Polymer electrolyte for a solid state battery

Patent metadata

Field	Value
Publication number	US-12266758-B2
Application number	US-202218058418-A
Country	US
Kind code	B2
Filing date	Nov 23, 2022
Priority date	Nov 23, 2022
Publication date	Apr 1, 2025
Grant date	Apr 1, 2025

Abstract

Provided is a composition containing a redox charge-transfer complex of an electron donor polymer and an electron acceptor compound where the anionic form of the electron acceptor has a reduction potential higher than the reduction potential of the electron donor polymer; at least one metal salt and at least one additive compound having a dielectric constant of 10 or greater. The composition is a free-flowing, substantially amorphous powder and is useful as a metal ion conducting component of electrolytic cells.

First claim

The invention claimed is:

1. A composition, consisting of:
a redox charge-transfer complex of an electron donor polymer and an electron acceptor compound where the anionic form of the electron acceptor compound has a reduction potential higher than a reduction potential of the electron donor polymer;
at least one salt selected from the group consisting of alkali metal salts, alkaline earth metal salts, zinc salts and aluminum salts;
a mixture of high dielectric materials including thietane-1,1-dioxide or an alkyl-substituted thietane-1,1-dioxide and at least one of a cyclic sulfone, a cyclic sultone and a sulfamide; and
optionally, a polymer different from the electron donor polymer, selected from the group consisting of polyalkyl(meth)acrylates, crosslinked-polyalkyl(meth)acrylates, poly(vinylsulfones) and polyacrylonitriles:
wherein
an ionic conductivity of the composition at 25° C. is 0.30 mS/cm or greater,
the composition is stable to oxidation at 4.2 V vs Li/Li + , and
the composition has less than 5% crystallinity, as determined by XRD analysis.

2. The composition of claim 1 , wherein the electron donor polymer comprises aromatic rings bridged with groups having electron donating heteroatoms selected from the group consisting of —O—, —S—, —Se—, —N(R)— and —P(R)—; wherein R is H, methyl or phenyl.

3. The composition of claim 2 , wherein the aromatic rings comprise at least one selected from the group consisting of 1,4-phenylene rings, 2,6-naphthalenyl rings, 4,4′-biphenyl rings and halogenated derivatives of any thereof.

4. The composition of claim 1 , wherein the electron donor polymer is at least one selected from the group consisting of poly(phenylene oxide), poly(2,6-dimethyl-1,4-phenylene oxide), poly(phenylene sulfide), poly[thio(2,3,5,6-tetrafluoro-1,4-phenylene)], fluorinated poly(phenylene sulfide) and poly(phenylene imine).

5. The composition of claim 1 , wherein the electron acceptor compound comprises a benzoquinone structure, a benzenecarbonitrile structure, an aromatic dianhydride structure, a fullerene structure or a metallo-porphine structure.

6. The composition of claim 1 , wherein the electron acceptor compound is at least one selected from the group consisting of tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane, tetrafluoro-1,4-benzoquinone, tetrachloro-1,4-benzoquinone and tetrabromo-1,4-benzoquinone.

7. The composition of claim 1 , wherein the at least one of a cyclic sulfone, a cyclic sultone and a sulfamide is selected from the group consisting of N,N,N′,N′-tetramethylsulfamide; tetrahydro-2,6-dimethyl-2H-1,2,6-thiadiazine-1,1-dioxide; 2,5-dimethyl-1,2,5-thiadiazolidine-1,1-dioxide; N,N′-diethyl-N,N′-dimethylsulfamide; N,N,N′,N′-tetraethylsulfamide; sulfolane; tetrahydro2-methyl-3-isothiazolidinone-1,1-dioxide; -2-methyl-3-isothiazolidinone-1,1-dioxide, and propane sultone.

8. The composition of claim 1 , wherein
a wt % of the redox charge transfer complex is from 25% to 80%,
a wt % of the at least one salt is from 5% to 30%, and
a content of the mixture of high dielectric materials is from 10% to 70 wt %.

9. The composition of claim 1 , comprising the polymer different from the electron donor polymer of the charge transfer complex.

10. The composition of claim 1 , wherein the composition is electrically insulating having an electrical conductivity of 3.0 nS/cm or less.

11. The composition of claim 1 , wherein the ionic conductivity is not changed upon exposure to dry-room air for 16 hours.

12. The composition of claim 1 which is a free flowing powder.

13. A solid state lithium ion battery, comprising:
an anode capable of insertion and extraction of Li + ions;
a cathode capable of insertion and extraction of Li + ions; and
a solid state electrolyte between the anode and cathode, comprising the composition of claim 1 ;
wherein the at least one salt is a lithium salt.

14. The solid state lithium ion battery of claim 13 wherein the anode comprises an active material selected from the group consisting of lithium, a lithium alloy, graphite, hard carbon, lithium titanate (LTO), a tin/cobalt alloy and a silicon/carbon composite.

15. The solid state lithium ion battery of claim 13 wherein the cathode comprises an active material selected from the group consisting of lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ), lithium nickel manganese cobalt oxide (NMC), elemental sulfur and a metal sulfide composite.

16. An electrode for a lithium ion battery, comprising:
an active material capable of insertion and extraction of Li + ions;
a carbon conductive additive;
the composition of claim 1 wherein the at least one salt is a lithium salt; and
a binder.

17. The electrode for a lithium ion battery of claim 16 , wherein
the electrode is a positive electrode, and
the active material is at least one selected from the group consisting of lithium cobalt oxide (LiCoO 2 ), lithium manganese oxide (LiMn 2 O 4 ), lithium iron phosphate (LiFePO 4 ), lithium nickel manganese cobalt oxide, elemental sulfur and a metal sulfide composite.

18. The electrode for a lithium ion battery of claim 16 , wherein
a wt % of the active material is from 40 wt % to 98 wt %, and
a wt % of the composition is from 5 wt % to 50 wt %.

19. The electrode for a lithium ion battery of claim 16 , wherein
the electrode is a negative electrode, and
the active material is at least one selected from the group consisting of lithium, a lithium alloy, graphite, hard carbon, lithium titanate (LTO), a tin/cobalt alloy and a silicon/carbon composite.

20. The electrode for a lithium ion battery of claim 19 , wherein
a wt % of the active material is from 40 wt % to 98 wta,
a wt % of the composition is from 5 wt % to 50 wt %.

Assignees

• Toyota Eng & Mfg North America
• Toyota Motor Co Ltd

Inventors

• Sugiura Ryuta
• Redko Mikhail
• Jones Michael
• Muldoon John G
• Bonnick Patrick J

Classifications

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M4/38

  of elements or alloys · CPC title

• H01M2300/0082

  Organic polymers · CPC title