Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/04—Processes of manufacture in general
  • H01M4/049—Manufacturing of an active layer by chemical means
  • H01M4/0492—Chemical attack of the support material
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
  • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/66—Selection of materials
  • H01M4/669—Steels
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/70—Carriers or collectors characterised by shape or form
  • H01M4/72—Grids
  • H01M4/74—Meshes or woven material; Expanded metal
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/64—Carriers or collectors
  • H01M4/70—Carriers or collectors characterised by shape or form
  • H01M4/72—Grids
  • H01M4/74—Meshes or woven material; Expanded metal
  • H01M4/747—Woven material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/021—Physical characteristics, e.g. porosity, surface area
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
  • Y02T10/00—Road transport of goods or passengers
  • Y02T10/60—Other road transportation technologies with climate change mitigation effect
  • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

• Lithium metal or Li metal terminology generally defines the technology in which the anode or negative electrode comprises metal, the electrolyte contains lithium ions, and the cathode or positive electrode comprises at least one reversibly electrochemically reactive material with lithium.
• the electrochemically reactive material reversibly with lithium is for example an insertion material, containing or not lithium.
• the electrolyte generally contains lithium ions, whether the electrolyte is liquid or a polymer loaded with lithium salt - in this case, generally speaking, dry polymer is used.
• Lithium ion (Li ion) terminology generally defines the technology in which the cathode comprises an insertion material comprising lithium, the anode comprises at least one electrochemically reactive material reversibly with lithium, and the electrolyte contains ions.
• the electrochemically reactive material reversibly with lithium is for example an insertion material, whether or not containing lithium, or carbon.
• the electrolyte generally contains lithium ions, whether in liquid form or in the form of polymer impregnated with liquid - in this case, generally speaking, plastic electrolyte is used.
• Lithium metal technology, and lithium ion technology are likely to meet the needs of electric vehicles, hybrids or plug-in hybrids, but remain at high prices given the nature of the materials used and an insufficient level of security.
• C 5 is the surface capacity of the negative electrode (Ah / m 2 )
• the capacity per unit weight of active material (C_ / m ma) is proportional to the number of electrons involved in the electrochemical reaction equation takes place at the electrode. It is fixed by the chemical nature of the electrochemically active material.
• the Applicant has found a way to increase the mass capacity of an electrode for lithium-ion or lithium-metal type accumulators, and consequently the mass energy density of these accumulators, by configuring one of the electrodes of such a cell.
• accumulator in the form of a textile based on son and / or metal fibers (electron collector) comprising a coating of electrochemically active nanostructured material as described in the application FR 2 870 639.
• the subject of the present invention is therefore an electrode, for a lithium-ion or lithium-metal accumulator, comprising
• the present invention is an improvement, the nanostructured layer containing nanoparticles of at least one compound of a transition metal present in the electron collector is a conversion layer, that is to say a layer obtained by chemical or electrochemical transformation of the metal surface of the support.
• a conversion layer that is to say a layer obtained by chemical or electrochemical transformation of the metal surface of the support.
• the formation of an electrochemically active layer by depositing a coating on the textile structure entails a significant risk of closing the openings (meshes) of the textile which would nullify the advantages inherent to such a textile structure. This risk of closing the openings of the textile is obviously all the stronger as the openings are small.
• the main objective of the present invention is to provide electrodes for lithium-ion or lithium-metal accumulators having a maximum active surface for a minimum of electron collector mass (reduction of the costs related to the raw material metal) and for a minimum of space (miniaturization of the accumulators).
• the Applicant has succeeded in preparing electrodes having a specific surface area (expressed per unit area) of between 2 and 100 m 2 / m 2 , preferably between 20 and 80 m 2 / m 2 of geometric electrode surface, or a developed surface per unit of electrode mass of between 10 ⁇ 3 and 5 m 2 / g, preferably between 10 ⁇ 2 and 3 m 2 / g of electrode.
• the electrode according to the present invention differs from that disclosed and claimed in the application FR 2 870 639 of the Applicant mainly by its textile structure.
• the technical characteristics of the electrode of the present invention are similar to those disclosed in FR 2 870 639, except that it is necessary to selecting among the metals and metal alloys disclosed herein those having a drawing and weaving suitability.
• the at least one transition metal of the Electron collectors are selected from the group consisting of nickel, cobalt, manganese, copper, chromium and iron, preferably from iron and chromium.
• these metals are converted by a suitable treatment, described in more detail below, into a compound of said transition metal (s).
• This compound is preferably a mineral compound and is advantageously chosen from chalcogenides and halides, preferably from chalcogenides.
• the metal compound present in the conversion layer is a metal oxide.
• the transition metal compound is a compound of formula M x O 7 , where 1 ⁇ x ⁇ 3 and 1 ⁇ y ⁇ 5, preferably 1 ⁇ y ⁇ 4, and M is at least one transition metal.
• This compound is preferably selected from the group formed by AB 2 O 4 spinel structures, where A is at least one transition metal selected from the group consisting of Fe, Mn, Cr, Ni, Co and Cu, and B is at least one metal selected from the group consisting of Fe, Cr and Mn, and / or in the group formed by the sesquioxides M ' 2 C> 3, where M' is at least one transition metal selected from the group formed by Fe, Mn, Cr, Ni, Co and Cu.
• the transition metal compound is in particular Cr 2 C> 3 or a compound corresponding to the formula Fe X 'CryMn 2 O 4 , where: 0 ⁇ x' ⁇ 1, 0 ⁇ z ' ⁇ 1, and x' + y '+
• the conversion layer of the textile electrode of the present invention is a "nanostructured" layer containing nanoparticles having a mean diameter of between 1 and
• the nanoparticles are preferably grouped and agglomerated to each other, the agglomerates preferably having a mean size of between 1 and 10,000 nm, in particular between 10 and 3000 nm.
• the porous structure based on nanoparticle agglomerates can be demonstrated for example by scanning electron microscopy.
• the conversion layer (electrochemically active material) preferably covers the entire surface of the electron collector and preferably has a thickness between 30 nm and
• 15000 nm in particular between 30 nm and 12000 nm.
• the electron collector is a fabric formed of an alloy containing chromium, for example an alloy iron and chrome.
