IP Library › Granted Patent US 10,910,674
Granted Patent B2
US 10,910,674 · App. 15/769,854 · Granted Feb 2, 2021

Additive for increasing lifespan of rechargeable zinc-anode batteries

Inventors: Xia Wei (New York, NY); Michael Nyce (New York, NY); Gautam G. Yadav (New York, NY); Alexander Couzis (New York, NY); Sanjoy Banerjee (New York, NY)
Assignee: RESEARCH FOUNDATION OF THE CITY UNIVERSITY OF NEW NEW YORK
H01M10/26H01M4/38H01M4/42H01M10/05H01M10/0567H01M10/0568H01M10/0569H01M10/28H01M10/36H01M10/4235H01M2004/027H01M2300/0014
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Quick Facts
Patent No.
US 10,910,674
App. No.
15/769,854
Granted
Feb 2, 2021
Kind
B2
Abstract

A rechargeable battery can include a cathode, an anode current collector, an anode comprising zinc, and an electrolyte in ionic communication with both the cathode and the anode current collector. The electrolyte can include an organic ammonium halide. The organic ammonium halide can include an ammonium bromide in some instances.

Claims (47)

1. A rechargeable battery, comprising:

a cathode, wherein the cathode comprises nickel, nickel oxide hydroxide, nickel oxyhydroxide, manganese dioxide, or any combination thereof;

an anode current collector;

an anode comprising zinc, wherein the zinc is present in the anode in an amount between 50 wt. % and 90 wt. %; and

an aqueous electrolyte in ionic contact with both the cathode and the anode current collector, wherein the aqueous electrolyte comprises an organic quaternary ammonium halide.

2. The rechargeable battery of claim 1 , wherein the aqueous electrolyte comprises a tin salt and polyethylene oxide.

3. The rechargeable battery of claim 1 , wherein the cathode comprises nickel, nickel oxide hydroxide, nickel oxyhydroxide, or any combination thereof.

4. The rechargeable battery of claim 1 , wherein the cathode comprises manganese dioxide.

5. The rechargeable battery of claim 1 , wherein the cathode comprises vanadium, cadmium, bromide, copper, chlorine, lithium, silver, air, sodium, or any combination thereof.

6. The rechargeable battery of claim 1 , wherein the aqueous electrolyte comprises an aqueous solution of potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium hydroxide, or any combination thereof.

7. The rechargeable battery of claim 1 , wherein the aqueous electrolyte is an acidic electrolyte comprising zinc sulfate, zinc chloride, or any combination thereof.

8. The rechargeable battery of claim 1 , further comprising: a pump configured to cause the electrolyte to flow.

9. The rechargeable battery of claim 1 , wherein the organic ammonium halide is selected from the group consisting of: hexadecyltrimethyl ammonium bromide (CTAB), ammonium bromide, tetrapropylammonium bromide, terakis(decyl)ammonium bromide, (12-Dodecylphosphonic acid)N,N-Dimethyl-N-octadecyl ammonium bromide, trimethyltetradecylammonium bromide, myristyltrimethylammonium bromide, domiphen bromide, (1-(4-methoxy-benzoyl)-undecyl)-trimethyl-ammonium bromide, (2-dodecanoylamino-ethyl)-dimethyl-tetradecyl-ammonium bromide, 3-benzyl-3H-benzothiazol-2-ylidene-ammonium bromide, acetyl-benzyl-diethyl-ammonium bromide, allyloxycarbonylmethyl-ethyl-ammonium bromide, allyloxycarbonylmethyl-trimethyl-ammonium bromide, benzyloxycarbonylmethyl-triethyl-ammonium bromide, benyloxycarbonylmethyl-trimethyl-ammonium bromide, bis-decyl-di ethyl-ammonium bromide, decyl-dimethyl-(2,3,4,5,6-pentahydroxy-hexyl)-ammonium bromide, decyl-tris-(2-decyloxy-ethyl)-ammonium bromide, dibenzyl-methoxycarbonylmethyl-ammonium bromide, diethylmethyl(2-(3-methyl-2-phenylvaleryloxy)-ethyl) ammonium bromide, trimethyl(2,4,5-trimethylbenzyl)ammonium bromide, trimethyl-(2-oxo-benzothiazol-3-ylmethyl)-ammonium bromide, stearyltrimethyl ammonium bromide, tetrabutylammonium bromide, sodium dodecyl trimethyl ammonium bromide, tetramethylammonium chloride (TMAC), and any combination thereof.

10. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: an organic additive comprising sodium dodecyl benzene sulfonate (SDBS), salicylaldehyde (SAL), benzylideneacetone (BDA), benzylacetone (BA), butylbenzene (BB) or any combination thereof.

11. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: an organic additive comprising benzyl alcohol, naphthalin, benzyl chloride, coumarin, decylamine (DA), 1-decano (DE), dihydrocoumarin, sorbitol, aniline, or any combination thereof.

12. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: a surfactant selected from the group consisting of: F1110 (C 6 F 13 C 2 H 4 (OC 2 H 4 ) 12 OH), nonionic surfactant FC-170C, cationic surfactant FC-135, anionic surfactant FC-129, triton X-10, triton X-100, sodium methylene bis (naphthalene sulfonate) (NNO), phenylbenzylketone (PBK), CH-1, sodium dodecyl sulfate (SDS), sodium lauryl sulphate (SLS), sodium dodecyl benzene sulphonate, and any combination thereof.

13. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: an organic additive comprising a polymer compound, wherein the polymer compound comprises polyethylene glycol (PEG), polyethylene oxide, dicarboxylic acid modified PEG, polypropylene glycol (PPG) 725, terathane, PEG dodecyl ether, PEG diacid 600, brij30, brij 35, a polymer compound containing a main component ethylene oxide group, polyoxyethylene alkyl phosphate ester acid (GAFAC RA 600), polyacrylamide thiourea, chloride solution-ethoxylated-polyflouro-alcohol (FPEA), benzoic acid (BA), 1,4-bis(2-etylhexyl) sulphosuccinate (AOT), thiourea (TU), cellulose, or any combination thereof.

14. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: a polymer comprising glycerol, a glue, a gum, or any combination thereof.

15. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: a rochelle salt (RS), a nicotinic acid (NA), triethanolamine (TEA), tetra-ethylene pentammine (TEPA), polyvinyl alcohol (PVA), polyamine PA-I, polyamine PA-II, imidazole-polyamine (PA-Imid), trisodium nitrilotriacetic (NTA), thiourea, dextrin, vanillin (VA), Piperonal (PA), veratraldehyde (VER), anisaldehyde (ANI), benzimidazole (BZ), PVA, bis (2-ethylhexyl) sodium sulfosuccinate (AOT), (N-[(1E)-(4 methoxyphenyl)methylene] hydrazinecarbothioamide (ATSC), disodium ethylenediaminetetraacetate (EDTA), damssisa, hlfabar, piperonal, or any combination thereof.

16. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: sodium citrate, potassium sodium tartrate, calcium gluconate, phosphoric acid, acetic acid, tartaric acid, succinic acid, citric acid, hydroxyphenylpropionic acid, benzoic acid, or any combination thereof.

17. The rechargeable battery of claim 1 , wherein the aqueous electrolyte further comprises: a metal compound which has higher over potential for hydrogen than zinc.

18. A rechargeable battery, comprising:

a cathode, wherein the cathode comprises nickel, nickel oxide hydroxide, nickel oxyhydroxide, manganese dioxide, or any combination thereof,

an anode current collector,

an anode comprising zinc, wherein the zinc is present in the anode in an amount between 50 wt. % and 90 wt. %; and

an aqueous electrolyte in ionic contact with both the cathode and the anode current collector, wherein the aqueous electrolyte comprises an alkyl quaternary ammonium compound.

19. The rechargeable battery of claim 18 , wherein the cathode comprises nickel, sodium, vanadium, lithium, bromine, chlorine, cadmium, copper, silver, or manganese oxide.

