WO2012163426A1 - Matériau d'électrode pour batteries au lithium et au lithium-ion - Google Patents

Matériau d'électrode pour batteries au lithium et au lithium-ion Download PDF

Info

Publication number
WO2012163426A1
WO2012163426A1 PCT/EP2011/059148 EP2011059148W WO2012163426A1 WO 2012163426 A1 WO2012163426 A1 WO 2012163426A1 EP 2011059148 W EP2011059148 W EP 2011059148W WO 2012163426 A1 WO2012163426 A1 WO 2012163426A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
acid
nanoparticles
lithium
carbon
Prior art date
Application number
PCT/EP2011/059148
Other languages
English (en)
Inventor
Elie Paillard
Dominic BRESSER
Martin Winter
Stefano Passerini
Marinella STRICCOLI
Enrico BINETTI
Roberto COMPARELLI
Maria Lucia CURRI
Original Assignee
Westfälische Wilhelms Universität
Consiglio Nazionale Delle Ricerche
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Westfälische Wilhelms Universität, Consiglio Nazionale Delle Ricerche filed Critical Westfälische Wilhelms Universität
Priority to PCT/EP2011/059148 priority Critical patent/WO2012163426A1/fr
Priority to EP11725660.2A priority patent/EP2715843A1/fr
Publication of WO2012163426A1 publication Critical patent/WO2012163426A1/fr

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to a method for manufacturing electrode material.
  • the present invention relates to the use of a nanoparticle-carbon-composite prepared by the method as active material for electrodes used in lithium and lithium ion batteries. Due to their high energy density, long cycle life, and efficient energy storage, lithium ion batteries are currently being considered as the leading candidate to meet the demands of electrochemical energy storage for hybrid and electric vehicles and renewable energy sources.
  • the up-scaling of the present chemistry which is based on LiCo0 2 and graphite, raises issues on materials availability, costs, and safety.
  • nano structured materials have the disadvantage of agglomeration during the electrode preparation process.
  • improvements in the preparation of nano structured electrode materials are agglomeration during the electrode preparation process.
  • the object underlying the present invention was to provide electrode material usable in lithium and lithium ion batteries
  • the problem is solved by a method for manufacturing electrode material particularly for lithium and lithium ion batteries comprising the following steps:
  • step b) heat-treatment of the monocarboxylic acid coated nanoparticles of step a) for carbonization of the monocarboxylic acid coating.
  • the method of the invention using monocarboxylic acid for coating nanoparticles takes advantage of the organic capping as dispersing agent to avoid particle agglomeration during the preparation. Further, the monocarboxylic acid coating, upon thermally-induced conversion into carbon, can contribute to the electron conductive percolating network. Advantageously, the carbonization of the monocarboxylic acid provides the opportunity to create a coating on the electrode material.
  • electrodes based on the nanoparticles prepared by the method taking advantage of the capping with monocarboxylic acids showed improved high rate performance and cycling stability.
  • electrodes based on the nanoparticle-carbon- composite demonstrated improved results in terms of combined reversible capacity, long-term cycle performance, and safety, particularly for titanium based composite materials, wherein the operative potential window was within the electrochemical stability window of common electrolytes.
  • the nanoparticle-carbon-composite prepared by the method of the invention provide an appealing anode material candidate for the realization of safe, high performance, large electrochemical energy storage devices that are strongly required for the development of sustainable electric vehicles and effective use of renewable energies.
  • carbonization refers to the conversion of an organic substance, particularly a monocarboxylic acid, into carbon or a carbon-containing residue.
  • nanoparticles in step b) is performed at a temperature in the range of > 250°C to ⁇ 850°C, preferably in the range of > 300°C to ⁇ 550°C, more preferably in the range of > 300°C to ⁇ 400°C.
  • Low temperatures can provide a gentle carbonization of the nanoparticles.
  • low temperatures can prevent a phase transformation of nanoparticles.
  • heat- treatment of anatase titanium dioxide nanoparticles at low temperatures can prevent a transformation to rutile titanium dioxide nanoparticles.
  • monocarboxylic acids provide the possibility to perform a carbonization at temperatures in the range of > 300°C to ⁇ 550°C, preferably in the range of > 300°C to ⁇ 400°C.
