# US 10,115,998 B2 · Cathode additives to provide an excess lithium source for lithium ion batteries

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,115,998 B2
- Document ID: US10115998B2
- Status: Granted
- Kind: B2
- Application number: 14/745,747
- Filed: 2015-06-22
- Published: 2016-12-22
- Granted: 2018-10-30
- Earliest claimed: 2015-06-22
- Assignees: Sinode Systems, Inc.
- Applicants: SiNode Systems, Inc.
- Inventors: Cary Michael Hayner; Rachid Amine; Christine A. Frysz
- Web page: https://patentgrep.com/patent/US10115998B2

## CPC

- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- 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 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 10/0567: characterised by the additives
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0025: Organic electrolyte
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. batteries
- 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
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

A lithium ion electrochemical cell is described in which an electrode comprises a lithiation agent. The lithiation agent, which comprises a lithium constituent, is designed to provide an excess source of lithium to minimize capacity loss of the lithium ion electrochemical cell. The anode of the lithium ion cell comprises a material matrix comprising carbon, graphene and an active element such as silicon or tin.

## Claims

### Claim 1

An electrochemical cell, comprising:
a negative electrode comprising carbon, a negative electrode active material comprising silicon, and graphene;
a positive electrode comprising LiNixCoyAlzO2, where x, y, and z are greater than 0 and x+y+z=1;
an ionically conductive electrolyte located between the positive electrode and the negative electrode; and
a lithiation agent located in at least one of the positive electrode and the negative electrode, the lithiation agent comprising LiN3 or Li5FeO4,
wherein during operation of the electrochemical cell, lithium from the lithiation agent irreversibly reacts with the negative electrode active material to form a lithium compound in and/or on the negative electrode.

### Claim 2 (depends on 1)

The electrochemical cell of claim 1 wherein:
the cell comprises a secondary lithium ion battery which further comprises a separator located between the positive electrode and the negative electrode; and
the lithium deintercalates from the lithiation agent, at a lithiation agent extraction voltage and irreversibly reacts with the negative electrode active material to form the lithium compound which does not substantially deintercalate lithium during a subsequent discharge step of the battery.

### Claim 3 (depends on 1)

The electrochemical cell of claim 1 wherein the negative electrode active material further comprises carbon, antimony, lead, tin, germanium, and combinations thereof.

### Claim 4 (depends on 1)

The electrochemical cell of claim 1 wherein the lithiation agent comprises from about 0.01 weight percent to about 15 weight percent of the positive electrode or the negative electrode.

### Claim 5 (depends on 1)

The electrochemical cell of claim 1 wherein the lithium compound comprises an organic or inorganic compound comprising lithium.

### Claim 6 (depends on 1)

The electrochemical cell of claim 1 wherein a solid electrolyte-interphase layer on an exterior surface of the negative electrode comprises the lithium compound.

### Claim 7 (depends on 1)

The electrochemical cell of claim 1 wherein the electrolyte comprises a Group IA metal salt dissolved in a nonaqueous solvent.

### Claim 8 (depends on 1)

The electrochemical cell of claim 1 wherein the lithiation agent comprises a specific capacity of at least 400 mAh/g.

### Claim 9 (depends on 1)

The electrochemical cell of claim 1 wherein the lithium compound is located in the negative electrode or in a solid electrolyte-interphase layer located on an exterior surface of the negative electrode.

### Claim 10

A negative electrode of an electrochemical cell, comprising a mixture of:
a negative electrode active material selected from the group consisting of silicon, carbon, antimony, lead, tin, germanium, and combinations thereof; and
a lithiation agent comprising LixMFx, where 0.1≤X≤3 and M is selected from the group consisting of iron, manganese, cobalt, nickel, copper, vanadium, chromium and bismuth.

### Claim 11

An electrochemical cell comprising:
a negative electrode comprising a negative electrode active material;
a positive electrode comprising a positive electrode active material comprising lithium;
an ionically conductive electrolyte located between the positive electrode and the negative electrode; and
a lithiation agent comprising LixMFx, where 0.1≤X≤3 and M is selected from the group consisting of iron, manganese, cobalt, nickel, copper, vanadium, chromium, and bismuth disposed in at least one of the positive electrode and the negative electrode,
wherein during operation of the electrochemical cell, lithium from the lithiation agent irreversibly reacts with the negative electrode active material to form a lithium compound in and/or on the negative electrode.

### Claim 12 (depends on 11)

The electrochemical cell of claim 11 wherein:
the positive electrode active material is selected from the group consisting of a lithium metal oxide, a lithium metal fluoride, a lithium sulfide, a lithium metal sulfide, a lithium metal phosphate, a lithium metal silicate, and combinations thereof, wherein the metal comprises a transition metal from the Periodic Table of Elements.

