IP Library Granted Patent US 12,412,901
Granted Patent B2
US 12,412,901 · App. 16/524,690 · Granted Sep 9, 2025

Interfacial bonding layer for an anode-free solid-state-battery

Inventors: Ken Ogata (Kanagawa, JP); Yang Yang (Kanagawa, JP); Hajime Hoshi (Kanagawa, JP); Masatsugu Nakano (Kanagawa, JP); Hiroshi Imoto (Kanagawa, JP)
Assignee: TeraWatt Technology Inc.
H01M4/628H01M10/0565H01M10/0585H01M50/461H01M2300/0085
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Quick Facts
Patent No.
US 12,412,901
App. No.
16/524,690
Granted
Sep 9, 2025
Kind
B2
Abstract

An anode-free solid-state battery may include a cathode layer; an anode current collector layer; and a separator layer between the cathode layer and the anode current collector layer. The battery can further include an anti-dendrite layer located between the separator layer and the anode current collector layer. The battery further includes an interfacial bonding layer located between the anti-dendrite layer and the anode current collector layer. The interfacial bonding layer increases an amount of electrical connectivity between the anode current collector layer. A first amount of adhesion between the interfacial bonding layer and the anode current collector layer can be greater than a second amount of adhesion between the anti-dendrite layer and the interfacial bonding layer.

Claims (77)

1. An anode-free solid-state battery, comprising:

a cathode layer comprising lithium ions;

an anode current collector layer comprising copper;

a lithium-gel separator layer between the cathode layer and the anode current collector layer, wherein the lithium-gel separator layer comprises:

a scaffolding material having spaces within the scaffolding material; and

a lithium gel formed from a liquid electrolyte filled in the spaces and comprising a salt, a solvent, and a cross-linked polymer of a polymer additive and a cross-linker additive;

an anti-dendrite layer located between the lithium-gel separator layer and the anode current collector layer, wherein the anti-dendrite layer comprises one or more materials selected from the group consisting of: carbon black; acetylene black; ketchen black; silver; zinc; gold; bismuth; tin; polymide (PI); polyacrylic acid (PAA); and carboxymethyl cellulose styrene-butadiene rubber (CMC-SBR), the anti-dendrite layer discourages dendrite formation; and

an interfacial bonding layer located between the anti-dendrite layer and the anode current collector layer, wherein:

the interfacial bonding layer is in direct contact on a first side with the anode current collector layer;

the interfacial bonding layer consists of a conductive agent, metal particles, and a binder material, wherein the binder material is selected from the group consisting of polyvinylidene fluoride (PvDF), styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC), poly(acrylic acid) (PAA), and any combinations thereof, the conductive agent is selected from the group consisting of acetylene black, carbon black, and a combination thereof, the metal particles are selected from the group consisting of Bi particles, Sn particles, Ag particles, Au particles, Pt particles, and any combinations thereof, the interfacial bonding layer is free from lithium and encourages formation of lithium deposits between the interfacial bonding layer and the anti-dendrite layer;

the interfacial bonding layer increases an amount of electrical connectivity between the anode current collector layer and lithium deposited on the interfacial bonding layer during charging of the anode-free solid-state battery;

a first amount of adhesion between the interfacial bonding layer and the anode current collector layer is greater than a second amount of adhesion between the anti-dendrite layer and the interfacial bonding layer; and

a lithium metal layer plates between the anti-dendrite layer and the interfacial bonding layer when the anode-free solid-state battery is charging.

2. The anode-free solid-state battery of claim 1 , wherein the anti-dendrite layer is formed of an alloy of one or more metals selected from the group consisting of: silver; zinc; gold; bismuth; and tin.

3. The anode-free solid-state battery of claim 1 , wherein the scaffolding material has a spider-web structure.

4. The anode-free solid-state battery of claim 1 , wherein:

the salt, the polymer additive, and the cross-linker additive are dissolved into the solvent to form the liquid electrolyte;

the liquid electrolyte is dispersed in the spaces throughout the scaffolding material; and

the liquid electrolyte, after being dispersed throughout the scaffolding material is converted to the lithium gel.

5. The anode-free solid-state battery of claim 1 , wherein:

the interfacial bonding layer is between 0.05 μm and 5 μm; and

the anti-dendrite layer is between 0.05 micrometers and 10 micrometers in thickness.

6. A method for creating an anode-free solid-state battery, the method comprising:

depositing an interfacial bonding layer onto an anode current collector layer;

creating a lithium-gel separator layer;

depositing an anti-dendrite layer onto the lithium-gel separator layer;

layering a cathode and cathode current collector onto the lithium-gel separator layering the anti-dendrite layer onto the interfacial bonding layer, wherein:

a first amount of adhesion between the anti-dendrite layer and the interfacial bonding layer is less than a second amount of adhesion between the interfacial bonding layer and the anode current collector layer; and

the interfacial bonding layer increases an amount of electrical connectivity between the anode current collector layer and lithium deposited on the interfacial bonding layer; and

wherein the anode current collector layer comprises copper;

wherein the cathode layer comprises lithium ions;

wherein the anti-dendrite layer comprises one or more materials selected from the group consisting of: carbon black; acetylene black; ketchen black; silver; zinc; gold; bismuth; tin; polymide (PI); polyacrylic acid (PAA); and carboxymethyl cellulose styrene-butadiene rubber (CMC-SBR);

wherein the lithium-gel separator layer comprises:

a scaffolding material having spaces within the scaffolding material; and

a lithium gel formed from a liquid electrolyte filled in the spaces and comprising a salt, a solvent, and across-linked polymer of a polymer additive and a cross-linker additive;

wherein the interfacial bonding layer:

is in direct contact on a first side with the anode current collector layer;

consists of a conductive agent, metal particles, and a binder material, wherein the binder material is selected from the group consisting of polyvinylidene fluoride (PvDF), styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC), poly(acrylic acid) (PAA), and any combinations thereof, the conductive agent is selected from the group consisting of acetylene black, carbon black, and a combination thereof, the metal particles are selected from the group consisting of Bi particles, Sn particles, Ag particles, Au particles, Pt particles, and any combinations thereof, the interfacial bonding layer is free from lithium and encourages formation of lithium deposits between the interfacial bonding layer and the anti-dendrite layer; and

a lithium metal layer plates between the anti-dendrite layer and the interfacial bonding layer when the anode-free solid-state battery is charging.

7. The method for creating the anode-free solid-state battery of claim 6 , wherein a presence of the interfacial bonding layer decreases an impedance of the anode-free solid-state battery.

8. The method for creating the anode-free solid-state battery of claim 6 , wherein creating the lithium-gel separator layer comprises:

attaching a first adhesive layer to scaffolding material wherein the scaffolding material defines voids within the scaffolding material;

attaching a second adhesive layer to the scaffolding material; and

permeating the liquid electrolyte into the spaces within the scaffolding material.

9. The method for creating the anode-free solid-state battery of claim 8 , wherein the anti-dendrite layer is deposited onto the lithium-gel separator layer prior to the liquid electrolyte being permeated into the spaces within the scaffolding material.

10. The method for creating the anode-free solid-state battery of claim 8 , wherein creating the lithium-gel separator layer further comprises:

after permeating the liquid electrolyte into the spaces within the scaffolding material, applying heat to the lithium-gel separator layer that causes the liquid electrolyte to become the lithium gel.

11. The method for creating the anode-free solid-state battery of claim 6 , wherein the anti-dendrite layer consists of an alloy of one or more metals selected from the group consisting of: silver; zinc; gold; bismuth; and tin.

12. A pouch-style anode-free solid-state battery, comprising:

a flexible pouch;

a cathode layer comprising lithium ions;

an anode current collector layer comprising copper;

a lithium-gel separator layer between the cathode layer and the anode current collector layer, wherein the lithium-gel separator layer comprises:

a scaffolding material having spaces within the scaffolding material; and

a lithium gel formed from a liquid electrolyte filled in the spaces and comprising a salt, a solvent, and a cross-linked polymer of a polymer additive and a cross-linker additive;

an anti-dendrite layer located between the lithium-gel separator layer and the anode current collector layer, wherein the anti-dendrite layer comprises one or more materials selected from the group consisting of: carbon black; acetylene black; ketchen black; silver; zinc; gold; bismuth; tin; polymide (PI); polyacrylic acid (PAA); and carboxymethyl cellulose styrene-butadiene rubber (CMC-SBR), the anti-dendrite layer discourages dendrite formation; and

