U.S. patent application number 13/749960 was filed with the patent office on 2013-08-08 for electrophoretic assembly of electrochemical devices.
This patent application is currently assigned to A123 Systems, Inc.. The applicant listed for this patent is A123 Systems, Inc., Massachusetts Institute of Technology. Invention is credited to Yet-Ming Chiang, Benjamin Hellweg, Richard K. Holman, Dong-Wan Kim, Steven M. Tobias, Ryan C. Wartena.
Application Number | 20130202959 13/749960 |
Document ID | / |
Family ID | 46304368 |
Filed Date | 2013-08-08 |
United States Patent
Application |
20130202959 |
Kind Code |
A1 |
Chiang; Yet-Ming ; et
al. |
August 8, 2013 |
ELECTROPHORETIC ASSEMBLY OF ELECTROCHEMICAL DEVICES
Abstract
Methods are provided for making bipolar electrochemical devices,
such as batteries, using electrophoresis. A bipolar device is
assembled by applying a field that creates a physical separation
between two active electrode materials, without requiring insertion
of a discrete separator film or electrolyte layer.
Inventors: |
Chiang; Yet-Ming; (Weston,
MA) ; Hellweg; Benjamin; (New York, NY) ;
Holman; Richard K.; (Wellesley, MA) ; Tobias; Steven
M.; (Cambridge, MA) ; Kim; Dong-Wan; (Seoul,
KR) ; Wartena; Ryan C.; (Los Angeles, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Massachusetts Institute of Technology;
A123 Systems, Inc.; |
Cambridge
Waltham |
MA
MA |
US
US |
|
|
Assignee: |
A123 Systems, Inc.
Waltham
MA
Massachusetts Institute of Technology
Cambridge
MA
|
Family ID: |
46304368 |
Appl. No.: |
13/749960 |
Filed: |
January 25, 2013 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
12692460 |
Jan 22, 2010 |
|
|
|
13749960 |
|
|
|
|
11108602 |
Apr 18, 2005 |
7662265 |
|
|
12692460 |
|
|
|
|
10206662 |
Jul 26, 2002 |
7579112 |
|
|
11108602 |
|
|
|
|
10021740 |
Oct 22, 2001 |
7553584 |
|
|
10206662 |
|
|
|
|
60308360 |
Jul 27, 2001 |
|
|
|
60242124 |
Oct 20, 2000 |
|
|
|
60563026 |
Apr 16, 2004 |
|
|
|
60583850 |
Jun 29, 2004 |
|
|
|
Current U.S.
Class: |
429/209 ;
204/471; 204/622 |
Current CPC
Class: |
H01M 4/0457 20130101;
H01M 4/139 20130101; H01M 4/08 20130101; H01M 10/0565 20130101;
H01M 4/525 20130101; C25D 13/00 20130101; C25D 17/00 20130101; H01M
10/0472 20130101; H01M 10/058 20130101; H01M 2004/021 20130101;
H01M 2004/025 20130101; H01M 6/18 20130101; H01M 4/02 20130101;
H01M 4/808 20130101; H01M 10/0436 20130101; H01M 10/052 20130101;
Y02E 60/13 20130101; G02F 2001/1555 20130101; Y02E 60/10 20130101;
H01G 11/56 20130101; H01M 10/04 20130101; H01M 4/0438 20130101;
H01M 6/40 20130101; H01G 11/26 20130101; H01M 10/44 20130101; H01M
6/181 20130101; H01M 4/661 20130101; H01G 11/64 20130101; H01M
10/0525 20130101 |
Class at
Publication: |
429/209 ;
204/622; 204/471 |
International
Class: |
H01M 4/04 20060101
H01M004/04; C25D 13/00 20060101 C25D013/00; C25D 17/00 20060101
C25D017/00 |
Goverment Interests
GOVERNMENT RIGHTS
[0002] This invention was made with government support under Grant
Number F49620-02-1-0406, awarded by the Air Force, and Grant Number
NMA501-03-01-2004, awarded by the Department of Defense. The
government has certain rights in the invention.
Claims
1. A device, comprising: a first terminal and a second terminal
having a different electrical potential than the first terminal;
and a continuous bridge of conductive particles comprising an
electroactive material between the first and second terminals.
2. The device of claim 1, wherein the first terminal has a positive
polarity and the second terminal has a negative polarity.
3. The device of claim 1, wherein the electroactive material
comprises carbon.
4. The device of claim 1, wherein the electroactive material
comprises at least one lithium intercalation compound.
5. The device of claim 1, wherein at least some of the particles
are coated with conductive material.
6. The device of claim 1, comprising: a third terminal proximate
the second terminal; a fourth terminal; and a second continuous
bridge of conductive particles comprising a second electroactive
material between the third and fourth terminals.
7. The device of claim 1, wherein the first terminal comprises a
metal.
8. The device of claim 7, wherein the second terminal comprises a
metal.
9. The device of claim 1, wherein the second terminal has a
longitudinal axis that is substantially parallel to a longitudinal
axis of the first terminal.
10. A method of making an electrode comprising: providing a first
terminal; providing conductive particles of an electroactive
material in a medium; providing a second terminal; applying an
electrical potential between the first and the second terminal to
deposit conductive particles of the electroactive material at the
first terminal thereby forming an electronically continuous
electrode; forming a continuous bridge of conductive particles of
the electroactive material between the first and second terminals;
and removing the applied electrical potential.
11. The method of claim 10, further comprising: providing a third
terminal; providing conductive particles of a second electroactive
material in a medium; providing a fourth terminal; applying an
electrical potential between the third and the fourth terminals to
deposit conductive particles of the second electroactive material
at the third terminal thereby forming a second electronically
continuous electrode; forming a second continuous bridge of
conductive particles of the second electroactive material between
the third and fourth terminals; and removing the applied electrical
potential.
12. An electrode made by the method of claim 10.
13. A battery comprising: a substrate; a first terminal; a second
terminal; and a localized conductive region comprising
electroactive material formed on the substrate and surrounded by an
insulating region, wherein at least one of the first or second
terminals is electronically connected to the conductive region.
14. The battery of claim 13, wherein the localized conductive
region has an area of less than 100 nanometers squared.
15. The battery of claim 13, having a volume of less than 1 cubic
millimeter.
Description
[0001] This application is a continuation of U.S. patent
application Ser. No. 12/692,460, filed Jan. 22, 2010, which is a
continuation of U.S. patent application Ser. No. 11/108,602, filed
Apr. 18, 2005. U.S. patent application Ser. No. 11/108,602 claims
priority to U.S. Provisional Patent Application Ser. No.
60/563,026, filed Apr. 16, 2004, and U.S. Provisional Patent
Application Ser. No. 60/583,850, filed Jun. 29, 2004. U.S. patent
application Ser. No. 11/108,602 is also a Continuation In Part of
U.S. patent application Ser. No. 10/206,662, filed Jul. 26, 2002,
which claims priority to U.S. Provisional Application Ser. No.
60/308,360, filed Jul. 27, 2001. U.S. patent application Ser. No.
10/206,662 is also a Continuation In Part of U.S. patent
application Ser. No. 10/021,740, filed Oct. 22, 2001, which claims
priority to U.S. Provisional Patent Application Ser. No.
60/242,124, filed Oct. 20, 2000. Each of these applications are
incorporated by reference herein.
BACKGROUND
[0003] 1. Field
[0004] The field includes methods of making bipolar devices using
electrical potentials and electric fields, and in particular
methods of making bipolar electrochemical devices, such as
batteries, using electrophoresis.
[0005] 2. Summary of the Related Art
[0006] Batteries, and particularly rechargeable batteries, are
widely used in a variety of devices such as cellular telephones,
laptop computers, personal digital assistants, and toys.
Manufacturing constraints generally limit the available shapes of
batteries, with common form factors including cylinders, button
cells (thin discs), and prismatic forms. The energy density of such
batteries is relatively low, due to poor volumetric utilization of
space within the electrochemical devices. Recently
"three-dimensional batteries" have been proposed, which have anodes
and cathodes with active surface areas exposed in three dimensions,
and potentially exhibit improved performance results compared to
standard battery geometries. A need exists for new manufacturing
methods to create electrochemical devices with improved energy
density, power density, and cycle life, as well as reduced
manufacturing cost.
[0007] Electrophoresis, the motion of charged particles under an
applied electric field, is used to characterize the behavior of
solutions and suspensions, and has also been used to deposit
materials in the form of thin films, coatings, and even bulk
products. The formation of battery electrodes by electrophoretic
deposition has been disclosed (e.g., Kanamura et al.,
Electrochemical and Solid-State Letters, 3:259-262 (2000)).
Typically, a coating is electrophoretically deposited on a metal
substrate from a suspension of particles in a liquid. The deposited
coating is then removed from the apparatus or bath in which the
deposition was carried out, and subsequently used for a desired
application. For example, to prepare a battery, an
electrophoretically-deposited electrode is removed from its liquid
deposition bath, dried, and used as a component in a device
assembly. However, the act of electrophoresis does not by itself
create a complete device.
SUMMARY
[0008] Methods are provided for making bipolar electrochemical
devices using electrophoresis. Potentials (e.g., electrical
potentials) and fields (e.g., electrical fields) are used to
assemble a variety of electrochemical device architectures,
including two-dimensional and three-dimensional constructions for
batteries, capacitors, fuel cells, electrochromic displays, and
sensors. The disclosed electrophoretic assembly methods do not
require insertion of a discrete separator film or electrolyte
layer, and are useful for producing devices with reduced
manufacturing cost and improved energy density, power density, and
cycle life.
