U.S. patent application number 14/073302 was filed with the patent office on 2015-05-07 for capacitors having conditioned carbon for electrodes.
The applicant listed for this patent is Retriev Technologies Incorporated. Invention is credited to Joel R. McCloskey, W. Novis Smith.
Application Number | 20150125760 14/073302 |
Document ID | / |
Family ID | 53007278 |
Filed Date | 2015-05-07 |
United States Patent
Application |
20150125760 |
Kind Code |
A1 |
Smith; W. Novis ; et
al. |
May 7, 2015 |
CAPACITORS HAVING CONDITIONED CARBON FOR ELECTRODES
Abstract
There is provided an improvement for capacitors having activated
carbon electrodes by the use of an electrolyte solution containing
a carbonate of the formula RO(C.dbd.O)OR.sup.1 and a conductive
salt such as a lithium salt or a quaternary ammonium salt at a
concentration of from 0.6 to 3 mol/l.
Inventors: |
Smith; W. Novis;
(Philadelphia, PA) ; McCloskey; Joel R.;
(Philadelphia, PA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Retriev Technologies Incorporated |
Anaheim |
CA |
US |
|
|
Family ID: |
53007278 |
Appl. No.: |
14/073302 |
Filed: |
November 6, 2013 |
Current U.S.
Class: |
429/338 ;
361/502; 429/188; 429/200; 429/201; 429/342; 558/276 |
Current CPC
Class: |
H01M 4/587 20130101;
H01M 10/056 20130101; H01G 11/34 20130101; H01M 10/0569 20130101;
H01G 11/28 20130101; Y02E 60/10 20130101; H01G 11/60 20130101; Y02E
60/13 20130101; H01G 11/62 20130101; C07C 68/06 20130101; H01M
10/0567 20130101; H01M 10/052 20130101; C07C 68/06 20130101; C07C
69/96 20130101 |
Class at
Publication: |
429/338 ;
429/188; 429/342; 429/201; 429/200; 361/502; 558/276 |
International
Class: |
H01G 11/62 20060101
H01G011/62; H01M 10/056 20060101 H01M010/056 |
Claims
1. An electrochemical device comprising the combination of a
conditioned and heat treated carbon electrode comprised of a metal
collector and a layer comprised of activated carbon formed on the
metal collector, wherein the activated carbon has been heated after
acid washing at a temperature of 1100.degree. C. to 1500.degree. C.
under an inert atmosphere and consists essentially of carbon, and
an electrolyte solution, the electrolyte solution comprising a
non-aqueous solvent system comprising 20 to 100% by weight of one
or more symmetrical and/or asymmetrical carbonates of the general
formula: RO(C.dbd.O)OR.sup.1 wherein R is selected from the group
consisting of methyl, ethyl, isopropyl, propyl,
CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
R''OCH.sub.2CH.sub.2-- and R''--O--(CH.sub.2).sub.n--, n is 2, 3 or
4, R.sup.1 is selected from the group consisting of
CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2-- and R''--O--CH.sub.2CH.sub.2--,
and R'' is methyl, ethyl, propyl or isopropyl, and a conductive
salt which is selected from the group consisting of quaternary
ammonium tetrafluoroborates and quaternary ammonium triflates at a
concentration of from 0.6 to 3 mol/l.
2. The electrochemical device of claim 1 wherein the non-aqueous
solvent system is comprised of at least 20% by weight
methyl-(2-methoxyethyl)-carbonate.
3. The electrochemical device of claim 1 wherein the non-aqueous
solvent system is comprised of at least 20% by weight
bis(2-methoxyethyl) carbonate.
4. The electrochemical device of claim 1 wherein the activated
carbon of the carbon electrode has a surface area greater than 1200
m.sup.2/g.