  • the heat-treatment can be performed in an inert atmosphere.
  • the heat- treatment can be performed in air. Performing the heat-treatment in air advantageously spares the need for an inert atmosphere and thus provides a cheaper and less complicated
  • a heat-treatment of the monocarboxylic acid coated nanoparticles in step b) is carried out for a time period in the range of > 3 h to ⁇ 24 h, preferably in the range of > 8 h to ⁇ 20 h, more preferably in the range of > 11 h to ⁇ 13 h.
  • the method provides a cost-sensitive method for the preparation of electrode material by omitting the need for high reaction temperatures, the use of inert gases, long reaction times, and high number of reaction steps.
  • a carbon-based coating layer can be formed on the surface of the nanoparticles.
  • the obtained nanoparticle- carbon-composite thus can comprise a carbonaceous coating.
  • the nanoparticle-carbon-composite for example Ti0 2 -nanorod-carbon-composite, preferably comprises a weight ratio of nanoparticle to carbon, for example Ti0 2 /C, in the range of > 50 : 50 to ⁇ 98 : 2, more preferably in the range of > 75 : 25 to ⁇ 90 : 10, and most preferred in a weight ratio of 85 : 15.
  • the nanoparticle-carbon-composite advantageously provides an active electrode material which can be deposited on a substrate to form battery electrodes.
  • the nanoparticle-carbon- composite particularly provides an electrode material for use in lithium and lithium ion batteries.
  • no additional carbon needs to be used for the electrode
  • the carbon-based coating can increase the electronic conductivity and inhibit particle agglomeration during the subsequent electrode preparation process. By this, higher capacities, enhanced high rate capability, and better cycling stability of the resulting electrodes can be obtained.
  • an oleic acid-coating on the nanoparticles is sufficient for providing a sufficient carbon-based coating of the nanoparticles after carbonization.
  • conductive carbon can be added to further contribute to the electron conducting carbonaceous percolating network. Adding carbonaceous material further can increase the electronic conductivity of the electrode material.
  • the method further comprises, particularly before the heat- treatment of step b), adding carbonaceous material to the monocarboxylic acid coated nanoparticles.
  • carbonaceous material can be added to the monocarboxylic acid coated nanoparticles in a weight ratio of monocarboxylic acid coated nanoparticles to carbonaceous material in the range of > 1 : 1 to ⁇ 40 : 1, more preferably in the range of > 7 : 3 to ⁇ 20 : 1 , and most preferred in a weight ratio of 9 : 1.
  • the mixture of carbonaceous material and coated nanoparticles can be homogenized, for example using a planetary ball mill.
  • the carbonaceous material can be added to the nanoparticles coated with a monocarboxylic acid which can either be dried or dispersed in an organic liquid compound for example selected from the group comprising dichloromethane, chloroform, alkanes, and monocarboxylic acids. If the carbonaceous material is added to the coated nanoparticles dispersed in an organic liquid compound, the mixture can be allowed to dry before heat-treatment.
  • the carbonaceous material preferably is selected from the group comprising carbon black, synthetic or natural graphite, graphenes, carbon nanotubes, carbon wires, carbon fibres, and fullerenes. Any one or combinations of two or more thereof may be used.
  • a usable carbon black for example commercially is available under the tradename
  • Ketjenblack® A preferably usable conductive carbon black commercially is available under the tradenames Super P® and Super P® Li. Of these, SuperP® conductive carbon is especially preferred.
  • Illustrative examples of usable electrically conductive graphite include flake graphite, lump graphite, artificial graphite, cashew graphite, amorphous carbon, and expanded graphite .
  • the carbonaceous material preferably is a carbonaceous powder. It is desirable for the conductive carbonaceous powder to have an average particle size within a range of 1 nm to 500 ⁇ , preferably 5 nm to 1 um. Especially preferred is the use of a conductive
  • carbonaceous powder having an average particle size in a range of 10 nm to 50 nm.
  • the average particle diameter may be 20 ⁇ or smaller, preferably 15 ⁇ or smaller, more preferably 10 ⁇ or smaller, especially in a range of 10 nm to 50 nm.
  • the average particle diameter refers to the median diameter (50% particle diameter) in a volume-based particle diameter distribution for example obtained with a laser diffraction type particle diameter distribution analyzer.
