All-solid-state lithium-sulfur polymer electrochemical cells and production methods thereof

Patent metadata

Field	Value
Publication number	US-2016149261-A1
Application number	US-201414899788-A
Country	US
Kind code	A1
Filing date	Jun 20, 2014
Priority date	Jun 21, 2013
Publication date	May 26, 2016
Grant date	—

Abstract

All-solid-state lithium-sulfur electrochemical cells and production methods thereof are described. The Li—S electrochemical cells comprise at least one multilayer component which comprises an ion-conductive solid electrolyte film, a positive electrode film containing a sulfur composite, and a negative electrode film containing lithium. Positive electrodes films, prefabricated electrolyte-positive electrode elements, their uses as well as methods of their production are also described.

First claim

1 . An electrochemical cell comprising at least one multilayer component which comprises:
a positive electrode film comprising sulfur as an electrochemically active material; a negative electrode film comprising lithium as an electrochemically active material; and a solid electrolyte film between the negative and positive electrode films, said solid electrolyte film comprising at least one lithium salt and at least one polymer.

2 . The electrochemical cell according to claim 1 , wherein the solid electrolyte film comprises at least one polymeric layer.

3 . The electrochemical cell according to claim 2 , wherein the solid electrolyte film is an ion-conductive film and further comprises at least one inorganic compound in the polymeric layer or in a separate ion-conductive solid layer.

4 . The electrochemical cell according to claim 3 , wherein the solid electrolyte film comprises at least one lithium salt dissolved in the ion-conductive solid layer.

5 . The electrochemical cell according to any one of claims 1 to 4 , wherein the polymer consists of a block copolymer composed of at least one lithium-ion solvating segment and at least one cross-linkable segment.

6 . The electrochemical cell according to claim 5 , wherein the lithium-ion solvating segment is selected from homo- and copolymers having repeating units of Formula (I):

wherein,
R is selected from H, C 1 -C 10 alkyl, or —(CH 2 —O—R a R b );
R a is (CH 2 —CH 2 —O) y ;
R b is selected from H and a C 1 -C 10 alkyl group;
x is an integer selected from the range of 10 to 200,000; and
y is an integer selected from the range of 0 to 10.

7 . The electrochemical cell according to claim 5 or 6 , wherein the cross-linkable segment is a polymer segment comprising at least one functional group cross-linkable multi-dimensionally by irradiation or thermal treatment.

8 . The electrochemical cell according to any one of claims 1 to 7 , wherein the lithium salt is of formula Li+X − , wherein X − is an anion with a delocalized charge, preferably an anion selected from PF 6 − , BF 4 − , AsF 6 − , ClO 4 − , CF 3 SO 3 − , (CF 3 SO 2 ) 2 N − (TFSI), and (C 2 F 6 SO 2 ) 2 N − (BETI).

9 . The electrochemical cell according to any one of claims 3 to 8 , wherein the inorganic compound in the solid electrolyte film is selected from SiO 2 , Al 2 O 3 , TiO 2 , lithium ion-conductive glasses or ceramics, and other lithium ion-conductive solids, and combinations thereof.

10 . The electrochemical cell according to claim 9 , wherein the lithium ion-conductive glasses or ceramics are selected from NASICON, LISICON, thio-LISICON, Garnet, either in crystalline or amorphous form, and combinations thereof.

11 . The electrochemical cell according to claim 9 or 10 , wherein the lithium ion-conductive glass or ceramic has a lithium ion conductivity of at least 10 −4 S/cm at 25° C.

12 . The electrochemical cell according to any one of claims 3 to 11 , wherein the solid electrolyte film has a thickness between 10 and 200 μm, between 10 and 100 μm, or between 20 and 50 μm.

13 . The electrochemical cell according to any one of claims 1 to 12 , wherein the positive electrode film further comprises a polymer binder.

14 . The electrochemical cell according to claim 13 , wherein the polymer binder is a block copolymer composed of at least one lithium ion-solvating segment and at least one cross-linkable segment.