5. The electrochemical device of claim 1 wherein the conductive
salt is selected from the group consisting of tetraethyl ammonium
tetrafluoroborate, triethylmethylammonium tetrafluoroborate,
diethyldimethylammonium tetrafluoroborate, ethyltrimethylammonium
tetrafluoroborate, dimethylpyrrolidinium tetrafluoroborate,
diethylpyrrolidinium tetrafluoroborate, ethylmethylpyrrolidinium
tetrafluoroborate, and spiro-(1,1.sup.1)-bipiperidinium
tetrafluoroborate, piperidine-1-spiro-1.sup.1-pyrrolidinium
tetrafluoroborate and the triflates thereof.
6. (canceled)
7. The electrochemical device of claim 1 wherein the carbon after
heat treatment has a surface area greater than 1200 m.sup.2/g.
8. The electrochemical device of claim 1 wherein the non-aqueous
solvent system includes a solvent selected from the group
consisting of dimethyl carbonate, ethyl methyl carbonate, ethylene
carbonate, propylene carbonate and diethyl carbonate.
9. The electrochemical device of claim 1 wherein the
electrochemical device is an ultra capacitor.
10. The electrochemical device of claim 1 wherein the
electrochemical device is an electrochemical double layer
capacitor.
11. The electrochemical device of claim 1 wherein the electrolyte
solution has a liquidus range from -70.degree. C. to greater than
150.degree. C.
12. The electrochemical device of claim 1 wherein the non-aqueous
solvent system consists of asymmetric methyl-(2-methoxy
ethyl)-carbonate.
13. (canceled)
14. The electrochemical device of claim 1, wherein the non-aqueous
solvent system is comprised of 25 to 75% by weight of one or more
symmetrical and/or asymmetrical carbonates of the general formula:
RO(C.dbd.O)OR.sup.1
15. The electrochemical device of claim 14, wherein the non-aqueous
solvent system is additionally comprised of ethylene carbonate.
16. A process for preparing a symmetrical or asymmetrical carbonate
of the general formula: RO(C.dbd.O)OR.sup.1 wherein R is selected
from the group consisting of methyl, ethyl, isopropyl, propyl,
CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
R''OCH.sub.2CH.sub.2-- and R''--O--(CH.sub.2).sub.n--, n is 2, 3 or
4, R.sup.1 is selected from the group consisting of
CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2-- and R''--O--CH.sub.2CH.sub.2--,
and R'' is methyl, ethyl, propyl or isopropyl, wherein the method
comprises reacting a compound of the general formula RO(C.dbd.O)OR
with a compound of the general formula R.sup.1OH in the presence of
a basic catalyst.
17. The process of claim 16, wherein the basic catalyst is sodium
methoxide.
18. The process of claim 16, wherein dimethyl carbonate is reacted
with 2-methoxyethanol to produce methyl-(2-methoxyethyl)carbonate,
bis(2-methoxyethyl carbonate, or a mixture thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to novel electrolyte solutions
for electrochemical devices such as capacitors and having carbon
electrodes with conditioned carbon elements. More particularly,
there is a synergism found with the use of the electrolyte
solutions with the conditioned carbon cathodes which improves the
energy density with a conductive salt such as a lithium salt or
quaternary ammonium salt.
BACKGROUND OF THE INVENTION
[0002] The performance of ultra capacitor and lithium batteries
electrolytes at low temperature is a continuing problem since the
conductivity of the electrolyte will go to zero if it freezes
before a desired low temperature performance is achieved. Various
blends of organic carbonates have been used along with the addition
of ethers and low molecular weight esters to achieve low
temperature (-60.degree. C.) freezing points of the mixed solvents
containing lithium hexafluorophosphate for low temperature
lithium-ion battery performance. The use of mixtures of ethylmethyl
carbonate with dimethyl carbonate and small quantities of ethylene
carbonate have allowed performance down to -20.degree. C. and even
-30.degree. C. in some cases for lithium battery electrolytes. The
use of tetrahydrofuran (THF) and methyl formate and methyl acetate
and dimethyl ethylene glycol (glyme) or dimethoxy ethane (DME) has
allowed some battery electrolytes to achieve -40.degree. C. or even
-50.degree. C. performance. The problem is that the performance of
these electrolytes at high temperature such as >70.degree. C.
causes high vapor pressures in the batteries with these volatile
low boiling solvents. In the case of ultra capacitors based on
organic electrolytes the situation is similar except most current
ultra capacitor electrolytes are based on the use of acetonitrile
(low boiling with by 82.degree. C.) containing tetraethylammonium
tetrafluoroborate. These ultra capacitor electrolytes have an upper
operating voltage limitation of 2.7 V. The use of capacitor
electrolyte solvents based on the organic carbonates and containing
tetralkylammonium tetrafluoroborates has also been limited because
of solubility limitations when using propylene carbonate, or by low
temperature performance when using mixtures containing ethylene
carbonate.
