Hybrid solid-state electrolytes and methods of forming the same

Patent metadata

Field	Value
Publication number	US-12580220-B2
Application number	US-202217896821-A
Country	US
Kind code	B2
Filing date	Aug 26, 2022
Priority date	Aug 26, 2022
Publication date	Mar 17, 2026
Grant date	Mar 17, 2026

Abstract

A hybrid solid-state electrolyte layer for use in an electrochemical cell is provided. The hybrid solid-state electrolyte layer includes a polymeric material, a ceramic material, and an interfacial material adhering the polymeric material and the ceramic material. The interfacial material includes a branched copolymer that includes dopamine and a second monomer. The second monomer forms a polymeric moiety in the copolymer that is the same or similar to the polymeric material. In certain variations, the polymeric material defines a polymeric layer, the ceramic material defines a ceramic layer, and the interfacial material defines an interfacial layer that is disposed between the polymeric layer and the ceramic layer. In other variations, the polymeric material defines a polymeric matrix, the ceramic material defines a plurality of ceramic particles dispersed in the polymeric matrix, and the plurality of ceramic particles are coated with the interfacial material.

First claim

What is claimed is:

1 . A hybrid solid-state electrolyte layer for use in an electrochemical cell that cycles lithium ions, the hybrid solid-state electrolyte layer comprising:
a polymeric material defining a polymeric matrix; a solid-state electrolyte ceramic material defining a plurality of solid-state electrolyte ceramic particles, the plurality of solid-state electrolyte ceramic particles dispersed in the polymeric matrix; and an interfacial material adhering the polymeric material and the solid-state electrolyte ceramic material by coating the plurality of solid-state electrolyte ceramic particles, the interfacial material comprising a branched copolymer that comprises dopamine and a second monomer.

2 . The hybrid solid-state electrolyte layer of claim 1 , wherein the hybrid solid-state electrolyte layer comprises:
greater than or equal to about 20 wt. % to less than or equal to about 90 wt. % of the polymeric material; greater than or equal to about 10 wt. % to less than or equal to about 80 wt. % of the solid-state electrolyte ceramic material; and greater than or equal to about 0.01 wt. % to less than or equal to about 1 wt. % of the interfacial material.

3 . The hybrid solid-state electrolyte layer of claim 1 , wherein the hybrid solid-state electrolyte layer has an average thickness greater than or equal to about 5 micrometers to less than or equal to about 200 micrometers.

4 . The hybrid solid-state electrolyte layer of claim 1 , wherein the solid-state electrolyte ceramic particles have an average particle size greater than or equal to about 10 nanometers to less than or equal to about 10 micrometers, and
the interfacial material has an average thickness greater than or equal to about 2 nanometers to less than or equal to about 10 nanometers.

5 . The hybrid solid-state electrolyte layer of claim 1 , wherein the polymeric material is selected from the group consisting of: polyethylene oxide (PEO), poly(methacrylic acid) (PMMA), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP), poly(acrylonitrile) (PAN), poly(2-vinylpyridine) (P2VP), polyethylenimine (PEI), poly(propylene oxide) (PPO), and combinations thereof.

6 . The hybrid solid-state electrolyte layer of claim 1 , wherein the solid-state electrolyte ceramic material is selected from the group consisting of: lithium lanthanum zirconium oxide, lithium lanthanum titanate, lithium zinc germanate, and combinations thereof.

7 . The hybrid solid-state electrolyte layer of claim 1 , wherein the second monomer forms a polymeric moiety in the copolymer selected from the group consisting of: polyethylene oxide (PEO), poly(methacrylic acid) (PMMA), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP), poly(acrylonitrile) (PAN), poly(2-vinylpyridine) (P2VP), polyethylenimine (PEI), poly(propylene oxide) (PPO), and combinations thereof.

8 . The hybrid solid-state electrolyte layer of claim 1 , wherein the solid-state electrolyte ceramic material is selected from the group consisting of: Li 7 La 3 Zr 2 O 12 , Li 0.33 La 0.56 TiO 3 , Li 14 Zn(GeO 4 ) 4 , and combinations thereof.

