Granted Patent B2

US 12,412,928 · App. 17/710,900 · Granted Sep 9, 2025

Inventors: Qili Su (Shanghai, CN); Zhe Li (Shanghai, CN); Mengyan Hou (Shanghai, CN); Yong Lu (Shanghai, CN); Haijing Liu (Shanghai, CN)

Assignee: GM GLOBAL TECHNOLOGY OPERATIONS LLC

H01M10/0565H01M4/62H01M10/0525H01M2300/0082H01M2300/0085H01M2300/0091

Abstract

Claims (41)

1. An electrochemical cell that cycles lithium ions, the electrochemical cell comprising:

a first electrode comprising a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte, the first polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive comprising a compound having an unsaturated carbon bond, a sulfur-containing compound, a halogen-containing compound, a methyl substituted glycolide derivative, a maleimide (MI), a compound containing an electron withdrawing group, and combinations thereof;

a second electrode comprising a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte that is different from the first polymeric gel electrolyte, the second polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive that is different from the first additive; and

an electrolyte layer disposed between the first electrode and the second electrode, the electrolyte layer comprising a third polymeric gel electrolyte that is different from both the first polymeric gel electrolyte and the second polymeric gel electrolyte.

2. The electrochemical cell of claim 1 , wherein the unsaturated carbon bond containing compound comprises vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and combinations thereof;

the sulfur-containing compound comprises ethylene sulfite(ES), propylene sulfite (PyS), and combinations thereof; and

the halogen-containing compound comprises fluoroethylene carbonate (FEC), chloro-ethylene carbonate (CI-EC), and combinations thereof.

3. The electrochemical cell of claim 1 , wherein the second additive comprises a boron-containing compound, a silicon-containing compound, a phosphorus-containing compound, a compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group, and combinations thereof.

4. The electrochemical cell of claim 3 , wherein the boron-containing compound comprises lithium bis(oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), tris(trimethylsilyl) borate (TMSB), and combinations thereof;

the silicon-containing compound comprises tris(trimethylsilyl)phosphate (TMSP), tris(trimethylsilyl) borate (TMSB), and combinations thereof;

the phosphorus-containing compound comprises triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), and combinations thereof; and

the compound containing at least one of a phenyl group, a thiophene aniline group, a maleimide group, an aniline group, an anisole group, an adamantyl group, a furan group, and a thiophene group comprises biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

5. The electrochemical cell of claim 1 , wherein the first polymeric gel electrolyte and the second polymeric gel electrolyte each further comprises greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host.

6. The electrochemical cell of claim 5 , wherein the first polymeric gel electrolyte and the second polymeric gel electrolyte each comprise a polymer host independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof.

7. The electrochemical cell of claim 1 , wherein the first polymeric gel electrolyte and the second polymeric gel electrolyte each further comprises greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

8. The electrochemical cell of claim 1 , wherein the third polymeric gel electrolyte comprises greater than or equal to about 0.1 wt. % to less than or equal to about 50 wt. % of a polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a liquid electrolyte.

9. The electrochemical cell of claim 8 , wherein the polymer host is selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

10. The electrochemical cell of claim 8 , wherein the electrolyte layer is a free-standing membrane defined by the third polymeric gel electrolyte, wherein the free-standing membrane has a thickness greater than or equal to about 5 micrometers to less than or equal to about 1,000 micrometers.

11. The electrochemical cell of claim 8 , wherein the electrolyte layer further comprises greater than 0 wt. % to less than or equal to about 80 wt. % of a plurality of solid-state electrolyte particles.

12. The electrochemical cell of claim 1 , wherein the electrochemical cell further comprises:

a first bipolar current collector disposed on or adjacent to an exposed surface of the first electrode and parallel with the electrolyte layer;

a second bipolar current collector disposed on or adjacent to an exposed surface of the second electrode and parallel with the electrolyte layer; and

one or more polymer blockers coupled to and extending between the first bipolar current collector and the second bipolar current collector.