[0003] Propylene carbonate has been used in mixtures with other
organic carbonates for capacitor electrolytes but this solvent also
limits cell voltage to about 3 V and the solubility of the
tetrafluoroborate salt decreases rapidly on cooling and results in
low conductivity of the electrolyte at temperatures below
-20.degree. C. The use of ethylene carbonate (mp 35.degree. C.)
with cyclic organic carbonate mixtures containing organic
quaternary tetrafluoroborate salts for capacitor use gives higher
operating cell voltage in ultra capacitors, but these electrolytes
freeze before -20.degree. C. is reached. Low temperature cycling
performance (non-freezing) is desired (required for the use of
ultra capacitor performance in vehicle performance down to
-30.degree. C.). In aircraft, the temperature desired is down to
-40.degree. C. At the same time these applications desire high
temperature performance (>70.degree. C.) with low vapor
pressure. This means that volatile solvents which are used for low
temperature performance cause problems at the high end of the
desired performance range.
[0004] Activated carbon is the preferred material for use in
preparing electrodes for carbon electrode capacitors. This
activated carbon is prepared from a number of different sources
such as coconut shells, wood, sugar, cellulosics and phenolic
resins. After converting these materials to carbon under steam
controlled conditions, the carbons are "activated" in a second step
using steam or catalyzed with KOH, NaOH and/or carbon dioxide and
KOH to increase the surface area to very high surface areas such as
1000 to 2400 m.sup.2/g. These activated carbons usually contain
about 2% oxygen after they have been thoroughly dried and traces of
inorganic salts. This oxygen is probably present as quinones,
hydroquinones, esters, phenols, carboxylic acids, furans and
possibly ketones etc. with some nitrogen compounds present--all of
which under high voltage conditions greater than 3 V. will undergo
electrochemical oxidation/reduction as the voltage is increased
past 3.3 V. At lower voltages, these functional groups actually
improve the energy storage capacity of the carbon and are desirable
at voltages below 3.2 V.
[0005] The basic components of electrical capacitors include
conductive electrodes connected to an electric power supply and a
dielectric material separating the electrodes. Electrolytic
capacitors and electrochemical double layer capacitors also have an
electrolyte. In an electrolyte capacitor, the electrodes are
provided by an oxide or carbon layer formed on metal foil and are
separated by a porous non-conducting membrane such as paper, porous
polymer, etc. The liquid electrolyte provides electrical contact to
the opposite electrode through the separator. The inherently high
resistance of electrolytic capacitors is generally mitigated by
rolling a large sheet of the electrode material into a roll to give
high surface area. In an electrochemical double layer capacitor,
the dielectric is provided by the electrolyte. In this type of
capacitor the resistance of the electrolyte is a significant factor
in the total device resistance. In capacitors that use
electrolytes, the temperature has a major influence on the
electrolyte in the performance of the capacitor since the
conductivity of the electrolyte decreases with temperature.
[0006] Electrochemical double layer capacitors including super
capacitors, typically comprise electrodes, electrical contacts to a
power supply, separators for electrodes and/or cells, and
electrolyte and environmental seals. As mentioned above, a key
component of electrolytic and electrochemical double layer
capacitors is the electrolyte, which typically comprises a
combination of a conductive salt and a solvent. Desirable
electrolytes are typically liquid with low viscosity, low density,
and high conductivity over a range of ambient temperature
conditions. They should also be commercially inexpensive,
chemically and electrochemically stable, and compatible with
carbon. Aqueous electrolyte systems have been used extensively and
provide voltage restricted below 1.8 V. For example, ultra
capacitors in Japan are not permitted to use acetonitrile for the
electrolyte. A need exists for improved electrolyte systems that
provide optimum capacitance for capacitors to achieve high power
density, a wide temperature range, and a long lifetime without
memory effects.
