacetate, Tetramethyl orthosilicate,
Decamethylcyclopentasiloxane, Tris(trimethylsilyloxy)ethylene,
Ethoxytrimethylsilane, Octakis(dimethylsiloxy)-t8-silsesquioxane,
Isopropenoxytrimethylsilane, Hexamethyldisiloxane,
Phenyltrimethoxysilane, Pentafluorophenyltriethoxysilane,
Hexamethylcyclotrisiloxane, Tris(trimethylsilyl)phosphite,
N,O-Bis(trimethylsilyl)acetamide, Tris(trimethylsilyl) borate,
Tetrakis(trimethylsilyloxy)silane,
Tetrakis(dimethylsilyloxy)silane,
Bis(tridecafluoro-1,1,2,2-tetrahydrooctyl)tetramethyldisiloxane,
(Cyclohexenyloxy)trimethylsilane, Mono-(trimethylsilyl) phosphite,
2-(3,4-Epoxycyclohexyl)ethyltrimethoxysilane,
Trimethyl-n-propoxysilane, Methoxytrimethylsilane,
Tetrakis(trimethylsiloxy)titanium, Bis(trimethoxysilylpropyl)urea,
1,3-Bis(trifluoropropyl)tetramethyldisiloxane,
Methacryloxypropylsilatrane, Triethoxysilylundecanal ethylene
glycol acetal, Tris(trimethylsiloxy)antimony,
Trivinylmethoxysilane, Tetradecamethylhexasiloxane,
Methyltris(trimethylsiloxy)silane, Dodecamethylcyclohexasiloxane,
Bis(trimethylsilyl)itaconate, Methylsilatrane, Hexavinyldisiloxane,
3-Ethylheptamethyltrisiloxane,
1,3-Bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,
Trivinylethoxysilane, 1,1,1,3,3-Pentamethyl-3-acetoxydisiloxane,
Bis(trimethylsilyl)adipate, Allyltris(trimethoxysilyloxy)silane,
Trimethylsilyl polyphosphate, Dodecamethylcyclohexasiloxane, and
combinations thereof.
[0147] In certain preferred embodiments, X.sub.1, X.sub.2, and
X.sub.3 are alkyl groups, and in particular methyl groups. In such
preferred embodiments where each of X.sub.1, X.sub.2, and X.sub.3
are methyl groups, these silicon-containing compounds are referred
to as OTMS compounds after the silicon-oxygen bond ("O") and the
trimethylsilyl ("TMS") provided by each of X.sub.1, X.sub.2, and
X.sub.3 being methyl groups. As described in more detail below,
OTMS compounds exhibit desirable properties as additives according
to certain embodiments of the invention.
[0148] Examples of suitable OTMS compounds include, but are not
limited to: 1,3-Bis(trimethylsiloxy)-1,3-dimethyldisiloxane,
decamethyltetrasiloxane, Trimethylsilyl trifluoroacetate,
Ethoxytrimethylsilane, Isopropenoxytrimethylsilane,
Hexamethyldisiloxane, Tris(trimethylsilyl)phosphate,
Tris(trimethylsilyl)phosphite, Tetrakis(trimethylsilyloxy) silane,
Tetrakis(trimethylsilyloxy)silane, Tris(dimethylsilyloxy)ethylene,
N,O-Bis(trimethylsilyl)acetamide, Tris(trimethylsilyl) borate,
Bis(tridecafluoro-1,1,2,2-tetrahydrooctyl)tetramethyldisiloxane,
Trimethyl-n-propoxysilane, (Cyclohexenyloxy)trimethylsilane,
Mono-(trimethylsilyl) phosphite, Methoxytrimethylsilane,
Tetrakis(trimethylsiloxy)titanium,
1,3-Bis(trifluoropropyl)tetramethyldisiloxane,
Tris(trimethylsiloxy)antimony, Trivinylmethoxysilane,
Tetradecamethylhexasiloxane, Methyltris(trimethylsiloxy)silane,
Dodecamethylcyclohexasiloxane, Bis(trimethylsilyl)itaconate,
3-Ethylheptamethyltrisiloxane,
1,3-Bis(heptadecafluoro-1,1,2,2-tetrahydrodecyl)tetramethyldisiloxane,
1,1,1,3,3-Pentamethyl-3-acetoxydisiloxane,
Bis(trimethylsilyl)adipate, Allyltris(trimethoxysilyloxy)silane,
Trimethylsilyl polyphosphate, and combinations thereof.
[0149] Desirable performance characteristics can be obtained by the
inclusion of at least one A and at least one silicon-A bond in the
silane according to formula (3), where A is a carbon atom or a
heteroatom, such as one selected from boron, aluminum, silicon,
phosphorus, sulfur, fluorine, chlorine, bromine, and iodine atoms.
For example, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4
can include A that is bonded to the silicon of formula (3), and
remaining ones of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. It is contemplated that multiple ones of X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can each include A that is bonded to the
silicon of formula (3), such that the silane according to formula
(3) can include multiple silicon-A bonds, such as in the range of 2
to 4 or 3 to 4. It is also contemplated that multiple ones of
X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can include different and
respective A's that are bonded to the silicon of formula (3), such
that the silane according to formula (3) can include multiple
silicon-A bonds (with respect to the different A's), such as in the
range of 2 to 4 or 3 to 4. The number of silicon-A bonds can be
increased beyond 4, for example, by the inclusion of silicon and
silicon-A bonds within one or more of X.sub.1, X.sub.2, X.sub.3,
and X.sub.4.
[0150] Desirable performance characteristics also can be obtained
by the inclusion of at least one A and at least one silicon-O-A
bond in the silane according to formula (3), where O is oxygen, and
A is a carbon atom or a heteroatom, such as one selected from
boron, aluminum, silicon, phosphorus, and sulfur atoms. For
example, at least one of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
include O-A that is bonded to the silicon of formula (3) via a
silicon-O-A bond, and remaining ones of X.sub.1, X.sub.2, X.sub.3,
and X.sub.4 can be independently selected from, for example,
hydride group, hydroxy group, alkyl groups, alkenyl groups, alkynyl
groups, aryl groups, iminyl groups, alkoxy groups, alkenoxy groups,
alkynoxy groups, aryloxy groups, carboxy groups, alkylcarbonyloxy
groups, alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. It is contemplated that multiple ones of X.sub.1, X.sub.2,
X.sub.3, and X.sub.4 can each include O-A that is bonded to the
silicon of formula (3) via a silicon-O-A bond, such that the silane
according to formula (3) can include multiple silicon-O-A bonds,
such as in the range of 2 to 4 or 3 to 4. It is also contemplated
that multiple ones of X.sub.1, X.sub.2, X.sub.3, and X.sub.4 can
include different and respective A's that are bonded to the silicon
of formula (3) via oxygen atoms, such that the silane according to
formula (3) can include multiple silicon-O-A bonds (with respect to
the different A's), such as in the range of 2 to 4 or 3 to 4. The
number of silicon-O-A bonds can be increased beyond 4, for example,
by the inclusion of silicon, oxygen, and silicon-O-A bonds within
one or more of X.sub.1, X.sub.2, X.sub.3, and X.sub.4.
[0151] In the case that A is boron, particular examples of
silicon-containing compounds according to formula (3) include
silicon-containing boranes represented with reference to the
formulas:
##STR00003##
In formulas (4) through (7), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be the same or
different, and, in some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 is an organic group including from
1 to 20 carbon atoms. For other embodiments, at least one of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 includes an ether
linkage, and, in other embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. In formula (7), R.sub.12 is a bivalent, organic group
including from 1 to 20 carbon atoms in some embodiments, and, for
other embodiments, R.sub.12 is a bivalent, organic group including
more than 20 carbon atoms. R.sub.12 can be selected from, for
example, alkylene groups, alkenylene groups, and alkynylene
groups.
[0152] In the case that A is aluminum, particular examples of
silicon-containing compounds according to formula (3) include those
represented with reference to the formulas:
##STR00004##
In formulas (8) through (11), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be the same or
different, and, in some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 is an organic group including from
1 to 20 carbon atoms. For other embodiments, at least one of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 includes an ether
linkage, and, in other embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. In formula (11), R.sub.12 is a bivalent, organic group
including from 1 to 20 carbon atoms in some embodiments, and, for
other embodiments, R.sub.12 is a bivalent, organic group including
more than 20 carbon atoms. R.sub.12 can be selected from, for
example, alkylene groups, alkenylene groups, and alkynylene
groups.
[0153] In the case that A is carbon, particular examples of
silicon-containing compounds according to formula (3) include those
represented with reference to the formulas:
##STR00005##
In formulas (12) through (17), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14,
and R.sub.15 can be the same or different, and, in some
embodiments, at least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11,
R.sub.12, R.sub.13, R.sub.14, and R.sub.15 is an organic group
including from 1 to 20 carbon atoms. For other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 is an organic group including more than 20
carbon atoms. In some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, and
R.sub.15 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 can be independently selected from, for
example, hydride group, hydroxy group, alkyl groups, alkenyl
groups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,
alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,
alkylcarbonyloxy groups, alkenylcarbonyloxy groups,
alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio
groups, alkenylthio groups, alkynylthio groups, arylthio groups,
cyano groups, N-substituted amino groups, alkylcarbonylamino
groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonylamino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups, and
N-substituted arylcarbonylamino groups. In formulas (16) and (17),
R.sub.16 is a bivalent, organic group including from 1 to 20 carbon
atoms in some embodiments, and, for other embodiments, R.sub.16 is
a bivalent, organic group including more than 20 carbon atoms.
R.sub.16 can be selected from, for example, alkylene groups,
alkenylene groups, and alkynylene groups.
[0154] In the case that A is carbon, additional examples of
silicon-containing compounds according to formula (3) include those
represented with reference to the formulas:
##STR00006##
In formulas (18) and (19), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 can be the same or different, and, in some embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 is an organic group including from 1 to 20 carbon
atoms. For other embodiments, at least one of R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 includes a silicon atom or another heteroatom. R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. In some embodiments, R.sub.7 does not include any carbonyl
group of the form --CO--, and, in other embodiments, R.sub.7 does
not include any sulfonyl group of the form --SO.sub.2--.
[0155] In certain preferred embodiments, compounds of formula (19)
alkyl groups comprise R.sub.1, R.sub.2, and R.sub.3. In some
embodiments, R.sub.1, R.sub.2, and R.sub.3 are methyl groups.
