# US 8,541,129 B1 · Active membrane having uniform physico-chemically functionalized ion channels

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- Number: US 8,541,129 B1
- Document ID: US8541129B1
- Status: Granted
- Kind: B1
- Application number: 12/838,608
- Filed: 2010-07-19
- Granted: 2013-09-24
- Earliest claimed: 2004-01-07
- Assignees: U.S. Department of Energy
- Applicants: Rex E. Gerald, II; Katarina J. Ruscic; Devin N. Sears; Luis J. Smith; Robert J. Klingler; Jerome W. Rathke
- Inventors: Rex E. Gerald, II; Katarina J. Ruscic; Devin N. Sears; Luis J. Smith; Robert J. Klingler; Jerome W. Rathke
- Web page: https://patentgrep.com/patent/US8541129B1

## CPC

- H01M 10/0562: Solid materials
- C25D 11/045: {for forming AAO templates}
- C25D 11/08: containing inorganic acids
- H01M 6/185: {with oxides, hydroxides or oxysalts as solid electrolytes}
- H01M 6/187: {Solid electrolyte characterised by the form}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 50/434: Ceramics
- H01M 50/437: Glass
- H01M 50/489: Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M 50/491: Porosity
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention relates to a physicochemically-active porous membrane for electrochemical cells that purports dual functions: an electronic insulator (separator) and a unidirectional ion-transporter (electrolyte). The electrochemical cell membrane is activated for the transport of ions by contiguous ion coordination sites on the interior two-dimensional surfaces of the trans-membrane unidirectional pores. One dimension of the pore surface has a macroscopic length (1 nm-1000 μm) and is directed parallel to the direction of an electric field, which is produced between the cathode and the anode electrodes of an electrochemical cell. The membrane material is designed to have physicochemical interaction with ions. Control of the extent of the interactions between the ions and the interior pore walls of the membrane and other materials, chemicals, or structures contained within the pores provides adjustability of the ionic conductivity of the membrane.

## Claims

### Claim 1

A physicochemically active monolithic separator-electrolyte membrane comprising: a specialized material layer of defined width having a plurality of pores running the width of the layer, the pores having diameters ranging from 2 nm to 150 nm, wherein the membrane has a defined porosity and wherein the pores have an inner wall surface, the inner wall surface having a surface coating selected from the group consisting of salts, anions, cations and combinations thereof, wherein the surface coating has a thickness of less than half the pore diameter and further wherein the pores are not otherwise filled.

### Claim 2 (depends on 1)

The active membrane of claim 1, wherein the surface coating has a thickness of less than about one half the diameter of the pores of the specialized material layer.

### Claim 3 (depends on 1)

The active membrane of claim 1, wherein the surface coating has a thickness of less than about, one quarter the diameter of the pores of the specialized material layer.

### Claim 4 (depends on 1)

The active membrane of claim 1, wherein the pores have diameters ranging from 2 nm to 50 nm.

### Claim 5 (depends on 1)

The active membrane of claim 1, wherein the specialized material layer is selected from the group of ion coordinating materials consisting of: metal oxides, specialized plastics, silicate glasses, and combinations thereof.

### Claim 6 (depends on 5)

The active membrane of claim 5, wherein the specialized material layer is a metal oxide selected from the group consisting of: aluminum oxide, silicone oxide, titanium oxide, magnesium oxide, vanadium oxide, zirconium oxide, germanium oxide, tin oxide, gallium oxide, indium oxide, iron oxide, chromium oxide, molybdenum oxide, nickel oxide, copper oxide, zinc oxide and combinations thereof.

### Claim 7 (depends on 6)

The active membrane of claim 6, wherein the specialized material is an aluminum oxide compound selected from the group consisting of amorphous aluminum oxide, dialuminum trioxide, alumina, crystalline alpha aluminum oxide, crystalline beta aluminum oxide, crystalline gamma aluminum oxide, or combinations thereof.

### Claim 8 (depends on 1)

The active membrane of claim 1, wherein the specialized material is anodized aluminum oxide (AAO).

### Claim 9 (depends on 1)

The active membrane of claim 1, wherein the membrane has a porosity of at least 30%.

### Claim 10 (depends on 1)

The active membrane of claim 1, wherein the membrane has a tortuosity of less than about 2.

### Claim 11 (depends on 1)

The active membrane of claim 1, wherein, the membrane has a mean thickness of between about 1 micron and 500 microns.

### Claim 12 (depends on 1)

The active membrane of claim 1, wherein the membrane has a mean thickness of between about 10 nm and 1 micron.

### Claim 13 (depends on 1)

The active membrane of claim 1, wherein the coating is a salt.

### Claim 14 (depends on 1)

The active membrane of claim 1, wherein the inner walls of the pores are irreversibly coated with a compound selected from the group consisting of: SiO2, Al2O3, TiO2, VO2, TiN2 and combinations thereof.

### Claim 15 (depends on 1)

The active membrane of claim 1, wherein the membrane has a first outer face and a second outer face opposite the first face, the pores running between the first and second faces, wherein a laminate is deposited upon the first and second faces.

### Claim 16 (depends on 15)

The active membrane of claim 15, wherein the laminate comprises a polymer.

### Claim 17 (depends on 15)

The active membrane of claim 15, wherein the laminate comprises a polymer selected from the group consisting of: polyether, polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polymethyl methacrylate, polymethyl acrylate, polyvinyl alcohol, polymethacrylonitrile, polyvinyl acetate, polyvinylpyrrolidone, polyethyleneimine, polybutadiene, polystyrene, polyisoprene, vinylidene fluoride-hexafluoropropylene coploymer, poly(ethylene oxide), poly(propylene oxide), polyethylene glycols, polypropylene glycols, propylene carbonate, ethylene carbonate, dioctyl sebacate, diethyl phthalate, derivatives of these polymers and combinations thereof.

### Claim 18

A physicochemically active monolithic separator-electrolyte membrane comprising: a specialized material layer of defined width having a plurality of pores running the width of the layer, the pores having diameters ranging from 2 nm to 150 nm, wherein the membrane has a defined porosity and wherein the pores have an inner wall surface, the inner wall surface having a surface coating comprising a lithium-containing salt, wherein the thickness of the surface coating is less than one half of the diameter of the pore and wherein the pores are not otherwise filled.

### Claim 19

A physicochemically active monolithic separator-electrolyte membrane comprising: a specialized material layer of defined width having a plurality of pores running the width of the layer, the pores having diameters ranging from 2 nm to 150 nm, wherein the membrane has a defined porosity and wherein the pores have an inner wall surface, the inner wall surface having a surface coating comprising a lithium-containing salt, wherein the thickness of the surface coating is less than one half of the diameter of the pore and wherein the pores are not otherwise filled, and further wherein the membrane has a first outer face and a second outer face opposite the first face, the pores running between the first and second faces, wherein a laminate comprising a polymer is deposited upon the first and second faces.
