Prelithiated current collector and secondary lithium cells containing same

Patent metadata

Field	Value
Publication number	US-9385397-B2
Application number	US-201113199058-A
Country	US
Kind code	B2
Filing date	Aug 19, 2011
Priority date	Aug 19, 2011
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

The present invention provides a battery or supercapacitor current collector which is prelithiated. The prelithiated current collector comprises: (a) an electrically conductive substrate having two opposed primary surfaces, and (b) a mixture layer of carbon (and/or other stabilizing element, such as B, Al, Ga, In, C, Si, Ge, Sn, Pb, As, Sb, Bi, Te, or a combination thereof) and lithium or lithium alloy coated on at least one of the primary surfaces, wherein lithium element is present in an amount of 1% to 99% by weight of the mixture layer. This current collector serves as an effective and safe lithium source for a wide variety of electrochemical energy storage cells, including the rechargeable lithium cell (e.g. lithium-metal, lithium-ion, lithium-sulfur, lithium-air, lithium-graphene, lithium-carbon, and lithium-carbon nanotube cell) and the lithium ion based supercapacitor cell (e.g, symmetric ultracapacitor, asymmetric ultracapacitor, hybrid supercapacitor-battery, or lithium-ion capacitor).

First claim

The invention claimed is:

1. A lithium cell or electrochemical cell containing an anode current collector or cathode current collector, an anode active material layer, a cathode active material layer, a separator between said anode active material layer and said cathode active material layer, and electrolyte in ionic contact with said anode active material layer and cathode active material layer, wherein said anode current collector or cathode current collector is a prelithiated current collector, separate from said anode active material layer or cathode active material layer, comprising:
(a) an electrically conductive substrate having two opposed primary surfaces, and
(b) a mixture layer of lithium or lithium alloy co-deposited with a lithium-stabilizing agent;
said mixture layer being coated on at least one of said primary surfaces, wherein lithium element in said mixture layer is present in an amount of 1% to 99% by weight of the mixture layer and said mixture layer is air stable, not reacting with oxygen or moisture in the air;
wherein said anode active material layer or cathode active material layer is a separate, discrete, continuous layer apart from said mixture layer and wherein said lithium cell contains no unstable lithium metal phase, no lithium metal particles, and no prelithiated anode active material when the lithium cell is made.

2. The lithium cell of claim 1 , wherein the lithium-stabilizing agent is selected from an element in the group consisting of B, Al, Ga, In, C, Si, Ge, Sn, Pb, As, Sb, Bi, Te, and combinations thereof.

3. The lithium cell of claim 1 , wherein said lithium-stabilizing agent is carbon (C).

4. The lithium cell of claim 3 , wherein said mixture layer of carbon and lithium or lithium alloy further comprises an element selected from alkali metal, alkaline earth metal, transition metal, boron (B), aluminum (Al), gallium (Ga), indium (In), tin (Sn), silicon (Si), germanium (Ge), lead (Pb), selenium (Se), antimony (Sb), or bismuth (Bi).

5. The lithium cell of claim 1 , wherein said carbon in said mixture layer is amorphous carbon.

6. The lithium cell of claim 1 , wherein said lithium-stabilizing agent is selected from B, Al, Ga, In, C, Si, Ge, Sn, Pb, As, Sb, Bi, Te, a transition metal, or a combination thereof; said mixture layer being coated on both primary surfaces.

7. The lithium cell of claim 1 , wherein said prelithiated current collector further comprises a discrete carbon layer deposited on said mixture layer.

8. The lithium cell of claim 7 , wherein said conductive substrate is selected from a graphite layer, flexible graphite foil, foil of graphene sheets, foil of graphene oxide sheets, copper foil, nickel foil, stainless steel foil, nickel-coated stainless steel foil, copper-coated steel foil, titanium foil, chrome plated steel sheet, aluminum foil, carbon-coated aluminum foil, metal-coated polymer film, intrinsically conductive polymer film, conductive filler-polymer composite film, a porous nano-structured layer composed of graphene, graphene oxide, graphene fluoride, doped graphene, doped graphene oxide, carbon nano-fiber, carbon nano-tube, carbon black, activated carbon, disordered carbon, soft carbon, hard carbon, meso-phase carbon, nano carbon particle, and/or nano graphite particle, or a combination thereof.