[0009] In certain embodiments, the methods described herein utilize
the electric-field assisted deposition of an electroactive material
from a medium. The electroactive material is suspended in the
medium, and may be in the form of colloidal particles,
macromolecules, molecules, or ions. Hereafter, it should be
understood that the term "particles" refers to any of the above
forms.
[0010] One aspect provides a method of assembling a bipolar device
including a first terminal and a second terminal, and a device made
according to the method. The method includes providing the first
terminal and providing particles of a first electroactive material
in a medium. The method further includes providing the second
terminal electronically connected to a second electroactive
material. The method further includes generating a field causing
particles of the first electroactive material to form an
electronically continuous electrode, and creating an electronically
insulating separation between the first and second electroactive
materials. The electronically insulating separation between the
first and second electroactive materials is preserved in the final
device.
[0011] In certain embodiments, the method comprising generating an
electrical field causing particles of the first electroactive
material to form an electronically continuous electrode, and
creating an electronically insulating separation between the first
and second electroactive materials. The electrical field can be
generated by applying an electrical potential between the first
terminal and the second terminal; or, between one of the first and
second terminals and a third terminal. The electrical field can
attract particles of the first electroactive material to the first
terminal. In some cases, the electrical field attracts particles of
the first electroactive material to the first terminal and/or
repels particles of the first electroactive material from the
second electroactive material in the medium.
[0012] In certain embodiments, the method also includes providing
an ionically conductive material in the electronically insulating
separation between the first and second electroactive materials. In
some embodiments, the ionically conductive material is a liquid
electrolyte. In some embodiments, the medium includes a polymer,
and preserving the electronically insulating separation between the
first and second electroactive materials includes solidifying, or
drying, the polymer to form a solid polymer electrolyte.
[0013] In some embodiments, the method further comprises depositing
particles of the first electro active material on the first
terminal.
[0014] In certain embodiments, the second electroactive material
has a three-dimensional structure defining a void space, and
wherein the field causes particles of the first electroactive
material to concentrate in the void space. The second electroactive
material may be a porous electrode, and wherein the field causes
particles of the first electroactive material to concentrate in the
pore space of the porous electrode. The porous electrode may be a
reticulated open-cell carbon, metal or ceramic foam.
[0015] In some embodiments, wherein particles of at least one of
the first and second electroactive materials are coated with a
conductive material.
[0016] In some embodiments, at least one of the terminals is
patterned to include a serpentine, spiral, or comb-like region and
further comprising depositing electroactive material in the region.
In some cases, the first and second terminals are constructed and
arranged to be interdigitated.
[0017] In some embodiments, the method further comprises depositing
particles of the first electroactive material on the first terminal
thereby forming an electronically continuous first electrode; and,
generating a second field causing particles of the second
electroactive material to deposit on the second terminal, thereby
forming an electronically continuous second electrode. The method
may further comprise creating an electronically insulating
separation between the first and second electrodes; and, preserving
the electronically insulating separation between the first and
second electrodes.
The first and second electrodes may be formed simultaneously, or
sequentially.
[0018] In certain embodiments, the method also includes applying an
electrical potential to the first terminal, thereby creating an
attractive force between the first electroactive material and the
first terminal. In at least some such embodiments, particles of the
first electroactive material are deposited at the first
terminal.
[0019] In some embodiments, the second electroactive material has a
three-dimensional structure defining a void space, and the
repulsive force between the first and second electroactive
materials causes particles of the first electroactive material to
concentrate in the void space. In certain embodiments, the second
electroactive material is a porous electrode, and the repulsive
force between the first and second electroactive materials causes
particles of the first electroactive material to concentrate in the
pore space of the porous electrode. In some embodiments, the porous
electrode is a reticulated open-cell carbon, metal or ceramic
foam.
[0020] In certain embodiments, particles of at least one of the
first and second electroactive materials are coated with a
conductive material.
[0021] Another aspect provides a method of making an electrode and
an electrode made according to the method. The method includes
providing a first terminal and providing conductive particles of an
electroactive material in a medium. The method further includes
providing a second terminal. An electrical potential is applied
between the first and the second terminal to deposit conductive
particles of the electroactive material at the first terminal
thereby forming an electronically continuous electrode. A
continuous bridge of conductive particles of the electroactive
material is formed between the first and second terminals. The
applied electrical potential is removed.
[0022] In some embodiments, the method further comprises providing
a third terminal and providing conductive particles of a second
electroactive material in a medium. The method further comprises
providing a fourth terminal and applying an electrical potential
between the third and the fourth terminals to deposit conductive
particles of the second electroactive material at the third
terminal thereby forming a second electronically continuous
electrode. A second continuous bridge of conductive particles of
the second electroactive material is formed between the third and
fourth terminals. The applied electrical potential is removed.
[0023] Another aspect provides a battery. The battery comprises a
substrate, a first terminal, a second terminal; and a localized
conductive region comprising electroactive material formed on the
substrate and surrounded by an insulating region. At least one of
the first and second terminals is electronically connected to the
conductive region.
[0024] Other aspects, embodiments and features of the invention
will become apparent from the following detailed description of the
invention when considered in conjunction with the accompanying
drawings. The accompanying figures are schematic and are not
intended to be drawn to scale. In the figures, each identical, or
substantially similar component that is illustrated in various
figures is represented by a single numeral or notation. For
purposes of clarity, not every component is labeled in every
figure. Nor is every component of each embodiment of the invention
shown where illustration is not necessary to allow those of
ordinary skill in the art to understand the invention. All patent
applications and patents incorporated herein by reference are
incorporated by reference in their entirety. In case of conflict,
the present specification, including definitions, will control.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 is a schematic illustration of depositing an
electrochemically active material using electrophoresis according
to certain embodiments.
[0026] FIGS. 2A-B are schematic illustrations of the formation of
layered battery configurations using electrophoretic deposition and
simultaneous separation according to certain embodiments.
[0027] FIG. 3 is a schematic illustration of a system for spatially
concentrating a cathode material in the pore space of a porous foam
anode using electrophoresis according to certain embodiments.
[0028] FIG. 4A is a schematic illustration of spatially
concentrating a cathode material in the pore space of a porous foam
anode using electrophoresis according to certain embodiments. FIG.
4B is an expanded view of the foam.
[0029] FIG. 5 is a top view of a microelectrode array deposited on
glass, which is useful for carrying out electrophoresis according
to certain embodiments.
[0030] FIG. 6 is a chart showing a cyclic voltammetry scan of a
heat treated carbon foam, tested in a Swagelok.RTM. cell against a
lithium metal foil electrode, showing reversible electrochemical
insertion of lithium at the expected potential for carbon
anodes.
[0031] FIG. 7 is a chart showing cyclic voltammetry results from
several samples of devices assembled by electrophoresis according
to certain embodiments. Testing was performed at various scan rates
between 0 and 4.2V at room temperature. In each case, the sample
resistance remained high up to the maximum voltage, showing that
electrical insulation was preserved.
[0032] FIG. 8A is a top view of a microelectrode array with
LiCoO.sub.2 and Super P.TM. carbon electrophoretically deposited at
one electrode according to certain embodiments.
[0033] FIG. 8B is a top view of a microelectrode array with
LiCoO.sub.2 and Super P.TM. carbon electrophoretically deposited at
one electrode and mesoporous microbeads (MCMB) electrophoretically
deposited at the other electrode according to certain
embodiments.
[0034] FIG. 9 is a plot illustrating galvanostatic cycling (30
mA/g) vs. lithium metal of reticulated vitreous carbon, fired at
2400.degree. C. in He gas for 4 hours, showing low first-cycle
irreversibility and low capacity fade to 10 cycles.
[0035] FIGS. 10A-C are plots of galvanostatic voltage-capacity
curves at C/24 rate for an electrophoretically assembled cell,
calculated for LiCoO.sub.2 mass. FIG. 10A shows a first charge
curve exhibiting large excess capacity attributed to the reversal
of electrochemical reactions induced during electrophoresis. FIG.
10B shows discharge curves for the first few cycles exhibiting
similar voltage profiles, with the capacity varying with upper
voltage limit during charge. FIG. 10C shows the sixth cycle
exhibiting polarization during charge and discharge of .about.0.2V
about the open circuit voltage.
[0036] FIGS. 11A-B are schematic illustrations of cell designs in
which a can and a tab are used as working electrodes for
electrophoretic forming, and subsequently are used as current
collectors of the resultant battery.
[0037] FIGS. 12A-B show a two-step deposition process for the
electrophoretic assembly of a battery as described in Example
8.
[0038] FIG. 13 shows the charge and discharge for cycle number 40
for the battery of FIGS. 12A and 12B as described in Example 8.
[0039] FIGS. 14A-B show a two-step process for making a battery by
electrophoretic deposition on a set of four electrodes as described
in Example 8.
[0040] FIGS. 15A-C show the deposition from a mixture of 1 wt %
LiCoO.sub.2 in acetone at 2, 2.5 and 3 V, respectively, as
described in Example 9.
[0041] FIGS. 16A-C show the deposition from a mixture of 1 wt %
LiCoO.sub.2 in acetone at 5 V as described in Example 9.
[0042] FIG. 17 shows a reticulated carbon foam attached to a second
Pt mesh current collector, and placed above a first Pt mesh current
collector as described in Example 7.
[0043] FIG. 18 shows the current measured between two current
collectors as a function of time for two values of applied voltage
as described in Example 7.
