Carbon electrodes and electrochemical capacitors
View Patent ↗An electrochemical device having an operational voltage up to 4.5 V in combination with a high concentration of an electrolyte salt consisting of a tetrafluoroborate salt and a eutectic of two solvents in which ethylene carbonate is one and an improved carbon electrode a preferred electrochemical device is a capacitor.
1. An electrochemical device which comprises the combination of at least one carbon electrode comprising;
a) a metal collector on the top and bottom surfaces;
b) optionally, a first conductive carbon layer on each of the top and bottom interior surfaces of the collectors;
c) a porous second conductive carbon layer on each of said first conductive carbon layers, said second conductive carbon layers being substantially free of oxygen and heteroatoms containing functional groups;
d) a porous inert separator between said second conductive carbon layers; and
e) an electrolyte which comprises at least one conductive salt selected from the group consisting of a compound of the general formula:
wherein R 1 , R 2 , R 3 and R 4 are the same or different and consisting of an alkyl group having 1 to 4 carbon atoms, R 5 and R 6 are hydrogen or methyl and a solvent free of a nitrile solvent comprising ethylene carbonate and a member of the group consisting of propylene carbonate, dimethyl carbonate, gamma butyrolactone, 1,2-dimethoxy ethane, and triethylene glycol dimethyl ether, said salt being in a concentration of 1.5 to 4.5 M and said solvent comprising about 10 to 70% by weight of ethylene carbonate whereby there is a eutectic mixture of the solvents and/or the solvents and the salt.
2. The electrochemical device of claim 1 wherein the salt concentration of the electrolyte is 2.0 to 4.8 M.
3. The electrochemical device of claim 1 wherein the electrode is an aluminum metal collector.
4. The electrochemical device of claim 1 wherein the electrolyte solvent comprises two members selected from the group consisting of ethylene carbonate, propylene carbonate, gamma butyrolactone and dimethyl carbonate.
5. The electrochemical device of claim 1 including up to 10% by weight of a solvent selected from the group consisting of methyl acetate, ethyl acetate, acetone, and methyl formate in said electrolyte.
6. The electrochemical device of claim 1 wherein the conductive salt of said electrolyte is a tetraalkyl ammonium tetrafluoroborate selected from the group consisting of methyltriethyl ammonium tetrafluoroborate, diethyldimethylammonium tetrafluoroborate, and ethyltrimethylammonium tetrafluoroborate and tetraethylammonium tetrafluoroborate.
7. The electrochemical device of claim 1 wherein the conductive salt of said electrolyte is selected from the group consisting of N,N-ethylmethyl pyrrolidinyl tetrafluoroborate, N,N-dimethyl pyrrolidinyl tetrafluoroborate, N,N-dimethyl-2-methylpyrrolidinyl tetrafluoroborate, and N,N-dimethyl-3-methylpyrrolidinyl tetrafluoroborate.
8. The electrochemical device of 1 wherein the solvent of said electrolyte consists essentially of ethylene carbonate and a member selected from the group consisting of propylene carbonate, gamma butyrolactone.
9. The electrochemical device of claim 1 wherein the conductive salt said electrolyte is spiro pyrrolidinyl pyrrolidinyl tetrafluoroborate.
10. The electrochemical device of claim 1 wherein said carbon in the electrode was heat treated to remove oxygen, nitrogen and sulfur functional groups and silica by heating at a temperature between 850 and 1300° C., in an inert atmosphere and comprises 6 to 12 g of conductive carbon per 100 g of carbon.
11. The electrochemical device of claim 1 which is a capacitor.
12. The electrochemical device of claim 11 in which the electrolyte for the electrode comprise a conductive tetraammonium salt of the formula:
R,R 1 ,R 2 ,R 3 ,N B F 4
wherein R, R 1 , R 2 , R 3 are ethyl or methyl groups or together R, R 1 , R 2 and R 3 are one or two pyrrolidinyl groups in an aprotic solvent.
13. The electrochemical device of claim 11 wherein the electrolyte solvent is at least two members of the group consisting of ethylene carbonate, propylene carbonate dimethyl carbonate and gamma butyrolactone.
14. The electrochemical device of claim 11 wherein the salt concentration of the electrolyte is about 1.5 to 4.8 M.
15. The electrochemical device of claim 11 wherein the electrolyte solvent comprises about 40-60% ethylene carbonate.
16. The electrochemical device of claim 11 which comprises an annealed aluminum collector.
17. The electrochemical device of claim 11 wherein said carbon in the electrode is acid washed prior to heat treatment to remove ash and salts.