[0007] The key requirements for the electrolyte in both non-aqueous
batteries and capacitors are high voltage stability, low
temperature performance and electrochemical stability. U.S. Pat.
No. 6,743,947 to Xu, et al. discloses an electrolyte system
comprising a mixture of ethylene carbonate and dimethyl carbonate
at a concentration of the electrolyte salt at 0.5-2.5 M which has
poor conductivity at low temperatures.
[0008] U.S. Pat. No. 7,924,549 to Smith, et al discloses
conditioned carbon electrodes for capacitors and lithium batteries
having conditioned carbon electrodes that have also been heat
treated and used in an electrolyte comprising a quaternary ammonium
tetrafluorobotrate salt in an aprotic solvent.
[0009] U.S. Patent Application Publication No. 20070002522
discloses capacitors having electrodes with alkali-activated carbon
electrodes in electrolytic solutions comprising a quaternary
ammonium salt and a solvent containing a carboxylic ester.
[0010] Electrochemical double layer capacitors capable of high
energy density, known as "super-capacitors", have been assembled
from a variety of materials. In general, it is desirable to
construct super-capacitors with light weight materials and
electrolytes that are stable and non-reactive, as described in U.S.
Pat. No. 5,260,855 issued to Kaschmitter et al., the teachings of
which are hereby incorporated by reference. This type of
super-capacitor incorporates electrodes based on carbon that may be
prepared from organic gels.
[0011] U.S. Pat. No. 6,902,683 to Smith et al., which is herein
incorporated by reference, relates to electrolytes of a complex
salt formed by mixing of a tetraalkyl ammonium salt of hydrogen
fluoride with an imidazolium compound in a nitrile solvent which
operate at temperatures between -60 and 150 degrees C.
[0012] The article of Ue in J. Electrochem. Soc. Vol 141, No. 11,
November 1994 entitled "Electrochemical Properties of Organic
Liquid Electrolytes Based on Quaternary Onium Salts for Electrical
Double-Layer Capacitors" which is herein incorporated by reference,
discloses high permittivity solvents and onium salts for
double-layer capacitors. Specifically studied were quaternary onium
tetrafluoroborate salts which showed greater solubility in the
solvents with good stability and conductivity.
[0013] U.S. Pat. No. 6,980,415 to Higono et al, which is herein
incorporated by reference, discloses an electrolyte for capacitors
comprising dimethyl carbonate and a spiro tetrafluoroborate salt.
The tetrafluoroborate salt can be used in the present invention
with the present electrolyte solutions.
SUMMARY OF THE INVENTION
[0014] According to one embodiment of the invention, there is
provided lithium ion batteries and capacitors containing carbon
electrodes, an electrolyte solution which comprises a conductive
salt such as a lithium salt or a quaternary ammonium salt and a
solvent system comprised of at least 20% by weight (i.e., 25 to 75%
by weight) of one or more symmetrical and unsymmetrical
(asymmetrical) carbonates of the formula:
RO(C.dbd.O)OR.sup.1
wherein R is selected from the group consisting of methyl, ethyl,
propyl, isopropyl, CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
R''OCH.sub.2CH.sub.2-- and R''--O--(CH.sub.2).sub.n--, n is 2, 3 or
4, R.sup.1 is selected from the group consisting of
CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2-- and R''--O--CH.sub.2CH.sub.2--,
and R'' is methyl, ethyl, propyl or isopropyl.
[0015] According to another embodiment of the invention, the novel
carbonates of the invention can be mixed with each other or with
other organic cyclic or linear carbonates, ethers and carboxylic
esters such that they comprise at least 20% by weight of the
solvent systems. For example, the solvent system employed in the
electrolyte solution may be comprised of 20 to 100% by weight of a
carbonate, or a combination of carbonates, meeting the
aforementioned formula RO(C.dbd.O)OR.sup.1, with the balance of the
solvent system being one or more solvents selected from the group
consisting of cyclic carbonates, linear carbonates not having the
formula RO(C.dbd.O)OR.sup.1, ethers, carboxylic esters, and
combinations thereof.