[0044] FIG. 19 shows a pattern of terminals having a serpentine
configuration as described in Example 10.
[0045] FIG. 20 shows a pattern of terminals having a spiral
configuration as described in Example 10.
[0046] FIG. 21 illustrates configurations of terminals allowing
deposition corresponding to the method of Example 3 as described in
Example 11.
[0047] FIG. 22 illustrates configurations of terminals allowing
deposition corresponding to the method of Example 8 as described in
Example 11.
DETAILED DESCRIPTION
[0048] The invention provides methods of assembling bipolar
electrochemical devices using electrophoresis. Electrical
potentials and electric fields are used to form electrochemical
junctions between positive and negative electrodes, and
electrochemical devices are fabricated with a variety of internal
designs or architectures, including one-, two-, and
three-dimensional constructions. By way of non-limiting example,
methods as disclosed herein are useful for making laminated
devices, bobbin construction batteries and variants thereof, planar
interpenetrating electrode structures, and three-dimensional
interdigitated and interpenetrating structures, such as those based
on the infiltration of one porous electrode with an opposing
electrode. Many such device architectures are described in detail
in U.S. patent application Ser. No. 10/206,662, published as US
2003/0099884 A1, which is incorporated by reference herein.
Non-limiting examples of device configurations suitable for
assembly by electrophoretic methods as described herein include a
cell comprising a single pair of parallel linear electrodes, a
single planar cell stack consisting of a laminate having one
positive and one negative electrode, multiple laminates or
multilayer stacks, a two-dimensional array of alternating linear
electrodes, a two-dimensional interdigitated electrode array, a
three-dimensional array of interdigitated electrodes,
three-dimensional interpenetrating electrode arrays,
three-dimensional interpenetrating electrode arrays in which at
least one electrode is in the form of an open-cell foam, a sintered
porous particle aggregate, a mat of fibers or ribbons, a weave of
fibers or ribbons, stacked mats or weaves of fibers or ribbons, and
non-interpenetrating or non-interdigitated cells in which at least
one electrode is porous.
[0049] Methods of the invention are useful for assembling
electrochemical devices including but not limited to batteries (of
primary or secondary type), capacitors, fuel cells, electrochromic
displays and windows, and sensors. Advantageously, assembly of
devices according to electrophoretic methods as described herein
does not require insertion of a discrete separator film or
electrolyte layer, as is conventionally done in the fabrication of
electrochemical devices. Devices assembled as described herein can
be "separatorless" because an electronically insulating, ionically
conductive layer is formed in situ between the anode and cathode
during electrophoretic assembly. Methods as described herein are
useful for assembling devices with lower manufacturing cost, higher
energy density and power density, and longer cycle life than
comparable devices produced by conventional methods.
[0050] In at least some embodiments, electrophoretic assembly of a
device is carried out by applying an electrical potential between
two electrodes that subsequently are used as the terminals or
working electrodes of the device. For example, in certain
embodiments, electrophoresis is used to deposit a first
electrochemically active material, and optionally additives, at a
first electrode, current collector, or terminal of a device.
Electrophoresis is effected by applying an electrical potential
between the first electrode and a second electrode, current
collector, or terminal of the device. The potential applied to the
second electrode causes it to repel the first active material. In
at least some instances, the first active material is also
attracted to the first electrode. By applying an electrical
potential between the two terminals of the device, a physical
separation is produced between the two active electrode materials
without requiring the insertion of a discrete separator film or
electrolyte layer, as is conventionally done in the fabrication of
electrochemical devices such as batteries, capacitors, fuel cells,
and electrochromic devices. In at least some embodiments,
electrophoresis is carried out in a fluid medium that remains
between the electrophoretically separated materials. In certain
embodiments, by limiting the volume available to the
electrophoretically mobile particles, a device is produced with
very small diffusion distances between electrodes.
[0051] In some embodiments, the second electrode of the device
being assembled by electrophoresis is a terminal or current
collector at which a second active material previously has been
deposited, by electrophoretic or other means. In certain
embodiments, the second electrode is itself made up of a functional
electrochemically active material. In some instances, the second
electrode is assembled by electrophoresis simultaneously with the
first electrode, or sequentially before or after the first
electrode.
[0052] FIG. 1 illustrates an exemplary arrangement for depositing
electroactive materials by electrophoresis, as described in more
detail in Example 1 below. As shown in FIG. 1, two parallel films
of gold 10, 11 sputtered on glass are placed in a beaker 12. A
suspension 14 of electrophoretically mobile particulates 16 of one
or more materials is placed in the beaker 12. In the illustrated
embodiment, the particulates are LiCoO.sub.2, a lithium
intercalation cathode active material for lithium ion batteries,
and Super P.TM., a high surface area conductive carbon used in
lithium battery electrode formulations. A DC power supply 18 is
used to apply a voltage to the electrodes 10, 11. The voltage
causes the particulates 16 to be repelled from one electrode 10 and
migrate toward, and eventually deposit on, the other electrode
11.
[0053] Non-limiting examples of layered or laminated battery cells
made using electrophoretic deposition and simultaneous separation
are shown in FIGS. 2A-B. Referring to FIG. 2A, to carry out
electrophoretic assembly, a voltage is applied between a sheet or
mesh cathode current collector 20 and an anode current collector
21, which is connected to a lithium metal or carbon anode 22. A
colloidal suspension 23 containing particles of an intercalation
compound 24, a polymer electrolyte 25, and a lithium salt (e.g.,
LiClO.sub.4), with or without an organic solvent, is provided
between the current collectors 20, 21. Upon application of voltage,
the particles of intercalation compound 24 are deposited to form an
electronically conducting network on the cathode current collector
20. The polymer electrolyte 25 is solidified, and forms a permanent
separator between the electrodes. Referring to FIG. 2B, a fluid
mixture of anode particles 26 in a molten polymer or polymer
solution is provided between an anode current collector 21, and a
cathode current collector 20, which is connected to a cathode film
27. Upon application of a voltage across the current collectors 20,
21, the anode particles 26 are deposited on the anode current
collector 21, and an in situ formed isolation layer 28 is created
between the electrodes.
[0054] Non-limiting examples of suitable electrochemically active
materials for use in electrophoretic methods as described herein
include ion storage materials for assembling a battery,
electrochromically active materials for assembling certain
electrochromic devices, high surface area active materials for
assembling certain electrochemical capacitors, active materials for
hybrid battery-capacitor devices utilizing both Faradic and
capacitive charge storage, and electrodes or catalysts for certain
fuel cell assemblies. Useful additives include but are not limited
to conductive particles that increase the electrical conductivity
of the deposited material, such as conductive carbon, metallic
particles, or conductive polymer dispersions, or binders that
improve the adherence of the deposited particles to each other or
to a current collector.
[0055] Suitable materials for electrophoretic assembly are
identified by their ability to meet a desired function in the
subject electrochemical device. For example, in a rechargeable
lithium ion battery, an intercalation oxide able to reversibly
store lithium at a high potential with respect to lithium metal is
useful as the active material at the positive electrode. Such
materials are well-known to those having ordinary skill in the art,
and include ordered-rocksalt compounds such as LiCoO.sub.2,
LiNiO.sub.2, Li(Al, Ni, Mn)O.sub.2, LiMnO.sub.2, and solid
solutions or doped combinations thereof; spinel structure compounds
such as LiMn.sub.2O.sub.4 and its doped counterparts or solid
solutions with other metal oxides; ordered olivines such as
LiFePO.sub.4, LiMnPO.sub.4, LiCoPO.sub.4, and their doped
counterparts or solid solutions; and other ordered transition metal
phosphates such as those of so-called Nasicon structure type and
their derivatives and related structures. For the active material
at the negative electrode of a lithium-ion battery, examples of
suitable compounds include compounds such as graphitic or
disordered carbons; metal oxides that intercalate lithium such as
Li.sub.4Ti.sub.5O.sub.12 spinel and its derivatives; and other
metal oxides or their solid solutions that undergo intercalation or
displacement reactions such as tin oxide, indium tin oxide, or
first-row transition metal oxides; and crystalline or amorphous
metals and alloys of metals or metalloids such as Si, Al, Zn, Sn,
Ag, Sb, and Bi. For a primary battery, suitable electrode-active
materials include without limitation those well-known to those of
ordinary skill in the art to form useful electrochemical couples,
such as Zn and MnO.sub.2 in the case of the aqueous Leclanche or
alkaline-manganese cells, zinc and mercuric oxide in the case of a
"mercury cell," or lithium and copper oxide or lithium and
manganese oxide in the case of primary lithium batteries. For an
electrochemical capacitor or hybrid battery-capacitor, useful
electrode materials include without limitation high surface area
carbons or metal oxides. For an electrochromic displaying or
transmitting device, useful active materials include but are not
limited to transition metal oxides and other chromophoric compounds
that change color or optical transmission upon being
electrochemically oxidized or reduced. For a fuel cell membrane
assembly, useful active materials include without limitation
conductor and catalyst particles serving as the positive or
negative electrode.
[0056] Materials and materials combinations for electrophoretic
assembly are also selected by the direction and rate at which they
migrate under an applied electric field. Electrophoresis can be
effected for charged entities of widely ranging sizes, as large as
particulates many micrometers in size or as small as individual
molecules and ions. In a liquid medium, charged particles and
molecules have an electrophoretic mobility whose sign is given by
the direction of motion, and whose magnitude is given by the
velocity of the entity under a given magnitude of electric field.