20. The rechargeable battery of claim 18 , wherein the anode current collector is resistant to corrosion in the electrolyte.

21. The rechargeable battery of claim 18 , wherein the anode comprises a pasted mixture of zinc paste, zinc oxide, and binder.

22. The rechargeable battery of claim 18 , wherein the alkyl quaternary ammonium compound is hexadecyltrimethyl ammonium bromide (CTAB).

23. The rechargeable battery of claim 18 , wherein the alkyl quaternary ammonium compound is an aliphatic quaternary ammonium compound.

24. The rechargeable battery of claim 23 , wherein the aliphatic quaternary ammonium compound is a halogenated salt.

25. The rechargeable battery of claim 23 , wherein the aliphatic quaternary ammonium compound is an ammonium bromide.

26. The rechargeable battery of claim 23 , wherein the aliphatic quaternary ammonium compound is selected from the group consisting of hexadecyltrimethyl ammonium bromide (CTAB), ammonium bromide, tetrapropylammonium bromide, terakis(decyl)ammonium bromide, (12-Dodecylphosphonic acid)N,N-Dimethyl-N-octadecyl ammonium bromide, trimethyltetradecylammonium bromide, myristyltrimethylammonium bromide, domiphen bromide, (1-(4-methoxy-benzoyl)-undecyl)-trimethyl-ammonium bromide, (2-dodecanoylamino-ethyl)-dimethyl-tetradecyl-ammonium bromide, 3-benzyl-3H-benzothiazol-2-ylidene-ammonium bromide, acetyl-benzyl-diethyl-ammonium bromide, allyloxycarbonylmethyl-ethyl-ammonium bromide, allyloxycarbonylmethyl-trimethyl-ammonium bromide, benzyloxycarbonylmethyl-triethyl-ammonium bromide, benyloxycarbonylmethyl-trimethyl-ammonium bromide, bis-decyl-di ethyl-ammonium bromide, decyl-dimethyl-(2,3,4,5,6-pentahydroxy-hexyl)-ammonium bromide, decyl-tris-(2-decyloxy-ethyl)-ammonium bromide, dibenzyl-methoxycarbonylmethyl-ammonium bromide, diethylmethyl(2-(3-methyl-2-phenylvaleryloxy)-ethyl) ammonium bromide, trimethyl(2,4,5-trimethylbenzyl)ammonium bromide, trimethyl-(2-oxo-benzothiazol-3-ylmethyl)-ammonium bromide, stearyltrimethyl ammonium bromide, tetrabutylammonium bromide, sodium dodecyl trimethyl ammonium bromide, and a combination of these bromide compounds.

27. A method of operating a battery comprising:

discharging a battery, wherein the battery comprises:

a cathode, wherein the cathode comprises nickel, nickel oxide hydroxide, nickel oxyhydroxide, manganese dioxide, or any combination thereof;

an anode current collector;

an anode comprising zinc, wherein the zinc is present in the anode in an amount between 50 wt. % and 90 wt. %; and

an aqueous electrolyte in ionic contact with both the cathode and the anode current collector, wherein the aqueous electrolyte comprises an alkyl quaternary ammonium compound;

dissolving zinc in the electrolyte during the discharging;

charging the battery; and

plating zinc on the anode current collector during the charging.

28. The method of claim 27 , further comprising:

circulating the aqueous electrolyte in contact with the cathode and the anode during the discharging and charging.

29. The method of claim 27 , wherein the alkyl quaternary ammonium compound comprises an organic ammonium halide.

30. The method of claim 29 , wherein the aqueous electrolyte further comprises a tin salt, and polyethylene oxide.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 3, 2020
From: WEI, XIA; YADAV, GAUTAM G.; NYCE, MICHAEL; COUZIS, ALEXANDER; BANERJEE, SANJOY
To: RESEARCH FOUNDATION OF THE CITY UNIVERSITY OF NEW YORK
Reel/Frame 054528/0186 →
Continuity (2)
Provisional Application 62244244 · Oct 21, 2015
Related Publication 20180316064A1 · Nov 1, 2018