Electrochemical Hydrogen Storage Electrodes and Cells

Patent metadata

Field	Value
Publication number	US-2016329560-A1
Application number	US-201615142109-A
Country	US
Kind code	A1
Filing date	Apr 29, 2016
Priority date	May 4, 2015
Publication date	Nov 10, 2016
Grant date	—

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

1 . A stable silicon-based hydrogen storage negative electrode for electrochemical uses; the electrode comprising a hydrogen storage material comprising >27 wt % silicon.

2 . An electrode according to claim 1 where the hydrogen storage material comprises amorphous silicon.

3 . An electrode according to claim 1 where the hydrogen storage material is hydrogenated.

4 . An electrode according to claim 1 where the hydrogen storage material is comprised in a film in adherence to a substrate selected from metal, glass, inorganics and plastic.

5 . An electrode according to claim 1 where the hydrogen storage material contains ≧50 wt % Si based on the total weight of the hydrogen storage material.

6 . An electrode according to claim 1 comprising ≧50% by weight Si, based on the total weight of the negative electrode.

7 . An electrode according to claim 1 in contact with an electrolyte composition which is pH neutral or acidic and allows for transport of protons.

8 . An electrode according to claim 7 where 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.

9 . An electrode according to claim 7 where 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.

10 . An electrode according to claim 7 where 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.

11 . An electrode according to claim 7 where the electrolyte composition comprises an ionic compound containing a carboxylate anion of formula RCOO − where R is hydrogen or hydrocarbyl.

12 . An electrode according to claim 7 where 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.

13 . An electrode according to claim 7 where the electrolyte composition comprises an ionic liquid.

14 . An electrode according to claim 7 where 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, methylbutylammonium hydrogensulfate, ethylbutylammonium hydrogensulfate, trimethylammonium hydrogensulfate, triethylammonium hydrogensulfate, tributylammonium hydrogensulfate, dimethylethylammonium hydrogensulfate, dibutylammonium fluorohydrogen phosphate, triethylammonium fluorohydrogen phosphate, tributylammonium fluorohydrogen phosphate, hydronium dihydrogen phosphate, methylammon

Assignees

• Basf Corp

Inventors

• Young Kwo
• Meng Tiejun
• Fetcenko Michael A

Classifications

• H01M10/345

  Gastight metal hydride accumulators · CPC title

• H01M2300/0025

  Organic electrolyte · CPC title

• H01M4/386

  Silicon or alloys based on silicon · CPC title

• H01M4/383 Primary

  Hydrogen absorbing alloys · CPC title

• H01M2300/0045

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