Examples of such trimethylsilyl compounds in which R.sub.7 is
chosen such that the compound comprises an ester include, but are
not limited to: Silicon tetraacetate, Bis(trimethylsilyl)itaconate,
Bis(trimethylsilyl)adipate,
1,1,1,3,3-Pentamethyl-3-acetoxydisiloxane, Trimethylsilyl
trifluoroacetate, and combinations thereof.
[0156] In the case that A is silicon, particular examples of
silicon-containing compounds according to formula (3) include
silanes represented with reference to the formulas:
##STR00007##
In formulas (20) through (25), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14,
and R.sub.15 can be the same or different, and, in some
embodiments, at least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11,
R.sub.12, R.sub.13, R.sub.14, and R.sub.15 is an organic group
including from 1 to 20 carbon atoms. For other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 is an organic group including more than 20
carbon atoms. In some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, and
R.sub.15 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 can be independently selected from, for
example, hydride group, hydroxy group, alkyl groups, alkenyl
groups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,
alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,
alkylcarbonyloxy groups, alkenylcarbonyloxy groups,
alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio
groups, alkenylthio groups, alkynylthio groups, arylthio groups,
cyano groups, N-substituted amino groups, alkylcarbonylamino
groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonylamino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups, and
N-substituted arylcarbonylamino groups. In formulas (24) and (25),
R.sub.16 is a bivalent, organic group including from 1 to 20 carbon
atoms in some embodiments, and, for other embodiments, R.sub.16 is
a bivalent, organic group including more than 20 carbon atoms.
R.sub.16 can be selected from, for example, alkylene groups,
alkenylene groups, and alkynylene groups. In some embodiments, the
silanes according to formulas (20) through (25) are non-polymeric
and have molecular weights no greater than about 10,000 daltons,
such as no greater than about 5,000 daltons, no greater than about
4,000 daltons, no greater than about 3,000 daltons, no greater than
about 2,000 daltons, no greater than about 1,000 daltons, no
greater than about 900 daltons, no greater than about 800 daltons,
no greater than about 700 daltons, no greater than about 600
daltons, or no greater than about 500 daltons.
[0157] Examples of compounds according to certain embodiments of
the invention in which A is silicon include, but are not limited
to: Decamethylcyclopentasiloxane,
Octakis(dimethylsiloxy)-t8-silsesquioxane,
Hexamethycyclotrisiloxane, Octaphenyl-t8-silsesquioxane,
Dodecamethylcyclohexasiloxane, and combinations thereof.
[0158] In the case that A is phosphorus, particular examples of
silicon-containing compounds according to formula (3) include
phosphines represented with reference to the formulas:
##STR00008##
In formulas (26) through (29), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be the same or
different, and, in some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 is an organic group including from
1 to 20 carbon atoms. For other embodiments, at least one of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 includes an ether
linkage, and, in other embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. In formula (29), R.sub.12 is a bivalent, organic group
including from 1 to 20 carbon atoms in some embodiments, and, for
other embodiments, R.sub.12 is a bivalent, organic group including
more than 20 carbon atoms. R.sub.12 can be selected from, for
example, alkylene groups, alkenylene groups, and alkynylene
groups.
[0159] In the case that A is phosphorus, additional examples of
silicon-containing compounds according to formula (3) include
phosphoranes represented with reference to the formulas:
##STR00009##
In formulas (30) through (37), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14,
R.sub.15, R.sub.16, R.sub.17, R.sub.18, and R.sub.19 can be the
same or different, and, in some embodiments, at least one of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14,
R.sub.15, R.sub.16, R.sub.17, R.sub.18, and R.sub.19 is an organic
group including from 1 to 20 carbon atoms. For other embodiments,
at least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12,
R.sub.13, R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, and
R.sub.19 is an organic group including more than 20 carbon atoms.
In some embodiments, at least one of R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10,
R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15, R.sub.16,
R.sub.17, R.sub.18, and R.sub.19 includes an ether linkage, and, in
other embodiments, at least one of R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10,
R.sub.11, R.sub.12, R.sub.13, R.sub.14, R.sub.15, R.sub.16,
R.sub.17, R.sub.18, and R.sub.19 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, and R.sub.19 can
be independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. In formulas (35) through (37), R.sub.20 is a bivalent,
organic group including from 1 to 20 carbon atoms in some
embodiments, and, for other embodiments, R.sub.20 is a bivalent,
organic group including more than 20 carbon atoms. R.sub.20 can be
selected from, for example, alkylene groups, alkenylene groups, and
alkynylene groups.
[0160] In the case that A is phosphorus, additional examples of
silicon-containing compounds according to formula (3) include
phosphates and phosphate derivatives represented with reference to
the formulas:
##STR00010##
In formulas (38) through (41), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be the same or
different, and, in some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 is an organic group including from
1 to 20 carbon atoms. For other embodiments, at least one of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 includes an ether
linkage, and, in other embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, and R.sub.11 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, and R.sub.11 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups. In formula (41), R.sub.12 is a bivalent, organic group
including from 1 to 20 carbon atoms in some embodiments, and, for
other embodiments, R.sub.12 is a bivalent, organic group including
more than 20 carbon atoms. R.sub.12 can be selected from, for
example, alkylene groups, alkenylene groups, and alkynylene
groups.
[0161] A particular example of a phosphate according to formula
(38) is Tris(trimethylsilyl) phosphate represented with reference
to the formula:
##STR00011##
In formula (42), it is contemplated that one or more of the methyl
groups can be modified, such as by substituting a constituent
hydrogen atom with another chemical element or functional group, or
can be replaced by another alkyl group, an alkenyl group, an
alkynyl group, or an aryl group, either in a substituted or an
unsubstituted form. Other functionalizations or modifications of
the phosphate set forth in formula (42) are contemplated. Other
examples of compounds according to certain embodiments of the
invention in which A is phosphorus include, but are not limited to:
Tris(trimethylsilyl)phosphate, Tris(trimethylsilyl)phosphite,
Trimethylsilyl polyphosphate, and combinations thereof.
[0162] In the case that A is sulfur, particular examples of
silicon-containing compounds according to formula (3) include
sulfides represented with reference to the formulas:
(R.sub.1R.sub.2R.sub.3Si)O--S--O(SiR.sub.4R.sub.5R.sub.6) (43)
(R.sub.1R.sub.2R.sub.3Si)O--S--R.sub.7 (44)
In formulas (43) and (44), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 can be the same or different, and, in some embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 is an organic group including from 1 to 20 carbon
atoms. For other embodiments, at least one of R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 includes a silicon atom or another heteroatom. R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups.
[0163] In the case that A is sulfur, additional examples of
silicon-containing compounds according to formula (3) include those
represented with reference to the formulas:
##STR00012##
In formulas (45) through (50), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14,
and R.sub.15 can be the same or different, and, in some
embodiments, at least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4,
R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11,
R.sub.12, R.sub.13, R.sub.14, and R.sub.15 is an organic group
including from 1 to 20 carbon atoms. For other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 is an organic group including more than 20
carbon atoms. In some embodiments, at least one of R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8,
R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13, R.sub.14, and
R.sub.15 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 includes a silicon atom or another
heteroatom. R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.13,
R.sub.14, and R.sub.15 can be independently selected from, for
example, hydride group, hydroxy group, alkyl groups, alkenyl
groups, alkynyl groups, aryl groups, iminyl groups, alkoxy groups,
alkenoxy groups, alkynoxy groups, aryloxy groups, carboxy groups,
alkylcarbonyloxy groups, alkenylcarbonyloxy groups,
alkynylcarbonyloxy groups, arylcarbonyloxy groups, alkylthio
groups, alkenylthio groups, alkynylthio groups, arylthio groups,
cyano groups, N-substituted amino groups, alkylcarbonylamino
groups, N-substituted alkylcarbonylamino groups,
alkenylcarbonylamino groups, N-substituted alkenyl carbonylamino
groups, alkynylcarbonylamino groups, N-substituted
alkynylcarbonylamino groups, arylcarbonylamino groups, and
N-substituted arylcarbonylamino groups. In formulas (49) and (50),
R.sub.16 is a bivalent, organic group including from 1 to 20 carbon
atoms in some embodiments, and, for other embodiments, R.sub.16 is
a bivalent, organic group including more than 20 carbon atoms.
R.sub.16 can be selected from, for example, alkylene groups,
alkenylene groups, and alkynylene groups.
[0164] In the case that A is sulfur, additional examples of
silicon-containing compounds according to formula (3) include
sulfoxides represented with reference to the formulas:
##STR00013##
In formulas (51) and (52), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 can be the same or different, and, in some embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 is an organic group including from 1 to 20 carbon
atoms. For other embodiments, at least one of R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 includes silicon or another heteroatom. R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups.
[0165] In the case that A is sulfur, additional examples of
silicon-containing compounds according to formula (3) include
sulfonates represented with reference to the formulas:
##STR00014##
In formulas (53) and (54), R.sub.1, R.sub.2, and R.sub.3 can
correspond to X.sub.1, X.sub.2, and X.sub.3 according to formula
(3). R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 can be the same or different, and, in some embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 is an organic group including from 1 to 20 carbon
atoms. For other embodiments, at least one of R.sub.1, R.sub.2,
R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 is an organic group
including more than 20 carbon atoms. In some embodiments, at least
one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and
R.sub.7 includes an ether linkage, and, in other embodiments, at
least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
and R.sub.7 includes a silicon atom or another heteroatom. R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups.
[0166] A particular example of a sulfonate according to formula
(54) includes R.sub.7 as a halo substituted alkyl group, namely
t-Butyldimethylsilyl trifluoromethane sulfonate represented with
reference to the formula:
##STR00015##
In formula (55), it is contemplated that one or more of the alkyl
groups and the alkylfluoride group can be modified, such as by
substituting a constituent hydrogen or fluorine atom with another
chemical element or functional group, or can be replaced by another
alkyl group, an alkenyl group, an alkynyl group, or an aryl group,
either in a substituted or an unsubstituted form. Other
functionalizations or modifications of the sulfonate set forth in
formula (55) are contemplated.
