Solid electrolytes comprising an ionic bifunctional molecule, and use thereof in electrochemistry

Patent metadata

Field	Value
Publication number	US-2025079513-A1
Application number	US-202318726615-A
Country	US
Kind code	A1
Filing date	Jan 13, 2023
Priority date	Jan 14, 2022
Publication date	Mar 6, 2025
Grant date	—

Abstract

The present technology relates to a solid electrolyte comprising inorganic particles and an ionic bifunctional molecule for use in electrochemical applications. Also described are electrochemical cells and batteries comprising said solid electrolyte.

First claim

What is claimed is:

1 . A solid electrolyte comprising inorganic particles and an ionic bifunctional molecule of Formulae I or II:

wherein,
A − is a delocalized anion;
R + is selected from —N + (R 1 R 2 R 3 ) and —P + (R 1 R 2 R 3 ) groups excluding cations derived from amidine, guanidine and phosphazene superbases;
R 1 , R 2 , and R 3 are independently selected from a substituted or unsubstituted linear or branched C 1-12 alkyl group; or R 1 and R 2 together with the nitrogen or phosphorus atom form a heterocycle having one or more rings and having from 3 to 12 members and R 3 is as previously defined; or R 1 , R 2 , and R 3 together with the nitrogen or phosphorus atom form a partially unsaturated heterocycle or heteroaromatic having one or more rings and having from 5 to 12 members;
L is a linear or branched C 2-4 alkylene;
X is O or S;
m is a number in the range from 1 to 6; and
n is a number in the range from 1 to 11.

2 . The solid electrolyte of claim 1 , wherein the delocalized anion is selected from hexafluorophosphate (PF 6 − ), bis(trifluoromethanesulfonyl)imide (TFSI − ), bis(fluorosulfonyl)imide (FSI − ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI − ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI − ), 4,5-dicyano-1,2,3-triazolate (DCTA − ), bis(pentafluoroethylsulfonyl)imide (BETI − ), difluorophosphate (DFP − ), tetrafluoroborate (BF 4 − ), bis(oxalato)borate (BOB − ), nitrate (NO 3 − ), perchlorate (ClO 4 − ), hexafluoroarsenate (AsF 6 − ), trifluoromethanesulfonate (CF 3 SO 3 − or − OTf), fluoroalkylphosphate ([PF 3 (CF 2 CF 3 ) 3 ] − or FAP − ), tetrakis(trifluoroacetoxy)borate ([B(OCOCF 3 ) 4 ] − or TFAB − ), bis(1,2-benzenediolato(2-)-O,O′)borate ([B(C 6 O 2 ) 2 ] − or BBB − ), difluoro(oxalato)borate (BF 2 (C 2 O 4 ) − or FOB − ), and an anion of formula BF 2 O 4 R x (R x =C 2-4 alkyl), preferably the delocalized anion is selected from hexafluorophosphate (PF 6 − ), bis(trifluoromethanesulfonyl)imide (TFSI − ), bis(fluorosulfonyl)imide (FSI − ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide (FTFSI − ), tetrafluoroborate (BF 4 − ), and trifluoromethanesulfonate (CF 3 SO 3 − or − OTf) and more preferably the delocalized anion is bis(trifluoromethanesulfonyl imide (TFSI − ).

3 - 4 . (canceled)

5 . The solid electrolyte of claim 1 , wherein R + is an —N m (R 1 R 2 R 3 ) group.

6 . The solid electrolyte of claim 5 , wherein:
(i) R 1 , R 2 , and R 3 are independently selected from substituted or unsubstituted linear or branched C 1-12 alkyl groups, (ii) R 1 , R 2 , and R 3 , are independently selected from linear or branched C 1-12 alkyl groups, or at least one of R 1 , R 2 , or R 3 is substituted by a halogen atom or an alkoxyl, ether, ester, or siloxy group, (iii) R 1 and R 2 together with the nitrogen atom form a heterocycle having one or more rings and having from 3 to 12 members and R 3 is as defined in claim 1 , preferably R 3 is a C 1-12 alkyl or a C 1-4 alkyl; or (iv) R 1 , R 2 , and R 3 together with the nitrogen atom form a partially unsaturated heterocycle or heteroaromatic having one or more rings and having from 5 to 12 members.

7 - 9 . (canceled)

10 . The solid electrolyte of claim 5 , wherein R + is selected from:

wherein,
R 3 is as defined in claim 1 , and preferably R 3 is an unsubstituted C 1-4 alkyl group preferably selected from a methyl group, an ethyl group, an n- or i-propyl group, and an n-, i-, s-, or t-butyl group;
R 4 is a substituted or unsubstituted linear or branched C 1-12 alkyl, C 1-12 alkenyl, or C 1-12 alkynyl group, and preferably R 4 is a C 1-12 alkyl group;
R 5 is a hydrogen atom, or a substituted or unsubstituted linear or branched C 1-12 alkyl, C 1-12 alkenyl, or C 1-12 alkynyl group, and preferably R 5 is a C 1-4 alkyl group; and
the heterocycle is optionally substituted.