[0016] According to an embodiment of the invention, the solvents
are utilized in combination with capacitors having carbon
electrodes which have been "activated" or post-treated to remove
all chemically bound oxygen, nitrogen and sulfur and preferably
heat treated after acid washing at temperatures of
1100-1500.degree. C. under an inert atmosphere. Preferably, the
surface area of the carbon present in the carbon electrode is
>1200 m.sup.2/g.
[0017] In another embodiment of the invention, the internal
resistance of the ultra capacitor cells is reduced or minimized by
lowering the functional Equivalent Series Resistance (ESR) as
measured on the RCL meter (Resistance Capacitance and Inductance)
which measures the capacitor's impedance in a circuit. The lower
the ESR the faster at which the capacitor can be charged and
discharged. The ESR limits the power at which the device can
operate from a direct or alternating current.
[0018] The term "capacitors" as used herein refers to all
capacitors which are provided with at least one activated carbon
electrode and include Electric Double Layer Capacitors (EDLC) and
Ultra Capacitors (UC).
[0019] It is a yet still further object of the invention to provide
an ultra capacitor having a stable operating cell voltage of about
4V when containing, as part of an electrolyte solution, about 2M of
a quaternary ammonium tetrafluoroborate salt at room
temperature.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] According to the present invention there is provided
capacitors having the synergistic combination of at least one
activated carbon electrode in an electrolyte solution comprising a
conductive salt (e.g., a lithium salt or a quaternary ammonium
salt) in a concentration of 0.6 to 3 M wherein the solvent system
used for the electrolyte solution is acetonitrile free and
comprises 20 to 100% by weight, preferably 25 to 75% by weight, of
one or more symmetrical and/or unsymmetrical carbonates of the
formula:
RO(C.dbd.O)OR.sup.1
wherein R is selected from the group consisting of methyl, ethyl,
isopropyl, propyl, CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
R''OCH.sub.2CH.sub.2-- and R''--O--(CH.sub.2).sub.n--, n is 2, 3 or
4, R.sup.1 is selected from the group consisting of
CH.sub.3OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2-- and R''--O--CH.sub.2CH.sub.2--,
and R'' is methyl, ethyl, propyl or isopropyl.
[0021] According to another embodiment of the invention the
carbonate solvents of the invention may be a mixture of themselves
or with other linear or cyclic carbonates, esters and/or ethers,
preferably ethylene carbonate.
[0022] Cyclic carbonates include ethylene carbonate (hereafter
designated as EC) and propylene carbonate (PC). Linear carbonates
include dimethyl carbonate (DMC), diethyl carbonate (DEC),
ethylmethyl carbonate (EMC), etc.
[0023] The carboxylic ester used herein preferably has three or
more carbon atoms and one or more carboxylic ester bonds. The upper
limit of the number of carbon atoms in the carboxylic ester is not
particularly limited. In view of the compatibility with the linear
carbonate and/or cyclic carbonate, the carboxylic ester preferably
has ten or less carbon atoms and more preferably eight or less
carbon atoms.
[0024] The number of carboxylic ester bonds in the carboxylic ester
is one or more as described above. Since an increase in the number
of carboxylic ester bonds generally leads to an increase in the
viscosity of the carboxylic ester, the number of carboxylic ester
bonds is preferably one or two.
[0025] Examples of suitable carboxylic esters include dimethyl
succinate, ethyl methyl succinate, diethyl succinate, dimethyl
2-methylsuccinate, ethyl methyl 2-methylsuccinate, dimethyl
glutarate, ethyl methyl glutarate, diethyl glutarate, dimethyl
2-methylglutarate, ethyl methyl 2-methylglutarate, diethyl
2-methylglutarate, dimethyl adipate, ethyl methyl adipate, diethyl
adipate, 1,2-diacetoxyethane, 1,2-diacetoxypropane,
1,4-diacetoxybutane, glycerin triacetate, methyl 4-acetoxybutyrate,
gamma butyrolactone, and methyl 2-acetoxyisobutyrate, ethyl acetate
and methyl acetate.
