Anode-free rechargeable battery

Patent metadata

Field	Value
Publication number	US-2016261000-A1
Application number	US-201414482312-A
Country	US
Kind code	A1
Filing date	Sep 10, 2014
Priority date	Sep 10, 2014
Publication date	Sep 8, 2016
Grant date	—

Abstract

An anode-free rechargeable battery is disclosed. The battery includes an anode current collector and a cathode containing an active cation M n+ , where n=1, 2, or 3. The anode-free rechargeable battery further includes a separator placed between the anode current collector and the cathode. The anode-free rechargeable battery also includes an electrolyte including a salt or salt mixture containing an active cation M n+ dissolved in a solvent or solvent mixture.

First claim

We claim:

1 . An anode-free rechargeable battery comprising:
a. an anode current collector; b. a cathode containing an active cation M n+ , where n=1, 2, or 3; c. a separator placed between the anode current collector and the cathode; and d. an electrolyte including a salt or salt mixture dissolved in a solvent, solvent mixture or polymer.

2 . The anode-free rechargeable battery of claim 1 wherein the active cation M n+ is the lithium cation (Li + ).

3 . The anode-free rechargeable battery of claim 1 wherein the active cation M n+ is selected from Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ , Al 3+ , or Ag + .

4 . The anode-free rechargeable battery of claim 1 wherein the separator is infused with the electrolyte including the M n+ salt dissolved in the solvent.

5 . The anode-free rechargeable battery of claim 1 wherein the concentration of the M n+ is between 1.1-8 M.

6 . The anode-free rechargeable battery of claim 1 wherein the separator is a porous polymer material.

7 . The anode-free rechargeable battery of claim 1 wherein the battery has a Coulombic Efficiency of at least 95% after the first cycle.

8 . The anode-free rechargeable battery of claim 2 wherein the separator is infused with the electrolyte including the lithium salt dissolved in the solvent.

9 . The anode-free rechargeable battery of claim 8 wherein the concentration of the lithium salt is between 1.1-8 M.

10 . The anode-free rechargeable battery of claim 8 wherein the lithium salt of the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), or a mixture thereof.

11 . The anode-free rechargeable battery of claim 10 wherein at least one of the following non-lithium salts are added to the lithium salts: CsFSI, CsTFSI, NaFSI—CsFSI, Mg(TFSI) 2 —CsTFSI, and Zn(TFSI) 2 .

12 . The anode-free rechargeable battery of claim 8 wherein the solvent of the electrolyte is an ether or solvent mixture which comprises 1,2-dimethoxyethane (DME), diglyme, triglyme, tetraglyme, diethyl ether, 1,3-dioxolane, 1,4-dioxane, tetrahydrofuran, 2,5-dimethyltetrahydrofuran, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, tris(2,2,2-trifluoroethyl)phosphite, dimethyl sulfone, ethyl methyl sulfone, sulfolane, sulfoxide, acetonitrile, propionitrile, butyronitrile, or a mixture thereof.

13 . The anode-free rechargeable battery of claim 8 wherein the lithium salt of the electrolyte is LiFSI dissolved in the DME solvent, and wherein the concentration of the LiFSI in the DME is between 1.1-8 M.

14 . The anode-free rechargeable battery of claim 8 wherein the anode current collector comprises copper, nickel, iron, stainless steel or other metals that are stable when in contact with Li and the electrolyte between the operating voltage window of the battery.

15 . The anode-free rechargeable battery of claim 14 wherein the anode current collector comprises copper, and the cathode is a free standing film including lithium-containing compounds mixed with a conductive additive and binder.

16 . The anode-free rechargeable battery of claim 14 further comprising a cathode current collector, and wherein the anode current collector comprises copper, the cathode includes lithium-containing compounds mixed with a conductive additive and binder, and the cathode current collector comprises aluminum, nickel or stainless steel.

17 . The anode-free rechargeable battery of claim 9 wherein the battery has a Coulombic Efficiency of at least 95% after the first cycle.

18 . The anode-free rechargeable battery of claim 9 wherein the anode current collector is pre-lithiated to compensate for Li loss during cycling.

19 . The anode-free rechargeable battery of claim 9 wherein the cathode is over-lithiated with lithium to compensate for Li loss during cycling.

20 . An electrolyte comprising 2.5-8 M concentration of lithium salt LiFSI dissolved in a DME solvent to enable dendrite free Li deposition with a Coulombic efficiency greater than about 95% at current densities greater than about 3 mAh/cm 2 .

21 . A method of forming an anode-free rechargeable battery comprising:
a. forming an anode current collector and a cathode; and b. placing a separator between the anode current collector and the cathode, wherein the separator is infused with an electrolyte including a lithium salt dissolved in a non-aqueous solvent or polymer; wherein an anode is formed in situ on an surface of the anode current collector facing the separator during the charging process of the battery, and wherein the anode is consumed during a discharging process of the battery.

22 . The method of claim 21 wherein the concentration of the lithium salt is between 1.1-8 M.

23 . The method of claim 21 wherein the separator is a porous polymer material.

24 . The method of claim 23 wherein the porous polymer material includes a ceramic coating.

25 . The method of claim 21 wherein the lithium salt of the electrolyte comprises LiFSI, LiAsF 6 , LiCF 3 SO 3 , LiTFSI, LiBOB, LiDFOB, LiClO 4 , LiBF 4 , or a mixture thereof.

26 . The method of claim 21 wherein the non-aqueous solvent of the electrolyte is an ether or solvent mixture which comprises DME, diglyme, triglyme, tetraglyme, diethyl ether, 1,3-dioxolane, 1,4-dioxane, tetrahydrofuran, 2,5-dimethyltetrahydrofuran, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, vinylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tris(2,2,2-trifluoroethyl)phosphate, tris(2,2,2-trifluoroethyl)phosphite, dimethyl sulfone, ethyl methyl sulfone, sulfolane, sulfoxide, acetonitrile, propionitrile, butyronitrile, or a mixture thereof.

27 . The method of claim 21 wherein the lithium salt of the electrolyte is LiFSI dissolved in a DME solvent, and wherein the concentration of the LiFSI in the DME is between 3-8 M.

28 . The method of claim 21 wherein the anode current collector comprises copper, nickel, iron, or other metals that are stable when in contact with Li and the electrolyte within an operating voltage window and operating temperature range of the battery.

29 . The method of claim 21 wherein the anode current collector comprises copper, and the cathode is a free standing film including lithium containing compounds mixed with a conductive additive and binder.

30 . The method of claim 21 further comprising a cathode current collector, wherein the anode current collector comprises copper, the cathode includes lithium containing compounds mixed with a conductive additive and binder, and the cathode current collector comprises aluminum.

31 . The method of claim 21 further comprising a cathode current collector, wherein the anode current collector comprises nickel, the cathode inclu

Assignees

• Battelle Memorial Institute

Inventors

• Zhang Ji-Guang
• Qian Jiangfeng
• Xu Wu
• Henderson Wesley A

Classifications

• H01M4/0445 Primary

  Forming after manufacture of the electrode, e.g. first charge, cycling · CPC title

• H01M2004/028

  Positive electrodes · CPC title

• H01M10/0525 Primary

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M10/0565

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M4/525

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title