Methods for determining electrophoretic mobility are well-known to
those having ordinary skill in the art of colloids, powder
materials processing, or surface chemistry. For many materials
dispersed in aqueous or nonaqueous media, the zeta potential, which
is defined as the electrical potential at a dividing plane
separating electrical charge that is fixed to the solid and that
which is freely mobile in the fluid, is tabulated or can be
predicted or can be measured by standard methods. The sign and
magnitude of the surface charge on particular material particles
can be selected or altered in a number of ways well-known to those
having ordinary skill in the art, including but not limited to
varying the solvent or solvents, pH of the suspension,
concentration of added salts, or by adding various charged
molecules or surfactants that adsorb to the particle surface. As
shown herein, the zeta potential can also be controlled by varying
the magnitude of the applied voltage between the electrodes
effecting deposition, such that at a low voltage the zeta potential
has one value, and at a higher voltage the zeta potential has a
different value or even a different sign. The voltage at which the
sign of the zeta potential may change differs for different
solvents or mixtures of solvents and dissolved salts or organic
species, and can also be determined through methods well-known to
those skilled in the art. One or more of these factors are employed
in order to select the materials and solvent system for
electrophoresis. The rate of deposition of particles at a
particular electrode is determined by controllable experimental
variables well-known to those of ordinary skill in the art,
including but not limited to the magnitude of the voltage and the
electric field, the particle concentration in suspension, magnitude
of the zeta potential, size and shape of the particle, and
viscosity of the medium. As illustrated in Example 1 below, direct
observation of the direction of motion and rate of deposition of a
desired particulate material under electric field is readily
performed, and is an effective means of screening or selecting
materials and materials combinations.
[0057] In some embodiments, the particles undergoing
electrophoretic migration are coated with a conductive material
that optionally also determines the zeta potential or
electrophoretic mobility of the particles. Suitable coatings
include carbonaceous materials; conductive oxides, including but
not limited to indium tin oxide, doped tin oxides, and doped zinc
oxides; and conductive polymers. Conductive polymer coatings are
useful for providing high electronic conductivities, adequate
lithium ion diffusivity, and lower elastic modulus, such that upon
contact the contact points are deformable, resulting in greater
contact area between particles and greater electronic conductivity
for the electrophoretically concentrated network. Suitable polymers
include, for example, commercially available conductive polymers
such as Baytron.RTM. P (Bayer AG, Leverkusen, Germany), poly
3,4-ethylenedioxythiophene/polystyrenesulfonic acid complex, and
conductive polymers described in U.S. patent application Ser. No.
10/876,179, published as US 2005/0034993 A1, which is incorporated
by reference herein. Some such polymers have electronic
conductivity of at least about 1 S/cm, and as high as about 75
S/cm. In some instances, the conductive component includes one or
more groups selected from polyaniline, polypyrrole, polyacetylene,
polyphenylene, polythiophene, polyalkylenedioxythiophene, and
combinations thereof. In certain embodiments, the conductive
polymer includes one or more groups selected from Structures
I-V:
##STR00001##
wherein Rf is a fluorinated alkyl group, aryl group, or combination
thereof, X is a linking group attaching Rf to the polymer backbone,
and R is a pendant group chosen from X--Rf, H, and methyl. In some
embodiments, X includes one or more groups selected from alkyl,
ether, thioether, ester, thioester, amine, amide, and benzylic
groups. In some embodiments, the polymer includes one or more
groups selected from EDOT-F (pentadecafluoro octanoic acid
2,3-dihydro-thieno[3,4-b][1,4]dioxin-2-ylmethyl ester), Th--O-1,7
(3-pentadecafluorooctyloxythiophene), Me--Th--O-1,7
(3-methyl-4-pentadecafluorooctyloxythiophene), and PrODOT-F
(propylenedioxythiophene pentadecafluorooctane ester).
[0058] In at least some embodiments, the mode of electrophoretic
deposition is determined by varying the composition of the particle
suspension from which deposition occurs, the dimensions and
separation of the electrodes, and/or the applied voltage. In
certain embodiments, the "mode" of electrophoretic deposition
includes one or more of the following. In one mode, highly
conductive particles that, upon deposition, form a continuous
network of conductive particles, have the effect of extending the
conductive electrode at which deposition occurs. The electric field
causing deposition is determined by the applied voltage, and the
separation between the electrodes. This mode of deposition is
susceptible to the formation of locally increased electric field
where particles deposit. This in turn increases the deposition
rate, leading to an instability of the deposited layer, which
causes the formation of branches or "dendrites." Such dendrites can
subsequently lead to a continuous bridge between electrodes,
causing an electrical short circuit, especially when the electrodes
are closely spaced in relation to the thickness of the desired
deposit (for example, an electrode spacing less than about five
times the thickness of the deposited layer, if deposited
uniformly). In certain embodiments, this mode of electrophoretic
deposition is used to practical advantage, to control the location
and amount of electrodeposited active material. In at least some
such embodiments, a pair of deposition electrodes is used to create
each final electrode.
[0059] When the deposited particles are largely insulating, the
mode of deposition generally differs from the previous one, in that
the deposited particles do not cause significant increase in the
electric field through the narrowing of the electrode gap. In this
mode, referred to as "plating," the deposited layer of particles
typically remains relatively uniform in thickness as the particles
deposit. Another mode of deposition that results in a uniform
thickness of deposit occurs when the electrophoretic velocity of
the particles is sufficiently greater than the diffusional velocity
of the particles. In this mode, the particles are deposited before
they have an opportunity to diffuse laterally under Brownian motion
to an extent allowing the formation of dendrites, and the deposit
is typically uniform. This mode generally occurs under high
electric fields, e.g., for closely spaced electrodes and/or high
applied voltages, and the particles deposited are primarily limited
to those present between the electrodes when the field is initially
applied. A certain extent of dendrite formation is allowable before
electrical shorting between the electrodes occurs. The ratio of
electrophoretic velocity to diffusional velocity necessary to
prevent shorting due to dendrite formation depends on the density
of particles in the suspension, the thickness of the deposit, the
electrode geometry and the spacing of electrodes, amongst other
factors, and is readily determined by direct experimentation.
[0060] Yet another mode of deposition typically occurs under high
applied voltage in electrolytic solutions. It was surprisingly
observed that the bridging phenomenon leading to electrical
shorting between deposition electrodes can be avoided when the
applied voltage is sufficiently large, greater than about 5 volts
and preferably about 10 volts. In this case, even closely spaced
electrodes or deposits do not electrically short, and a densely
packed electrode system is facilitated. Since our discovery,
similar observations of this phenomenon during the
electrodeposition of carbon nanotubes have been reported by Kamat
et al., J. Am. Chem. Soc. 126:10757-10762 (2004). In another
embodiment, electrical shorting between electrodes is prevented by
providing in liquid suspension or solution other constituents that
are electronically insulating and deposit more quickly than the
electronically conductive active materials. Such constituents
include, for example, a polymer or other organic material,
components of a dissolved lithium salt, or a reaction product
formed at the electrode surface upon the electrodeposition of such
a constituent. The reaction product results from a reaction between
the deposited constituent and another constituent of the
suspension, or between the deposited constituent and the electrode
material itself, such as a lithium carbonate forming on the surface
of a carbon electrode.
[0061] In at least some embodiments, selection of a separator or
electrolyte material that remains between the electrophoretically
separated materials is carried out in the following manner. The
separator material is electronically insulating. In some
embodiments, the separator is itself an ion-conducting electrolyte,
or is rendered ionically conducting after electrophoretic
separation, for example, by infusing with an electrolyte. Suitable
separator materials include organic, inorganic, and
organic-inorganic hybrid materials. By way of non-limiting example,
to create a solid polymer electrolyte in a final device, a solvent
such as acetonitrile is selected, in which the following are
soluble: a polymer that is the basis for a solid polymer
electrolyte, such as polyethylene oxide (PEO); and a lithium salt
that dissociates in the polymer and renders it ionically
conducting, such as LiClO.sub.4. Many such lithium salts are known
to those of ordinary skill in the art. After electrophoretic
separation and drying, a LiClO.sub.4-doped PEO solid electrolyte
remains.
[0062] In certain embodiments, electrophoretic separation is
conducted in the polymer electrolyte itself, at an elevated
temperature where it is molten. That is, the molten electrolyte is
the liquid solvent. After separation is conducted at elevated
temperature, the device is cooled to a lower temperature to
preserve the structure. In such embodiments, operation of the
device takes place at a temperature equal to or lower than the
electrophoretic separation temperature.
[0063] In some embodiments, the separator is a material that is
cross-linked or otherwise rendered rigid during or after
electrophoretic separation. For example, a polymer that is
UV-curable or chemically curable or thermosetting is used as the
liquid medium, optionally with a solvent. Polymerization is
effected during or after electrophoretic separation has occurred.
In some instances, the separator is a binder material that is not
itself ionically conductive, but is infused with electrolyte after
separation. As a non-limiting example, for a non-aqueous battery, a
polymer binder such as polyvinylidine fluoride (PVDF) is dissolved
in a compatible solvent, such as acetone or N-methyl pyrrolidinone
(NMP) or gamma-butyrolactone, forming a solution in which
electrophoretic separation is effected. Following drying, the
device is infused with an organic liquid electrolyte. Such porous
or infusible binders also include inorganic substances such as a
sol-gel derived oxide, or an organic-inorganic hybrid.