• the electron collector is stainless steel.
• the formation of the nanostructured conversion layer is described in application FR 2 870 639.
• the treatment used in this document can be applied without any other precautions or modifications to the metal textiles described above.
• Said conversion treatment is, for example, a high temperature heat treatment in a reducing, neutral or oxidizing atmosphere. These treatments are treatments known to those skilled in the art and are commonly used.
• It may be for example a hydrogen treatment at a temperature between 500 and 1000 0 C, preferably between 600 and 800 0 C, for example at a temperature of 700 0 C, for a duration of Ih at 16 o'clock.
• the conversion layer formed at the end of the oxidizing or reducing heat treatment does not generally have the desired definite nanostructured structure of the textile electrode of the invention.
• the final nanostructuration of the electrode that is to say the formation of nanoparticles, occurs only during the first discharge of the accumulator. It is of course possible to subject the textile electrode to such a discharge before incorporating it into a lithium battery.
• This first discharge can be done for example by reduction of the textile electrode relative to a lithium electrode in an organic electrolyte charged with lithium salt, at a reduced current density (0.05 to 0.5 mA / cm 2 electrode geometrical surface area) up to a potential of 20 mV with respect to lithium, then oxidation of said textile electrode at a reduced current density (0.05 to 0.5 mA / cm 2 of geometrical surface area). electrode) up to a potential of 3000 mV with respect to lithium.
• the present invention further relates to an electrochemical half-battery and an electrochemical accumulator containing a textile electrode as described above.
• An electrochemical half-battery according to the invention comprises a textile electrode with a nanostructured conversion layer, as described above, said textile electrode being covered over its entire surface with a coating providing the function of battery electrode separator.
• This coating is intended to electrically separate the two electrodes of the accumulator.
• This separator must also be able to be impregnated with a liquid electrolyte comprising at least one lithium salt and therefore preferably a porous structure or a polymer type structure that can be swollen by the electrolyte.
• the deposition of the separator must not close the openings or meshes of the metal textile forming the electrode, but must preferably preserve at least 50%, in particular at least 70% and ideally all the openings of the starting metal fabric . Closing or preserving these openings depends inter alia on the thickness of the separator deposited. This must have a sufficiently small thickness so that at least a portion of the openings of the textile electrode are not closed by said separator.
• the deposition of such a separator can be done by various suitable methods, such as immersion, spraying or chemical vapor deposition, the deposition of this coating is preferably electrochemically and in particular according to a technique known as cataphoresis.
• This technique where the metal structure or the wire to be coated is introduced, as a cathode, into an aqueous solution containing the basic components of the coating to deposit, allows indeed an extremely fine deposit, regular and continuous, covering the entire surface of a structure, even very complex geometry.
• the component to be deposited must have a positive charge.
• the separator is deposited by cataphoresis from an aqueous solution containing such cationic monomers, preferably cationic monomers having quaternary amine functions.
• the separator is cataphoretically deposited from said aqueous solution onto the textile electrode with a nanostructured conversion layer as previously described.
• the separator is deposited by cataphoresis, from said aqueous solution, on the son or metal fibers having a nanostructured conversion layer, as described above, before these are assembled by example by a weaving or knitting technique for producing a textile structure.
• the half-accumulator described above formed by the textile electrode coated with a separator, can be incorporated in an electrochemical accumulator, object of the present invention comprising, in addition to said half-accumulator, a liquid electrolyte impregnating the separator of the half-accumulator, and an electrode of opposite polarity to that of the half-accumulator, preferably completely covering the surface of the separator impregnated with the electrolyte.
• the accumulator is a lithium-ion battery, comprising (i) a half-battery as described above, comprising an anode with a separator,
• a liquid electrolyte containing a lithium salt impregnating the separator of the half-accumulator, (iii) as a cathode, a mixture comprising a lithium ion insertion material, a polymeric binder and a secondary electronic conductor, covering the surface of the separator impregnated with the electrolyte, and (iv) a current collector of the cathode, for example aluminum.
• Liquid electrolytes comprising a lithium salt, usable in lithium-ion accumulators are known to those skilled in the art.
• LiBF 4 a lithium salt selected from the group consisting of LiCF 3 SO 3 , LiClO 4 , LiPF 6 , and LiBF 4 .
• a textile structure comprising both (a) metal wires containing one or more transition metals of groups 4 to 12 of the Periodic Table of Elements, having a nanostructured conversion layer containing nanoparticles having a mean diameter between 1 and 1000 nm and containing at least one compound of said transition metal or said transition metals, providing the function of negative electrode, said metal wires (a) being covered over their entire surface with a separator, and (b) of metal wires suitable as an electron collector for the positive electrode, (ii) a liquid electrolyte containing a lithium salt, impregnating the separator of the half-accumulator, (iii) as a cathode, a mixture comprising a lithium ion insertion material, a polymeric binder and a secondary electronic conductor, the mixture covering the entire surface of the textile structure (i) comprising the electrolyte impregnated separator; (ii).
• the invention finally relates to a supercapacitor comprising a textile electrode according to the present invention.
• FIG IA shows a diagram of a half-accumulator according to the invention, seen from above (FIG IA) and in section (FIG IB) along line AA 'of FIG IA.
• Such a half-accumulator 200 comprises an electron collector 100, typically in the form of tissue seen on its edge in FIG. 1A, on the surface of which a layer 101 of active material has been formed. This layer of active material has been produced by heat treatment, for example in high temperature air, of the collector 100.
• the collector 100 is typically made of stainless steel.
• No external material has been added, such as a secondary electronic conductor such as carbon black, a binder or other metal.
• a separator layer 102 in the form of a thin film completely covering the surface of the wires of the metal fabric with their conversion layer.
• This coating 102 has been deposited so as not to close the apertures 103 of the fabric which can be distinguished in FIG.
• This separator has the particularity of being impregnated by a liquid electrolyte for lithium-ion battery.