[0167] Further examples of suitable silicon-containing compounds
include silicon-containing polymers, such as a polyphosphate with
silicon-containing side groups represented with reference to the
formula:
##STR00016##
In formula (56), n is a non-negative integer that is at least one
or greater than one and represents the number of repeat units
included in the polyphosphate. For certain embodiments, n is in the
range of 1 to 10, such as 2 to 10, and, in other embodiments, n is
at least 10, such as at least 20, at least 50, at least 100, at
least 500, or at least 1,000, and up to 5,000, up to 10,000, up to
50,000, up to 100,000 or more. R.sub.1, R.sub.2, R.sub.3, R.sub.4,
and R.sub.5 can be the same or different, and, in some embodiments,
at least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 is
an organic group including from 1 to 20 carbon atoms. For other
embodiments, at least one of R.sub.1, R.sub.2, R.sub.3, R.sub.4,
and R.sub.5 is an organic group including more than 20 carbon
atoms. In some embodiments, at least one of R.sub.1, R.sub.2,
R.sub.3, R.sub.4, and R.sub.5 includes an ether linkage, and, in
other embodiments, at least one of R.sub.1, R.sub.2, R.sub.3,
R.sub.4, and R.sub.5 includes a silicon atom or another heteroatom.
R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 can be
independently selected from, for example, hydride group, hydroxy
group, alkyl groups, alkenyl groups, alkynyl groups, aryl groups,
iminyl groups, alkoxy groups, alkenoxy groups, alkynoxy groups,
aryloxy groups, carboxy groups, alkylcarbonyloxy groups,
alkenylcarbonyloxy groups, alkynylcarbonyloxy groups,
arylcarbonyloxy groups, alkylthio groups, alkenylthio groups,
alkynylthio groups, arylthio groups, cyano groups, N-substituted
amino groups, alkylcarbonylamino groups, N-substituted
alkylcarbonylamino groups, alkenylcarbonylamino groups,
N-substituted alkenyl carbonylamino groups, alkynylcarbonylamino
groups, N-substituted alkynylcarbonylamino groups,
arylcarbonylamino groups, and N-substituted arylcarbonylamino
groups.
[0168] Further, compounds of the various formulas (3) through (56)
may be formulated as salts along with suitable ions. Such compounds
can contain any of the many substitutions described in the formulas
(3) through (56) in order to interact with a counter-ion. Examples
of suitable silicon-containing salts include, but are not limited
to: Calcium metasilicate,
Tris[N,N-bis(trimethylsilyl)amide]erbium(III), Sodium
hexafluorosilicate, and combinations thereof.
[0169] It is understood that certain compounds fall into more than
one family or group as described in formulas (3) through (56) and
the associated description. Many compounds of embodiments of the
invention preferably contain one or more TMS structures. Such TMS
structures can facilitate the appropriate decomposition of
additives to improve the performance of conventional electrolytes.
Without being bound by a particular theory or mode of action, the
presence of silicon in additives can facilitate the formation of a
silicon-containing film, layer, coating, or region on or within
electrode materials. Such film formation is described in more
detail below.
[0170] Referring back to formulas (1) and (2), an amount of a
particular compound can be expressed in terms of a weight percent
of the compound relative to a total weight of the electrolyte
solution (or wt. %). For example, an amount of a compound can be in
the range of about 0.01 wt. % to about 30 wt. %, such as from about
0.05 wt. % to about 30 wt. %, from about 0.01 wt. % to about 20 wt.
%, from about 0.2 wt. % to about 15 wt. %, from about 0.2 wt. % to
about 10 wt. %, from about 0.2 wt. % to about 5 wt. %, or from
about 5 wt. % to about 10 wt. %, and, in the case of a combination
of multiple compounds, a total amount of the compounds can be in
the range of about 0.01 wt. % to about 30 wt. %, such as from about
0.05 wt. % to about 30 wt. %, from about 0.01 wt. % to about 20 wt.
%, from about 0.2 wt. % to about 15 wt. %, from about 0.2 wt. % to
about 10 wt. %, from about 0.2 wt. % to about 5 wt. %, or from
about 5 wt. % to about 10 wt. %. An amount of a compound also can
be expressed in terms of a ratio of the number of moles of the
compound per unit surface area of either, or both, electrode
materials. For example, an amount of a compound can be in the range
of about 10.sup.-7 mol/m.sup.2 to about 10.sup.-2 mol/m.sup.2, such
as from about 10.sup.-7 mol/m.sup.2 to about 10.sup.-5 mol/m.sup.2,
from about 10.sup.-5 mol/m.sup.2 to about 10.sup.-3 mol/m.sup.2,
from about 10.sup.-6 mol/m.sup.2 to about 10.sup.-4 mol/m.sup.2, or
from about 10.sup.-4 mol/m.sup.2 to about 10.sup.-2 mol/m.sup.2. As
further described below, a compound can be consumed or can react,
decompose, or undergo other modifications during initial battery
cycling. As such, an amount of a compound can refer to an initial
amount of the compound used during the formation of the electrolyte
solutions according to formulas (1) or (2), or can refer to an
initial amount of the additive within the electrolyte solution
prior to battery cycling (or prior to any significant amount of
battery cycling).
[0171] Resulting performance characteristics of a battery can
depend upon the identity of a particular compound used to form the
high voltage electrolyte according to formulas (1) or (2), an
amount of the compound used, and, in the case of a combination of
multiple compounds, a relative amount of each compound within the
combination. Accordingly, the resulting performance characteristics
can be fine-tuned or optimized by proper selection of the set of
compounds and adjusting amounts of the compounds in formulas (1) or
(2). For example, in the case of certain phosphates when used as an
additive compound, such as tris(trimethylsilyl) phosphate, a
desirable amount of the compound can be in the range of about 0.5
wt. % to about 3 wt. %, such as from about 1 wt. % to about 2 wt.
%. Fine-tuning of an amount of an additive compound can depend upon
factors such as battery configuration and characteristics of a
cathode material or anode material.
[0172] The formation according to formulas (1) or (2) can be
carried out using a variety of techniques, such as by mixing the
base electrolyte and the set of additives, dispersing the set of
additives within the base electrolyte, dissolving the set of
additives within the base electrolyte, or otherwise placing these
components in contact with one another. The set of additives can be
provided in a liquid form, a powdered form (or another solid form),
or a combination thereof. The set of additives can be incorporated
in the electrolyte solutions of formulas (1) or (2) prior to,
during, or subsequent to battery assembly.
[0173] The electrolyte solutions described herein can be used for a
variety of batteries containing a high voltage cathode or a low
voltage cathode, and in batteries operated at high temperatures.
For example, the electrolyte solutions can be substituted in place
of, or used in conjunction with, conventional electrolytes for
Li-ion batteries for operations at or above 4.2 V.
[0174] FIG. 1 illustrates a Li-ion battery 100 implemented in
accordance with an embodiment of the invention. The battery 100
includes an anode 102, a cathode 106, and a separator 108 that is
disposed between the anode 102 and the cathode 106. In the
illustrated embodiment, the battery 100 also includes a high
voltage electrolyte 104, which is disposed between the anode 102
and the cathode 106 and remains stable during high voltage battery
cycling.
[0175] The operation of the battery 100 is based upon reversible
intercalation and de-intercalation of Li ions into and from host
materials of the anode 102 and the cathode 106. Other
implementations of the battery 100 are contemplated, such as those
based on conversion chemistry. Referring to FIG. 1, the voltage of
the battery 100 is based on redox potentials of the anode 102 and
the cathode 106, where Li ions are accommodated or released at a
lower potential in the former and a higher potential in the latter.
To allow both a higher energy density and a higher voltage platform
to deliver that energy, the cathode 106 includes an active cathode
material for high voltage operations at or above 4.2 V. Suitable
high voltage cathode materials include those having a specific
capacity of at least about 10 mAh/g, at least about 20 mAh/g, at
least about 30 mAh/g, at least about 40 mAh/g, or at least about 50
mAh/g, as measured upon discharge at a rate of 0.1 C (or another
reference rate higher or lower than 0.1 C, such as 0.05 C, 0.5 C,
or 1 C) from about 6 V to about 4.5 V, from about 6 V to about 5 V,
from about 5.5 V to about 4.5 V, or from about 5 V to about 4.5 V
relative to a lithium metal anode (Li/Li.sup.+ anode) or other
counterelectrode. Suitable high voltage cathode materials also
include those having a specific capacity of at least about 10
mAh/g, at least about 20 mAh/g, at least about 30 mAh/g, at least
about 40 mAh/g, or at least about 50 mAh/g, as measured upon
discharge at a substantially constant current of 15 mA/g (or
another reference current higher or lower than 15 mA/g, such as 7.5
mA/g, 75 mA/g, or 150 mA/g) from about 6 V to about 4.5 V, from
about 6 V to about 5 V, from about 5.5 V to about 4.5 V, or from
about 5 V to about 4.5 V relative to a lithium metal anode
(Li/Li.sup.+ anode) or other counterelectrode. The stated values
for specific capacity and current can be per unit mass of a cathode
active material, and can be expressed in units of mAh/(g of the
cathode active material) and mA/(g of the cathode active material),
respectively. Examples of suitable high voltage cathode materials
include phosphates, fluorophosphates, fluorosulphates,
fluorosilicates, spinels, Li-rich layered oxides, and composite
layered oxides. Further examples of suitable cathode materials
include: spinel structure lithium metal oxides, layered structure
lithium metal oxides, lithium-rich layered structured lithium metal
oxides, lithium metal silicates, lithium metal phosphates, metal
fluorides, metal oxides, sulfur, and metal sulfides. Examples of
suitable anode materials include conventional anode materials used
in Li-ion batteries, such as lithium, graphite ("Li.sub.xC.sub.6"),
and other carbon, silicate, or oxide-based anode materials.
[0176] For example, a class of suitable high voltage phosphates can
be represented as:
Li.sub.a(M1.sub.bM2.sub.cM3.sub.dM4.sub.e).sub.fPO.sub.4, where M1,
M2, M3, and M4 can be the same or different, M1 is Mn, Co, or Ni,
M2 is a transition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr,
Nb, or Mo, M3 is a transition metal or a main group element,
optionally excluding elements of Group VIA and Group VIIA, M4 is a
transition metal or a main group element, optionally excluding
elements of Group VIA and Group VIIA, 1.2.gtoreq.a.gtoreq.0.9 (or
1.2>a>0.9), 1.gtoreq.b.gtoreq.0.6 (or 1>b>0.6),
0.4.gtoreq.c.gtoreq.0 (or 0.4>c>0), 0.2.gtoreq.d.gtoreq.0 (or
0.2>d>0), 0.2.gtoreq.e.gtoreq.0 (or 0.2>e>0), and
1.2.gtoreq.f.gtoreq.0.9 (or 1.2>f>0.9). Additional details
regarding this class of cathode materials can be found in
Goodenough et al., "Challenges for Rechargeable Li Batteries,"
Chemistry of Materials 22, 587-603 (2010); Marom et al., "A review
of advanced and practical lithium battery materials," J. Mater.
