Stable lithium fluoride-based cathodes for metal and metal-ion batteries

Patent metadata

Field	Value
Publication number	US-2017018768-A1
Application number	US-201615209619-A
Country	US
Kind code	A1
Filing date	Jul 13, 2016
Priority date	Jul 13, 2015
Publication date	Jan 19, 2017
Grant date	—

Abstract

A battery electrode composition is provided that comprises composite particles. Each composite particle may comprise, for example, active lithium fluoride/metal nanocomposite material optionally embedded into a nanoporous, electrically-conductive skeleton matrix material particle(s), where each of these composite particles is further encased in a Li-ion permeable, chemically and mechanically robust, protective outer shell that is impermeable to electrolyte solvent molecules. The active lithium fluoride/metal nanocomposite material is provided to store and release Li ions during battery operation.

First claim

1 . A Li or Li-ion battery electrode composition comprising composite particles, each composite particle comprising:
a mixture of metal and lithium fluoride (LiF) materials provided to store and release Li ions during battery operation; a skeleton matrix material into which the mixture is embedded to form an active material core; and a Li-ion permeable shell at least partially encasing the active material core and protecting the metal and LiF materials from interaction with a battery electrolyte.

2 . The battery electrode composition of claim 1 , wherein the composite particles are of a substantially-spherical shape and exhibit an average diameter in the range of about 50 nm to about 10 microns.

3 . The battery electrode composition of claim 1 , wherein the Li-ion permeable shell has an average shell thickness among the composite particles in the range of about 1 nm to about 100 nm.

4 . The battery electrode composition of claim 1 , wherein the skeleton matrix material makes up an average volume fraction among the composite particles in the range of about 3 vol. % to about 40 vol. %.

5 . The battery electrode composition of claim 4 , wherein the volume fraction of the skeleton matrix material near the perimeter of each composite particle is on average at least 10% larger than in the center of each composite particle.

6 . The battery electrode composition of claim 1 , wherein the skeleton matrix material is in the form of a monolithic particle.

7 . The battery electrode composition of claim 1 , wherein the skeleton matrix material comprises about 20 at. % to about 100 at. % carbon.

8 . The battery electrode composition of claim 1 , wherein the skeleton matrix material comprises more than about 0.05 at. % fluorine.

9 . The battery electrode composition of claim 1 , wherein the metal of the mixture comprises 10-100 at. % Cu and 0-90 at. % of at least one of the following: Fe, Co, Ni, Ti, Zn, Bi, Pb, Sb, Sn, Cd, Cr, Zr, Nb, Mo, Hf, Ta, Si, La, or Ce.

10 . The battery electrode composition of claim 1 , wherein the Li-ion permeable shell is a composite material that has at least two components.

11 . The battery electrode composition of claim 1 , wherein the Li-ion permeable shell comprises about 20 at. % to about 100 at. % carbon.

12 . The battery electrode composition of claim 1 , wherein each composite particle further comprises one or more functional groups forming a coating on the Li-ion permeable shell.

13 . A Li or Li-ion battery, comprising:
anode and cathode electrodes, wherein the cathode electrode comprises the battery electrode composition of claim 1 ; an electrolyte ionically coupling the anode and the cathode electrodes; and a separator electrically separating the anode and the cathode electrodes.

14 . A method of fabricating a Li or Li-ion battery electrode composition comprising composite particles, wherein, for each composite particle, the method comprises:
embedding one or more metal, metal oxide, or metal salt precursors into a skeleton matrix material; inducing conversion of the one or more precursors into a metal fluoride embedded into the skeleton matrix material via a fluorination reaction to form an active material core; and at least partially encasing the active material core with a Li-ion permeable shell to protect the active material core from interaction with a battery electrolyte.

15 . The method of claim 14 , wherein the one or more precursors comprise a mixture of least two different precursor compositions.

16 . The method of claim 14 , wherein a plasma source is utilized for the formation of fluorine radicals involved in the fluorination reaction.

17 . The method of claim 14 , further comprising chemical lithiation of the metal fluoride embedded into the skeleton matrix material.

18 . The method of claim 17 , wherein the chemical lithiation proceeds by using one or more chemical lithiation reagents that are soluble in organic solvents.

19 . The method of claim 18 , wherein the one or more chemical lithiation reagents comprise at least one of the following: (i) a lithium alkylborohydride, (ii) an alkyllithium magnesate, (iii) a radical anion of polycyclic aromatic hydrocarbons, (iv) a lithium ketone radical anion, or (v) a lithium aluminum hydride.

20 . The method of claim 18 , wherein the one or more chemical lithiation reagents comprise (i) lithium borohydride or (ii) an alkyllithium reagent.

21 . The method of claim 18 , wherein the fluorination reaction comprises using a non-lithium-containing reducing agent to reduce metal ions in a metal fluoride composition to a corresponding metallic state and a separate lithium-containing salt to provide lithium ions to form lithium fluoride (LiF).

Assignees

• Sila Nanotechnologies Inc

Inventors

• Yushin Gleb
• Berdichevsky Eugene
• Zdyrko Bogdan
• Jacobs Alexander
• Gordon Daniel
• Ingle Nicholas
• Gerber Laura

Classifications

• H01M4/38

  of elements or alloys · CPC title

• H01M4/5835

  Comprising fluorine or fluoride salts · CPC title

• H01M4/364

  as mixtures · CPC title

• H01M4/13

  Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof · CPC title

• H01M4/366 Primary

  as layered products · CPC title