# US 11,309,539 B2 · Electrochemical cell and method of manufacturing

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- Number: US 11,309,539 B2
- Document ID: US11309539B2
- Status: Granted
- Kind: B2
- Application number: 16/131,875
- Filed: 2018-09-14
- Published: 2019-07-04
- Granted: 2022-04-19
- Earliest claimed: 2018-01-04
- Assignees: GM Global Technology Operations LLC
- Applicants: GM Global Technology Operations LLC
- Inventors: Fang Dai; Meinan He; Shuru Chen; Mei Cai
- Web page: https://patentgrep.com/patent/US11309539B2

## CPC

- H01M 4/366: {as layered products}
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/0421: {involving vapour deposition}
- H01M 4/0452: {from solutions}
- H01M 4/0483: {by methods including the handling of a melt (H01M4/0438, take precedence)}
- H01M 4/134: Electrodes based on metals, Si or alloys
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/381: {Alkaline or alkaline earth metals elements (H01M4/40 takes precedence)}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/483: {for non-aqueous cells (H01M4/485 takes precedence)}
- H01M 4/5815: {Sulfides}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/667: {in the form of layers, e.g. coatings}
- H01M 4/742: {perforated material}
- H01M 4/747: {Woven material}
- H01M 4/808: {Foamed, spongy materials}
- H01M 10/052: Li-accumulators
- H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
- Y02E 60/10: Energy storage using 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

## Abstract

An electrochemical cell comprising an alkali metal negative electrode layer physically and chemically bonded to a surface of a negative electrode current collector via an intermediate metal chalcogenide layer. The intermediate metal chalcogenide layer may comprise a metal oxide, a metal sulfide, a metal selenide, or a combination thereof. The intermediate metal chalcogenide layer may be formed on the surface of the negative electrode current collector by exposing the surface to a chalcogen or a chalcogen donor compound. Then, the alkali metal negative electrode layer may be formed on the surface of the negative electrode current collector over the intermediate metal chalcogenide layer by contacting at least a portion of the metal chalcogenide layer with a source of sodium or potassium to form a layer of sodium or potassium on the surface of the negative electrode current collector over the metal chalcogenide layer.

## Claims

### Claim 1

An electrochemical cell comprising:
a positive electrode layer electrically coupled to a positive electrode current collector;
an alkali metal negative electrode layer spaced apart from the positive electrode layer and electrically coupled to a negative electrode current collector; and
an electrolyte in ionic contact with the positive and negative electrode layers,
wherein the alkali metal negative electrode layer comprises a layer of sodium (Na) or potassium (K),
wherein the alkali metal negative electrode layer is physically and chemically bonded to a surface of the negative electrode current collector via an intermediate metal chalcogenide layer, and
wherein the intermediate metal chalcogenide layer extends continuously between the surface of the negative electrode current collector and the alkali metal negative electrode layer.

### Claim 2 (depends on 1)

The electrochemical cell of claim 1 wherein the metal chalcogenide layer comprises a metal oxide, a metal sulfide, a metal selenide, or a combination thereof.

### Claim 3 (depends on 1)

The electrochemical cell of claim 1 wherein the negative electrode current collector comprises copper (Cu), and wherein the intermediate metal chalcogenide layer comprises copper oxide, copper sulfide, copper selenide, or a combination thereof.

### Claim 4 (depends on 1)

The electrochemical cell of claim 1 wherein the negative electrode current collector comprises a non-porous metal foil, a perforated metal sheet, a porous metal mesh, or a porous open-cell metal foam.

### Claim 5 (depends on 1)

The electrochemical cell of claim 1 wherein the negative electrode current collector comprises a first surface and an opposite second surface, and wherein the first surface of the negative electrode current collector is physically and chemically bonded to a first alkali metal negative electrode layer via a first intermediate metal chalcogenide layer, and wherein the second surface of the negative electrode current collector is physically and chemically bonded to a second alkali metal negative electrode layer via a second intermediate metal chalcogenide layer.

### Claim 6 (depends on 1)

The electrochemical cell of claim 1 wherein the negative electrode current collector has a thickness in the range of 8-150 μm, the metal chalcogenide layer has a thickness in the range of one nanometer to 10 micrometers, and the alkali metal negative electrode layer has a thickness in the range of one micrometer to 1000 micrometers.

### Claim 7 (depends on 1)

The electrochemical cell of claim 1 wherein the alkali metal negative electrode layer comprises, by weight, greater than 97% sodium (Na) or greater than 97% potassium (K).

### Claim 8 (depends on 1)

A secondary lithium metal battery including a plurality of electrochemical cells as set forth in claim 1, wherein the electrochemical cells are connected in a series or parallel arrangement.

