# US 10,501,861 B2 · Electrochemical devices with current collector having an increased resistance to corrosion

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- Number: US 10,501,861 B2
- Document ID: US10501861B2
- Status: Granted
- Kind: B2
- Application number: 15/762,693
- Filed: 2016-09-19
- Published: 2018-09-20
- Granted: 2019-12-10
- Earliest claimed: 2015-09-29
- Assignees: Universite De Nantes
- Applicants: Universite De Nantes
- Inventors: Thierry Brousse; Cedric Martin; Anne-Lise Brisse
- Web page: https://patentgrep.com/patent/US10501861B2

## CPC

- C25D 9/02: with organic materials
- C25D 5/44: Aluminium
- C25D 7/00: Electroplating characterised by the article coated
- H01G 11/28: arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
- H01G 11/32: Carbon-based
- H01G 11/50: specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
- H01G 11/56: Solid electrolytes, e.g. gels; Additives therein
- H01G 11/60: characterised by the solvent
- H01G 11/62: characterised by the solute, e.g. salts, anions or cations therein
- H01G 11/68: characterised by their material
- H01G 11/84: Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G 11/86: specially adapted for electrodes (carbonisation or activation of carbon for the manufacture of electrodes H01G11/34)
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- 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 4/667: {in the form of layers, e.g. coatings}
- H01M 10/0427: {Button cells}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H01M 10/0568: characterised by the solutes
- H01M 10/54: Reclaiming serviceable parts of waste accumulators
- H01M 14/005: {Photoelectrochemical storage cells (light sensitive devices H01G9/20, semiconductors sensitive to light H10F)}
- H01G 2/12: Protection against corrosion (H01G2/10 takes precedence)
- H01G 11/06: with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- 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 4/587: for inserting or intercalating light metals
- H01M 2300/0037: Mixture of solvents
- Y02E 60/10: Energy storage using batteries
- Y02E 60/13: Energy storage using capacitors
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y02W 30/84: Recycling of batteries or fuel cells
- C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

Electrochemical device or photo-electrochemical device comprising an electrolyte containing a bistriflimide anion, hereafter named as TFSI—, at least two electrodes, each of these electrodes being in contact with a current collector comprising a metal support characterized in that at least one electrode has a current collector the metal support of which comprises an electro-active surface which is functionalized with linear or branched fluorinated carbon chains, such as perfluoroalkyl chains, in the form of a molecular layer which improves the corrosion resistance of said functionalized surface compared to a non-functionalized surface, wherein not impairing the passage of electrons between said electrode and its current collector, the functionalized surface being at the interface between said electrode and its current collector.

## Claims

### Claim 1

Electrochemical device or photo-electrochemical device comprising;
an electrolyte containing a bistriflimide anion, hereafter named as TFSI″, at least two electrodes, each of these electrodes being in contact with a current collector comprising a metal support
wherein at least one electrode has a current collector the metal support of which comprises an electro-active surface which is functionalized with linear or branched fluorinated carbon chains, such as perfluoroalkyl chains, in the form of a molecular layer which improves the corrosion resistance of said functionalized surface compared to a non-functionalized surface, wherein not impairing the passage of electrons between said electrode and its current collector, the functionalized surface being at the interface between said electrode and its current collector.

### Claim 2 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1, wherein the fluorinated carbon chains of the functionalized electro-active surface comprise perfluoroalkyl aryl moieties.

### Claim 3 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1, wherein the perfluoroalkyl aryl moiety is an aromatic cycle which is mono- or di- substituted by respectively one or two linear or branched perfluoroalkyl chain(s), preferably linear or branched perfluoro C1 to C20 alkyl chain(s), more preferably linear or branched perfluoro C1 to C10 alkyl chain(s).

### Claim 4 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1, wherein the linear or branched fluorinated carbon chain is a perfluoroalkyl chain chosen among the following groups: trifluoromethyl, perfluorohexyl and perfluorooctyl group.