11 - 14 . (canceled)

15 . The solid electrolyte of claim 1 , wherein R + is a —P + (R 1 R 2 R 3 ) group.

16 . The solid electrolyte of claim 15 , wherein:
(i) R 1 , R 2 , and R 3 are independently selected from substituted or unsubstituted linear or branched C 1-12 alkyl groups; or (ii) R 1 , R 2 , and R 3 , are independently selected from linear or branched C 1-12 alkyl groups, or at least one of R 1 , R 2 , or R 3 is substituted by a halogen atom or an alkoxyl, ether, ester, or siloxy group.

17 . (canceled)

18 . The solid electrolyte of claim 1 , wherein n is a number in the range from 2 to 10, or from 3 to 8, or from 4 to 6.

19 . The solid electrolyte of claim 1 , wherein the ionic bifunctional molecule is selected from the group consisting of 1,1′-(1,6-hexamethylene) bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide, 1,1′(1,12-dodecamethylene) bis(1-methyl pyrrolidinium bis(trifluoromethanesulfonyl)imide, 1,1′-(2,2′-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium) bis(trifluoromethanesulfonyl)imide, 1,1′-(thiol bis(1,2-ethane) bis(1-methylpyrrolidinum) bis(trifluoromethanesulfonyl)imide, and 3,3′-(1,6-hexamethylene) bis(1,2-dimethylimidazolium) bis(trifluoromethanesulfonyl)imide.

20 - 23 . (canceled)

24 . The solid electrolyte of claim 1 , wherein the ionic bifunctional molecule is present at a concentration of from about 0.5 wt. % to about 50 wt. %, or from about 2 wt. % to about 30 wt. %, or from about 4 wt. % to about 20 wt. %, or from about 5 wt. % to about 15 wt. % in the solid electrolyte.

25 . The solid electrolyte of claim 1 , wherein the inorganic particles comprise a material selected from glasses, glass-ceramics, ceramics, nanoceramics, and a combination of at least two thereof.

26 - 27 . (canceled)

28 . The solid electrolyte of claim 25 , wherein the inorganic particles comprise:
(i) a fluoride-, phosphide-, sulfide-, oxysulfide- or oxide-based ceramic, glass, or glass-ceramic; (ii) a LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite, oxide, sulfide, oxysulfide, phosphide or fluoride compound in crystalline and/or amorphous form, or a combination of at least two thereof; (iii) a compound selected from inorganic compounds of formulae MLZO (for example, M 7 La 3 Zr 2 O 12 , M (7-a) La 3 Zr 2 Al b O 12 , M (7-a) La 3 Zr 2 Ga b O 12 , M (7-a) La 3 Zr (2-b) Ta b O 12 , and M (7-a) La 3 Zr (2-b) Nb b O 12 ); MLTaO (for example, M 7 La 3 Ta 2 O 12 , M 5 La 3 Ta 2 O 12 , and M 6 La 3 Ta 1.5 Y 0.5 O 12 ); MLSnO (for example, M 7 La 3 Sn 2 O 12 ); MAGP (for example, M 1+a Al a Ge 2−a (PO 4 ) 3 ); MATP (for example, M 1+a Al a Ti 2−a (PO 4 ) 3 ); MLTiO (for example, M 3a La (2/3−a) TiO 3 ); MZP (for example, M a Zr b (PO 4 ) c ); MCZP (for example, M a Ca b Zr c (PO 4 ) d ); MGPS (for example, M a Ge b P c S d such as M 10 GeP 2 S 12 ); MGPSO (for example, M a Ge b P c S d O e ); MSiPS (for example, M a Si b P c S d such as M 10 SiP 2 S 12 ); MSiPSO (for example, M a Si b P c S d O e ); MSnPS (for example, M a Sn b P c S d such as M 10 SnP 2 S 12 ); MSnPSO (for example, M a Sn b P c S d O e ); MPS (for example, M a P b S c such as M 7 P 3 S 11 ); MPSO (for example, M a P b S c O d ); MZPS (for example, M a Zn b P c S d ); MZPSO (for example, M a Zn b P c S d O e ); xM 2 S-yP 2 S 5 ; xM 2 S-yP 2 S 5 -zMX; xM 2 S-yP 2 S 5 -zP 2 O 5 ; xM 2 S-yP 2 S 5 -zP 2 O 5 -wMX; xM 2 S-yM 2 O-zP 2

Assignees

• Hydro Quebec

Inventors

• Fleutot Benoit
• Zhang Xuewei
• Garitte Emmanuelle

Classifications

• C07D295/037

  with quaternary ring nitrogen atoms · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/0567

  characterised by the additives · CPC title