### Claim 9

A method of manufacturing an electrochemical cell, the method comprising:
providing a porous or non-porous metal substrate;
exposing a surface of the metal substrate to a chalcogen or a chalcogen donor compound such that a conformal metal chalcogenide layer forms directly on the surface of the metal substrate; and
contacting at least a portion of the conformal metal chalcogenide layer on the surface of the metal substrate with a source of sodium (Na) or potassium (K) to form a layer of sodium or potassium on the surface of the metal substrate over the conformal metal chalcogenide layer
wherein the layer of sodium or potassium is physically and chemically bonded to the surface of the metal substrate via the conformal metal chalcogenide layer, and
wherein the conformal metal chalcogenide layer extends continuously between the surface of the metal substrate and the layer of sodium or potassium.

### Claim 10 (depends on 9)

The method of claim 9 wherein the chalcogen comprises oxygen, sulfur, selenium, or a combination thereof, and wherein the metal chalcogenide layer comprises a metal oxide, a metal sulfide, a metal selenide, or a combination thereof.

### Claim 11 (depends on 9)

The method of claim 9 wherein the metal substrate comprises copper, and wherein the metal chalcogenide layer comprises copper oxide, copper sulfide, copper selenide, or a combination thereof.

### Claim 12 (depends on 9)

The method of claim 9 wherein the chalcogen comprises oxygen, and wherein the conformal metal chalcogenide layer is formed on the surface of the metal substrate by exposing the metal substrate to gaseous oxygen by heating the metal substrate in air such that the gaseous oxygen chemically reacts with and bonds to the surface of the metal substrate.

### Claim 13 (depends on 9)

The method of claim 9 wherein the chalcogen comprises sulfur or selenium, and wherein the conformal metal chalcogenide layer is formed on the surface of the metal substrate by exposing the metal substrate to gaseous sulfur or selenium by heating a volume of solid phase sulfur or selenium to release a volume of gaseous sulfur or selenium therefrom and exposing the surface of the metal substrate to the volume of gaseous sulfur or selenium such that the gaseous sulfur or selenium chemically reacts with and bonds to the surface of the metal substrate.

### Claim 14 (depends on 9)

The method of claim 9 wherein the conformal metal chalcogenide layer is formed on the surface of the metal substrate by applying a chalcogenide precursor solution to the surface of the metal substrate, wherein the chalcogenide precursor solution comprises a chalcogen-donor compound dissolved in a solvent, and wherein the chalcogen-donor compound comprises at least one of an oxygen donor compound, a sulfur donor compound, or a selenium donor compound.

### Claim 15 (depends on 9)

The method of claim 9 wherein the layer of sodium or potassium is formed directly on the metal chalcogenide layer over the surface of the metal substrate by immersing at least a portion of the metal substrate in a volume of molten sodium or potassium such that the molten sodium or potassium chemically reacts with and actively wets the metal chalcogenide layer on the surface of the metal substrate.

### Claim 16 (depends on 9)

The method of claim 9 wherein the layer of sodium or potassium is formed directly on the metal chalcogenide layer over the surface of the metal substrate by:
(i) heating a volume of molten sodium or potassium in a subatmospheric pressure environment to release a volume of gaseous sodium or potassium therefrom and exposing the metal chalcogenide layer on the surface of the metal substrate to the volume of gaseous sodium or potassium such that the gaseous sodium or potassium chemically reacts with and actively wets the metal chalcogenide layer on the surface of the metal substrate;
(ii) at least partially immersing the metal substrate in a nonaqueous liquid electrolyte solution comprising an alkali metal salt dissolved in a polar aprotic organic solvent and establishing an electrical potential between the metal substrate and a counter electrode immersed in the nonaqueous liquid electrolyte solution such that alkali metals ions in the electrolyte solution are reduced and deposited on the surface of the metal substrate over the metal chalcogenide layer to form the layer of sodium or potassium on the surface of the metal substrate over the metal chalcogenide layer; or
(iii) laminating a sodium or potassium metal foil onto the metal chalcogenide layer on the surface of the metal substrate such that the sodium or potassium metal foil physically and chemically bonds to the metal chalcogenide layer on the surface of the metal substrate.

### Claim 17 (depends on 9)

The method of claim 9 wherein the metal substrate is non-porous and includes a first major surface and an opposite second major surface, and wherein the metal chalcogenide layer and the layer of sodium or potassium are sequentially formed on the first and second major surface of the metal substrate.

### Claim 18 (depends on 9)

The method of claim 9 wherein the metal substrate is porous and includes a first side, an opposite second side, and a plurality of pores defined by wall surfaces extending between the first and second sides of the metal substrate, and wherein the metal chalcogenide layer and the layer of sodium or potassium are sequentially formed on the first and second sides of the metal substrate and on the wall surfaces extending between the first and second sides of the metal substrate, without blocking the pores of the metal substrate.

### Claim 19 (depends on 1)

The electrochemical cell of claim 1 wherein the alkali metal negative electrode layer is formed directly on the intermediate metal chalcogenide layer and is physically and chemically bonded to the intermediate metal chalcogenide layer.

### Claim 20 (depends on 9)

The method of claim 9 wherein the layer of sodium or potassium is formed directly on the conformal metal chalcogenide layer and is physically and chemically bonded to the conformal metal chalcogenide layer.