Landscapes

• Chemical & Material Sciences (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Battery Electrode And Active Subsutance (AREA)
• Secondary Cells (AREA)
• Cell Electrode Carriers And Collectors (AREA)
• Inert Electrodes (AREA)
• Cell Separators (AREA)
• Electric Double-Layer Capacitors Or The Like (AREA)

Priority Applications (9)

Applications Claiming Priority (2)

Publications (2)

Family

ID=37668123

Family Applications (1)

Country Status (13)

Cited By (3)

Families Citing this family (33)

Citations (8)

Family Cites Families (6)

• 2006
  • 2006-05-24 FR FR0604693A patent/FR2901641B1/fr not_active Expired - Fee Related
• 2007
  • 2007-05-18 ES ES07766073T patent/ES2349345T3/es active Active
  • 2007-05-18 JP JP2009511554A patent/JP5559533B2/ja not_active Expired - Fee Related
  • 2007-05-18 CA CA2653114A patent/CA2653114C/fr not_active Expired - Fee Related
  • 2007-05-18 EP EP07766073A patent/EP2022116B1/fr not_active Not-in-force
  • 2007-05-18 WO PCT/FR2007/051299 patent/WO2007135331A1/fr not_active Ceased
  • 2007-05-18 US US12/301,822 patent/US8815442B2/en not_active Expired - Fee Related
  • 2007-05-18 AT AT07766073T patent/ATE476760T1/de active
  • 2007-05-18 KR KR1020087031458A patent/KR101485974B1/ko not_active Expired - Fee Related
  • 2007-05-18 CN CN2007800188150A patent/CN101449409B/zh not_active Expired - Fee Related
  • 2007-05-18 PT PT07766073T patent/PT2022116E/pt unknown
  • 2007-05-18 DE DE602007008232T patent/DE602007008232D1/de active Active
  • 2007-05-18 DK DK07766073.6T patent/DK2022116T3/da active

Patent Citations (8)

Also Published As

Similar Documents

Legal Events