[0064] In addition to the electrophoretic deposition of materials,
in certain embodiments the electrochemical deposition of materials
from a fluid medium is also used. For example, in some instances
metal or salt ions in liquid solution are deposited under applied
electrical potential in order to deposit an ion storage compound or
conductive additive at an electrode of an electrochemical device.
In certain embodiments, the electrophoretic deposition of particles
or electrochemical deposition of compounds is increased by
replenishing the fluid medium during deposition, for example by
repeated infiltration by the fluid or effecting continuous flow of
the fluid through the device undergoing deposition.
[0065] In certain embodiments, electrical potential is applied to
repel a first active material (and optionally additives having the
same sign of electrophoretic mobility) from a second electrode that
has a three-dimensional structure defining a pathway or void space
therein. The electric field repels the first active material from
the second electrode, thereby concentrating the first active
material in the void space of the second electrode. In at least
some such embodiments, the process of electrostatic repulsion
substantially densifies the first active material, causing it to
form an electrically continuous electrode. This continuous
electrode, electrically connected to a first terminal or current
collector, is then the first electrode of the device. By limiting
the volume available to the electrophoretically mobile particles, a
densely packed network of the first active material is formed,
while electrical separation is maintained between the two
electrodes.
[0066] In some instances, the second electrode is a porous
electrode. In certain embodiments, the porous electrode is a
reticulated open-cell foam. Such foams are available in materials
including carbon, various metals and ceramics. These materials are
easily machined into arbitrary shapes, useful for fabricating
batteries of complex nonstandard form factors. One non-limiting
example of a useful porous electrode is a continuous carbon
structure having substantial open porosity, such as a carbon foam
or carbon fiber mat. In particular embodiments, a carbon foam is
used as an anode network to form a three-dimensional lithium ion
battery. The pore space within the carbon foam is infiltrated with
a cathode particulate network that is electrophoretically separated
from the carbon structure to form the device. In specific
embodiments, the carbon anode foam is infiltrated with a suspension
containing a cathode active material, a polymer, and optionally
additives. The cathode suspension is infiltrated into the anode
carbon foam at elevated temperature. An electrical potential is
applied so that the cathode material is repelled from the anode
foam. Because the cathode suspension resides in a confined volume
and cannot exit the sample, the particles are electrophoretically
concentrated in the pore space of the foam, forming a continuous,
interpenetrating network of the positive electrode material. This
electrophoretically separated structure is fixed by cooling the
system to solidify the polymer while still applying the electrical
potential. In some alternative embodiments, the cathode suspension
contains a solvent, and the structure is fixed by drying the
solvent, rather than heating and subsequent cooling of the polymer.
In some embodiments, the infiltration of the porous electrode by
the suspension is expedited by carrying out infiltration with a
pressure gradient across the porous electrode, or by applying a
vacuum to a porous electrode immersed in a suspension, thereby
removing trapped gas in the porous electrode. In certain
embodiments, the drying of the infiltrated porous electrode is
expedited by heating, application of vacuum, or both.
[0067] FIGS. 3 and 4 illustrate an exemplary arrangement for a
three-dimensional concentrating electrophoretic method using a
carbon foam anode, as described in more detail in Example 2 below.
Referring to FIG. 3, a carbon foam anode 30 is connected to a
copper current collector 32, and a cylindrical container 34 is
placed around the foam 30. A suspension 36 containing polymer and
cathode material is poured into the container 34 and allowed to
infiltrate the foam 30. An aluminum current collector 38 is
connected to the cathode suspension 36 without contacting the foam
30. In some alternative embodiments, the current collector 38 is
another suitable material, such as platinum, instead of aluminum. A
voltage is applied between the copper 32 attached to the foam 30
and the aluminum current collector 38, with the aluminum current
collector 38 at negative potential and the copper 32 at positive
potential. Upon application of the voltage, as shown in FIG. 4,
cathode particles 40 are concentrated into the pore space 42 of the
foam 30. Simultaneously the cathode suspension 36 is
electrophoretically attracted to the upper current collector, where
it forms a good electrical contact. This process can be directly
monitored by observing current flow between the current collectors;
electrical isolation between the two electrodes is seen as the
decay of current to negligible values. Upon cooling (or otherwise
solidifying the polymer), the electrophoretically separated
configuration is fixed in the final device.
[0068] In some alternative embodiments, a liquid electrolyte cell
is prepared. In this case, a solvent is employed, for example, that
can dissolve polymer binders or gel network formers. To complete
the electrochemical cell, the electrophoretically separated system
is dried and infiltrated with a standard liquid electrolyte. Since
most particulate materials can be induced to have a surface charge
in appropriate liquids, this approach is applicable to a wide range
of active materials. The identification of a suitable system is
illustrated in Example 4 below. Exemplary alternative arrangements
for a three-dimensional concentrating electrophoretic method using
a reticulated foam electrode include those described in Example 6
below. In some alternative embodiments, the stationary porous
network is the positive electrode material, and the infiltrant a
suspension of negative electrode material.
[0069] In certain embodiments, electrophoretic methods are used to
produce devices in which it is desirable to have a high volume
fraction of active materials, e.g., storage batteries. In at least
some such embodiments, due to electrophoretic assembly, the volume
available within the fabricated device is predominantly occupied by
the active materials, with only a minority of the volume occupied
by a fluid phase. As a non-limiting example, a device is assembled
using a suspension of particles of a first active material in a
fluid phase or phases including a binder or a polymer electrolyte,
optionally combined with a solvent. Electrophoretic separation is
effected by applying an electrical potential between first and
second electrodes or terminals of the device, causing the second
electrode to repel the particles of the first active material. In
some embodiments, particles are deposited at one electrode, and an
insulating layer of material is electrodeposited at the opposite
electrode. The electrophoretically separated device structure is
preserved, for example, by cooling the device, removing the solvent
by drying, or crosslinking the binder or polymer by thermal,
chemical, or radiative means (e.g., using a UV crosslinkable
polymer) while still applying the electric potential. In this
manner, a thin but electronically insulating separation is obtained
between the two electrodes. Electrochemical function is then
available, or becomes available upon infusion of an electrolyte
into the device. The electrolyte infuses the space between the
electroactive materials, and in at least some instances also
infuses pore space within the electroactive materials. When a
binder is present between the electroactive materials, the
electrolyte infuses the available pore space unoccupied by the
binder, and in at least some instances is partially absorbed by the
binder itself.
[0070] The electrophoretic assembly methods described herein are
especially useful for fabricating three-dimensional
interpenetrating device architectures, in which reliable electrical
separation between two high surface area interpenetrating
electrodes can be difficult to achieve. Such structures include,
but are in no way limited to, the porous foam electrode structures
described in Example 2 below. Electrophoretic assembly as described
herein provides an alternative to coating the internal surfaces of
an anode foam with a thin layer of a separator material, and then
infiltrating the remaining pore space with a cathode particulate
suspension, as described in U.S. patent application Ser. No.
10/206,662, published as US 2003/0099884 A1.
[0071] Electrophoretic assembly methods as described herein are
also useful in producing standard battery architectures. By way of
non-limiting example, primary batteries of cylindrical form factor
typically have a bobbin construction, in which the anode (e.g.,
made of powdered zinc) is a central post, and the cathode (e.g.,
made of manganese oxide and other constituents) forms an outer
bobbin. According to conventional methods, a continuous sheet of
porous separator film is used to isolate the cathode and anode, and
the whole is infused with aqueous electrolyte. Electrophoretic
methods according to certain embodiments are useful for fabricating
such batteries more simply and economically, to yield a cell having
a greater volume fraction of storage materials, and therefore
higher energy, than cells produced by conventional techniques.
[0072] In one embodiment, a battery of cylindrical form factor
having a bobbin construction is assembled using electrophoresis.
The battery has a central anode that serves as one working
electrode for carrying out electrophoretic separation. A can
housing the battery is filled with a suspension of cathode active
material in a solvent that also contains a polymer solution or
dispersion. A potential is applied so that the cathode active
material is repelled from the central anode post and concentrated
by electrophoretic forces. This repulsion and concentration of the
cathode material causes the formation of a gap between the anode
and cathode, which is filled by the solvent and polymer. The
solvent is allowed to dry, and the polymer deposits between the
anode and cathode, so that the anode and cathode remain
electrically isolated without the use of a separate separator film.
In some instances, the polymer also deposits within the electrodes
and acts as a binder. The polymer and the formulations used are
selected by methods well-known to those of ordinary skill in the
art for leaving behind a porous separator layer. The battery is
then infused with liquid electrolyte.
[0073] The following non-limiting examples further illustrate
certain embodiments.
Example 1
[0074] The direction of electrophoretic migration was determined
for several materials and solvent systems useful in batteries as
follows. Measurements were made of the direction of motion of
powders suspended in solvents between two gold working electrodes
under an applied voltage. The gold electrode configuration was one
of the following: (1) as shown in FIG. 1, two parallel films of
gold 10, 11 sputtered on glass placed .about.0.5 cm to .about.1 cm
apart in a small glass beaker 12 (20 ml or 30 ml) in which the
suspension 14 was placed, (2) two sputtered gold electrode films 1
cm apart in a glass plate with a shallow well within which the
suspension was placed, or (3) as shown in FIG. 5, individually
addressable gold microband electrodes 50 (ABTECH Scientific,
Richmond, Va.) deposited on glass, typically of 20 micron width and
20 micron separation, onto which a suspension was placed. For the
microband electrodes, the polarity alternated between bands.
