# US 2021/0242487 A1 · Aqueous manganese ion battery

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- Number: US 2021/0242487 A1
- Document ID: US20210242487A1
- Status: Published application
- Kind: A1
- Application number: 16/778,175
- Filed: 2020-01-31
- Published: 2021-08-05
- Earliest claimed: 2020-01-31
- Assignees: Uchicago Argonne, LLC
- Applicants: Uchicago Argonne, LLC
- Inventors: Sanja TEPAVCEVIC; Nigel Hajj BECKNELL; Pietro Papa LOPES; Dusan STRMCNIK; Vojislav STAMENKOVIC
- Web page: https://patentgrep.com/patent/US20210242487A1

## CPC

- H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
- H01M 10/36: Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/38: of elements or alloys
- H01M 4/50: of manganese
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/583: Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/622: {being polymers}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 4/663: {containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres}
- H01M 4/669: {Steels}
- H01M 50/411: Organic material
- H01M 50/426: Fluorocarbon polymers
- H01M 50/44: Fibrous material
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/027: {Negative electrodes}
- H01M 2004/028: {Positive electrodes}
- H01M 2300/0002: Aqueous electrolytes
- 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 alternative grid energy storage system is described herein. In one embodiment, an electrochemical cell comprises a high specific surface area cathode (e.g., a cathode comprising a carbon nanofoam paper, a carbon nanotube mesh, a particulate carbon material, electrolytic manganese dioxide, or a manganese dioxide film), a zinc or lead anode (e.g., Zn or Pb foil), a selective ion-conductive separator that does not conduct zinc ions (e.g., a NAFION sulfonated tetrafluoroethylene based fluoropolymer-copolymer separator) between the anode and the cathode, and an aqueous electrolyte comprising a manganese salt (e.g., aqueous manganese sulfate) contacting the electrodes and the separator. A battery comprising two or more of the electrochemical cells electrically connected together in series, parallel, or both, also is described.

## Claims

### Claim 1

An aqueous manganese ion electrochemical cell comprising a high specific surface area cathode, an anode, a selective ion-conductive separator between the anode and the cathode, and an aqueous electrolyte comprising a manganese salt contacting the anode, the cathode, and the separator; wherein the anode comprises metallic Zn or metallic Pb; the cathode has an area-to-volume specific surface area greater than or equal to 106 m−1; and wherein the separator does not conduct zinc ions.

### Claim 2 (depends on 1)

The electrochemical cell of claim 1, wherein the cathode comprises at least one material selected from the group consisting of (a) a carbon nanofoam paper, (b) a carbon nanotube mesh, (c) nanoparticulate manganese dioxide dispersed in a carbon nanotube mesh, and (d) a particulate material coated on a current collector; wherein the particulate material comprises a particulate carbon material, a particulate manganese dioxide material, or a combination thereof.

### Claim 3 (depends on 1)

The electrochemical cell of claim 1, wherein the cathode comprises a nanoparticulate carbon material coated on a metal current collector.

### Claim 4 (depends on 3)

The electrochemical cell of claim 3, wherein the nanoparticulate carbon material comprises at least one material selected from the group consisting of carbon nanotubes, carbon nanofibers, multi-walled carbon nanotubes, and graphene.

### Claim 5 (depends on 1)

The electrochemical cell of claim 1, wherein the cathode comprises a carbon nanofoam paper.

### Claim 6 (depends on 5)

The electrochemical cell of claim 5, wherein the carbon nanofoam paper has an area-to-volume specific surface area greater than or equal to 1.5×108 m−1.

### Claim 7 (depends on 1)

The electrochemical cell of claim 1, wherein the anode comprises metallic Zn.

### Claim 8 (depends on 1)

The electrochemical cell of claim 1, wherein the manganese salt comprises manganese sulfate, manganese chloride, manganese nitrate, or a combination of two or more thereof

### Claim 9 (depends on 1)

The electrochemical cell of claim 1, wherein the manganese salt is present in the electrolyte at a concentration in the range of about 0.05 to about 5 molar (M).

### Claim 10 (depends on 1)

The electrochemical cell of claim 1, wherein the separator comprises a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.

### Claim 11 (depends on 2)

The electrochemical cell of claim 2, wherein the particulate material is coated on the current collector with a polymeric binder.

### Claim 12 (depends on 1)

The electrochemical cell of claim 1, wherein the current collector comprises carbon or a metal.

### Claim 13 (depends on 1)

The electrochemical cell of claim 1, wherein the current collector comprises stainless steel, aluminum, or titanium.

### Claim 14

An aqueous manganese ion electrochemical cell comprises a cathode, an anode, a selective ion-conductive separator between the anode and the cathode, and an aqueous electrolyte comprising a manganese salt contacting the anode, the cathode, and the separator; wherein the anode comprises metallic Zn; the cathode comprises either (a) a carbon nanofoam paper, (b) a carbon nanotube mesh, (c) nanoparticulate manganese dioxide dispersed in a carbon nanotube mesh, and (d) a particulate material coated on a current collector; wherein the particulate material comprises a particulate carbon material, a particulate manganese dioxide material, or a combination thereof; and wherein the separator does not conduct zinc ions.

### Claim 15 (depends on 14)

The electrochemical cell of claim 14, wherein the cathode has an area-to-volume specific surface area greater than or equal to 106 m−1.

### Claim 16 (depends on 14)

The electrochemical cell of claim 14, wherein the manganese salt is present in the electrolyte at a concentration in the range of about 0.05 to about 5 M.

### Claim 17 (depends on 14)

The electrochemical cell of claim 14, wherein the separator comprises a sulfonated tetrafluoroethylene based fluoropolymer-copolymer.

### Claim 18 (depends on 14)

The electrochemical cell of claim 14, wherein the cathode comprises at least one particulate carbon material selected from the group consisting of carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, and graphene.

### Claim 19 (depends on 1)

A battery comprising a plurality of electrochemical cells of claim 1 electrically connected together in series, in parallel, or in both series and parallel.

### Claim 20 (depends on 14)

A battery comprising a plurality of electrochemical cells of claim 14 electrically connected together in series, in parallel, or in both series and parallel.