[0026] The electrolyte solutions of the present invention for
capacitors comprise the solvent systems of the invention and at
least one conductive salt dissolved as an electrolyte.
[0027] The conductive salt may be any that is capable of being used
in electrical storage devices, such as lithium secondary cells,
lithium ion secondary cells and electrical double-layer capacitors.
Conductive salts that may be used include alkali metal salts and
quaternary ammonium salts. Combinations and mixtures of different
conductive salts may be utilized.
[0028] Preferred alkali metal salts are lithium salts, sodium salts
and potassium salts. Specific examples include: (1) lithium salts
such as lithium tetrafluoroborate, lithium hexafluorophosphate,
lithium perchlorate, lithium trifluoromethanesulfonate, sulfonyl
imide lithium salts, sulfonyl methide lithium salts, lithium
acetate, lithium trifluoroacetate, lithium benzoate, lithium
p-toluenesulfonate, lithium nitrate, lithium bromide, lithium
iodide and lithium tetraphenylborate; (2) sodium salts such as
sodium perchlorate, sodium iodide, sodium tetrafluoroborate, sodium
hexafluorophosphate, sodium trifluoromethanesulfonate and sodium
bromide; and (3) potassium salts such as potassium iodide,
potassium tetrafluoroborate, potassium hexafluorophosphate and
potassium trifluoromethanesulfonate.
[0029] Highly conductive quaternary ammonium and related
imidazolium salts and triflates and mixtures thereof as
tetrafluoroborates have synergistic effect on their solubilities
and conductivities at low temperatures when dissolved in the
solvent systems of the invention.
[0030] Preferable specific examples of the quaternary ammonium salt
useful in the present invention include, but are not limited to,
triethylmethylammonium tetrafluoroborate, diethyldimethylammonium
tetrafluoroborate, ethyltrimethylammonium tetrafluoroborate,
dimethylpyrrolidinium tetrafluoroborate, diethylpyrrolidinium
tetrafluoroborate, ethylmethylpyrrolidinium tetrafluoroborate,
spiro-(1,1.sup.1)-bipyrrolidinium tetrafluoroborate,
dimethylpiperidinium tetrafluoroborate, diethyl piperidinium
tetrafluoroborate, spiro-(1,1.sup.1)-bipiperidinium
tetrafluoroborate, piperidine-1-spiro-1.sup.1-pyrrolidinium
tetrafluoroborate, and the triflates thereof. The quaternary
ammonium tetrafluoroborate salts preferably have a molecular weight
in the range of 178-240.
[0031] Of these, triethylmethylammonium tetrafluoroborate,
spiro-(1,1.sup.1)-bipyrrolidinium tetrafluoroborate, diethyl
pyrrolidinium tetrafluoroborate, dimethyl pyrrolidinium
tetrafluoroborate, and the like are particularly preferable.
[0032] The concentration of the conductive salt in the electrolytic
solution of the present invention is preferably from 0.6 to 3
mol/l, particularly preferably from 1 M to 2 M of the electrolytic
solution.
[0033] If the concentration of the conductive salt is less than 0.6
mol/l, the conductivity may be insufficient; if more than 3 mol/l,
the low temperature performance and economical efficiency may be
impaired.
[0034] What is needed are solvents with high operating voltages
greater than 3 V for the ultra capacitor in which conductive salts
are very soluble and which have a wide liquidus range, preferably
from -70.degree. C. to >150.degree. C. In addition, the
electrolyte solution should remain liquid with high salt
concentrations of salt, e.g., from >1 M up to 2 M. The organic
carbonates of the invention meet all of these requirements. The
preferred solvent is methyl methoxyethyl carbonate
(CH.sub.3O(C.dbd.O)OCH.sub.2CH.sub.2OCH.sub.3), (MMC). The liquidus
range of this solvent is about -65.degree. C. to 170.degree. C.,
providing outstanding low temperature and high temperature
performance while dissolving a high level of conductive salt. This
solvent has a stable operating cell voltage of about 4 V in ultra
capacitor performance when containing 2 M diethyldimethyl ammonium
tetrafluoroborate at room temperature. Other quaternary
alkylammonium tetrafluoroborates can also be used for this same
stable high operating voltage in this solvent and related solvents.
