Electrochemical hydrogen storage electrodes and cells

Patent metadata

Field	Value
Publication number	US-10522827-B2
Application number	US-201615142109-A
Country	US
Kind code	B2
Filing date	Apr 29, 2016
Priority date	May 4, 2015
Publication date	Dec 31, 2019
Grant date	Dec 31, 2019

Abstract

Hydrogen storage negative electrodes based on group IV elements, for example hydrogen storage negative electrodes based on silicon and/or carbon, are highly effective towards reversibly charging/discharging hydrogen in an hydride electrochemical cell.

First claim

The invention claimed is:

1. A rechargeable electrochemical cell comprising:
a stable silicon-based hydrogen storage negative electrode, a positive electrode capable of reversibly absorbing and desorbing hydrogen, and an electrolyte composition;
wherein the negative electrode comprises a hydrogen storage material comprising >27 wt % silicon, and is in contact with the electrolyte composition, wherein the hydrogen storage material comprises amorphous silicon;
wherein the electrolyte composition is pH neutral or acidic and allows for transport of protons; and
wherein during charge/discharge cycles the negative electrode reversibly charges and discharges hydrogen.

2. The electrochemical cell according to claim 1 , wherein the hydrogen storage material is comprised in a film in adherence to a substrate selected from metal, glass, inorganics and plastic.

3. The electrochemical cell according to claim 1 , wherein the hydrogen storage material contains >50 wt % Si based on the total weight of the hydrogen storage material.

4. The electrochemical cell according to claim 1 , wherein the negative electrode comprises >50% by weight Si, based on the total weight of the negative electrode.

5. The rechargeable electrochemical cell according to claim 1 , wherein the electrolyte composition comprises a protic acid.

6. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises one or more ionic compounds selected from the group consisting of protic acids, protic ammonium compounds, protic oxonium compounds, aprotic ammonium compounds, aprotic oxonium compounds, aprotic phosphonium compounds and alkali or alkali earth metal salts.

7. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises an ionic compound containing a cation selected from the group consisting of NH 4 , methylammonium, ethylammonium, dimethylammonium, diethylammonium, trimethylammonium, triethylammonium, tributylammonium, diethylmethylammonium, hydroxyethylammonium, methoxymethylammonium, dibutylammonium, methylbutylammonium, anilinium, pyridinium, 2-methylpyridinium, imidazolium, 1-methylimidazolium, 1,2-dimethylimidazolium, imidazolinium, 1-ethylimidazolium, 1-(4-sulfobutyl)-3-methylimidazolium, 1-allylimidazolium, quinolinium, isoquinolinium, pyrrolinium, pyrrolininium or pyrrolidinium; 1-butyl-1-methylpyrrolidinium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, n-butyl-tri-ethylammonium, benzyl-tri-methylammonium, tri-n-butylmethylammonium, benzyl-tri-ethylammonium, 1-methylpyridinium, 1-butyl-3,5-dimethylpyridinium, 1,2,4-trimethylpyrazolium, trimethylhydroxyethylammonium, tri-(hydroxyethyl)methylammonium, dimethyl-di(polyoxyethylene)ammonium, 1,2,3-trimethylimidazolium, 1-butyl-3-methylimidazolium, 1-ethyl-2,3-dimethylimidazolium, 1-allyl-3-methylimidazolium, 1-hydroxyethyl-3-methylimidazolium, 1,3-dimethylimidazolium, 1-ethyl-1-methylpiperidinium, 4-ethyl-4-methylmorpholinium, 1-(cyanomethyl)-3-methylimidazolium, 1-(3-cyanopropyl)pyridinium, 1,3-bis(cyanomethyl)imidazolium, 1-hexyl-3-methylimidazolium or 1-ethyl-3-methylimidazolium; and methyltriphenylphosphonium, tetraphenylphosphonium, tetrabutylphosphonium, tributylmethylphosphonium, triethylmethylphosphonium, trihexyltetradecylphosphonium, triphenylpropylphosphonium or tetrakis(hydroxymethyl)phosphonium; and
containing an anion selected from the group consisting of carboxylates, imides, methides, nitrate, bifluoride, halides, borates, phosphates, phosphinates, phosphonates, sulfonates, sulfates, carbonates and aluminates.

8. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises an ionic compound containing an anion selected from the group consisting of F 2 P(C 2 F 5 ) 4 − , F 3 P(C 2 F 5 ) 3 − , F 4 P(C 2 F 5 ) 2 − , F 2 P(C 3 F 7 ) 4 − , F 3 P(C 3 F 7 ) 3 − , F 4 P(C 3 F 7 ) 2 − , F 2 P(C 4 F 9 ) 4 − , F 3 P(C 4 F 9 ) 3 − , F 4 P(C 4 F 9 ) 2 − , perfluoroalkylcarboxylate, perfluoroalkylsulfonate, bis(perfluoroalkylsulfonyl)imide, (perfluoroalkylsulfonyl)(perfluoroalkylcarboxyl)imide, tris(perfluoroalkylsulfonyl)methide, trifluoroacetate, trifluoromethanesulfonate, bis(trifluoromethylsulfonyl)imide, tris(trifluoromethylsulfonyl)methide, tetrafluoroborate, bisoxalatoborate, difluorooxalatoborate, di(trifluoroacetato)oxalatoborate, trisoxalatophosphate, tetrafluorooxalatophosphate and di(trifluoroacetato)oxalatoaluminate.

9. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises an ionic compound containing a carboxylate anion of formula RCOO − where R is hydrogen or hydrocarbyl.

10. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises an ionic compound containing an anion selected from the group consisting of dicyanamide, N(SO 2 F) 2 − , [N(SO 2 CF 3 ) 2 ] − , bis(pentafluoroethylsulfonyl)imide, N(CF 3 SO 2 )(CF 3 (CF 2 ) 3 SO 2 ) − or a (perfluoroalkylsulfonyl)(perfluoroalkylcarboxyl)imide; C(CF 3 SO 2 ) 3 − ; HF 2 − ; chloride, bromide, iodide or fluoride; orthoborate, tetrahydroxyborate, tetraborate, tetraphenylborate, [B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 [ − , B(C 2 O 4 ) 2 − (bis(oxalato)borate), difluoro(oxalato)borate, di(trifluoroacetato)oxalatoborate, B(C 6 F 5 ) 4 − or BF 4 − ; dihydrogen phosphate, hydrogen phosphate, alkyl phosphate, dialkyl phosphate, phosphate, PF 6 − , HPO 3 F − , trisoxalatophosphate, tetrafluorooxalatophosphate, F 2 P(C 2 F 5 ) 4 − , F 3 P(C 2 F 5 ) 3 − , F 4 P(C 2 F 5 ) 2 − , F 2 P(C 3 F 7 ) 4 − , F 3 P(C 3 F 7 ) 3 − , F 4 P(C 3 F 7 ) 2 − , F 2 P(C 4 F 9 ) 4 − , F 3 P(C 4 F 9 ) 3 − or F 4 P(C 4 F 9 ) 2 − ; trifluoromethanesulfonate, p-toluenesulfonate or methanesulfonate; hydrogensulfate, sulfate, thiosulfate, methylsulfate or ethylsulfate; carbonate, hydrogencarbonate, methylcarbonate, ethylcarbonate or butylcarbonate; and Al(OC(CF 3 ) 3 ) 4 − , di(trifluoroacetato)oxalatoaluminate, tetrachloroaluminate, tetrafluoroaluminate, tetraiodoaluminate or tetrabromoaluminate.

11. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises an ionic liquid.

12. The electrochemical cell according to claim 1 , wherein the electrolyte composition comprises an ionic liquid selected from the group consisting of diethylmethylammonium trifluoromethanesulfonate, ethylammonium nitrate, triethylammonium methanesulfonate, 2-methylpyridinium trifluoromethanesulfonate, ammonium fluoride, methylammonium nitrate, hydroxyethylammonium nitrate, ethylammonium nitrate, dimethylammonium nitrate, 1-methylimidazolium nitrate, 1-ethylimidazolium nitrate, t-butylammonium tetrafluoroborate, hydroxyethylammonium tetrafluoroborate, methylbutylammonium tetrafluoroborate, triethylammonium tetrafluoroborate, imidazolium tetrafluoroborate, 1-methylimidazolium tetrafluoroborate, 1,2-dimethylimidazolium tetrafluoroborate, t-butylammonium triflate, 2-fluoropyridinium triflate, hydroxyethylammonium triflate, 1,2-dimethylimidazolium triflate, imidazolium triflate, 1-methylimidazolium hydrogensulfate, 1-methylimidazolium chloride, 1-methylimidazolium triflate, hydronium triflate, methylammonium mesylate, ethylammonium mesylate, butylammonium mesylate, methoxyethylammonium mesylate, dimethylammonium mesylate, dibutylammonium mesylate, triethylammonium mesylate, dimethylethylammonium mesylate, hydronium hydrogensulfate, ammonium hydrogensulfate, methylammonium hydrogensulfate, ethylammonium hydrogensulfate, propylammonium hydrogensulfate, n-butylammonium hydrogensulfate, t-butylammonium hydrogensulfate, dimethylammonium hydrogensulfate, diethylammonium hydrogensulfate, di-n-butylammonium hydrogensulfate, methylbu

Assignees

• Basf Corp

Inventors

• Young Kwo
• Meng Tiejun
• Fetcenko Michael A

Classifications

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M10/0566

  Liquid materials · CPC title

• H01M2300/0045

  Room temperature molten salts comprising at least one organic ion · CPC title

• H01M10/345

  Gastight metal hydride accumulators · CPC title

• H01M4/386

  Silicon or alloys based on silicon · CPC title