[0075] A powder suspension was prepared by placing the powder or
powders of interest into a solvent, typically at a concentration of
1 mg of solid powder per 1 ml of solvent. A constant voltage
(typically 3-10V) was applied to the electrodes, and then the
suspension was placed into contact with the electrodes. After 10
min. to 30 min. for the first two electrode configurations, and 30
sec. to 5 min. for the microband electrodes, the deposition of
powder was observed in order to determine the direction of
electrophoretic migration. This allowed the subsequent selection of
solid and solvent/polymer systems.
[0076] The solid powders tested included LiCoO.sub.2 (Alfa-Aesar,
Ward Hill, Mass.), mesoporous microbeads (MCMB) (Osaka Gas Co.,
Japan), Super P.TM. carbon (Timcal, Belgium), indium tin oxide
(ITO) powder (Aldrich Chemical, Milwaukee, Wis.), and doped lithium
iron phosphate from A123Systems (Boston, Mass.).
[0077] The pure solvents and solvent mixtures tested included the
following: [0078] 1) acetonitrile [0079] 2) acetone [0080] 3)
isopropanol [0081] 4) dimethyl formamide [0082] 5) acetonitrile
with dissolved polyethylene glycol (PEG, 1500-8000 molecular
weight) or polyethylene oxide (PEO, 200,000 MW) and LiClO.sub.4
[0083] 6) acetone with dissolved polyvinylidine fluoride (PVDF,
534,000 MW) and LiClO.sub.4.
[0084] The following migration directions were observed.
LiCoO.sub.2 migrated toward the positive electrode in solvents 1
and 2, and toward the negative electrode in solvents 4, 5 and 6.
MCMB migrated toward the positive electrode in solvent 2, and
toward the negative electrode in solvents 1, 4, 5, and 6. Super
P.TM. migrated toward the positive electrode in solvent 2, and
toward the negative electrode in solvents 1, 5, and 6. ITO migrated
toward the positive electrode in solvents 1, 2, and 5, and toward
the negative electrode in solvent 3. LiFePO.sub.4 migrated toward
the negative electrode in solvent 5.
[0085] Experiments were also conducted to observed the direction of
electrophoretic migration and deposition for several polymers
commonly used in lithium ion battery systems. In pure acetone,
polyvinylidene fluoride (PVdF) having a molecular weight of 60,000
(Polysciences Inc), and Kynar 461, a PVdF homopolymer (Atofina)
were both observed to deposit on the positive electrode, indicating
existence of a negative zeta potential. When LiClO.sub.4 salt was
added to acetone, however, the Kynar 461 did not exhibit migration
under electric field, indicating that the zeta potential is readily
compensated. Kynar 2801, a PVdF-HFP copolymer (Atofina) did not
exhibit electrophoretic migration even in pure acetone, indicating
negligible zeta potential. This demonstrates that combinations of
materials can be readily selected in which a polymer constituent as
well as particles of inorganic active materials are
electrophoretically deposited or not. Electrodeposition of a
polymer can serve useful functions such as being a binder for other
particles or to provide an electronically insulating layer or
"in-situ" separator layer.
[0086] These results allow for the selection of single materials or
combinations of materials that will migrate to or from a given
electrode under a certain applied voltage. For example, in solvent
5, which upon drying forms a solid polymer electrolyte, LiCoO.sub.2
and Super P.TM. (as a conductive additive) migrate in the same
direction, and can be co-deposited or co-aggregated to form an
electrode. FIG. 1 illustrates the obtained result of LiCo.sub.2 and
Super P.TM. 16 co-depositing at one electrode 11. The same can be
done with LiFePO.sub.4 and Super P.TM. in solvent 5. The same
co-deposited electrodes (LiCoO.sub.2 and Super P.TM., LiFePO.sub.4
and Super P.TM.) can be formed in solvent 6. In this instance, the
solution of solvent with PVDF and LiClO.sub.4 (or solvent and PVDF
alone) will dry to form a binder that can be infused with a liquid
electrolyte.
[0087] Examples of layered or laminated battery cells made using
electrophoretic deposition and simultaneous separation are shown in
FIGS. 2A-B. As illustrated in FIGS. 2A-B, electrophoretic
deposition of LiCoO.sub.2 and Super P.TM. at one electrode can be
used to simultaneously create an insulating gap between that
electrode and the counterelectrode, which in this example is a
lithium foil or carbon electrode, both selected to be capable of
accepting lithium from the LiCoO.sub.2 when the resulting cell is
charged.
Example 2
[0088] This example demonstrates the assembly of an electrochemical
device using a continuous carbon structure having substantial open
porosity, such as a carbon foam or carbon fiber mat, as one working
electrode during electrophoretic processing. This porous electrode
also becomes a working electrochemical storage electrode in the
final device, which is a three-dimensional lithium ion battery.
[0089] In one series of experiments, reticulated carbon foams
(Duocel.TM., ERG Materials and Aerospace, Oakland, Calif.) having
pore dimensions of between 45 pores-per-inch (ppi) and 100 ppi were
used. In some cases, the carbon foam was fired to high temperature
(2300.degree. C. to 2400.degree. C.) in helium in order to improve
the electrochemical storage capability. FIG. 6 shows a cyclic
voltammetry scan of a heat treated carbon foam, tested in a
Swagelok.RTM. cell against a lithium metal foil electrode, showing
reversible electrochemical insertion of lithium at the expected
potential for carbon anodes.
[0090] The pore space within the carbon foam was then infiltrated
with a cathode particulate network that was electrophoretically
separated from the carbon structure in order to form the device. A
cathode suspension was prepared from LiCoO.sub.2, Super P.TM.,
acetonitrile, PEG or PEO, and LiClO.sub.4. One typical formulation
used was 5 ml acetonitrile, 0.6 g LiClO.sub.4, 2.12 g PEG 1500, 3.2
g LiCoO.sub.2, and 0.16 g Super P.TM..
[0091] FIG. 3 illustrates the configuration that was used for
electrophoretic assembly. A cylindrical piece of foam 30 .about.16
mm in diameter by .about.10 mm in height was attached to a copper
current collector 32 with good electrical contact. A cylindrical
container 34 (polypropylene or Teflon.RTM.
(polytetrafluoroethylene, DuPont, Wilmington, Del.)) was placed
around the foam. The cathode suspension 36 was mixed uniformly,
poured into the container 34, and allowed to infiltrate the foam
30. The container 34 was filled with a sufficient volume of the
cathode suspension 36 to fill the foam 30, leaving some excess to
which an aluminum foil current collector 38 was connected at the
top of the sample without contacting the carbon foam 30.
Cross-sections of an infiltrated sample showed penetration
throughout the foam 30 by the LiCoO.sub.2 and Super P.TM..
[0092] A 10V potential difference was applied between the copper 32
attached to the carbon foam 30 and the aluminum current collector
38. The aluminum current collector 38 was at negative potential and
the copper 32 at positive potential. The sample was placed in a
vacuum oven and heated to 100.degree. C., at which time a vacuum
was applied to speed up drying of the sample. The current between
the two electrodes was observed, and decayed to negligible values.
The sample was then cooled to room temperature and removed from the
oven.
[0093] After cooling, the dc resistance between the copper and
aluminum current collectors 32, 38 was >20 Mohms (measurable
value being limited by the multimeter used). As shown in FIG. 4A,
the LiCoO.sub.2 and Super P.TM. particulates 40 were
electrophoretically repelled from the carbon anode 30 and attracted
towards the aluminum current collector 38, but remained trapped
within the porosity 42 of the foam 30. Thus, the cathode active
material 40 and the anode network 30 were electrophoretically
separated from one another. FIG. 4B shows an expanded view of the
infiltrated foam.
[0094] Cyclic voltammetry (CV) was performed to further demonstrate
that the cathode and anode remained electrically isolated up to
high voltages characteristic of lithium ion battery systems. FIG. 7
shows CV results from several samples tested at various scan rates
between 0 and 4.2 V at room temperature. In each case, the sample
resistance remained high up to the maximum voltage, showing that
electrical insulation was preserved. FIG. 7 also shows CV results
for a sample made using a suspension containing LiFePO.sub.4 and
Super P.TM. as the solid phases, demonstrating that electrical
isolation was achieved using this suspension as well.
Example 3
[0095] A two-dimensional electrophoretically separated device was
fabricated using the following procedure. A 20 micron width
microelectrode array 50 deposited on glass (ABTECH Scientific,
Richmond, Va.) as shown in FIG. 5 was used. A suspension of
LiCoO.sub.2 and Super P.TM. powder in acetonitrile, PEO 200,000,
and LiClO.sub.4 was prepared using the same ratios as in Example 2,
and the suspension was then further diluted with additional
acetonitrile. The suspension was applied to the microelectrodes and
a 1 volt potential difference was applied to the array. As shown in
FIG. 8A, deposition of the LiCoO.sub.2 and Super P.TM. 80 at the
negative electrodes 82 was observed, with no detectable deposition
at the positive electrode 84.
[0096] Next, a suspension of MCMB in the same solvent mixture was
applied, with the voltage being applied as shown in FIG. 8B. MCMB
was found, like LiCoO.sub.2 and Super P.TM. to migrate to the
negative electrode in this solvent mixture. Therefore, in order to
deposit MCMB 86 at the opposite electrode 84 from the LiCoO.sub.2
and Super P.TM. 80, the voltage was reversed from that used to
deposit the LiCoO.sub.2 and Super P.TM. 80. It was observed that
MCMB 86 deposited at the opposite electrode 84 from the LiCoO.sub.2
and Super P.TM. 80 as expected.