This same stable solvent with 2 M quaternary ammonium
tetrafluoroborate salt will reversibly charge/discharge cycle at
-45.degree. C. in an ultra capacitor.
Preparation of Novel Carbonate Solvents
[0035] A direct synthesis for the symmetrical and asymmetrical
members of the family of organic carbonates is the following
equilibration:
RO(C.dbd.O)OR.sup.1+R''OHRO(C.dbd.O)OR.sup.1+R''O(C.dbd.O)OR.sup.1+R''O(-
C.dbd.O)OR''+R.sup.1OH+ROH
(in the presence of basic catalyst such as sodium methoxide) In the
case of dimethyl carbonate and 2-methoxy ethanol this becomes:
CH.sub.3O(C.dbd.O)OCH.sub.3
(DMC)+CH.sub.3OCH.sub.2CH.sub.2OHCH.sub.3O(C.dbd.O)OCH.sub.2CH.sub.2OCH.s-
ub.3(MMC)
CH.sub.3OCH.sub.2CH.sub.2O(C.dbd.O)OCH.sub.2CH.sub.2OCH.sub.3
(BMC)+CH.sub.3OH
[0036] After equilibration, the catalyst can be neutralized with an
acid or acid salt and the reaction mixture distilled to remove the
alcohols and obtain pure organic carbonate components or a useful
mixture of organic carbonates. Using an excess of the DMC in this
case favors more of the desired MMC (asymmetrical component) as
opposed to the symmetrical component bis-2-methoxyethyl carbonate
(BMC). Mixtures of both with the starting material can be used as
long as the alcohols are removed. The MMC is a preferred solvent of
these series of organic carbonates. MMC may be isolated in pure
form by distillation.
Preparation of Preferred Carbon Electrodes
[0037] The preferred carbon electrodes of the invention can be
prepared following the procedure disclosed in U.S. Pat. No.
7,924,549 of Smith, et al., incorporated herein by reference in its
entirety for all purposes.
[0038] The capacitor requires two electrodes. Electrodes may be
made of 90% treated carbon and 10% Kynar.RTM. binder in an acetone
slurry. A 1-mil thick sheet of aluminum foil pre-treated with a
conductive carbon layer may be trimmed to size and prepared for
coating. A draw knife may be used to deliver the proper thickness
of slurry coating onto the foil. Once coated onto the treated
aluminum sheet, the acetone evaporates and then the other side of
the aluminum foil may be coated. Once the second side has been
coated, proper sized rectangles may be cut from the aluminum sheet
with small plain aluminum tabs still attached to one end. Once cut,
the electrodes may be baked under vacuum to remove any residual
moisture.
[0039] Once removed from the baking/vacuum treatment small squares
of Surlyn.RTM. resin sheets may be welded to the small plain
aluminum tabs. This allows for future secure welding to the
assembled flexible foil pouch.
[0040] To improve the functioning components in order to increase
the performance of the ultra capacitor (UC) at higher voltage, we
have been able to have stable cycling at 3.9-4.0 V with selected
electrolytes and carbons. An additional aspect for better
performance is to minimize the internal resistance of the UC, which
depends on the measured ESR of the cell. It was found that one can
lower the functional ESR of our UC cells by heat treating at higher
temperatures the activated carbons used in the cells. It was found
that with cleaned carbons under inert atmosphere one can continue
to gain improvement by going from 1100.degree. C. up to
1300.degree. C. However, while going up to about 1400.degree. C.
may offer further reduction in ESR the effect did not appear to be
different than 1300.degree. C., and the surface area (capacity)
appeared to start being affected negatively. Therefore, the range
of post heat treatment after acid washing of the carbon is
1100.degree. C. to 1500.degree. C., with the preferred range being
1250-1300.degree. C. under inert atmosphere.