  • the carbonaceous powder may be subjected to size reduction and other suitable particle preparation operations so as to bring the average particle size into a usable range.
  • fine conductive carbonaceous powder can be obtained by pulverizing a conductive
  • the method further comprises adding carbonaceous material to the nanoparticle-carbon-composite obtained in step b), particularly after the heat- treatment of step b).
  • the method can comprise adding carbonaceous material to the monocarboxylic acid coated nanoparticles before the carbonization and to the nanoparticle- carbon-composite obtained in step b).
  • monocarboxylic acid refers to organic acids having one carboxylic function, the hydrocarbon chain being the saturated or unsaturated, branched or not branched, aliphatic or aromatic.
  • fatty acid refers to medium to long-chain saturated and unsaturated monocarboxylic acids, with an even number of carbons.
  • the monocarboxylic acid is an aliphatic straight-chain saturated or unsaturated monocarboxylic acid.
  • the monocarboxylic acid can be an aliphatic straight-chain saturated acid having a chain length of 8 to 20 carbon atoms, preferably selected from the group of octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and eicosanoic acid.
  • the monocarboxylic acid is a saturated fatty acid selected from the group comprising capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid.
  • the monocarboxylic acid is an aliphatic straight-chain saturated acid having a chain length of 8 to 14 carbon atoms.
  • the aliphatic straight-chain saturated monocarboxylic acid is decanoic or capric acid.
  • the hydrocarbon chain length can influence the size of the nanoparticles.
  • the monocarboxylic acid is a mono or polyunsaturated fatty acid having a chain length of 8 to 20 carbon atoms, preferably selected from the group comprising oleic acid, palmitoleic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, and arachidonic acid.
  • the monocarboxylic acid is a monounsaturated fatty acid selected from the group of oleic acid and palmitoleic acid. Palmitoleic acid also is denoted (Z)-9-hexadecenoic acid according to the IUPAC nomenclature.
  • the monocarboxylic acid is oleic acid which also is denoted (9Z)-Octadec-9-enoic acid according to the IUPAC nomenclature.
  • the nanoparticles are rod-shaped.
  • the term "rod-shaped nanoparticles” refers to nanosized cylindrical structures, particularly nanorods, nanowires, nanotubes, and nano fibers. These nanosized cylindrical structures are also referred to as one- dimensional nano structures.
  • nanometer-sized particles with a one-dimensional structure such as nanotubes, nanorods, and nanowires, particularly in lithium ion batteries can provide easy Li + ion diffusion into the host structure caused by their high specific surface area and low particle size.
  • the nanoparticles are rod-shaped nanoparticles having an average diameter in the range of > 2 nm to ⁇ 35 nm and an average length in the range of > 5 nm to ⁇ 200 nm.
  • rod-shaped nanoparticles have an average diameter in the range of > 2 nm to ⁇ 20 nm and an average length in the range of > 10 nm to ⁇ 100 nm, more preferably an average diameter in the range of > 3 nm to ⁇ 5 nm and an average length in the range of > 25 nm to ⁇ 35 nm.
  • the rod- shaped nanoparticles have an average diameter in the range of > 3 nm to ⁇ 4 nm and an average length in the range of > 25 nm to ⁇ 35 nm.
  • the nanoparticles are rod-shaped nanoparticles.
  • the term "sphere-shaped nanoparticles" refers to nanosized spherical structures, particularly nanospheres and nanodots.
  • sphere-shaped nanoparticles have an average diameter in the range of > 2 nm to ⁇ 100 nm, preferably an average diameter in the range of > 5 nm to ⁇ 50 nm, more preferably an average diameter in the range of > 7 nm to ⁇ 25 nm. Also sphere-shaped nanoparticles can exhibit good Li- insertion capability and electrodes based on sphere-shaped nanoparticles were able to deliver high rate reversible capacities.
  • the nanoparticles are titanium dioxide nanoparticles.
  • titanium oxides (Ti0 2 ) in lithium ion batteries provides the ability to reversibly insert considerable amounts of lithium within the electrochemical stability window of common organic electrolytes. Beside this, Ti0 2 offers several other advantages as being biocompatible, environmentally friendly, abundant and inexpensive. For example, the high lithium insertion potential, compared to graphite, prohibits the risk of electrolyte
  • titanium dioxide has a polymorph selected from the group comprising rutile, anatase, brookite and titanium dioxide (B).