[0097] After deposition and drying, electrical measurements showed
a >20 Mohm resistance between the two deposited electrodes.
Thus, electrophoresis was used to fabricate a two-dimensional
battery array consisting of interpenetrating electrode structures,
with electrical isolation between the two. The intervening space
between the electrodes can be filled with PEO and LiClO.sub.4 solid
polymer electrolyte, or infused with liquid electrolyte.
Example 4
[0098] As in Example 2, a Duocel.TM. non-graphitizing reticulated
vitreous carbon foam was used as a stationary electrode. The foam
had linear pore-per-inch (ppi) counts of 45, 60 and 100, and a bulk
density of 0.05 g/cm.sup.3. The as-received reticulated carbons
were heat treated in a graphite resistance-heated furnace (Astro
Corp., Santa Barbara, Calif.) at 2400.degree. C. for 4 hours in He
gas in order to improve their lithium storage capacity. A copper
current collector was attached to a cylindrical sample of the
reticulated carbon (16 mm in diameter by 10 mm in height), forming
a negative electrode structure that was placed within a
close-fitting polypropylene container. Aluminum foil or platinum
mesh was used as a working electrode/current collector on the
positive electrode side, as illustrated in FIG. 3. The cell was
infiltrated with a suspension of cathode active material,
LiCoO.sub.2 and Super P.TM. carbon, in binder and solvent. After
infiltration, which occurred on the time scale of seconds to
minutes, a voltage of 10 volts was applied across the two current
collectors to effect electrophoretic separation of the cathode
active material from the stationary anode, as illustrated in FIG.
4. To complete the electrochemical cell, the electrophoretically
separated system was dried and infiltrated with a standard liquid
electrolyte.
[0099] Cell balancing was then taken into account in selecting a
specific suspension formulation. The LiCoO.sub.2 concentration in
the suspension was chosen to yield a slightly cathode-deficient
composition in the final cell, i.e., one in which the lithium ion
source is cathode-limited, in order to avoid lithium metal
precipitation at the negative electrode during charge. A typical
suspension formulation in weight percentage was 69.3% acetone, 3.5%
LiClO.sub.4, 8.7% PVDF (66,000 MW), 17.3% LiCoO.sub.2, and 1.3%
Super P.TM.. Taking the components of the electrode formulation
alone, the weight proportions were 31.8% PVDF, 63.5% LiCoO.sub.2,
and 4.8% Super P.TM., which is binder-rich compared to typical
cathode formulations, but useful for cell balancing.
[0100] Cell infiltration and electrophoretic forming was conducted
as follows. A quantity of the LiCoO.sub.2 suspension sufficient to
completely infiltrate the anode framework and contact the upper
working electrode was poured into the cell. The cell was placed in
a vacuum chamber at room temperature, and evacuated to facilitate
infiltration of the suspension into the reticulated carbon. After
infiltration, a 10V dc voltage was applied across the two current
collectors. Due to the positive zeta potential of the particles,
the negative potential appears at the current collector to which
the LiCoO.sub.2 and Super P.TM. are attracted (FIGS. 3 and 4).
Relative to the final operation of the lithium ion battery, this is
the polarity used for discharging. The large overpotential results
in an initially "overdischarged" state of the cell, as shown below.
The infiltrated cell was held at 10V dc voltage for a total of 6
hours, the first 2 hours at room temperature, and the following 4
hours at 45.degree. C. to complete drying. During electrophoretic
forming, the current dropped to <4 mA over a period of about 2
hours, and after drying, the dc resistance between the current
collectors after electrophoretic forming was >10 M.OMEGA..
Control experiments conducted without the applied voltage showed
complete electrical shorting between the current collectors,
confirming that the electrical isolation was due to
electrophoresis. Upon drying, the space between the positive and
negative electrodes was occupied by the PVDF binder, acting as a
porous separator. The cell was then flooded with liquid electrolyte
(1:1 ethylene carbonate:diethyl carbonate (EC:DEC) mixture with 1 M
LiPF.sub.6) in an argon-filled glove box, and subjected to
electrochemical testing.
[0101] Electrochemical test results were carried out for the
reticulated carbon in a Swagelok.RTM. design lithium half-cell. The
as-fired reticulated anode was crushed in a mortar and pestle and
formulated with PVDF binder as an electrode coating, then assembled
in the cell using lithium metal foil as the counterelectrode and
Celgard.RTM. 2400 (Celgard Inc., Charlotte, N.C.) as the separator
membrane. FIG. 9 shows galvanostatic testing at 30 mA/g current
rate between 0 and 2V. The first-cycle irreversible capacity loss
of the carbon was extremely low, and there was only .about.4%
capacity fade over 10 cycles. Due to the half-cell configuration,
any lithium consumed in passivating the carbon was not detected,
but would be present (several percent first cycle capacity loss) in
a lithium-ion configuration. The carbon gravimetric capacity of 120
mAh/g was considerably less than that of optimized graphite anodes
(typically .about.350 mAh/g). The lithium storage capacity of
carbons is known to vary widely; in this instance the lower
capacity may have been due to the dense nature of the amorphous
carbon and the relatively thick cross-section of the struts in the
reticulated structure of about 50 .mu.m. This may be too large a
cross-section to allow complete lithiation at the current rates
used. For comparison, the particle diameter of a typical optimized
graphitized MCMB (mesocarbon microbeads) anode is less than 25
.mu.m. Nonetheless, taking the gravimetric capacity of the carbon
to be 120 mAh/g, the LiCoO.sub.2 suspension was formulated to
provide a cathode-limited cell. The reticulated carbon samples used
had a mass of .about.0.1 g, providing a capacity of 12 mAh. The
LiCoO.sub.2 suspension composition yielded, after infiltration and
drying, a cathode active mass infiltrated within the reticulated
foam of .about.0.072 g. Given a typical LiCoO.sub.2 gravimetric
capacity of 140 mAh/g, the positive electrode capacity was then
10.1 mAh.
[0102] The first galvanostatic (C/24 rate) charge-discharge cycle
of a completed cell is shown in FIG. 10A. The open circuit voltage
of the cells after assembly and drying, and even after filling by
electrolyte, was negative (.about.-1V after filling). Upon charging
however, the potential immediately became positive, as seen in FIG.
10A. The first-charge curve (to 4.1V) was noisy and exhibited a
larger capacity (275 mAh/g based on cathode active mass) than could
be provided by the LiCoO.sub.2 present. In the first discharge,
however, the voltage profile was typical for a LiCoO.sub.2/carbon
couple, exhibiting an average voltage of .about.3.8V, and showing a
discharge capacity that when evaluated on the basis of the
LiCoO.sub.2 mass infiltrated into the cell was .about.100 mAh/g.
The first discharge capacity in lithium ion cells is always lower
than the first charge capacity due to coulombic inefficiencies such
as irreversible consumption of lithium in forming the
solid-electrolyte interphase (SEI) on the carbon, and other side
reactions. Nonetheless, the observed discharge capacity shows that
at least 70% of the infiltrated LiCoO.sub.2 was electrochemically
accessible.
[0103] FIG. 10B shows discharge curves for the first few cycles
exhibiting similar voltage profiles, with the capacity varying with
upper voltage limit during charge. The first and second cycles were
charged to 4.1V limit, and the third cycle to 4.2V. The sharp drop
in voltage near the end of discharge for the second and third
cycles was due to incomplete charging during their respective
charge cycles. FIG. 10C shows the sixth charge/discharge cycle, in
the middle of which a 16 hour hold at zero current was conducted,
showing that the open circuit voltage (OCV) stabilized at about
4.1V. FIG. 10C also shows that there was a significant polarization
of .about.0.2V upon charge and discharge about the equilibrium
voltage. This limits the state of charge during continuous cycling;
as seen in FIGS. 10A and 10C, the charge curve did not terminate
with a sharp rise in voltage. (The system was not charged to higher
voltages than 4.3V in order to prevent electrolyte decomposition.)
The discharge capacity curves after the first cycle, seen in FIGS.
10B-C, showed a sharp drop-off in voltage that was consistent with
incomplete charging, whereas the first discharge showed a gradual
roll-off consistent with lithiation of the carbon anode to near its
capacity limit (FIG. 9). Other cells prepared similarly to the one
reported in FIG. 10 behaved similarly.
[0104] Thus, these cells showed complete electrochemical
functionality: they held an open circuit voltage, and charged and
discharged reversibly with substantial utilization of the active
materials contained within. Defining the basic "cell" to be all
components contained within the volume defined by the reticulated
carbon sample (i.e., excluding the current collectors, excess
slurry, and container), the first-discharge capacity data in FIG.
10B corresponds to a cell gravimetric energy density of 120 Wh/kg.
This may be compared with the theoretical upper limit of 386 Wh/kg
for a perfectly capacity-balanced LiCoO.sub.2-graphite system with
no inactive materials, and .about.140 Wh/kg for currently available
lithium ion cells.
Example 5
[0105] This example describes a three-dimensional interpenetrating
electrode nickel-metal hydride battery. Nickel metal foams are
available, and suitable for use as the stationary electrode, as
described in Example 4, for electrophoretic fabrication of an
aqueous electrolyte, nickel metal-hydride battery. A nickel metal
foam is infiltrated with a suspension of particles of its
counterelectrode and optionally conductive additives, which are
suspended in an organic solvent or aqueous solution, including
soluble binders. The zeta potentials of the particle phases are
measured or controlled through the methodology described in Example
4. After electrophoretic separation and drying, the cell is
infiltrated with an aqueous electrolyte, e.g., containing KOH,
completing the battery.
Example 6
[0106] This example describes the use of a can in which a
three-dimensional interpenetrating electrode battery is packaged as
the working electrode for electrophoretic separation. FIGS. 11A-B
show two such cell designs. In FIG. 11A, a reticulated foam 110 is
electrically connected to a current collector (tab) 112 exiting the
conductive metal can 114, and isolated from the metal can 114 by
insulating materials 116 such as o-rings, gaskets or sheets of
insulating film or fabric. Upon infiltrating the can 114 with a
counterelectrode suspension, a potential is applied between the can
114 and the current collector 112 so as to attract the suspension
particles to the can 114 and repel them from the foam 110. The
polarity shown corresponds to the materials described in Example 4,
where the foam 110 is carbon and the infiltrating suspension
contains LiCoO.sub.2 and Super P.TM.. Thus, the suspension
particles are attracted to the metal can 114 and repelled from the
carbon foam 110. Suitable materials for the can 114 in this
instance include aluminum and other metals stable at the positive
electrode potentials in a Li-ion cell. The top current collector
112 connected to the carbon foam 110 is copper or another metal
stable at the negative electrode potential.
[0107] An alternative construction is shown in FIG. 11B, in which
the foam 110 is electrically connected to the can 114, while the
current collector 112 is electrically isolated by the insulator 116
from the foam 110. In this case, the polarity is reversed from the
case illustrated in FIG. 11A.
Example 7
[0108] Electrophoretic assembly of a 3D battery was carried out in
the configuration shown in FIG. 17. The cathode formulation
consisted of acetone (6 g), PVdF (0.1 g), LiCoO.sub.2(0.2 g), and
Super P (0.01 g). A lower current collector consisting of Pt mesh
was placed onto the bottom of a 10 mL beaker. A cylindrical piece
of reticulated carbon foam (60 ppi) of .about.16 mm diameter by
.about.3 mm height was attached to a second Pt mesh current
collector, and placed above the first Pt mesh current collector, as
shown in FIG. 17, such that they were separated by .about.1 mm. The
cathode suspension, which has a low viscosity, was added so that it
filled the vessel well above the upper Pt mesh current collector
attached to the carbon foam. A dc voltage was then applied between
the upper and lower Pt mesh current collector, with the lower
current collector at positive potential and the upper at negative
potential. FIG. 18 shows the current measured between the two
current collectors as a function of time, for two values of applied
voltage. At 4.2V, the current remains significant (>0.5 mA) even
after 3 hours. However, at 10V, the current drops rapidly and is
below 0.1 mA after 4 h, effectively showing electrical isolation.
This assembly, after drying and infiltration with liquid
electrolyte as in Examples 2 and 4, shows lithium ion battery
functionality.
Example 8
[0109] This example describes the use of bridging between two
electrophoresis electrodes to form a single battery electrode.
FIGS. 12A-B shows the two step deposition process for the
electrophoretic assembly of a battery. In the first step, a set of
4 electrodes (Abtech Scientific, microband electrodes: 10 microns
wide, 20 microns pitch, 3 mm in length) were submerged into a
mixture containing acetone as a solvent, 2.8 wt % MCMB carbon (5-8
micron, 6-28, Osaka Gas Co.) and 0.55 wt % polymer (Kynar 2801). A
potential of 5V was applied between the pair of electrodes on the
left in FIG. 12A for 20 seconds and then the microband was removed
from the solution with the voltage still being applied. As observed
in FIG. 12A, the carbon deposited as to bridge between the two
electrodes. In the second step, the same set of electrodes were
submerged into a mixture containing acetone as a solvent, 6 wt %
LiCoO.sub.2 (Seimi, spelling?) and 0.46 wt % polymer (Kynar 2801).
The mixture was allowed to settle for 3 hours, effectively
decreasing the particle concentration in the mixture. A potential
of 5 V was applied between the pair of electrodes on the right in
FIG. 12B for 3 minutes and then the microband was removed from the
solution with the voltage still being applied. The sample was then
immersed in a liquid electrolyte consisting of a mixture of
ethylene carbonate and dimethyl carbonate with 1M LiPF.sub.6. FIG.
13 shows the charge and discharge for cycle number 40 for the
battery pictured in FIGS. 12A-B. The battery was charged at 5
nanoAmperes to 4.2V and discharged at the same current to 3V. The
typical charge time was 550 seconds and typical discharge time was
400 seconds and at cycle 40 the battery had a capacity of 1.7
nAh.
[0110] An alternative mixture was made to demonstrate that LiCoO2
can also be electrophoretically deposited by bridging. FIGS. 14A-B
show the two-step process to make a battery by electrophoretic
deposition on a set of four electrodes (Abtech Scientific,
microband electrodes: 20 microns wide, 40 microns pitch, 3 mm in
length) where both of the battery electrodes are deposited by
bridging. In the first step, the electrodes in FIG. 14A were
submerged in a mixture of 1-2 micron carbon (5 wt %) and acetone
(no polymer) with a potential of 4V applied the right set. In the
second step, the electrodes in FIG. 14B were submerged in a mixture
containing acetone as a solvent, 9 wt % of LiCoO.sub.2 and 5 wt %
polymer (PVdF, 60,000 MW). The mixture was not allowed to settle
before electrophoretic deposition. Electrophoretic deposition was
performed at 4V for 5 seconds and bridging of the LiCoO.sub.2 is
observed in FIG. 14B.
Example 9
[0111] This example describes the dependence exhibited of the
electrode on which particles with the absolute voltage and electric
field between the electrodes. FIGS. 15 A, B and C show the
deposition from a mixture of 1 wt % LiCoO.sub.2 in acetone at 2,
2.5 and 3V, respectively, on 20 micron wide Pt electrodes with 20
micron gaps. This corresponds to electric fields between the
electrodes of 1000, 1250 and 1500 V/cm, respectively. At these
potentials and fields, the direction of deposition follows the
measured zeta potential, in that the particles deposit on the
positive electrode. Additionally, these figures show that particles
deposit on the electrodes at low voltage and field (FIG. 15A) and
bridge across electrodes at higher voltage and field (FIGS. 15B,C
and 16A,B and C). FIGS. 16 A, B and C shows the deposition observed
at a higher voltage of 5V (field of 2500 V/cm) from a similar
mixture and on similar electrodes. At this higher potential and
field, the LiCoO.sub.2 particles deposit at the negative electrode.
The change in the direction of particle deposition is due to
combined effects of electrochemical reactions occurring at higher
voltages and magnitude of the field. Similar behavior showing a
switch in the electrode of deposition with increasing voltage and
electric field was also observed MCMB carbon particles.
Example 10
[0112] A pattern of terminals is formed on a flat or curved
surface, said pattern having an interdigitated, serpentine, or
spiral configuration, and thereby allowing formation of a battery
using the methods of Examples 3, 8 and 9. FIGS. 19 and 20 show a
serpentine and a spiral pattern, respectively. Depending on the
width and separation of the terminals, and the particle size of the
deposited material, batteries in which the electrode width and
spacing are as small as a few nanometers can be fabricated. Larger
dimensions from as submicrometer up to tens or hundreds of
micrometers can also be fabricated. Such batteries allow the
creation of a 2-dimensional (in the case of a flat substrate)
battery with a single set of terminals connecting to an external
device, making more efficient use of the available area than a
multiplicity of linear batteries as in Example 3, each separately
connected to the external device. The height of such an array can
vary considerably and can be as tall or even taller than the
narrowest dimension of the pattern. That is, the height to width
ratio of the deposited material can range from a very small value
to over unity. This allows the total thickness (height) of such
batteries to be controlled, and in some cases the thickness can be
many micrometers. As such, the energy (mAh) per unit area of the
substrate in such batteries can be much greater that those of
solid-state thin film batteries, in which the deposited film
thicknesses are typically a few micrometers or less.
Example 11
[0113] This example is directed towards the fabrication of
microscopic or nanoscopic "pinpoint" batteries, providing an
unobtrusive power source of very small volume, typically less than
1 cubic millimeter; and, in some cases, less than 0.1 cubic
millimeters. The methods of Examples 3, 8 or 9 are applied to a
pattern of terminals in which only a very limited area of the
terminal is exposed to the medium from which the electroactive
material is deposited. Thus deposition occurs in a localized area
on any suitable substrate, the specific dimensions of which are
determined by the dimensions of the terminals and the deposited
particles, suspension composition, and deposition conditions such
as time, voltage, electric field, etc. The localized area may be,
for example, less than 1 micron squared, less than 100 nanometers
squared and, in some cases, less than 10 nanometers squared. FIGS.
21 and 22 illustrate configurations of terminals allowing such
deposition, corresponding to the methods of Example 3 and 8
respectively. In FIG. 21, two terminals are provided, at each of
which an electroactive material is deposited, resulting in a pair
of electrodes comprising a device. In FIG. 22, four terminals are
provided, and between each pair of terminals, deposition of
particles limited by particle bridging is carried out, to create a
pair of electrodes comprising a device.
[0114] As will be apparent to one of skill in the art from a
reading of this disclosure, the present invention can be embodied
in forms other than those specifically disclosed above. The
particular embodiments described above are, therefore, to be
considered as illustrative and not restrictive. The scope of the
invention is as set forth in the appended claims, rather than being
limited to the examples contained in the foregoing description.
* * * * *