[0041] The ESR of cells was reduced as follows:
TABLE-US-00001 mAH Peak Temperature (2 hrs) of treated carbon
ESR-ohms Capacity at 3.9 V 1100.degree. C. 0.4 3.0 to 3.5
1200.degree. C. 0.3 3.4 to 3.7 1250.degree. C. 0.2 3.6 to 3.8
1300.degree. C. 0.18 3.8 to 4.0
[0042] Part of the reason for this improvement is the improvement
of carbon conductivity which occurs significantly in going from
1000.degree. C. to about 1400.degree. C. and then only very slowly
increases after that with increases in temperature. At the same
time a high surface area carbon such as an activated carbon begins
to rearrange and collapses to a more graphitic nature, thus losing
its high surface area which is needed for the performance of the
ultra capacitor. This surface collapse increases more and rapidly
as the temperature is increased starting at about 1200.degree. C.
and proceeding more rapidly as the temperature is raised past
1400.degree. C. Empirically, it was found that this optimum heating
range to achieve maximum conductivity before degradation of the
surface area is harmful to be about 1250.degree. C. to 1300.degree.
C. for two hours with purified activated carbons. In addition to
improving the conductivity while preserving the surface area, the
higher temperature (above 1100.degree. C.) chemically eliminates
most (if not all) chemically bound oxygen and nitrogen, which are
susceptible to electrochemical oxidation reduction at cell voltages
above approximately 3.4 V in the ultra capacitor. Their presence
contributes to leakage current (electrochemical oxidation currents
on charging the UC and accelerate self discharge) which degrades UC
performance, especially at operating voltages above 3.4V.
[0043] It is understood that conditioning the carbon electrodes
according to the present preferred process optimizes the
performance of the ultra capacitor when used with the electrolyte
solutions of the invention, the prior art carbon electrodes, for
example, which have been alkali conditioned will also be
synergistically improved with the electrolyte solutions of the
invention.
Example 1
Preparation of Electrolyte Solvent
[0044] In a 2 L 3-necked flask, 1749 g (21.9 moles) of
dimethylcarbonate (DMC), 246.14 g (3.24 moles) of 2-methoxy
ethanol, and 49.23 g (5 wt. %) of a 25% sodium methoxide in
methanol solution were added. A 250.degree. C. thermometer was
added to the flask and the reaction flask was then fitted to a
distillation apparatus containing a thermometer and a collection
flask. This was stirred at room temperature for 30 minutes until a
cloudy, white suspension began to form. The mixture was then heated
slowly to a reaction flask temperature of 73.degree. C. At this
point, the first drop of distillate was collected at 43.degree. C.
The distillate was continuously collected and checked by GC for the
presence of products (MMC and bis(2-methoxy ethyl)-carbonate
(BMC)). This was continued until the reaction flask reached a
temperature of 100.degree. C. and the distillation temperature
reached 72.degree. C. At this point, the reaction flask contents
contained only a small percentage of DMC and no methanol. The
reaction mixture was allowed to cool to room temperature. The
reaction mixture was then filtered to remove the sodium methoxide
catalyst. The slightly yellow filtrate was treated with
NaH.sub.2PO.sub.4, mixed, and re-filtered. This step was then
repeated and the filtrate checked to assure that no catalyst
remained. The filtrate was then transferred to a 500 mL 3-necked
flask and stirred. This was then vacuum-distilled slowly. The first
fraction started at a distillation temperature of 28.degree. C. and
a reaction flask temperature of 35.degree. C. These fractions were
mostly DMC. The MMC laden fractions were collected under vacuum (24
mm Hg) at a distillation temperature of 43.degree. C. and a
reaction flask temperature of 55.degree. C. The GC analysis showed
a 91% yield of MMC in the final fraction of MMC product collected.
The remainder of the mix was composed of 6% BMC and 3% 2-methoxy
ethanol.
* * * * *