Chem., 21, 9938 (2011); Zhi-Ping et al., "Li-Site and Metal-Site
Ion Doping in Phosphate-Olivine LiCoPO.sub.4 by First-Principles
Calculation," Chin. Phys. Lett. 26 (3) 038202 (2009); and Fisher et
al., "Lithium Battery Materials LiMPO.sub.4 (M) Mn, Fe, Co, and
Ni): Insights into Defect Association, Transport Mechanisms, and
Doping Behavior," Chem. Mater. 2008, 20, 5907-5915; the disclosures
of which are incorporated herein by reference in their
entirety.
[0177] For example, another class of suitable high voltage
phosphates can comprise lithium (Li), cobalt (Co), a first
transition metal (M1), a second transition metal (M2) different
from M1, and phosphate (PO.sub.4), where M1 and M2 are each
selected from iron (Fe), titanium (Ti), vanadium (V), niobium (Nb),
zirconium (Zr), hafnium (Hf), molybdenum (Mo), tantalum (Ta),
tungsten (W), manganese (Mn), copper (Cu), chromium (Cr), nickel
(Ni), and zinc (Zn) (e.g., as dopants and/or oxides thereof), and
can have molar ratios of Li:Co:M1:M2:PO.sub.4 defined by (1-x):
(1-y-z):y:z:(1-a), respectively, optionally represented (as a
shorthand notation) as:
Li.sub.(1-x):(1-y-z):Co.sub.(1-y-z):M1.sub.y:M2.sub.z:(PO.sub.4).sub.(1-a-
), where -0.3.ltoreq.x.ltoreq.0.3; 0.01.ltoreq.y.ltoreq.0.5;
0.01.ltoreq.z.ltoreq.0.3; -0.5.ltoreq.a.ltoreq.0.5; and
0.2.ltoreq.1-y-z.ltoreq.0.98. Preferably, M1 and M2 are each
selected from iron (Fe), titanium (Ti), vanadium (V) and niobium
(Nb) (e.g., as dopants and/or oxides thereof). Preferably, M1 is
iron (Fe) (e.g., as a dopant and/or oxide thereof), M2 is selected
from titanium (Ti), vanadium (V), and niobium (Nb) (e.g., as
dopants and/or oxides thereof). Preferably, -0.3.ltoreq.x<0,
-0.2.ltoreq.x<0, or -0.1.ltoreq.x<0. Preferably, M2 is Ti,
and 0.05.ltoreq.z.ltoreq.0.25 or 0.05.ltoreq.z.ltoreq.0.2.
Preferably, M2 is V, and 0.03.ltoreq.z.ltoreq.0.25 or
0.05.ltoreq.z.ltoreq.0.2. Preferably, 0.3.ltoreq.1-y-z.ltoreq.0.98,
0.5.ltoreq.1-y-z.ltoreq.0.98, or 0.7.ltoreq.1-y-z.ltoreq.0.98.
Additional details regarding this class of olivine cathode
materials can be found in co-pending and co-owned U.S. Provisional
Application No. 61/426,733, entitled "Lithium Ion Battery Materials
with Improved Properties" and filed on Dec. 23, 2010, the
disclosure of which is incorporated herein by reference in its
entirety.
[0178] For example, a class of suitable high voltage
fluorophosphates can be represented as:
Li.sub.a(M1.sub.bM2.sub.cM3.sub.dM4.sub.e).sub.fPO.sub.4F.sub.g,
where M1, M2, M3, and M4 can be the same or different, M1 is Mn,
Co, or Ni, M2 is a transition metal, such as Ti, V, Cr, Mn, Fe, Co,
Ni, Zr, Nb, or Mo, M3 is a transition metal or a main group
element, optionally excluding elements of Group VIA and Group VIIA,
M4 is a transition metal or a main group element, optionally
excluding elements of Group VIA and Group VIIA,
1.2.gtoreq.a.gtoreq.0.9 (or 1.2>a>0.9), 1.gtoreq.b.gtoreq.0.6
(or 1>b>0.6), 0.4.gtoreq.c.gtoreq.0 (or 0.4>c>0),
0.2.gtoreq.d.gtoreq.0 (or 0.2>d>0), 0.2.gtoreq.e.gtoreq.0 (or
0.2>e>0), 1.2.gtoreq.f.gtoreq.0.9 (or 1.2>f>0.9), and
1.2.gtoreq.g.gtoreq.0 (or 1.2>g>0).
[0179] For example, a class of suitable high voltage
fluorosilicates can be represented as:
Li.sub.a(M1.sub.bM2.sub.cM3.sub.dM4.sub.e).sub.fSiO.sub.4F, where
M1, M2, M3, and M4 can be the same or different, M1 is Mn, Co, or
Ni, M2 is a transition metal, such as Ti, V, Cr, Mn, Fe, Co, Ni,
Zr, Nb, or Mo, M3 is a transition metal or a main group element,
optionally excluding elements of Group VIA and Group VIIA, M4 is a
transition metal or a main group element, optionally excluding
elements of Group VIA and Group VIIA, 1.2.gtoreq.a.gtoreq.0.9 (or
1.2>a>0.9), 1.gtoreq.b.gtoreq.0.6 (or 1>b>0.6),
0.4.gtoreq.c.gtoreq.0 (or 0.4>c>0), 0.2.gtoreq.d.gtoreq.0 (or
0.2>d>0), 0.2.gtoreq.e.gtoreq.0 (or 0.2>e>0), and
1.2.gtoreq.f.gtoreq.0.9 (or 1.2>f>0.9).
[0180] For example, another class of suitable high voltage
fluorosilicates can be represented as:
Li.sub.a(M1.sub.bM2.sub.cM3.sub.dM4.sub.e).sub.fSiO.sub.4F.sub.g,
where M1, M2, M3, and M4 can be the same or different, M1 is Mn,
Co, or Ni, M2 is a transition metal, such as Ti, V, Cr, Mn, Fe, Co,
Ni, Zr, Nb, or Mo, M3 is a transition metal or a main group
element, optionally excluding elements of Group VIA and Group VIIA,
M4 is a transition metal or a main group element, optionally
excluding elements of Group VIA and Group VIIA,
1.2.gtoreq.a.gtoreq.0.9 (or 1.2>a>0.9), 1.gtoreq.b.gtoreq.0.6
(or 1>b>0.6), 0.4.gtoreq.c.gtoreq.0 (or 0.4>c>0),
0.2.gtoreq.d.gtoreq.0 (or 0.2>d>0), 0.2.gtoreq.e.gtoreq.0 (or
0.2>e>0), 1.2.gtoreq.f.gtoreq.0.9 (or 1.2>f>0.9), and
1.2.gtoreq.g.gtoreq.0 (or 1.2>g>0).
[0181] For example, a class of suitable high voltage spinels can be
represented as:
Li.sub.a(M1.sub.bM2.sub.cM3.sub.dM4.sub.e).sub.fSiO.sub.4F, where
M1, M2, M3, and M4 can be the same or different, M1 is Mn or Fe, M2
is Mn, Ni, Fe, Co, or Cu, M3 is a transition metal, such as Ti, V,
Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, and M4 is a transition metal or
a main group element, optionally excluding elements of Group VIA
and Group VILA, 1.2.gtoreq.a.gtoreq.0.9 (or 1.2>a>0.9),
1.7.gtoreq.b.gtoreq.1.2 (or 1.7>b>1.2),
0.8.gtoreq.c.gtoreq.0.3 (or 0.8>c>0.3), 0.1.gtoreq.d.gtoreq.0
(or 0.1>d>0), 0.1.gtoreq.e.gtoreq.0 (or 0.1>e>0), and
2.2.gtoreq.f.gtoreq.1.5 (or 2.2>f>1.5). LMNO-type cathode
materials, such as Li.sub.1.05Mn.sub.1.5Ni.sub.0.5O.sub.4 and
LMO-type materials, such as LiMn.sub.2O.sub.4 are included in this
class. Additional details regarding this class of cathode materials
can be found in Goodenough et al., "Challenges for Rechargeable Li
Batteries," Chemistry of Materials 22, 587-603 (2010); Marom et
al., "A review of advanced and practical lithium battery
materials," J. Mater. Chem., 21, 9938 (2011); and Yi et al.,
"Recent developments in the doping of LiNi.sub.0.5Mn.sub.1.5O.sub.4
cathode material for 5 V lithium-ion batteries," Ionics (2011)
17:383-389; the disclosures of which are incorporated herein by
reference in their entirety.
[0182] For example, a class of suitable high voltage, Li-rich
layered oxides can be represented as:
Li(Li.sub.aM1.sub.bM2.sub.cM3.sub.dM4.sub.e).sub.fO.sub.2, where
M1, M2, M3, and M4 can be the same or different, M1 is a transition
metal, such as Mn, Fe, V, Co, or Ni, M2 is a transition metal, such
as Mn, Fe, V, Co, or Ni, M3 is a transition metal, such as Mn, Fe,
V, Co, or Ni, M4 is a transition metal or a main group element,
optionally excluding elements of Group VIA and Group VIIA,
0.4.gtoreq.a.gtoreq.0.05 (or 0.4>a>0.05),
0.7.gtoreq.b.gtoreq.0.1 (or 0.7>b>0.1),
0.7.gtoreq.c.gtoreq.0.1 (or 0.7>c>0.1),
0.7.gtoreq.d.gtoreq.0.1 (or 0.7>d>0.1), 0.2.gtoreq.e.gtoreq.0
(or 0.2>e>0), and 1.2.gtoreq.f.gtoreq.0.9 (or
1.2>f>0.9). OLO-type cathode materials are included in this
class. Additional details regarding this class of cathode materials
can be found in Goodenough et al., "Challenges for Rechargeable Li
Batteries," Chemistry of Materials 22, 587-603 (2010); Marom et
al., "A review of advanced and practical lithium battery materials"
J. Mater. Chem., 21, 9938 (2011); Johnson et al., "Synthesis,
Characterization and Electrochemistry of Lithium Battery
Electrodes: xLi.sub.2MnO.sub.3
(1-x)LiMn.sub.0.333Ni.sub.0.333CO.sub.0.333O.sub.2
(0<x<0.7)," Chem. Mater., 20, 6095-6106 (2008); and Kang et
al., "Interpreting the structural and electrochemical complexity of
0.5Li.sub.2MnO.sub.3.0.5LiMO.sub.2 electrodes for lithium batteries
(M=Mn.sub.0.5-xNi.sub.0.5-xCo.sub.2x, 0=x=0.5)," J. Mater. Chem.,
17, 2069-2077 (2007); the disclosures of which are incorporated
herein by reference in their entirety.