9 . A hybrid solid-state electrolyte layer for use in an electrochemical cell that cycles lithium ions, the hybrid solid-state electrolyte layer comprising:
a first polymeric material defining a polymeric matrix; a plurality of solid-state electrolyte ceramic material particles; and an interfacial material adhering the polymeric matrix to the solid-state electrolyte ceramic material particles, the interfacial material comprising a branched copolymer that comprises dopamine and a second monomer that forms a second polymeric moiety, wherein the first polymeric material and the second polymeric moiety are the same.

10 . The hybrid solid-state electrolyte layer of claim 9 , wherein the polymeric matrix forms a first layer, the plurality of solid-state electrolyte ceramic material particles form a second layer, and the interfacial material defines a third layer disposed between the first layer and the second layer.

11 . The hybrid solid-state electrolyte layer of claim 10 , wherein the first layer has an average thickness greater than or equal to about 1 micrometer to less than or equal to about 120 micrometers,
the second layer has an average thickness greater than or equal to about 5 micrometers to less than or equal to about 1000 micrometers, and the third layer has an average thickness greater than or equal to about 10 nanometers to less than or equal to about 10 micrometers.

12 . The hybrid solid-state electrolyte layer of claim 9 , wherein the plurality of solid-state electrolyte ceramic material particles is dispersed in the polymeric matrix and the interfacial material coats the solid-state electrolyte ceramic material particles.

13 . The hybrid solid-state electrolyte layer of claim 12 , wherein the polymeric matrix has an average thickness greater than or equal to about 5 micrometers to less than or equal to about 200 micrometers,
the solid-state electrolyte ceramic particles have an average particle size greater than or equal to about 10 nanometers to less than or equal to about 10 micrometers, and the interfacial material has an average thickness greater than or equal to about 2 nanometers to less than or equal to about 10 nanometers.

14 . The hybrid solid-state electrolyte layer of claim 9 , wherein the first polymeric material and the second polymeric moiety are selected from the group consisting of: polyethylene oxide (PEO), poly(methacrylic acid) (PMMA), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP), poly(acrylonitrile) (PAN), poly(2-vinylpyridine) (P2VP), polyethylenimine (PEI), poly(propylene oxide) (PPO), and combinations thereof, and
the ceramic material particles comprise a ceramic material selected from the group consisting of: lithium lanthanum zirconium oxide, lithium lanthanum titanate, lithium zinc germanate, and combinations thereof.

15 . A method for forming a hybrid solid-state electrolyte layer for use in an electrochemical cell that cycles lithium ions, the method comprising:
preparing a receiving surface on a solid-state electrolyte ceramic material, the solid-state electrolyte ceramic material defining a plurality of solid-state electrolyte ceramic particles; and contacting an interfacial material to the receiving surface, the interfacial material comprising a branched copolymer that comprises dopamine and a second polymeric moiety selected from the group consisting of: polyethylene oxide (PEO), poly(methacrylic acid) (PMMA), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP), poly(acrylonitrile) (PAN), poly(2-vinylpyridine) (P2VP), polyethylenimine (PEI), poly(propylene oxide) (PPO), and combinations thereof.

16 . The method of claim 15 , wherein the preparing comprises treating the surface to remove contaminants and passivating materials.

17 . The method of claim 15 , wherein the contacting comprises a solution-based coating process.

18 . The method of claim 15 , wherein the receiving surface is on the ceramic material and the method further comprises:
contacting the interfacial material with a polymeric material.

Assignees

• Gm Global Tech Operations Llc
• Univ Wayne State

Inventors

• Xu Fan
• Schmidt Robert D
• Cai Mei
• Borras Manuela Ferreira
• Zhu Yingxi Elaine

Classifications

• H01M2300/0097

  with adhesive layers · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M2300/0071

  Oxides · CPC title

• Y02E60/10

  Energy storage using batteries · CPC title

• H01M2300/0091

  in the form of mixtures · CPC title