### Claim 13

An electrochemical cell comprising:
a negative electrode comprising a negative electrode active material;
a positive electrode comprising a positive electrode active material comprising lithium;
an ionically conductive electrolyte located between the positive electrode and the negative electrode;
a lithiation agent, wherein the lithiation agent comprises:
Li(3−x)MxN, where 0≤X≤0.8 and M is selected from the group consisting of cobalt, nickel, copper, and combinations thereof; or
Li2−x−yZyQxN wherein 0.1≤x≤0.8, 0.1≤y≤1, Z is a Li vacancy and Q is selected from the group of elements consisting of Co, Ni, Cu, and combinations thereof; and
wherein during operation of the electrochemical cell, lithium from the lithiation agent irreversibly reacts with the negative electrode active material to form a lithium compound in and/or on the negative electrode.

### Claim 14 (depends on 13)

The electrochemical cell of claim 13 wherein the positive electrode active material is selected from the group consisting of a lithium metal oxide, a lithium metal fluoride, lithium sulfide, a lithium metal sulfide, a lithium metal phosphate, a lithium metal silicate, and combinations thereof, wherein the metal comprises a transition metal from the Periodic Table of Elements.

### Claim 15 (depends on 13)

The electrochemical cell of claim 13 wherein the positive electrode active material is selected from the group consisting of LiNixCoyAlzO2, wherein x+y+z=1, LiCoO2, LiFePO4, LiMn2O4, Li2S, LiNixMnyCozO2, wherein 0.3≤x≤1.0, 0.1≤y≤0.45, 0.1≤z≤0.4 and x+y+z=1, MFx wherein 0.1≤x≤3, LixMFx wherein 0.1≤x≤3, LiMPO4, Li2MSiO4, and LiMn2O4—LiMO, wherein M is a transition metal from the Periodic Table of Elements.

### Claim 16 (depends on 13)

The electrochemical cell of claim 13 wherein the positive electrode active material comprises Li1+xNiaMnbCocAdO2−zFz, wherein x ranges from about 0.01 to about 0.3, a ranges from about 0.01 to about 0.40, b ranges from about 0.20 to about 0.65, c ranges from about 0.01 to about 0.46, d ranges from about 0 to about 0.15, Z ranges from about 0 to about 0.2, and wherein A is selected from the group of elements consisting of Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li, and combinations thereof.

### Claim 17 (depends on 13)

The electrochemical cell of claim 13 wherein the negative electrode active material is selected from the group consisting of silicon, carbon, antimony, lead, tin, germanium, and combinations thereof.

### Claim 18 (depends on 13)

The electrochemical cell of claim 13 wherein a solid electrolyte-interphase layer on an exterior surface of the negative electrode comprises the lithium compound.

### Claim 19 (depends on 13)

The electrochemical cell of claim 13 wherein the electrolyte comprises a Group IA metal salt dissolved in a nonaqueous solvent.

### Claim 20 (depends on 13)

The electrochemical cell of claim 13 wherein the lithium compound is located in the negative electrode or in a solid electrolyte-interphase layer located on an exterior surface of the negative electrode.

### Claim 21 (depends on 11)

The electrochemical cell of claim 11 wherein the negative electrode active material is selected from the group consisting of silicon, carbon, antimony, lead, tin, germanium, and combinations thereof.

### Claim 22 (depends on 11)

The electrochemical cell of claim 11 wherein the positive electrode active material is selected from the group consisting of LiNixCoyAlzO2, wherein x+y+z=1, LiCoO2, LiFePO4, LiMn2O4, Li2S, LiNixMnyCozO2, wherein 0.3≤x≤1.0, 0.1≤y≤0.45, 0.1≤z≤0.4 and x+y+z=1, MFx wherein 0.1≤x≤3, LixMFx wherein 0.1≤x≤3, LiMPO4, Li2MSiO4, and LiMn2O4—LiMO, wherein M is a transition metal from the Periodic Table of Elements.

### Claim 23 (depends on 11)

The electrochemical cell of claim 11 wherein the positive electrode active material comprises Li1+xNiaMnbCozAdO2−zFz, wherein x ranges from about 0.01 to about 0.3, a ranges from about 0.01 to about 0.40, b ranges from about 0.20 to about 0.65, c ranges from about 0.01 to about 0.46, d ranges from about 0 to about 0.15, Z ranges from about 0 to about 0.2, and wherein A is selected from the group of elements consisting of Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li, and combinations thereof.