[0183] For example, a class of suitable high voltage, composite
layered oxides can be represented as:
(Li.sub.2M1.sub.aM2.sub.bO.sub.3).sub.c
(LiM3.sub.dM4.sub.eM5.sub.fO.sub.2).sub.g, where M1, M2, M3, M4,
and M5 can be the same or different, M1 is a transition metal, such
as Mn, Fe, V, Co, or Ni, M2 is a transition metal, such as Mn, Fe,
V, Co, or Ni, M3 is a transition metal, such as Mn, Fe, V, Co, or
Ni, M4 is a transition metal, such as Mn, Fe, V, Co, or Ni, M5 is a
transition metal or a main group element, optionally excluding
elements of Group VIA and Group VIIA, 1.1.gtoreq.a.gtoreq.0 (or
1.1>a>0), 0.5.gtoreq.b.gtoreq.0 (or 0.5>b>0),
0.7.gtoreq.c.gtoreq.0 (or 0.7>c>0), 1.gtoreq.d.gtoreq.0 (or
1>d>0), 1.gtoreq.e.gtoreq.0 (or 1>e>0),
1.gtoreq.f.gtoreq.0 (or 1>f>0), and 1.gtoreq.g.gtoreq.0.5 (or
1>g>0.5). Additional details regarding this class of cathode
materials can be found in Goodenough et al., "Challenges for
Rechargeable Li Batteries," Chemistry of Materials 22, 587-603
(2010); Marom et al., "A review of advanced and practical lithium
battery materials," J. Mater. Chem., 21, 9938 (2011); Johnson et
al., "Synthesis, Characterization and Electrochemistry of Lithium
Battery Electrodes: xLi.sub.2MnO.sub.3
(1-x)LiMn.sub.0.333Ni.sub.0.333CO.sub.0.333O.sub.2
(0<x<0.7)," Chem. Mater., 20, 6095-6106 (2008); and Kang et
al., "Interpreting the structural and electrochemical complexity of
0.5Li.sub.2MnO.sub.3.0.5LiMO.sub.2 electrodes for lithium batteries
(M=Mn.sub.0.5-xNi.sub.0.5-xCo.sub.2x, 0=x=0.5)," J. Mater. Chem.,
17, 2069-2077 (2007); the disclosures of which are incorporated
herein by reference in their entirety.
[0184] Attention next turns to FIG. 2, which illustrates operation
of a Li-ion battery and an illustrative, non-limiting mechanism of
action of an improved electrolyte, according to an embodiment of
the invention. Without being bound by a particular theory not
recited in the claims, the inclusion of a set of one or more
stabilizing additive compounds in an electrolyte solution can, upon
operation of the battery (e.g., during conditioning thereof)
passivate a high voltage cathode material, thereby reducing or
preventing reactions between bulk electrolyte components and the
cathode material that can degrade battery performance.
[0185] Referring to FIG. 2, an electrolyte 202 includes a base
electrolyte, and, during initial battery cycling, components within
the base electrolyte can assist in the in-situ formation of a
protective film (in the form of a solid electrolyte interface
("SEI") 206) on or next to an anode 204. The anode SEI 206 can
inhibit reductive decomposition of the high voltage electrolyte
202. Preferably, and without being bound by theory not recited in
the claims, for operation at voltages at or above 4.2 V, the
electrolyte 202 can also include a set of additives that can assist
in the in-situ formation of a protective film (in the form of a SEI
208 or another derivative) on or next to a cathode 200. The cathode
SEI 208 can inhibit oxidative decomposition of the high voltage
electrolyte 202 that can otherwise occur during high voltage
operations. As such, the cathode SEI 208 can inhibit oxidative
reactions in a counterpart manner to the inhibition of reductive
reactions by the anode SEI 206. In the illustrated embodiment, the
cathode SEI 208 can have a thickness in the sub-micron range, and
can include a set of one or more chemical elements corresponding
to, or derived from, those present in the set of one or more
additives, such as silicon or other heteroatom included in the set
of one or more additives. Advantageously, the set of one or more
additives can preferentially passivate the cathode 200 and can
selectively contribute towards film formation on the cathode 200,
rather than the anode 204. Such preferential or selective film
formation on the cathode 200 can impart stability against oxidative
decomposition, with little or no additional film formation on the
anode 204 (beyond the anode SEI 206) that can otherwise degrade
battery performance through resistive losses. More generally, the
set of one or more additives can decompose below a redox potential
of the cathode material and above a redox potential of SEI
formation on the anode 204.
[0186] Without being bound by a particular theory not recited in
the claims, the formation of the cathode SEI 208 can occur through
one or more of the following mechanisms:
[0187] (1) The set of additive compounds can decompose to form the
cathode SEI 208, which inhibits further oxidative decomposition of
electrolyte components.
[0188] (2) The set of additive compounds can form an intermediate
product, such as a complex with LiPF.sub.6 or a cathode material,
which intermediate product then decomposes to form the cathode SEI
208 that inhibits further oxidative decomposition of electrolyte
components.
[0189] (3) The set of additive compounds can form an intermediate
product, such as a complex with LiPF.sub.6, which then decomposes
during initial charging. The resulting decomposition product can
then further decompose during initial charging to form the cathode
SEI 208, which inhibits further oxidative decomposition of
electrolyte components.
[0190] (4) The set of additive compounds can stabilize the cathode
material by preventing metal ion dissolution.
[0191] Other mechanisms of action of the electrolyte 202 are
contemplated, according to an embodiment of the invention. For
example, and in place of, or in combination with, forming or
improving the quality of the cathode SEI 208, the set of one or
more additives or a derivative thereof (e.g., their decomposition
product) can form or improve the quality of the anode SEI 206, such
as to reduce the resistance for Li ion diffusion through the anode
SEI 206. As another example, the set of one or more additives or a
derivative thereof (e.g., their decomposition product) can improve
the stability of the electrolyte 202 by chemically reacting or
forming a complex with other electrolyte components. As a further
example, the set of one or more additives or a derivative thereof
(e.g., their decomposition product) can scavenge decomposition
products of other electrolyte components or dissolved electrode
materials in the electrolyte 202 by chemical reaction or complex
formation. Any one or more of the cathode SEI 208, the anode SEI
206, and the other decomposition products or complexes can be
viewed as derivatives, which can include a set of one or more
chemical elements corresponding to, or derived from, those present
in the set of one or more additives, such as silicon or other
heteroatom included in the set of additives.
[0192] The electrolyte solutions described herein can be
conditioned prior to sale or use in a commercial application. For
example, batteries including the electrolyte solutions can be
conditioned by cycling prior to commercial sale or use in commerce.
A method of conditioning a battery can, for example, include
conditioning the battery for commercial sale. Such method can
include, for example, providing a battery, and cycling such battery
through at least 1, at least 2, at least 3, at least 4, or at least
5 cycles, each cycle including charging the battery and discharging
the battery at a rate of 0.05 C (e.g., a current of 7.5 mA/g)
between 4.95 V and 2.0 V (or another voltage range) versus a
reference counterelectrode, such as a graphite anode. Charging and
discharging can be carried out at a higher or lower rate, such as
at a rate of 0.1 C (e.g., a current of 15 mA/g), at a rate of 0.5 C
(e.g., a current of 75 mA/g), or at a rate of 1 C (e.g., a current
of 150 mA/g).
[0193] The electrochemical stability of the electrolyte in battery
cells can be assessed by measuring the residual current, or the
current that passes through the cell after the battery is fully
charged or discharged. Residual current can be measured by fully
charging the cell and then applying a voltage above the equilibrium
potential. As the cell is fully charged, the residual current
reflects the extent of electrochemical decomposition of the
materials in the cell. A low residual current as compared to
control demonstrates enhanced electrochemical stability. Without
being bound to a particular theory or mode of action, above the
equilibrium potential of the cell the electrochemical decomposition
of electrolytes will allow current to flow in a battery cell due at
least in part to electron transfer from the negative electrode to
the electrolyte and from the electrolyte to the cathode. Additive
compounds according to embodiments of the invention improve the
performance of electrolytes by any of the mechanisms proposed
herein under conditions that may ordinarily cause electrolyte
decomposition. Such improvements in electrochemical stability help
solve problems present in known electrolyte solutions.
[0194] As will be appreciated from the many examples that follow,
additive compounds of certain embodiments of the invention improve
the performance of conventional electrolytes in high voltage cells
both at room temperatures and at high temperatures. Further,
compounds of certain embodiments of the invention improve the
performance of conventional electrolytes in low voltage cells at
high temperatures.
[0195] Electrolytes containing certain OMTS additives have shown an
improvement in residual current as compared to conventional
electrolytes in standard CR2032 (Hohsen) coin cells. The cells were
held at 4.5V, 4.9V and 5.1V for 10 hours at 50 degrees C. and the
residual current was observed. The lower residual current for the
electrolytes containing certain OMTS additives indicates reduction
in electrolyte decomposition.
[0196] OTMS additives according to certain embodiments improve the
coulombic efficiency over the control electrolyte in a high voltage
cell. Certain OTMS additives have shown an improvement in coulombic
efficiency of as much as about 6% as compared to the control
electrolyte.
[0197] Certain OTMS additives have shown an improvement of as much
as about 19% in room temperature cycle life of a high voltage
spinel (LMNO-type) cathode material as compared to the control
electrolyte.
