Electrode material, electrode and solid-state battery comprising a complex oxide with an olivine structure

Patent metadata

Field	Value
Publication number	US-2019363363-A1
Application number	US-201816482924-A
Country	US
Kind code	A1
Filing date	Feb 2, 2018
Priority date	Feb 2, 2017
Publication date	Nov 28, 2019
Grant date	—

Abstract

Described are positive electrode materials comprising at least one complex oxide of olivine structure, the complex oxide comprising a transition metal in oxidation state III, the positive electrodes comprising them and their manufacturing processes. Electrochemical cells comprising these electrodes, a polymer electrolyte and a negative electrode are also contemplated.

First claim

1 . A positive electrode material comprising at least one complex oxide of olivine structure, the complex oxide comprising a transition metal in oxidation state III.

2 . The positive electrode material according to claim 1 , wherein the complex oxide is of formula MXO 4 , wherein M is at least one transition metal of oxidation III, and X is selected from the elements S, P, Si, B and Ge.

3 . The positive electrode material according to claim 2 , wherein M is Fe, Ni, Mn or Co or a combination of at least two thereof.

4 . The positive electrode material according to claim 2 or 3 , wherein X is P or Si, preferably X is P.

5 . The positive electrode material according to claim 4 , wherein X is P.

6 . The positive electrode material according to any one of claims 1 to 5 , wherein the complex oxide is iron(III) phosphate of olivine structure, wherein the iron(III) is optionally partly replaced with an element selected from Ni, Mn, and Co, or a combination thereof.

7 . The positive electrode material according to claim 6 , wherein the complex oxide is FePO 4 .

8 . The positive electrode material according to any one of claims 1 to 7 , wherein the complex oxide is in the form of particles.

9 . The positive electrode material according to claim 8 , wherein the particles comprise microparticles.

10 . The positive electrode material according to claim 8 , wherein the particles comprise nanoparticles.

11 . The positive electrode material according to any one of claims 1 to 10 , further comprising an electronically conductive material.

12 . The positive electrode material according to claim 11 , wherein the electronically conductive material comprises carbon black, Ketjen® carbon, Shawinigan carbon, graphite, graphene, carbon nanotubes, carbon fibers (such as vapor grown carbon fibers (VGCF)), non-powdery carbon obtained by carbonization of an organic precursor, or a combination of at least two thereof.

13 . The positive electrode material according to claim 12 , wherein the electronically conductive material comprises carbon black.

14 . The positive electrode material according to claim 12 or 13 , wherein the electronically conductive material comprises carbon fibers.

15 . The positive electrode material according to any one of claims 1 to 14 , further comprising a binder.

16 . The positive electrode material according to claim 15 , wherein the binder comprises a linear, branched and/or crosslinked polyether polymer binder, a water-soluble binder, a fluorinated polymer binder, or one of their combinations.

17 . The positive electrode material according to claim 16 , wherein the linear, branched and/or crosslinked polyether polymer binder is selected from polymers based on poly(ethylene oxide) (PEO), on poly(propylene oxide) (PPO) or a mixture thereof, optionally comprising crosslinkable units.

18 . The positive electrode material according to claim 16 , wherein the water-soluble binder is selected from SBR (styrene-butadiene rubber), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber), and their mixtures, and optionally comprising CMC (carboxymethylcellulose).

19 . The positive electrode material according to claim 16 , wherein the fluorinated polymer binder is selected from PVDF (polyvinylidene fluoride) and PTFE (polytetrafluoroethylene).

20 . The positive electrode material according to claim 17 , wherein the binder is crosslinked, the complex oxide is FePO 4 , said material further comprising a salt and an electronically conductive material.

21 . A process for the preparation of a positive electrode comprising a positive electrode material as defined in any one of claims 1 to 20 , the process comprising the steps of:
a) mixing the complex oxide and an electronically conductive material in the presence of a solvent;
b) applying the mixture obtained in (a) on a support; and
c) drying of the mixture applied in (b).

22 . The process according to claim 21 , wherein the support is a current collector.

23 . The process according to claim 21 or 22 , wherein step (a) further comprises adding a binder or a polymer binder precursor (e.g. monomer or oligomer).

24 . The process according to claim 23 , wherein step (a) comprises adding a polymer binder precursor based on a polyether polymer and a crosslinking agent, the process comprising a crosslinking step before, during and/or after step (c).

25 . A positive electrode comprising a positive electrode material as defined in any one of claims 1 to 20 or obtained by a process as defined in any one of claims 21 to 24 .

26 . An electrochemical cell comprising a positive electrode as defined in claim 25 , an electrolyte, and a negative electrode.

27 . The electrochemical cell according to claim 26 , wherein the negative electrode comprises a film of metallic lithium or of an alloy comprising at least 90% by weight of lithium.

28 . The electrochemical cell according to claim 26 , wherein the negative electrode comprises a complex oxide electrochemically compatible with the complex oxide of the positive electrode (for example, a lithium titanate).

29 . The electrochemical cell according to any one of claims 26 to 28 , wherein the electrolyte is a film comprising a salt dissolved in a polar and solvating solid polymer.

30 . The electrochemical cell according to claim 29 , wherein the salt is selected from LiTFSI, LiPF 6 , LiDCTA, LiBETI, LiFSI, LiBF 4 , LiBOB, and their combinations.

31 . The electrochemical cell according to claim 29 or 30 , wherein the polar and solvating solid polymer is a linear, branched and/or crosslinked polyether polymer.

32 . The electrochemical cell according to claim 31 , wherein the linear, branched and/or crosslinked polyether polymer is based on poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), or a mixture of both, and optionally crosslinkable units.

33 . The electrochemical cell according to any one of claims 26 to 32 , wherein the positive electrode comprises a binder, said binder being composed of a polymer identical to a polymer used in the composition of the electrolyte film.

Assignees

• Hydro Quebec

Inventors

• Zaghib Karim
• Armand Michel
• Guerfi Abdelbast
• Bouchard Patrick
• Dontigny Martin
• Hamel-Pâquet Julie
• Hovington Pierre

Classifications

• H01M2300/0082

  Organic polymers · CPC title

• H01M4/625

  Carbon or graphite · CPC title

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M4/136

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

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title