  • the polymorph of titanium dioxide is anatase.
  • Anatase and rutile are tetragonal
  • brookite is orthorhombic
  • titanium dioxide(B) is monoclinic.
  • titanium is coordinated octahedrally by oxygen, but the position of the octahedra differs between polymorphs.
  • the use of anatase titanium dioxide nanoparticles led to improved results of lithium ion electrodes in terms of high rate capability, rate and cycling stabilities as well as higher capacities.
  • the nanoparticles are lithium titanate nanoparticles.
  • the lithium titanate has a formula Li x Ti y 0 4 , wherein 0.8 ⁇ x ⁇ 1.4 and wherein 1.6 ⁇ y ⁇ 2.2, preferably the lithium titanate is I ⁇ TisO ⁇ .
  • the nanoparticles are silicon oxide nanoparticles, wherein preferably the silicon oxide has a formula SiO x , wherein 0 ⁇ x ⁇ 1.8.
  • the nanoparticles are transition metal oxide nanoparticles.
  • the transition metal oxide is selected from the group comprising transition metal oxides of the formula MO x wherein the transition metal M is selected from the group comprising Sn, Zn, Cu, Co, Ni, Mn, and Fe, and x is in the range of > 1 to ⁇ 2, and mixtures thereof, and transition metal oxides comprising at least one transition metal oxide of MO x , Fe 3 0 4 , Mn 3 0 4 , Co 3 0 4 , and mixtures thereof.
  • Transition metal oxides of the formula MO x wherein the transition metal M is selected from the group comprising Sn, Zn, Cu, Co, Ni, Mn, and Fe, and x is in the range of > 1 to ⁇ 2, are for example ZnO, CoO, CuO, Fe 3 0 4 , Mn 3 0 4 , Co 3 0 4 , and Sn0 2 .
  • Transition metal oxides of the formula MO x wherein the transition metal M is selected from the group comprising Sn, Zn, Cu, Co, Ni, Mn, and Fe, and x is in the range of > 1 to ⁇ 2 for example are oxides of the formula Cu x Sni_ x O wherein 0 ⁇ x ⁇ 1, ZnCo 2 0 4 , CoFe 2 0 4 , and ZnFe 2 0 4 .
  • Transition metal oxides comprising at least one transition metal oxide of MO x , Fe 3 0 4 , Mn 3 0 4 , and Co 3 0 4 are for example MgCo 2 0 4 and CdFe 2 0 4 . Also a use of transition metal oxide nanoparticles can provide electrodes for lithium and lithium ion batteries.
  • nanoparticles particularly one-dimensional nanoparticles of titanium dioxide
  • Chemical approaches for the preparation of nanoparticles include several methods comprising sol-gel methods, surfactant-directed methods, and hydrothermal methods.
  • the nanoparticles are prepared by a low-temperature synthesis.
  • a preferred preparation of nanoparticles is a one- step, low-temperature method.
  • the nanoparticles coated, or capped, with a monocarboxylic acid in step a) are prepared by hydrolysis of an alkoxide of titanium, lithium, silicon, a transition metal, or mixtures thereof solved in the monocarboxylic acid at a temperature in the range of > 80°C to ⁇ 100°C using tertiary amines or quaternary ammonium hydroxides as catalysts.
  • the molar ratio of the monocarboxylic acid to the alkoxide is in the range of > 15 : 1 to ⁇ 130 : 1.
  • This method provides the advantage of the preparation of well-crystallized nanoparticles of controlled size and shape. Without being bound to a specific theory, it is assumed that the monocarboxylic acid functions as a shape-controller for the formation of the nanoparticles.
  • Preferred tertiary amines and quaternary ammonium hydroxides are selected from the group comprising trimethylamino-N-oxide dihydrate, anhydrous trimethylamino-N-oxide, trimethylamine, tetramethylammonium-hydroxide, tetrabutylammonium-hydroxide, triethylamine, and tributylamine.
