Lithium metal secondary battery containing a conducting polymer network-based anode-protecting layer

Patent metadata

Field	Value
Publication number	US-11658290-B2
Application number	US-201916404109-A
Country	US
Kind code	B2
Filing date	May 6, 2019
Priority date	May 6, 2019
Publication date	May 23, 2023
Grant date	May 23, 2023

Abstract

Provided is a lithium metal secondary battery comprising a cathode, an anode, an electrolyte-separator assembly disposed between the cathode and the anode, wherein the anode comprises: (a) an anode active material layer containing a layer of lithium or lithium alloy optionally supported by an anode current collector; and (b) an anode-protecting layer in physical contact with the anode active material layer and in ionic contact with the electrolyte-separator assembly, having a thickness from 10 nm to 500 μm and comprising an electrically and ionically conducting network of cross-linked conjugated polymer chains having a lithium ion conductivity from 10−8 to 5×10−2 S/cm and an electron conductivity from 10−8 to 103 S/cm.

First claim

I claim:

1. A lithium metal secondary battery comprising a cathode, an anode, and an electrolyte-separator assembly disposed between said cathode and said anode, wherein said anode comprises:
a) an anode active material layer containing a layer of lithium or lithium alloy having greater than 70% by weight of lithium metal in said lithium alloy, in a form of a foil, coating, or multiple particles aggregated together, as an anode active material; and
b) an anode-protecting layer in physical contact with said anode active material layer and in ionic contact with said electrolyte-separator assembly, wherein said anode-protecting layer has a thickness from 10 nm to 500 μm and comprising an electrically and ionically conducting network of cross-linked polymer chains having a lithium ion conductivity from 10 −8 to 5×10 −2 S/cm and an electron conductivity from 10 −8 to 10 3 S/cm, wherein said conducting network of cross-linked polymer chains comprises a conjugated polymer selected from poly(3-alkylthiophenes), poly(isothianaphthene), alkoxy-substituted poly(p-phenylene vinylene), poly(2,5-bis(cholestanoxy) phenylene vinylene), poly(2,5-dialkoxy) paraphenylene vinylene, poly[(1,4-phenylene-1,2-diphenylvinylene)], poly(3′,7′-dimethyloctyloxy phenylene vinylene), polyparaphenylene, polyparaphenylene, polyparaphenylene sulphide, polyheptadiyne, poly(3-hexylthiophene), poly(3-octylthiophene), poly(3-cyclohexylthiophene), poly(3-methyl-4-cyclohexylthiophene), poly(2,5-dialkoxy-1,4-phenyleneethynylene), poly(2-decyloxy-1,4-phenylene), poly(9,9-dioctylfluorene), polyquinoline, a derivative thereof, a copolymer thereof, a sulfonated version thereof, or a combination thereof;
wherein said conducting network of cross-linked polymer chains further contains from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed therein; and
wherein said lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiClO 4 ), litlithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.

2. A lithium metal secondary battery comprising a cathode, an anode, an electrolyte-separator assembly disposed between said cathode and said anode, wherein said anode comprises:
A) an anode current collector; and
B) an anode-protecting layer supported by said anode current collector and in ionic contact with said electrolyte-separator assembly, wherein said anode-protecting layer has a thickness from 10 nm to 500 μm and comprising an electrically and ionically conducting network of cross-linked polymer chains having a lithium ion conductivity from 10 −8 to 5×10 −2 S/cm and an electron conductivity from 10 −8 to 10 3 S/cm, wherein said conducting network of cross-linked polymer chains comprises a conjugated polymer selected from poly(3-alkylthiophenes), poly(isothianaphthene), alkoxy-substituted poly(p-phenylene vinylene), poly(2,5-bis(cholestanoxy) phenylene vinylene), poly(2,5-dialkoxy) paraphenylene vinylene, poly[(1,4-phenylene-1,2-diphenylvinylene)], poly(3′,7′-dimethyloctyloxy phenylene vinylene), polyparaphenylene, polyparaphenylene, polyparaphenylene sulphide, polyheptadiyne, poly(3-hexylthiophene), poly(3-octylthiophene), poly(3-cyclohexylthiophene), poly(3-methyl-4-cyclohexylthiophene), poly(2,5-dialkoxy-1,4-phenyleneethynylene), poly(2-decyloxy-1,4-phenylene), poly(9,9-dioctylfluorene), polyquinoline, a derivative thereof, a copolymer thereof, a sulfonated version thereof, or a combination thereof;
wherein said conducting network of cross-linked polymer chains further contains from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed therein; and
wherein said lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiClO 4 ), litlithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.

3. The lithium metal secondary battery of claim 1 , wherein said electrolyte is selected from organic liquid electrolyte, ionic liquid electrolyte, polymer gel electrolyte, solid-state electrolyte, quasi-solid electrolyte having a lithium salt dissolved in an organic or ionic liquid with a lithium salt concentration higher than 2.0 M, or a combination thereof.

4. The lithium metal secondary battery of claim 1 , wherein said anode-protecting layer further comprises a liquid solvent that permeates into said conducting network of cross-linked polymer chains to form a conductive polymer gel.

5. The lithium metal secondary battery of claim 2 , wherein said anode-protecting layer further comprises a liquid solvent that permeates into said conducting network of cross-linked polymer chains to form a conductive polymer gel.

6. A lithium metal secondary battery comprising a cathode, an anode, and an electrolyte-separator assembly disposed between said cathode and said anode, wherein said anode comprises:
a) an anode active material layer containing a layer of lithium or lithium alloy having greater than 70% by weight of lithium metal in said lithium alloy, in a form of a foil, coating, or multiple particles aggregated together, as an anode active material; and
b) an anode-protecting layer in physical contact with said anode active material layer and in ionic contact with said electrolyte-separator assembly, wherein said anode-protecting layer has a thickness from 10 nm to 500 μm and comprising an electrically and ionically conducting network of cross-linked polymer chains having a lithium ion conductivity from 10 −8 to 5×10 −2 S/cm and an electron conductivity from 10 −8 to 10 3 S/cm, wherein said conducting network of cross-linked polymer chains further comprises from 0.01% to 50% of an electrically non-conducting reinforcement material dispersed in said conducting network of cross-linked polymer chains to form a conducting network polymer composite, wherein said reinforcement material is selected from a glass fiber, ceramic fiber, polymer fiber, glass particle, ceramic particle, polymer particle, or a combination thereof;
wherein said conducting network of cross-linked polymer chains further contains from 0.1% to 40% by weight of a lithium ion-conducting additive dispersed therein; and
wherein said lithium ion-conducting additive contains a lithium salt selected from lithium perchlorate (LiClO 4 ), litlithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-methanesulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphate (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lith

Assignees

• Nanotek Instruments Inc
• Global Graphene Group Inc

Inventors

• Jang Bor Z

Classifications

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M10/4235

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M10/052 Primary

  Li-accumulators · CPC title