9. The lithium cell of claim 7 , wherein said mixture layer of carbon and lithium or lithium alloy further comprises an element selected from alkali metal, alkaline earth metal, transition metal, boron (B), aluminum (Al), gallium (Ga), indium (In), tin (Sn), silicon (Si), germanium (Ge), lead (Pb), selenium (Se), antimony (Sb), or bismuth (Bi).

10. The lithium cell of claim 7 , wherein said mixture layer or said carbon layer is a continuous-length layer.

11. The lithium cell of claim 7 , wherein said mixture layer and said carbon layer do not fully cover said at least one primary surface, leaving an amount of exposed substrate surface free from the mixture of lithium or lithium alloy and a lithium-stabilizing agent.

12. The lithium cell of claim 7 wherein said prelithiated current collector is a cathode current collector.

13. The lithium-ion battery of claim 12 , wherein said cathode contains a lithium-free cathode active material selected from sulfur, a chalcogen compound, TiS 2 , MoS 2 , MnO 2 , CoO 2 , VO 2 , V 2 O 5 , V 3 O 8 , V 4 O 9 , V 6 O 13 , transition metal oxide, a non-lithiated intercalation compound, or a combination thereof.

14. A rechargeable lithium-metal battery containing an anode current collector of claim 7 , a porous anode, a separator and electrolyte in contact with said anode, a cathode in contact with said electrolyte, and a cathode current collector in contact with said cathode.

15. A rechargeable lithium cell containing an anode current collector as defined in claim 7 , wherein said cell is selected from
(a) A lithium-sulfur cell, comprising a nano-structured porous anode, a separator and electrolyte, a sulfur cathode, and a cathode current collector;
(b) A lithium-air cell, comprising a nano-structured porous anode, a separator and electrolyte, and an air cathode;
(c) A lithium-graphene cell, comprising a nano-structured porous anode, a separator and electrolyte, a cathode comprising nano sheets of graphene, graphene oxide, graphene fluoride, doped graphene, and/or doped graphene oxide;
(d) A lithium-carbon cell, comprising a nano-structured porous anode, a separator and electrolyte, a cathode comprising carbon nano-fiber, carbon nano-tube, carbon black, activated carbon, disordered carbon, soft carbon, hard carbon, meso-phase carbon, nano carbon particle, and/or nano graphite particle; or
(e) A symmetric ultracapacitor, asymmetric ultracapacitor cell, hybrid supercapacitor-battery cell, or lithium-ion capacitor cell, comprising an anode, a separator and electrolyte, and a cathode, wherein the anode and/or the cathode contains a porous nano-structure composed of graphene, graphene oxide, graphene fluoride, doped graphene, doped graphene oxide, carbon nano-fiber, carbon nano-tube, carbon black, activated carbon, disordered carbon, soft carbon, hard carbon, meso-phase carbon, nano carbon particle, and/or nano graphite particle.

16. The lithium cell of claim 1 , wherein the mixture layer of lithium or lithium alloy and the lithium-stabilizing agent is coated on each of said two primary surfaces.

17. The lithium cell of claim 16 , further comprising a carbon layer deposited on said mixture layer coated on at least one of the two primary surfaces.

18. The lithium cell of claim 1 , wherein said mixture layer has a thickness in the range of from 0.1 nm to 25 μm.

19. The lithium cell of claim 1 , wherein said mixture layer has a thickness less than 1 μm.

20. The lithium cell of claim 1 , wherein said mixture layer has a pattern of solid material regions and perforations or mixture material-free regions.

21. The lithium cell of claim 1 , wherein said conductive substrate is selected from a graphite layer, flexible graphite foil, foil of graphene sheets, foil of graphene oxide sheets, copper foil, nickel foil, stainless steel foil, nickel-coated stainless steel foil, copper-coated steel foil, titanium foil, chrome plated steel sheet, aluminum foil, carbon-coated aluminum foil, metal-coated polymer film, intrinsically conductive polymer film, conductive filler-polymer composite film, a porous nano-structured layer composed of graphene, graphene oxide, graphene fluoride, doped graphene, doped graphene oxide, carbon nano-fiber, carbo

Assignees

• Zhamu Aruna
• Wang Yanbo
• Jang Bor Z
• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• Wang Yanbo
• Jang Bor Z

Classifications

• B32B2457/10

  Batteries · CPC title

• H01M4/0459

  Electrochemical doping, intercalation, occlusion or alloying · CPC title

• Y02P70/54

  Cross-Sectional Technologies · mapped topic

• B32B15/013

  one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium · CPC title

• H01M12/08

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title