  • monocarboxylic acid preferably oleic acid
  • the molar ratio of the monocarboxylic acid to the titanium alkoxide preferably is in the range of > 15 : l to ⁇ 130 : 1.
  • a temperature in the range of > 80°C to ⁇ 100°C can yield anatase polymorphs of titanium dioxide.
  • a preferred titanium alkoxide for the preparation of titanium dioxide nanoparticles is titanium tetraisopropoxide.
  • a preferred preparation of rod-shaped titanium dioxide nanoparticles coated or capped with a monocarboxylic acid, preferably oleic acid, is performed using an aqueous solution of tertiary amines or quaternary ammonium hydroxides selected from the group comprising
  • rod-shaped titanium dioxide nanoparticles the solution of titanium tetraisopropoxide, monocarboxylic acid and catalyst preferably is reacted over a time period in the range of > 4 h to ⁇ 12 h, preferably in the range of > 6 h to ⁇ 12 h.
  • rod- shaped well-crystallised anatase titanium dioxide nanoparticles are obtainable using a fast hydrolysis in an aqueous solution of tertiary amines or quaternary ammonium hydroxides.
  • a preferred preparation of spherical titanium dioxide nanoparticles coated or capped with a monocarboxylic acid, preferably oleic acid, is performed using a solution of tertiary amines or quaternary ammonium hydroxides selected from the group comprising anhydrous
  • the solution of titanium tetraisopropoxide, monocarboxylic acid and catalyst preferably is reacted over a time period up to 60 h, preferably up to 48 h.
  • a slow hydrolysis in a non-aqueous solution spherical well-crystallised anatase titanium dioxide can be obtained.
  • the nanoparticles coated with a monocarboxylic acid can contain in the range of > 10 wt.-% to ⁇ 50 wt.-%, preferably in the range of > 20 wt.-% to ⁇ 35 wt.-%, more preferably in the range of > 22 wt.-% to ⁇ 26 wt.-%, of a monocarboxylic acid, based on the total weight of the coated nanorods.
  • a carbon-based coating layer can be formed on the surface of the nanoparticles.
  • a nanoparticle-carbon- composite can be obtained by the heat-treatment.
  • the nanoparticle-carbon-composite advantageously provides an active electrode material which can be deposited on a substrate to form battery electrodes.
  • the nanoparticle-carbon- composite particularly provides an electrode material for use in lithium and lithium ion batteries.
  • no additional carbon needs to be used for the electrode preparation.
  • the method further comprises the step of depositing the nanoparticle-carbon-composite of step b) on a conductive substrate for an electrode, particularly for a lithium or lithium ion battery.
  • the conductive substrate can serve as current collector in the electrode.
  • a preferred conductive substrate is a copper foil.
  • Further possible conductive substrates are nickel and aluminum foil, as well as alloys containing these metals, as well as stainless steel, titanium, graphite, as well as carbon, as well as conductive glasses or carbonaceous compounds in general.
  • the composite for example Ti0 2 -nanorod-carbon-composite
  • a binder for example poly(vinylidenedifluoride-hexafluoropropylene) (PVDF-HFP) copolymer.
  • PVDF-HFP poly(vinylidenedifluoride-hexafluoropropylene)
  • Further usable binders comprise simple polyvinylidene fluoride (PVDF), styrene butadiene rubber (SBR), or sodium carboxymethyl cellulose (Na-CMC), or poly(tetrafluoroethylene) (PTFE).
  • the weight ratio of nanoparticle-carbon-composite, for example Ti0 2 -nanorod-carbon- composite, and binder preferably is in the range of > 70 : 30 to ⁇ 97 : 3, more preferably in the range of > 80 : 20 to ⁇ 95 : 5. Most preferred the weight ratio of the nanoparticle-carbon- composite, for example Ti0 2 -nanorod-carbon-composite, and binder is 88: 12.
  • a mixture of nanoparticle-carbon-composite, binder, and conductive carbonaceous material can comprise in the range of > 50 to wt.-% ⁇ 95 wt.-% nanoparticle-carbon-composite, in the range of > 2 to wt.-% ⁇ 45 wt.-% conductive carbonaceous material, and in the range of > 2 to wt.-% ⁇ 20 wt.-% binder, respectively, wherein the total amount of the mixture will not exceed 100 wt.-%.