13. An electrochemical cell that cycles lithium ions, the electrochemical cell comprising:

a first electrode comprising a first plurality of solid-state electroactive material particles and a first polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a first additive, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a first polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a first liquid electrolyte;

a second electrode comprising a second plurality of solid-state electroactive material particles and a second polymeric gel electrolyte comprising greater than 0 wt. % to less than or equal to about 10 wt. % of a second additive that is different from the first additive and is selected from the group consisting of: lithium bis(oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), tris(trimethylsilyl) borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof, greater than or equal to about 0.1 wt. % to less than or equal to about 15 wt. % of a second polymer host, and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a second liquid electrolyte; and

an electrolyte layer disposed between the first electrode and the second electrode, the electrolyte layer comprising a third polymeric gel electrolyte comprising greater than or equal to about 10 wt. % to less than or equal to about 50 wt. % of a third polymer host and greater than or equal to about 5 wt. % to less than or equal to about 90 wt. % of a third liquid electrolyte.

14. The electrochemical cell of claim 13 , wherein the first liquid electrolyte, the second liquid electrolyte, and the third liquid electrolyte are different.

15. The electrochemical cell of claim 13 , wherein the first polymer host and the second polymer host are independently selected from the group consisting of: poly(ethylene oxide) (PEO), poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP), poly(methyl methacrylate) (PMMA), carboxymethyl cellulose (CMC), polyacrylonitrile (PAN), polyvinylidene difluoride (PVDF), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), lithium polyacrylate (LiPAA), and combinations thereof; and

the third polymer host is selected from the group consisting of: poly(acrylonitrile) (PAN), poly(ethylene oxide) (PEO), poly(ethylene glycol) (PEG), polyethylene carbonate (PEC), poly(trimethylene carbonate) (PTMC), poly(propylene carbonate) (PPC), polyvinylidene difluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP), and combinations thereof.

16. The electrochemical cell of claim 13 , wherein the first additive is selected from the group consisting of: vinylene carbonate (VC), vinyl ethylene carbonate (VEC), ethylene sulfite(ES), propylene sulfite (PyS), fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

17. A method for forming an electrochemical cell that cycles lithium ions, the method comprising:

preparing a first gel-assisted electrode, wherein preparing the first gel-assisted electrode comprises contacting a first precursor electrode and a first precursor liquid comprising a first solvent and a first additive comprising a compound having an unsaturated carbon bond, a sulfur-containing compound, a halogen-containing compound, a methyl substituted glycolide derivative, a maleimide (MI), a compound containing an electron withdrawing group, and combinations thereof and removing the first solvent to form the first gel-assisted electrode;

preparing a second gel-assisted electrode, wherein preparing the second gel-assisted electrode comprises contacting a second precursor electrode and a second precursor liquid comprising a second solvent and a second additive that is different from the first additive, and removing the second solvent to form the second gel-assisted electrode;

preparing an electrolyte layer comprising a third precursor liquid, wherein the first precursor liquid is different from the second and third precursor liquids and the second precursor liquid is different from the first and third precursor liquids; and

stacking the first gel-assisted electrode, the second gel-assisted electrode, and the electrolyte layer to form the electrochemical cell, wherein the electrolyte layer is disposed between the first gel-assisted electrode and the second gel-assisted electrode.

18. The method of claim 17 , wherein

the second additive is selected from the group consisting of: lithium bis(oxalato) borate (LiBOB), lithium difluoro (oxalato) borate (LiDFOB), tris(trimethylsilyl) borate (TMSB), tris(trimethylsilyl)phosphate (TMSP), triphenyl phosphine (TPP), ethyl diphenylphosphinite (EDP), triethyl phosphite (TEP), biphenyl (BP), o-terphenyl (OT), 2,2′-bis[4-(4 maleimidophenoxy)phenyl]propane (BMP), N,N-dimethyl-aniline (DMA), and combinations thereof.

19. The method of claim 17 , wherein the unsaturated carbon bond containing compound comprises vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and combinations thereof;

the sulfur-containing compound comprises ethylene sulfite(ES), propylene sulfite (PyS), and combinations thereof; and

the halogen-containing compound comprises fluoroethylene carbonate (FEC), chloro-ethylene carbonate (Cl-EC), and combinations thereof.

Assignments (1)

Priority Claims (1)

Continuity (1)

References Cited (106)