# US 9,039,788 B2 · Methods for making anodes for lithium ion batteries

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- Number: US 9,039,788 B2
- Document ID: US9039788B2
- Status: Granted
- Kind: B2
- Application number: 12/621,410
- Filed: 2009-11-18
- Published: 2011-05-19
- Granted: 2015-05-26
- Earliest claimed: 2009-11-18
- Assignees: Battelle Memorial Institute
- Applicants: Wu Xu; Nathan L. Canfield; Ji-Guang Zhang; Wei Liu; Jie Xiao; Deyu Wang; Z. Gary Yang
- Inventors: Wu Xu; Nathan L. Canfield; Ji-Guang Zhang; Wei Liu; Jie Xiao; Deyu Wang; Z. Gary Yang
- Web page: https://patentgrep.com/patent/US9039788B2

## CPC

- H01M 4/139: Processes of manufacture
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/621: {Binders}
- H01M 4/801: {Sintered carriers}
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/387: {Tin or alloys based on tin}
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- Y02E 60/10: Energy storage using batteries
- Y10T 29/49108: Electric battery cell making
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

Methods for making composite anodes, such as macroporous composite anodes, are disclosed. Embodiments of the methods may include forming a tape from a slurry including a substrate metal precursor, an anode active material, a pore-forming agent, a binder, and a solvent. A laminated structure may be prepared from the tape and sintered to produce a porous structure, such as a macroporous structure. The macroporous structure may be heated to reduce a substrate metal precursor and/or anode active material. Macroporous composite anodes formed by some embodiments of the disclosed methods comprise a porous metal and an anode active material, wherein the anode active material is both externally and internally incorporated throughout and on the surface of the macroporous structure.

## Claims

### Claim 1

A method comprising:
making a macroporous composite anode by:
preparing a slurry comprising a substrate precursor, 2 wt % to 30 wt % of an anode active material wherein the anode active material has an average particle diameter in the range of 5 nm to 500 nm, a pore-forming agent, a binder, and a solvent, wherein the substrate precursor is a metal oxide, metal salt, organometallic oxide, metal nitride, or a combination thereof;
forming a tape from the slurry;
removing the pore-forming agent and binder to produce a macroporous structure;
reducing the macroporous structure such that a significant portion of the substrate precursor is reduced, thereby producing a macroporous composite anode comprising the substrate and the anode active material wherein the anode active material is dispersed throughout the substrate;
incorporating the anode into a lithium-ion battery.

### Claim 2 (depends on 1)

The method of claim 1, further comprising sintering the macroporous composite anode.

### Claim 3 (depends on 1)

The method of claim 1, further comprising preparing a laminate structure from the tape, wherein the laminate structure comprises at least two layers of the tape, one on top of the other.

### Claim 4 (depends on 1)

The method of claim 1, the anode active material is selected from the group consisting of tin oxide, silicon oxide, titania, silicon and aluminum.

### Claim 5 (depends on 4)

The method of claim 4, wherein the removing the pore-forming agent and binder from the tape produces a macroporous structure devoid of pore-forming agent and binder.

### Claim 6 (depends on 4)

The method of claim 4, wherein sintering the tape produces a macroporous structure having a porosity of 30-60%.

### Claim 7 (depends on 4)

The method of claim 4, wherein the tape is sintered in an oxidizing environment.

### Claim 8 (depends on 1)

The method of claim 1, wherein the substrate precursor is completely reduced.

### Claim 9 (depends on 1)

The method of claim 1, wherein the substrate precursor is copper (I) oxide, copper (II) oxide, nickel (II) oxide or nickel (IV) oxide.

### Claim 10 (depends on 1)

The method of claim 1, wherein the anode active material is tin, a tin alloy, tin oxide, manganese oxide, chromium oxide, vanadium oxide, silicon, silicon oxide, titanium oxide, aluminum, or any combination thereof.

### Claim 11 (depends on 1)

The method of claim 1, wherein the pore-forming agent is carbon black, graphite, polymer beads, starch, or a mixture thereof.

### Claim 12 (depends on 1)

The method of claim 1, wherein the binder is poly(vinylbutyral).

### Claim 13 (depends on 1)

The method of claim 1, wherein the reducing the macroporous structure comprises heating the macroporous structure in a reducing atmosphere at a temperature and for a period of time such that the substrate precursor present in the macroporous structure is completely reduced.