[0198] NTMS additives according to certain embodiments improve the
room temperature cycle life over the control electrolyte in a high
voltage cell. Certain NTMS additives have shown an improvement of
as much as about 11% in room temperature cycle life of a high
voltage spinel (LMNO-type) cathode material as compared to the
control electrolyte.
[0199] Certain TMS additives according to certain embodiments
improve cycle life and coulombic efficiency at higher additive
concentrations than those used for certain OTMS and NTMS additives.
Certain TMS additives have shown an improvement in coulombic
efficiency of as much as about 3% as compared to the control
electrolyte. Certain TMS additives have shown an improvement of as
much as about 10% in room temperature cycle life of a high voltage
spinel (LMNO-type) cathode material as compared to the control
electrolyte.
[0200] Certain OTMS additives have shown an improvement of as much
as about 110% in high temperature cycle life of a high voltage
spinel (LMNO-type) cathode material as compared to the control
electrolyte. Certain OTMS additives have shown an improvement of as
much as about 200% in high temperature cycle life of an LMO-type
cathode material as compared to the control electrolyte. Certain
OTMS additives improve 1st cycle efficiency and 1.sup.st cycle
reversible capacity in a high voltage spinel (LMNO-type) cathode
material as compared to the control electrolyte.
[0201] Certain OTMS additives have shown an improvement of as much
as about 70% in high temperature cycle life of an NMC-type cathode
material as compared to the control electrolyte. OTMS additives
according to certain embodiments improve the room temperature cycle
life over the control electrolyte in a NMC-type cathode
material.
[0202] Certain OTMS additives have shown an improvement of as much
as about 70% in room temperature cycle life of lithiated layered
oxide (OLO-type) cathode materials as compared to the control
electrolyte. Certain OTMS additives have shown an improvement of as
much as about 130% in high temperature cycle life of high voltage
OLO-type cathode materials as compared to the control electrolyte.
Certain OTMS additives have shown an improvement of as much as
about 2.5% in room temperature energy efficiency of high voltage
OLO-type cathode materials as compared to the control
electrolyte.
[0203] Certain OTMS additives have shown an improvement of as much
as about 18% in coulombic efficiency of a high voltage olivine
cathode material (CM1-type) as compared to the control electrolyte.
Certain OTMS additives have shown an improvement of as much as
about 400% in room temperature cycle life of a high voltage
CM1-type cathode material as compared to the control
electrolyte.
[0204] NTMS additives according to certain embodiments improve the
room temperature cycle life over the control electrolyte in a high
voltage cell. Certain NTMS additives have shown an improvement of
as much as about 410% in room temperature cycle life of a high
voltage CM1-type cathode material as compared to the control
electrolyte.
EXAMPLES
[0205] The following examples describe specific aspects of some
embodiments of the invention to illustrate and provide a
description for those of ordinary skill in the art. The examples
should not be construed as limiting the invention, as the examples
merely provide specific methodology useful in understanding and
practicing some embodiments of the invention.
Example 1
Methodology for Formation and Characterization of Battery Cells
Including Stabilizing Additives
[0206] Battery cells were formed in a high purity argon filled
glove box (M-Braun, O.sub.2 and humidity content <0.1 ppm).
Initially, poly(vinylidene fluoride) (Sigma Aldrich), carbon black
(Super P Li, TIMCAL), and a doped LiCoPO.sub.4 cathode material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a))
were mixed in 1-methyl-2-pyrrolidinone (Sigma Aldrich), and the
resulting slurry was deposited on an aluminum current collector and
dried to form a composite cathode film. A lithium or graphite anode
was used. In case of a graphite anode, a graphitic carbon
(mesocarbon microbeads or MCMB) was mixed with poly(vinylidene
fluoride) (Sigma Aldrich), carbon black (Super P Li, TIMCAL), using
1-methyl-2-pyrrolidinone (Sigma Aldrich) as a solvent, and the
resulting slurry was deposited on a copper current collector and
dried to form a composite anode film. Each battery cell including
the composite cathode film, a Millipore glass fiber or a
polypropylene separator, and the lithium or graphite anode was
assembled in a coin cell-type assembly (CR2025, Hohsen). A
conventional electrolyte was mixed with a stabilizing additive
compound and added to the battery cell. The battery cell was sealed
and cycled between a particular voltage range (e.g., about 2 V to
about 4.95 V) at a particular temperature (e.g., room temperature
or 25.degree. C.).
Example 2
Characterization of Battery Cell Including Stabilizing Additive
[0207] Using the methodology of Example 1, performance
characteristics were measured for a test battery cell including
about 10 wt. % of tris(trimethylsilyl) phosphate as a stabilizing
additive (labeled as "ttsp") dispersed in a conventional
electrolyte (ethylene carbonate, dimethyl carbonate, and 1M
LiPF.sub.6) and for a control battery cell including the
conventional electrolyte but without the stabilizing additive
(labeled as "EC/DMC, 1M LiPF.sub.6"). Each of the test battery cell
and the control battery cell included a doped LiCoPO.sub.4 cathode
material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-
-a). FIG. 3A (top) compares capacity retention with and without the
stabilizing additive over several cycles, expressed in terms of a
percentage of an initial specific capacity upon discharge retained
at a particular cycle. As can be appreciated, the inclusion of the
stabilizing additive improved cycle life, retaining about 78% of
the initial discharge capacity after 26 cycles (compared to below
about 50% without the stabilizing additive). FIG. 3B (bottom)
compares coulombic efficiency with and without the stabilizing
additive over several cycles, with an inset providing a magnified
view of measured values of coulombic efficiency with the
stabilizing additive. As can be appreciated, the inclusion of the
stabilizing additive improved coulombic efficiency, which increased
from an initial value of about 95% and reached a plateau or
steady-state value of about 97% (compared to values in the range of
about 10% to about 45% without the stabilizing additive).
Example 3
Characterization of Battery Cell Including Stabilizing Additive
[0208] Using the methodology of Example 1, performance
characteristics were measured for a test battery cell including
tris(trimethylsilyl) phosphate as a stabilizing additive (labeled
as "ttsp") dispersed in a conventional electrolyte (ethylene
carbonate, ethyl methyl carbonate, and 1M LiPF.sub.6) and for a
control battery cell including the conventional electrolyte but
without the stabilizing additive (labeled as "EC:EMC, 1M
LiPF.sub.6"). Each of the test battery cell and the control battery
cell included a doped LiCoPO.sub.4 cathode material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a)),
and was cycled between about 2 V to about 4.95 V at a current of
about 150 mA/g and at room temperature (25.degree. C.). FIG. 4
compares capacity retention with and without the stabilizing
additive over several cycles, expressed in terms of a percentage of
an initial specific capacity upon discharge retained at a
particular cycle. As can be appreciated, the inclusion of the
stabilizing additive improved cycle life, retaining about 80% of
the initial discharge capacity after 100 cycles (compared to about
20% without the stabilizing additive) and about 68% of the initial
discharge capacity after 200 cycles (compared to under about 20%
without the stabilizing additive). The inclusion of the stabilizing
additive also improved coulombic efficiency, retaining a value
greater than about 98% after 100 cycles or more.
[0209] To assess stability at elevated temperatures, cycling was
also carried out at 50.degree. C. FIG. 5 superimposes results of
measurements of capacity retention at 50.degree. C. onto FIG. 4. As
can be appreciated, desirable cycle life characteristics are
retained at an elevated temperature of 50.degree. C.
Example 4
Characterization of Battery Cell Including Stabilizing Additive
[0210] Using the methodology of Example 1, performance
characteristics were measured for tris(trimethylsilyl) phosphate as
a stabilizing additive dispersed in a conventional electrolyte
(ethylene carbonate:ethyl methyl carbonate (1:2) and 1M
LiPF.sub.6). Each test battery cell included a doped LiCoPO.sub.4
cathode material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a))
and a graphite anode. Measurements were carried out at different
concentrations of the stabilizing additive, namely at about 0.25
wt. %, about 0.5 wt. %, about 1 wt. %, about 2 wt. %, about 10 wt.
%, and about 15 wt. %.
[0211] FIG. 6 is a plot of capacity retention (expressed in terms
of a percentage of a specific capacity upon discharge at the
5.sup.th cycle retained after 50 cycles) as a function of the
concentration of the stabilizing additive. As can be appreciated,
capacity retention varied with the concentration of the stabilizing
additive, ranging from about 60% at a low concentration of the
stabilizing additive to about 45% at a high concentration of the
stabilizing additive and peaking at about 90% for an intermediate
concentration of the stabilizing additive.
[0212] FIG. 7 is a plot of coulombic efficiency at the 50.sup.th
cycle as a function of the concentration of the stabilizing
additive. As can be appreciated, coulombic efficiency also varied
with the concentration of the stabilizing additive, increasing from
about 87% at a low concentration of the stabilizing additive to
about 98% for an intermediate concentration of the stabilizing
additive and exhibiting a slight decline for higher concentrations
of the stabilizing additive.
Example 5
Characterization of Battery Cell Including Stabilizing Additive
[0213] Using the methodology of Example 1, cyclic voltammetry
measurements were carried out for 2 wt. % tris(trimethylsilyl)
phosphate as a stabilizing additive dispersed in a conventional
electrolyte (ethylene carbonate:ethyl methyl carbonate (1:2) and 1M
LiPF.sub.6). Measurements were carried out for a battery cell
including a LiMn.sub.2O.sub.4 cathode and a Li anode. FIG. 8 sets
forth superimposed cyclic voltammograms for the 1.sup.st cycle
through the 3.sup.rd cycle, and FIG. 9 sets forth superimposed
cyclic voltammograms for the 4.sup.th cycle through the 6.sup.th
cycle. As can be appreciated, a large resistance build-up is
initially observed during the charge phase of the 1.sup.st cycle,
and this resistance decreases during subsequent cycles (as
indicated by the arrow labeled as "Resistance Decrease" in FIG. 8).
Also, a peak at about 3.6 V is initially observed during the
discharge phase of the 1.sup.st cycle, and this peak gradually
disappears during subsequent cycles (as indicated by the
dotted-line oval region labeled as "Peak Disappears" in FIG. 8).
Without being bound by a particular theory not recited in the
claims, this transient behavior observed in the cyclic
voltammograms can be indicative of formation of intermediate
products (e.g., derivatives of electrolyte additives) that may be
involved (directly or indirectly) in the formation of a protective
film (e.g., a cathode SEI) on a cathode.
Example 6
Characterization of Battery Cell Including Stabilizing Additive
[0214] Performance characteristics were measured for a test battery
cell including tris(trimethylsilyl) phosphate as a stabilizing
additive (labeled as "ttsp") dispersed in a conventional
electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M
LiPF.sub.6) and for a control battery cell including the
conventional electrolyte but without the stabilizing additive
(labeled as "EC:EMC(1:2), 1M LiPF.sub.6"). Each of the test battery
cell and the control battery cell included a doped LiCoPO.sub.4
cathode material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a)),
was kept in a fully charged state at about 50.degree. C. for 8
days, and was cycled between about 2 V to about 4.95 V at a rate of
about 1 C (150 mA/g) and at room temperature (25.degree. C.). FIG.
10 compares capacity retention with and without the stabilizing
additive over several cycles, expressed in terms of a percentage of
an initial specific capacity upon discharge retained at a
particular cycle. As can be appreciated, the inclusion of the
stabilizing additive improved cycle life subsequent to aging.
Example 7
Characterization of Battery Cells Including Stabilizing
Additive
[0215] The effectiveness of tris(trimethylsilyl) phosphate as a
stabilizing additive was tested for other cathode materials. In one
set of tests, performance characteristics were measured for a test
battery cell including tris(trimethylsilyl) phosphate as a
stabilizing additive (labeled as "ttsp") dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without the stabilizing
additive (labeled as "EC:EMC(1:2), 1M LiPF.sub.6"). Each of the
test battery cell and the control battery cell included a
LiMn.sub.1.5Ni.sub.0.5O.sub.4 cathode material, and was cycled
between about 3 V to about 4.9 V at a rate of about 1 C and about
50.degree. C., after formation at room temperature. FIG. 11
compares capacity retention with and without the stabilizing
additive over several cycles, expressed in terms of a percentage of
an initial specific capacity upon discharge retained at a
particular cycle. As can be appreciated, the inclusion of the
stabilizing additive improved cycle life for the
LiMn.sub.1.5Ni.sub.0.5O.sub.4 cathode material.
[0216] In another set of tests, performance characteristics were
measured for a test battery cell including tris(trimethylsilyl)
phosphate as a stabilizing additive (labeled as "ttsp") dispersed
in a conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without the stabilizing
additive (labeled as "EC:EMC(1:2), 1M LiPF.sub.6"). Each of the
test battery cell and the control battery cell included a
LiMn.sub.2O.sub.4 cathode material (about 4.2 V), and was cycled
between about 3 V to about 4.5 V at a rate of about 1 C and about
50.degree. C., after formation at room temperature. FIG. 12
compares capacity retention with and without the stabilizing
additive over several cycles, expressed in terms of a percentage of
an initial discharge capacity retained at a particular cycle. As
can be appreciated, the inclusion of the stabilizing additive also
improved cycle life for the LiMn.sub.2O.sub.4 cathode material. The
inclusion of the stabilizing additive also yielded reduced
self-discharge and a low residual current for the LiMn.sub.2O.sub.4
cathode material, as can be appreciated with reference to FIG. 13
(which sets forth open circuit voltage measurements at about
50.degree. C., after formation at room temperature) and FIG. 14
(which sets forth residual current measurements at a constant
voltage of about 5.1 V and at about 50.degree. C.).
Example 8
Characterization of Battery Cells Including Stabilizing
Additives
[0217] Performance characteristics were measured for various
stabilizing additives dispersed in a conventional electrolyte
(ethylene carbonate, dimethyl carbonate, and 1M LiPF.sub.6). Each
test battery cell and each control battery cell included a doped
LiCoPO.sub.4 cathode material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a))
and a lithium anode.
[0218] FIG. 15 compares capacity retention with and without
t-butyldimethylsilyl trifluoromethane sulfonate as a stabilizing
additive over several cycles, expressed in terms of a percentage of
an initial specific capacity upon discharge retained at a
particular cycle. As can be appreciated, the inclusion of the
stabilizing additives improved cycle life.
Example 9
Characterization of Battery Cells Including Stabilizing
Additives
[0219] Using the methodology of Example 1, performance
characteristics were measured for test battery cells including
different stabilizing additives dispersed in a conventional
electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M
LiPF.sub.6) and for a control battery cell including the
conventional electrolyte but without a stabilizing additive. FIG.
16 compares capacity retention of the battery cells over several
cycles, expressed in terms of a percentage of an initial specific
capacity upon discharge retained at a particular cycle. Two
different types of stabilizing additives were used. One type
included silicon, and another type lacked silicon. A concentration
of the stabilizing additives was about 2 wt. %. As can be
appreciated, the inclusion of the silicon-containing stabilizing
additives improved cycle life, retaining more than about 80% of the
initial discharge capacity after 100 cycles compared to below about
65% without the stabilizing additives. In this example, the
non-silicon-containing stabilizing additives deteriorated capacity
retention to about 45% after 100 cycles.
Example 10
Characterization of Battery Cells Including Stabilizing
Additives
[0220] Using the methodology of Example 1, performance
characteristics were measured for silicon-containing stabilizing
additives including different numbers of silicon-carbon bonds. FIG.
17 compares specific capacity upon discharge at the 50.sup.th cycle
for battery cells including the stabilizing additives. As can be
appreciated, the inclusion of stabilizing additives including 3 or
more silicon-carbon bonds yielded higher discharge capacities at
the 50.sup.th cycle compared to stabilizing additives including
less than 3 silicon-carbon bonds.
Example 11
Characterization of Battery Cells Including Stabilizing
Additives
[0221] Using the methodology of Example 1, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. Each of the stabilizing additives tested included a
Si--O-A moiety, with A=P, B, or Si. FIG. 18 compares capacity
retention of the battery cells over several cycles, expressed in
terms of a percentage of an initial specific capacity upon
discharge retained at a particular cycle. As can be appreciated,
the inclusion of each of the stabilizing additives including the
Si--O-A moiety improved cycle life.
Example 12
Characterization of Battery Cells Including Stabilizing
Additives
[0222] Using the methodology of Example 1, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. FIG. 19 compares specific capacity upon discharge at the
100.sup.th cycle for the battery cells. A concentration of the
stabilizing additives was about 2 wt. %. As can be appreciated, the
inclusion of the silicon-containing stabilizing additives improved
discharge capacity.
Example 13
Characterization of Battery Cells Including Stabilizing
Additives
[0223] Using the methodology of Example 1, performance
characteristics were measured for battery cells including about 2
wt. % tris(trimethylsilyl) phosphate as a stabilizing additive
(labeled as "TTSP") dispersed in a conventional electrolyte
(ethylene carbonate, ethyl methyl carbonate, and 1M LiPF.sub.6) and
including the conventional electrolyte but without the stabilizing
additive (labeled as "EC:EMC (1:2), 1M LiPF.sub.6"). To assess
stability at reduced temperatures, cycling was carried out at about
10.degree. C., about 0.degree. C., and about -10.degree. C., after
initial cycling at room temperature (25.degree. C.). FIG. 20
compares specific capacity upon discharge of the battery cells over
several cycles at different temperatures. As can be appreciated,
the inclusion of the stabilizing additive improved discharge
capacity at temperatures below room temperature.
Example 14
Characterization of Battery Cells Including Stabilizing
Additives
[0224] Using the methodology of Example 1, the effectiveness of
tris(trimethylsilyl) phosphate as a stabilizing additive was tested
for various cathode materials at an elevated temperature of about
50.degree. C. FIG. 21 compares capacity retention at the 25.sup.th
cycle for battery cells including about 2 wt. % of the stabilizing
additive (labeled as "TTSP") dispersed in a conventional
electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M
LiPF.sub.6) and including the conventional electrolyte but without
the stabilizing additive (labeled as "EC:EMC (1:2 v), 1M
LiPF.sub.6"). As can be appreciated, the inclusion of the
stabilizing additive improved capacity retention for each cathode
material.
Example 15
Characterization of Battery Cells Including Stabilizing
Additives
[0225] LiMn.sub.2O.sub.4 cathode films were assembled in half cells
(including Li metal as an anode) in a coin cell-type assembly
(CR2025, Hohsen). One cell included a conventional electrolyte
(ethylene carbonate, ethyl methyl carbonate, and 1M LiPF.sub.6)
with tris(trimethylsilyl)phosphate (labeled as "TTSP") as a
stabilizing additive, and another cell included the conventional
electrolyte without the stabilizing additive (labeled as "EC:EMC
(1:2), 1M LiPF.sub.6"). The cells were held at about 4.5V, about
4.9V, and about 5.1V for about 10 hours at 50.degree. C., and their
residual currents were measured, with results illustrated in FIG.
22. As can be appreciated, the cells including
tris(trimethylsilyl)phosphate had lower residual currents, which is
indicative of a reduction in electrolyte decomposition.
Example 16
Characterization of Battery Cells Including Stabilizing
Additives
[0226] Battery cells each including a LiMn.sub.1.5Ni.sub.0.5O.sub.4
cathode material and a graphite anode (MCMB) were assembled using
the methodology of Example 1. One cell included a conventional
electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M
LiPF.sub.6) with tris(trimethylsilyl)phosphate (labeled as "TTSP")
as a stabilizing additive, and another cell included the
conventional electrolyte without the stabilizing additive (labeled
as "EC:EMC (1:2), 1M LiPF.sub.6"). The cells were cycled at a rate
of about 0.1 C for several cycles, and their coloumbic efficiency
was measured at every cycle, with results illustrated in FIG. 23.
As can be appreciated, the inclusion of
tris(trimethylsilyl)phosphate improved coulombic efficiency.
Example 17
Characterization of Battery Cells Including Stabilizing
Additives
[0227] Battery cells each including a doped LiCoPO.sub.4 cathode
material and a graphite anode (MCMB) were assembled using the
methodology of Example 1. One cell included a conventional
electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M
LiPF.sub.6) with tris(trimethylsilyl)phosphate (labeled as "TTSP")
as a stabilizing additive, and another cell included the
conventional electrolyte without the stabilizing additive (labeled
as "EC:EMC (1:2), 1M LiPF.sub.6"). The cells were initially cycled
at room temperature (25.degree. C.) and were then stored at about
50.degree. C. for 8 days in a charged state. Subsequently, the
cells were cooled to room temperature and cycled again. FIG. 24
compares specific capacity upon discharge with and without the
stabilizing additive over several cycles. As can be appreciated,
the inclusion of tris(trimethylsilyl)phosphate improved discharge
capacity subsequent to storage at high temperatures, thereby
demonstrating enhanced thermal stability of the electrolyte and/or
battery cells.