an interfacial bonding layer located between the anti-dendrite layer and the anode current collector layer, wherein:

the interfacial bonding layer is in direct contact on a first side with the anode current collector layer;

the interfacial bonding layer consists of a conductive agent, metal particles, and a binder material, wherein the binder material is selected from the group consisting of polyvinylidene fluoride (PvDF), styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC), poly(acrylic acid) (PAA), and any combinations thereof, the conductive agent is selected from the group consisting of acetylene black, carbon black, and a combination thereof, the metal particles are selected from the group consisting of Bi particles, Sn particles, Ag particles, Au particles, Pt particles, and any combinations thereof, the interfacial bonding layer is free from lithium and encourages formation of lithium deposits between the interfacial bonding layer and the anti-dendrite layer;

the interfacial bonding layer increases an amount of electrical connectivity between the anode current collector layer and lithium deposited on the interfacial bonding layer;

a first amount of adhesion between the interfacial bonding layer and the anode current collector layer is greater than a second amount of adhesion between the anti-dendrite layer and the interfacial bonding layer;

the cathode layer, the anode current collector layer, the lithium-gel separator layer, the anti-dendrite layer, and the interfacial bonding layer are inserted within the flexible pouch; and

a lithium metal layer plates between the anti-dendrite layer and the interfacial bonding layer when the anode-free solid-state battery is charging.

13. The pouch-style anode-free solid-state battery of claim 12 , wherein the conductive agent is in a form of carbon particles with an average size from 3 nm to 20 nm.

14. The anode-free solid-state battery of claim 1 , wherein the binder material is selected from the group consisting of styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC), poly(acrylic acid) (PAA), and a combination thereof.

15. The pouch-style anode-free solid-state battery of claim 12 , wherein the binder material is selected from the group consisting of styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC), poly(acrylic acid) (PAA), and a combination thereof.

16. The anode-free solid-state battery of claim 1 , wherein

the lithium-gel separator layer functions as a solid electrolyte; and

the scaffolding material has a porosity of between 10% and 90%.

17. The anode-free solid-state battery of claim 1 , wherein the polymer additive comprises Poly (4-vinylpyridine) (P4VP); and the cross-linker additive is selected from the group consisting of N,N,N′,N′-Tetra(trifluoromethanesulfonyl)-dodecane-1,12-diamine (C12TFSA), N,N,N′,N′-Tetra(trifluoromethanesulfonyl)-hexane-1,6-diamine (C6TFSA), and a combination thereof.

18. The pouch-style anode-free solid-state battery of claim 12 , wherein

the lithium-gel separator layer functions as a solid electrolyte; and

the scaffolding material has a porosity of between 10% and 90%.

19. The pouch-style anode-free solid-state battery of claim 12 , wherein the anti-dendrite layer consists of an alloy of one or more metals selected from the group consisting of silver; zinc; gold; bismuth; and tin.

20. The pouch-style anode-free solid-state battery of claim 12 , wherein the polymer additive comprises Poly (4-vinylpyridine) (P4VP); and the cross-linker additive is selected from the group consisting of N,N,N′,N′-Tetra(trifluoromethanesulfonyl)-dodecane-1,12-diamine (C12TFSA), N,N,N′,N′-Tetra(trifluoromethanesulfonyl)-hexane-1,6-diamine (C6TFSA), and a combination thereof.

21. The anode-free solid-state battery of claim 1 , wherein the binder material is styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC).

22. The pouch-style anode-free solid-state battery of claim 12 , wherein the binder material is styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC).

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2020
From: OGATA, KEN; HOSHI, HAJIME; NAKANO, MASATSUGU; IMOTO, HIROSHI
To: CHONGQING JINKANG NEW ENERGY AUTOMOBILE CO., LTD.; SF MOTORS INC.
Reel/Frame 053125/0892 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2020
From: YANG, YANG
To: SF MOTORS, INC.
Reel/Frame 053126/0245 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2020
From: CHONGQING JINKANG NEW ENERGY AUTOMOBILE CO., LTD.
To: SF MOTORS, INC.
Reel/Frame 053126/0483 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 6, 2020
From: SF MOTORS, INC.
To: TERAWATT TECHNOLOGY INC.
Reel/Frame 053126/0658 →
Continuity (1)
Related Publication 20210036327A1 · Feb 4, 2021
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