### Claim 5 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1, wherein the metal support of the current collector is an aluminum substrate having a purity above 95%, preferably a purity equal or above 99% or an aluminum alloy comprising more than 95% Al, preferably more than 99% Al.

### Claim 6 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1, wherein the TFSI″ containing electrolyte is a liquid electrolyte, preferably a mixture of a salt containing the TFSI″ anion, such as LiTFSI, NaTFSI, or NH4TFSI, and an organic solvent or mixture of organic solvents or the former salts dissolved in pure or diluted molten salt, known as ionic liquids.

### Claim 7 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1, wherein the TFSI″ containing electrolyte is a solid electrolyte, preferably a polymer based electrolyte, preferably a mixture of a salt containing this anion, such as LiTFSI, NaTFSI, or NH4TFSI, and a polymer or mixture of polymer or a physical ionogel or a chemical ionogel comprising a silica matrix or a mixture of silica and a polymer matrix.

### Claim 8 (depends on 1)

Electrochemical device or photo-electrochemical device according to claim 1 wherein said device is chosen among: an energy storage device, a lithium-ion, sodium-ion, magnesium-ion, a calcium-ion or an aluminum battery, an electrochemical capacitor so called supercapacitor, a lithium-ion or a sodium-ion capacitor, a hybrid device intermediate between battery and supercapacitor, a photo-battery, or an electro-chromic device.

### Claim 9 (depends on 1)

Electrochemical device according to claim 1 wherein said device is a lithium-ion battery comprising
a graphite anode with a copper current collector,
a Nickel Manganese Cobalt cathode with a functionalized aluminum current collector, and
LiTFSI 0.75 M in Ethylene carbonate:Diethylcarbonate as electrolyte.

### Claim 10 (depends on 1)

Process for preparing the functionalized current collector of the electrochemical device or photo-electrochemical device of claim 1 comprising the following main steps:
Providing a current collector for electrochemical devices, said current collector comprising a support with a metallic surface;
Polishing said metallic surface with a fine abrasive to remove any oxide layer, then washing said surface with an organic solvent under ultra- sonication to obtain a polished electro-active surface;
Functionalizing the polished electro-active surface by dipping said surface of the current collector in a solution comprising a diazonium salt of a perfluoroalkyl moiety, preferably a perfluoroalkyl aryl moiety, under reducing conditions of the diazonium salt, and obtaining an electro-active surface functionalized with the perfluoroalkyl aryl moiety,
Optionally washing the functionalized surface with an organic solvent under ultra-sonication, to remove the non-functionalized molecules from the electro-active surface of the support.

### Claim 11 (depends on 10)

Process according to claim 10 wherein the functionalized step is performed in an any one of an electrochemical cell, a photochemical cell, a heated cell or a sonicated cell,
and/or with the help of a chemical reducer in said solution.

### Claim 12 (depends on 10)

Process according to claim 10 wherein the polishing step is a dry polishing step.

### Claim 13 (depends on 10)

Process according to claim 10 wherein the functionalizing step is performed in a chronoamperometric cell containing a solution comprising a diazonium salt of the functionalizing perfluoroalkyl aryl moiety, an auxiliary electrode, a reference electrode and said metallic support as working electrode, at a potential under the redox potential of said diazonium salt of the functionalizing perfluoroalkyl aryl moiety.

### Claim 14 (depends on 13)

Process according to claim 13 wherein the auxiliary electrode of the chronoamperometric cell is an electronically conductive plate, and the working electrode of the chronoamperometric cell is said metallic support of the current collector made of an aluminum substrate having a purity above 95%, or made of an aluminum alloy comprising than 95% Al.

### Claim 15 (depends on 14)

Process according to claim 14 wherein said aluminum substrate having a purity above 99%.

### Claim 16 (depends on 14)

Process according to claim 14 wherein said aluminum alloy comprising than 99% Al.