Anode-free rechargeable battery

Patent metadata

Field	Value
Publication number	US-10367189-B2
Application number	US-201414482312-A
Country	US
Kind code	B2
Filing date	Sep 10, 2014
Priority date	Sep 10, 2014
Publication date	Jul 30, 2019
Grant date	Jul 30, 2019

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 assembled rechargeable cell comprising:
in a state having charge,
a. an anode current collector,
b. a cathode containing lithium cations intercalated within the cathode,
c. a separator positioned between the anode current collector and the cathode,
d. a liquid electrolyte including a salt or salt mixture dissolved in a solvent or solvent mixture, wherein the salt or salt mixture 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, wherein the solvent 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, wherein the concentration of the lithium cation in the electrolyte is between 3-8 M, wherein the separator is infused with the electrolyte including the salt or salt mixture dissolved in the solvent, and wherein the salt or salt mixture and the solvent or solvent mixture are selected to provide the assembled rechargeable cell with an average Coulombic Efficiency of at least 99% after the first ten cycles, and
e. an in situ-formed anode on a surface of the anode current collector facing the separator; and

in an uncharged state,
a. the anode current collector, wherein the assembled rechargeable cell does not comprise an anode in the uncharged state,
b. the cathode containing lithium cations intercalated within the cathode,
c. the separator positioned between the anode current collector and the cathode, and
d. the liquid electrolyte including a salt or salt mixture dissolved in a solvent or solvent mixture.

2. The assembled rechargeable cell of claim 1 wherein the separator is a porous polymer material.

3. The assembled rechargeable cell of claim 1 wherein at least one of the following non-lithium salts is added to the electrolyte: CsFSI, CsTFSI, NaFSI-CsFSI, Mg(TFSI) 2 -CsTFSI, and Zn(TFSI) 2 .

4. The assembled rechargeable cell of claim 1 wherein the lithium salt of the electrolyte is LiFSI dissolved in DME.

5. The assembled rechargeable cell of claim 1 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 within the operating voltage window of the assembled rechargeable cell.

6. The assembled rechargeable cell of claim 5 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.

7. The assembled rechargeable cell of claim 5 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.

8. An assembled-rechargeable cell comprising:
in a state having charge,
a. a copper anode current collector,
b. a cathode including lithium containing compounds intercalated within the cathode,
c. a separator positioned between the anode current collector and the cathode,
d. a liquid electrolyte including LiFSI dissolved in DME, and
e. an in situ-formed anode on a surface of the anode current collector facing the separator; and

in an uncharged state,
a. the copper anode current collector, wherein the assembled rechargeable cell does not comprise an anode in the uncharged state,
b. the cathode including lithium containing compounds intercalated within the cathode,
c. the separator positioned between the anode current collector and the cathode, and
d. the liquid electrolyte including LiFSI dissolved in DME,

wherein the separator is infused with the liquid electrolyte, a concentration of the LiFSI in the DME is between 3-8 M, the assembled rechargeable cell does not comprise an anode in an uncharged state, and the assembled rechargeable cell has a Coulombic Efficiency of at least 99% after the first ten cycles.

9. The assembled rechargeable cell of claim 8 further comprising a cathode current collector, wherein the cathode current collector is aluminum, nickel, titanium, stainless steel, or carbon paper.

10. An assembled rechargeable cell comprising:
in an initial assembled and uncharged state,
a. an anode current collector, wherein the assembled rechargeable cell does not comprise an anode in the initial assembled and uncharged state,
b. a cathode containing lithium cations intercalated within the cathode,
c. a separator positioned between the anode current collector and the cathode, and
d. a liquid electrolyte including a salt or salt mixture dissolved in a solvent or solvent mixture, wherein the salt or salt mixture 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, wherein the solvent 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, wherein the concentration of the lithium cation in the electrolyte is between 3-8 M, wherein the separator is infused with the electrolyte including the salt or salt mixture dissolved in the solvent, and wherein the salt or salt mixture and the solvent or solvent mixture are selected to provide the assembled rechargeable cell with an average Coulombic Efficiency of at least 99% after the first ten cycles;

in a charged state,
a. the anode current collector,
b. the cathode containing lithium cations intercalated within the cathode,
c. the separator positioned between the anode current collector and the cathode, and
d. the liquid electrolyte including a salt or salt mixture dissolved in a solvent or solvent mixture, and
e. an in situ-formed anode on a surface of the anode current collector facing the separator; and

in a subsequent uncharged state,
a. the anode current collector, wherein the assembled rechargeable cell does not comprise an anode in the uncharged state,
b. the cathode containing lithium cations intercalated within the cathode,
c. the separator positioned between the anode current collector and the cathode, and
d. the liquid electrolyte including a salt or salt mixture dissolved in a solvent or solvent mixture.

Assignees

• Battelle Memorial Institute

Inventors

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

Classifications

• H01M4/661

  Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence) · CPC title

• H01M10/052

  Li-accumulators · CPC title

• H01M4/40

  Alloys based on alkali metals · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0568

  characterised by the solutes · CPC title