15 . The electrochemical cell according to claim 14 , wherein the lithium ion-solvating segment is selected from homo- or copolymers having repeating units of Formula (I) as defined in claim 4 .

16 . The electrochemical cell according to any one of claims 13 to 15 , wherein the polymer binder is the same as the polymer of the solid electrolyte film.

17 . The electrochemical cell according to any one of claims 13 to 15 , wherein the polymer binder is different from the polymer of the solid electrolyte film.

18 . The electrochemical cell according to any one of claims 1 to 17 , wherein the positive electrode film comprises a composite material including sulfur encapsulated in a coating material.

19 . The electrochemical cell according to claim 18 , wherein the coating material comprises an inorganic material selected from:
Li a M 1 b (XO 4 ), wherein 0≦a≦2, 0<b≦1; M 1 is selected from Fe, Mn, Co, Ni, and Ti, or combinations thereof, and X is selected from P, Si and S; and Li c M 2 d Z e , wherein 0≦c≦4, 0<d≦5, 0<e≦12; M 2 is selected from Mo, V, Ti, Al, and Si; and Z is selected from O, S, and Se.

20 . The electrochemical cell according to claim 19 , wherein the inorganic material is selected from LiFePO 4 , LiNiPO 4 , LiMnPO 4 , LiCoPO 4 , and LiFe 1-x Ti x PO 4 , where 0<x<1.

21 . The electrochemical cell according to claim 20 , wherein the inorganic material is LiFePO 4 .

22 . The electrochemical cell according to claim 19 , wherein the inorganic material is selected from TiO 2 , TiS 2 , V 2 O 5 , LiV 3 O 5 , Li 4 Ti 5 O 12 , MoS 2 , MoO 2 , SiO 2 , and Al 2 O 3 .

23 . The electrochemical cell according to any one of claims 19 to 22 , wherein the inorganic material is in the form of particles, optionally coated with carbon.

24 . The electrochemical cell according to any one of claims 18 to 23 , wherein the composite material is prepared by mechanofusion.

25 . The electrochemical cell according to any one of claims 13 to 24 , wherein the positive electrode film further comprises a conductive carbon.

26 . The electrochemical cell according to claim 25 , wherein the conductive carbon is a carbon powder or fiber selected from carbon black, activated carbon, graphite, graphene, and mixtures thereof.

27 . The electrochemical cell according to claim 26 , wherein the conductive carbon has a specific surface area of at least 5 m 2 /g, at least 50 m 2 /g, or at least 500 m 2 /g.

28 . The electrochemical cell according to any one of claims 1 to 27 , wherein the electrochemically active material of the negative electrode film comprises a lithium metal foil.

29 . The electrochemical cell according to any one of claims 1 to 27 , wherein the electrochemically active material of the negative electrode film comprises a lithium metal alloy.

30 . The electrochemical cell according to any one of claims 1 to 29 , wherein a surface of the electrochemically active material of the negative electrode film further includes a passivation layer formed in situ.

31 . The electrochemical cell according to any one of claims 1 to 30 , wherein the negative electrode film further comprises a protective layer.

32 . The electrochemical cell according to claim 29 , wherein the lithium metal alloy comprises at least 90% by weight of lithium.

33 . The electrochemical cell according to any one of claims 24 to 32 , wherein the electrochemically active material of the negative electrode film is a film having a thickness from about 5 μm to about 200 μm.

34 . The electrochemical cell according to any one of claims 24 to 33 , wherein the electrochemical cell further comprises an insulator layer adjacent to the negative electrode film.

Assignees

• Hydro Québec
• Hydro Quebec

Inventors

• Zaghib Karim
• Kim Chisu
• Guerfi Abdelbast
• Barray Francis
• Gagnon Catherine
• Trottier Julie

Classifications

• H01M4/667

  in the form of layers, e.g. coatings · CPC title

• H01M10/0587

  of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators · CPC title

• H01M10/058

  Construction or manufacture · CPC title

• H01M4/134

  Electrodes based on metals, Si or alloys · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title