Example 18
Characterization of Battery Cells Including Stabilizing
Additives
[0228] Battery cells each including a doped LiCoPO.sub.4 cathode
material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a))
and a graphite anode (MCMB) were assembled using the methodology of
Example 1. One cell included a conventional electrolyte (ethylene
carbonate, ethyl methyl carbonate, and 1M LiPF.sub.6) with
tris(trimethylsilyl)phosphate (labeled as "TTSP") as a stabilizing
additive, and another cell included the conventional electrolyte
without the stabilizing additive (labeled as "EC:EMC (1:2), 1M
LiPF.sub.6"). Signature rate test was carried out at the 101.sup.st
cycle, and rate capability of the battery cells was measured. FIG.
25 compares capacity retention of the battery cells at different
charging and discharging rates, expressed in terms of a percentage
of a low rate (0.05 C) specific capacity retained at a particular
rate. As can be appreciated, the inclusion of
tris(trimethylsilyl)phosphate improved rate capability both during
charging and discharging.
Example 19
Characterization of Battery Cells Including Stabilizing
Additives
[0229] Battery cells each including a LiMn.sub.1.5Ni.sub.0.5O.sub.4
cathode material and a graphite anode (MCMB) were assembled using
the methodology of Example 1. One cell included a conventional
electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M
LiPF.sub.6) with tris(trimethylsilyl)phosphate as a stabilizing
additive, and another cell included the conventional electrolyte
without the stabilizing additive (labeled as "EC:EMC (1:2), 1M
LiPF.sub.6"). The cells were cycled at a rate of about 0.1 C for
several cycles. FIG. 26 compares capacity retention with and
without the stabilizing additive. As can be appreciated, the
inclusion of tris(trimethylsilyl)phosphate improved capacity
retention.
Example 20
Characterization of Battery Cells Including Stabilizing
Additives
[0230] Battery cells each including a doped LiCoPO.sub.4 cathode
material
(Li.sub.(1-x):Co.sub.(1-y-z):Fe.sub.y:Ti.sub.z:(PO.sub.4).sub.(1-a))
and a graphite anode (MCMB) were assembled using the methodology of
Example 1. One cell included a conventional electrolyte (ethylene
carbonate, ethyl methyl carbonate, and 1M LiPF.sub.6) with about 2
wt. % of tris(trimethylsilyl)phosphate as a stabilizing additive,
and another cell included the conventional electrolyte without the
stabilizing additive (labeled as "EC:EMC (1:2), 1M LiPF.sub.6").
The cells were cycled at room temperature (25.degree. C.), and
their voltage profiles at the 1.sup.st and 100.sup.th cycles during
charging are set forth in FIG. 27. Higher voltage during charging
is indicative of a resistance build-up. As can be appreciated, the
inclusion of tris(trimethylsilyl)phosphate yielded a reduced cell
resistance.
Example 21
Characterization of Battery Cells Including Stabilizing
Additives
[0231] Half cells (including Li metal as an anode) were assembled
using the methodology of Example 1. One cell included a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) with about 2 wt. % of
tris(trimethylsilyl)phosphate (labeled as "TTSP") as a stabilizing
additive, and another cell included the conventional electrolyte
without the stabilizing additive (labeled as "EC:EMC (1:2), 1M
LiPF.sub.6"). The cells were cycled at room temperature (25.degree.
C.), and their voltage profiles at the 3.sup.rd cycle during
discharging are set forth in FIG. 28. As can be appreciated, the
inclusion of tris(trimethylsilyl)phosphate yielded a reduced cell
resistance.
Example 22
Methodology for Formation and Characterization of Battery Cells
Including Stabilizing Additives
[0232] Battery cells were formed in a high purity argon filled
glove box (M-Braun, O2 and humidity content <0.1 ppm).
Initially, poly(vinylidene fluoride) (Sigma Aldrich), carbon black
(Super P Li, TIMCAL), and a cathode material were mixed in
1-methyl-2-pyrrolidinone (Sigma Aldrich), and the resulting slurry
was deposited on an aluminum current collector and dried to form a
composite cathode film. A lithium or graphite anode was used. In
case of a graphite anode, a graphitic carbon was mixed with
poly(vinylidene fluoride) (Sigma Aldrich), carbon black (Super P
Li, TIMCAL), using 1-methyl-2-pyrrolidinone (Sigma Aldrich) as a
solvent, and the resulting slurry was deposited on a copper current
collector and dried to form a composite anode film. Each battery
cell including the composite cathode film, a Millipore glass fiber
or a polypropylene separator, and the lithium or graphite anode was
assembled in a coin cell-type assembly (CR2025, Hohsen). Cells with
Li anodes are tested in Hohsen CR2032 cells. A conventional
electrolyte was mixed with a stabilizing additive and added to the
battery cell. The battery cell was sealed and cycled between a
particular voltage range for each cathode at a particular
temperature (e.g., room temperature or 25.degree. C.). Table 1
shows cycling voltage range for each cathode in full cell. The
upper cutoff voltage is 0.05V higher in a half cell than in a full
cell.
TABLE-US-00001 TABLE 1 Cycling voltage range in full cell for
different cathode Cathode Cycling voltage, V LMNO-type 3-4.85
CM1-type 3-4.9 LMO-type 3-4.45 NMC-type 3-4.1 NMC-type 3-4.45
OLO-type 2-4.6
Example 23
Characterization of Battery Cells Including Stabilizing
Additives
[0233] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMNO-type. FIG.
29 compares coulombic efficiency of the battery cells at the first
cycle. It can be appreciated that several OTMS additives performed
better than control.
Example 24
Characterization of Battery Cells Including Stabilizing
Additives
[0234] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMNO-type and
the test was performed at room temperature. FIG. 30 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that several OTMS additives performed better than
control.
Example 25
Characterization of Battery Cells Including Stabilizing
Additives
[0235] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMNO-type and
the test was performed at room temperature. FIG. 31 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that several NTMS additives performed better than
control.
Example 26
Characterization of Battery Cells Including Stabilizing
Additives
[0236] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMNO-type and
the test was performed at room temperature. FIG. 32 compares
coulombic efficiency of the battery cells at the first cycle. It
can be appreciated that several TMS additives performed better than
control.
Example 27
Characterization of Battery Cells Including Stabilizing
Additives
[0237] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMNO-type and
the test was performed at room temperature. FIG. 33 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that several TMS additives performed better than
control.
Example 28
Characterization of Battery Cells Including Stabilizing
Additives
[0238] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was CM1-type. FIG.
34 compares coulombic efficiency of the battery cells at the first
cycle. It can be appreciated that several OTMS additives performed
better than control.
Example 29
Characterization of Battery Cells Including Stabilizing
Additives
[0239] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was CM1-type. FIG.
35 compares coulombic efficiency of the battery cells at the first
cycle. It can be appreciated that several OTMS additives performed
better than control.
Example 30
Characterization of Battery Cells Including Stabilizing
Additives
[0240] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was CM1-type the
test was performed at room temperature. FIG. 36 compares capacity
retention of the battery cells over several cycles, expressed in
terms of a percentage of an initial specific capacity upon
discharge retained at a particular cycle. It can be appreciated
that several OTMS additives performed better than control.
Example 31
Characterization of Battery Cells Including Stabilizing
Additives
[0241] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was CM1-type and
the test was performed at room temperature. FIG. 37 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that several OTMS additives performed better than
control.
Example 32
Characterization of Battery Cells Including Stabilizing
Additives
[0242] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was CM1-type and
the test was performed at room temperature. FIG. 38 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that several NTMS additives performed better than
control.
Example 33
Characterization of Battery Cells Including Stabilizing
Additives
[0243] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was NMC-type and
the test was performed at high temperature. FIG. 39 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
Example 34
Characterization of Battery Cells Including Stabilizing
Additives
[0244] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was NMC-type and
the test was performed at high temperature. FIG. 40 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
Example 35
Characterization of Battery Cells Including Stabilizing
Additives
[0245] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was OLO-type and
the test was performed at room temperature. FIG. 41 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
Example 36
Characterization of Battery Cells Including Stabilizing
Additives
[0246] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was OLO-type and
the test was performed at high temperature. FIG. 42 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
Example 36
Characterization of Battery Cells Including Stabilizing
Additives
[0247] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was OLO-type and
the test was performed at room temperature. FIG. 43 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
Example 37
Characterization of Battery Cells Including Stabilizing
Additives
[0248] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was OLO-type and
the test was performed at room temperature. FIG. 44 compares energy
efficiency of the battery cells over several cycles. It can be
appreciated that OTMS additives performed better than control.
Example 38
Characterization of Battery Cells Including Stabilizing
Additives
[0249] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMNO-type and
the test was performed at high temperature. FIG. 45 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
Example 39
Characterization of Battery Cells Including Stabilizing
Additives
[0250] Using the methodology of Example 22, performance
characteristics were measured for test battery cells including
different silicon-containing stabilizing additives dispersed in a
conventional electrolyte (ethylene carbonate, ethyl methyl
carbonate, and 1M LiPF.sub.6) and for a control battery cell
including the conventional electrolyte but without a stabilizing
additive. In this example, the cathode material was LMO-type and
the test was performed at high temperature. FIG. 46 compares
capacity retention of the battery cells over several cycles,
expressed in terms of a percentage of an initial specific capacity
upon discharge retained at a particular cycle. It can be
appreciated that OTMS additives performed better than control.
[0251] While the invention has been described with reference to the
specific embodiments thereof, it should be understood by those
skilled in the art that various changes may be made and equivalents
may be substituted without departing from the true spirit and scope
of the invention as defined by the appended claims. In addition,
many modifications may be made to adapt a particular situation,
material, composition of matter, method, or process to the
objective, spirit and scope of the invention. All such
modifications are intended to be within the scope of the claims
appended hereto. In particular, while the methods disclosed herein
have been described with reference to particular operations
performed in a particular order, it will be understood that these
operations may be combined, sub-divided, or re-ordered to form an
equivalent method without departing from the teachings of the
invention. Accordingly, unless specifically indicated herein, the
order and grouping of the operations are not limitations of the
invention.
* * * * *