  • the dry weight of a mixture of nanoparticle-carbon-composite, for example Ti0 2 -nanorod-carbon- composite, and binder comprises 75 wt.-% nanoparticles, 13 wt.-% carbon and 12 wt.-% binder, for example PVDF-HFP, based on the total weight of the mixture.
  • the nanoparticle-carbon-composite of step b) is deposited on a conductive substrate for a battery electrode, particularly for a lithium or lithium ion battery, with a wet film thickness in the range of > 50 ⁇ to ⁇ 300 ⁇ , preferably in the range of > 90 ⁇ to ⁇ 150 ⁇ , more preferably in the range of > 110 ⁇ to ⁇ 130 ⁇ .
  • the nanoparticle-carbon-composite of step b) is deposited on a conductive substrate for a battery electrode, particularly for a lithium or lithium ion battery, with a mass loading in the range of > 0.2 mg cm “2 to ⁇ 30 mg cm “2 , preferably in the range of > 1 mg cm “2 to ⁇ 10 mg cm “2 , more preferably in the range of > 1.5 mg cm “2 to ⁇ 1.7 mg cm “2 .
  • a wet film thickness and/or mass loading can provide a good performance of electrochemical energy storage devices, especially lithium or lithium ion batteries.
  • a method for preparing an electrode based on nanoparticle-carbon- composite comprises the steps of admixing the nanoparticle-carbon-composite with carbon black, binder, and a solvent, e.g. N- methylpyrrolidinone (NMP), acetone, or water, or without in case of PTFE as binder, stirring the admixture, depositing the admixture onto a surface of conductive substrate for an electrode preparation and obtaining electrodes from the spread particulate admixture, and drying the obtained electrodes.
  • NMP N- methylpyrrolidinone
  • Another aspect of the invention refers to an electrode material for electrochemical energy storage devices particularly for lithium and lithium ion batteries prepared by the method according to the invention.
  • the electrode material manufactured by the method according to the invention provides improved high rate performance and cycling stability of the resulting electrodes.
  • the method for manufacturing electrode material comprises to the following steps:
  • step b) heat-treatment of the monocarboxylic acid coated nanoparticles of step a) for carbonization of the monocarboxylic acid coating.
  • the heat-treatment of the monocarboxylic acid coated nanoparticles in step b) is performed at a temperature in the range of > 250°C to ⁇ 850°C, preferably in the range of > 300°C to ⁇ 550°C, more preferably in the range of > 300°C to ⁇ 400°C.
  • Another aspect of the invention refers to an electrode comprising electrode material, particularly a nanoparticle-carbon-composite, prepared by the method according to the invention.
  • the electrode comprising the nanoparticle-carbon-composite is an anode for a lithium or lithium ion battery.
  • a lithium- ion battery for example comprises a first electrode of a cathodic material, a second electrode of an anodic material and an electrolyte.
  • electrodes based on the nanoparticles prepared by the method taking advantage of the capping with monocarboxylic acids showed improved high rate performance and cycling stability. Further, electrodes based on the nanoparticle-carbon- composite demonstrated improved results in terms of combined reversible capacity, long-term cycle performance, and safety, particularly for titanium based composite materials, wherein the operative potential window was within the electrochemical stability window of common electrolytes. Especially, the use of the nanoparticle-carbon-composite led to excellent high rate performance and excellent cycle life performance of electrodes based on the nanoparticle- carbon-composite.
  • anatase Ti0 2 -nanorod electrodes showed excellent electrochemical performance in terms of reversible capacity, cycling stability, faradic efficiency and high rate capability.
  • the nanoparticles for the electrode material are rod-shaped.
  • the nanoparticles are rod-shaped nanoparticles having an average diameter in the range of > 2 nm to ⁇ 35 nm and an average length in the range of > 5 nm to ⁇ 200 nm.
  • rod-shaped nanoparticles have an average diameter in the range of > 2 nm to ⁇ 20 nm and an average length in the range of > 10 nm to ⁇ 100 nm, more preferably an average diameter in the range of > 3 nm to ⁇ 5 nm and an average length in the range of > 25 nm to ⁇ 35 nm.
  • the rod- shaped nanoparticles have an average diameter in the range of > 3 nm to ