Solid-state electrochemical cells, processes for their preparation and uses thereof

Patent metadata

Field	Value
Publication number	US-2023136818-A1
Application number	US-202117907633-A
Country	US
Kind code	A1
Filing date	Apr 27, 2021
Priority date	Apr 27, 2020
Publication date	May 4, 2023
Grant date	—

Abstract

All-solid-state electrochemical cells comprising an inorganic particle-polymer composite, where the polymer is a crosslinked polymer and the content of inorganic particles in the composite is at least 50 wt. % are described. Also described are processes for the preparation of such all-solid-state electrochemical cells, all-solid-state batteries comprising them and their uses in mobile devices, electric or hybrid vehicles, or in renewable energy storage.

First claim

1 . An all-solid-state electrochemical cell comprising a positive electrode comprising a positive electrode electrochemically active material, a negative electrode comprising a negative electrode electrochemically active material, and an electrolyte between the positive electrode and the negative electrode, wherein:
the positive electrode, the negative electrode and the electrolyte each form a solid layer; and at least one of the positive electrode, the negative electrode, and the electrolyte comprises a composite material comprising alkali or alkaline earth metal ion-conducting inorganic particles and a crosslinked aprotic polymer, and wherein:
the content of inorganic particles in the composite material is in the range of 50 wt. % to 99.9 wt. %; and
the crosslinked aprotic polymer is in solid form at 25° C. while its polymer precursor before crosslinking is in liquid form at 25° C.

2 . The all-solid-state electrochemical cell of claim 1 , wherein the inorganic particles comprise an ionically conducting inorganic compound of the amorphous, ceramic or glass-ceramic type, for example, oxide, sulfide or oxysulfide.

3 . The all-solid-state electrochemical cell of claim 2 , wherein the inorganic particles comprise an oxide, sulfide or oxysulfide compound having a structure selected from garnets, NASICON, LISICON, thio-LISICON, LIPON, perovskite, anti-perovskite, argyrodites, or comprise a compound comprising the element combinations M-P—S, M-P—S—O, M-P—S—X, where M is an alkali or alkaline earth metal, and X is F, Cl, Br, I or a mixture thereof, the element combination optionally including one or more additional elements (metals, metalloids, or non-metals), the compound being in crystalline, amorphous, glass-ceramic form, or a mixture of at least two thereof.

4 . The all-solid-state electrochemical cell of claim 2 , wherein the inorganic particles comprise at least one compound selected from:
MLZO (such as 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 , M (7-a) La 3 Zr (2-b) NbbO 12 ); MLTaO (such as M 7 La 3 Ta 2 O 12 , M 5 La 3 Ta 2 O 12 , M 6 La 3 Ta 1.5 Y 0.5 O 12 ); MLSnO (such as M 7 La 3 Sn 2 O 12 ); MAGP (such as M 1+a Al a Ge 2-a (PO 4 ) 3 ); MATP (such as M 1+a Al a Ti 2-a (PO 4 ) 3 ); MLTiO (such as M 3a La (2/3-a) TiO 3 ); MZP (such as M a Zr b (PO 4 ) c ); MCZP (such as M a Ca b Zr c (PO 4 ) d ); MGPS (such as M a Ge b P c S d , for example, M 10 GeP 2 S 12 ); MGPSO (such as M a Ge b P c S d O e ); MSiPS (such as M a Si b P c S d , for example, M 10 SiP 2 S 12 ); MSiPSO (such as M a Si b P c S d O e ); MSnPS (such as M a Sn b P c S d , for example, M 10 SnP 2 S 12 ); MSnPSO (such as M a Sn b P c S d O e ); MPS (such as M a P b S c , for example M 7 P 3 S 11 ); MPSO (such as M a P b S c O d ); MZPS (such as M a Zn b P c S d ); MZPSO (such as 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 S 5 ; xM 2 S-yM 2 O-zP 2 S 5 -wMX; xM 2 S-yM 2 O-zP 2 S 5 -wP 2 O 5 ; xM 2 S-yM 2 O-zP 2 S 5 -wP 2 O 5 -vMX; xM 2 S-ySiS 2 ; MPSX (such as M a P b S c X d , for example, M 7 P 3 S 11 X, M 7 P 2 S 8 X, M 6 PS 5 X); MPSOX (such as M a P b S c O d X e ); MGPSX (M a Ge b P c S d X e ); MGPSOX (M a Ge b P c S d O e X f ); MSIPSX (M a Si b P c S d X e ); MSiPSOX (M a Si b P c S d O e X f ); MSnPSX (M a Sn b P c S d X e ); MSnPSOX (M a Sn b P c S d O e X f ); MZPSX (M a Zn b P c S d X e ); MZPSOX (M a Zn b P c S d O e X f ); M 3 OX; M 2 HOX; M 3 PO 4 ; M 3 PS 4 ; or M a PO b N c (with a=2b+3c−5); in crystalline, amorphous, glass-ceramic form, or a mixture of at least two thereof; wherein: M is an alkali metal ion, an alkaline earth metal ion or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality; X is F, Cl, Br, I or a combination thereof; a, b, c, d, e and f are numbers other than zero and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y, and z are numbers other than zero and are, independently in each formula, selected to obtain a stable compound.

5 . The all-solid-state electrochemical cell of claim 3 or 4 , wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination thereof.

6 . The all-solid-state electrochemical cell of claim 3 or 4 , wherein M is lithium.

7 . The all-solid-state electrochemical cell of claim 3 or 4 , wherein M comprises Li and at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba.

8 . The all-solid-state electrochemical cell of claim 3 or 4 , wherein M is Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, or a combination thereof.

9 . The all-solid-state electrochemical cell of claim 3 or 4 , wherein M is Na, K, Mg, or a combination thereof.

10 . The all-solid-state electrochemical cell of any one of claims 1 to 9 , wherein the crosslinked aprotic polymer is stable at >4V (vs. Li + /Li).

11 . The all-solid-state electrochemical cell of any one of claims 1 to 10 , wherein the crosslinked aprotic polymer comprises at least one aprotic polymer segment selected from polyether, polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polysiloxane, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, and polyurethane segments, or a copolymer or combination of at least two thereof.

12 . The all-solid-state electrochemical cell of any one of claims 1 to 10 , wherein the crosslinked aprotic polymer comprises at least one aprotic polymer segment comprising a block copolymer with at least two different repeating units to reduce the crystallinity of the crosslinked polymer.

13 . The all-solid-state electrochemical cell of claim 12 , wherein the aprotic polymer segment comprises, before crosslinking, a block copolymer comprising at least one alkali or alkaline earth metal ion solvating segment and a crosslinkable segment comprising crosslinkable units.

14 . The all-solid-state electrochemical cell of claim 13 , wherein the alkali or alkaline earth metal ion solvating segment is selected from homo- and copolymers comprising repeating units of Formula (I):

wherein,
R is selected from H, C 1 -C 10 alkyl, and —(CH 2 —O—R a R b );
R a is (CH 2 —CH 2 —O) y ; and
R b is a C 1 -C 10 alkyl group.

15 . The all-solid-state electrochemical cell of claim 13 or 14 , wherein the crosslinkable units comprise functional groups selected from acrylates, methacrylates, allyls, vinyls, and one of their combinations.

16 . The all-solid-state electrochemical cell of any one of claims 1 to 14 , wherein the composite material forms the electrolyte layer.

17 . The all-solid-state electrochemical cell of claim 16 , wherein the crosslinked aprotic polymer is present between the inorganic particles.

18 . The all-solid-state electrochemical cell of any one of claims 1 to 17 , wherein the electrolyte layer further comprises at least one salt, for example comprising a cation of an alkali or alkaline earth metal, and an anion selected from anions hexafluorophosphate (PF 6 − ), bis(trifluoromethanesulfonyl)imide (TFSI − ), bis(fluorosulfonyl)imide (FSI − ), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI) − ), 2-trifluoromethyl-4,5-dicyanoimidazolate (TDI − ), 4,5-dicyano-1,2,3-triazola

Assignees

• Hydro Quebec

Inventors

• Kim Chisu
• Darwiche Ali
• Fleutot Benoit
• Garitte Emmanuelle
• Koh Ki Seok
• Girard Marc-Andre
• Gagnon Catherine
• Zaghib Karim

Classifications

• H01M4/62

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/5825

  Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/136

  Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy · CPC title