### Claim 14 (depends on 13)

The method of claim 13, wherein the temperature and the period of time are selected such that the substrate precursor is completely reduced.

### Claim 15 (depends on 13)

The method of claim 13, wherein the reducing atmosphere comprises H2, CO, CH4, or a mixture thereof.

### Claim 16 (depends on 13)

The method of claim 13, wherein the macroporous structure is heated in the reducing atmosphere at a temperature and for a period of time such that at least a portion of the anode active material is reduced.

### Claim 17 (depends on 16)

The method of claim 16, wherein the macroporous structure is heated in the reducing atmosphere at a temperature and for a period of time such that the anode active material is completely reduced.

### Claim 18 (depends on 13)

The method of claim 13, wherein the temperature and period of time are selected such that the macroporous structure is concurrently reduced and sintered.

### Claim 19 (depends on 1)

The method of claim 1, further comprising sintering the macroporous composite anode after reducing the macroporous structure.

### Claim 20 (depends on 19)

The method of claim 19, wherein the macroporous composite anode is sintered in a nitrogen or nitrogen/hydrogen atmosphere.

### Claim 21 (depends on 1)

The method of claim 1, wherein a) the substrate precursor is a metal oxide, b) the anode active material is selected from the group consisting of tin, a tin alloy, tin oxide, manganese oxide, chromium oxide, vanadium oxide, silicon, silicon oxide, titanium oxide, aluminum, or any combination thereof, c) the pore-forming agent comprises carbon black, graphite, starch, polymer beads, or a mixture thereof, and d) the binder comprises poly(vinylbutyral), ethylcellulose, or a mixture thereof, the slurry further comprising e) a dispersant, f) a plasticizer comprising benzyl butyl phthalate, poly(ethylene glycol), dibutyl phthalate, or a mixture thereof, and g) a solvent comprising lower alkyl ketones, lower alkyl alcohols, or a mixture thereof, the method further comprising:
preparing a laminate structure from the tape, wherein the laminate structure comprises at least two layers of the tape;
sintering the laminate structure to remove the pore-forming agent and binder and produce a macroporous structure devoid of the pore-forming agent and the binder; and
reducing the macroporous structure in a reducing atmosphere at a temperature and for a period of time such that the substrate precursor is reduced, thereby producing the macroporous composite anode.

### Claim 22 (depends on 1)

The method of claim 1 wherein the anode active material comprises tin oxide, silicon oxide, or titanium oxide and remains an oxide after the reducing step.

### Claim 23

A method for preparing an anode, comprising:
preparing a slurry comprising a copper substrate metal, an anode active material, a pore-forming agent, a binder, and a solvent, wherein the anode active material is selected from the group consisting of tin, a tin alloy, tin oxide, manganese oxide, chromium oxide, vanadium oxide, silicon, silicon oxide, titanium oxide, aluminum, or any combination thereof;
forming a tape from the slurry;
sintering the tape in an oxygen-free atmosphere to produce a macroporous composite anode, wherein sintering the tape removes the pore-forming agent, the binder, and the solvent; and
incorporating the anode into a lithium-ion battery.

### Claim 24

A method comprising:
making a macroporous composite anode by:
preparing a slurry comprising a substrate precursor, an anode active material is selected from the group consisting of tin, a tin alloy, tin oxide, manganese oxide, chromium oxide, vanadium oxide, silicon, silicon oxide, titanium oxide, aluminum, or combinations thereof, a pore-forming agent that produces a macroporous structure having a porosity of at least 30% when the pore forming agent is removed, a binder, and a solvent, wherein the substrate precursor is a metal oxide, metal salt, organometallic oxide, metal nitride, or a combination thereof;
forming a tape from the slurry;
removing the pore-forming agent and binder to produce a macroporous structure;
reducing the macroporous structure such that a significant portion of the substrate precursor is reduced, thereby producing a macroporous composite anode comprising the substrate and the anode active material wherein the anode active material is dispersed throughout the substrate; and
including the anode in a lithium-ion battery.

### Claim 25 (depends on 24)

The method of claim 24, wherein the substrate precursor is copper (I) oxide or copper (II) oxide.

### Claim 26 (depends on 24)

The method of claim 24 comprising 2 wt % to 30 wt % of the anode active material.

### Claim 27 (depends on 25)

The method of claim 25 wherein the anode active material comprises tin oxide, silicon oxide, or titanium oxide and remains an oxide after the reducing step.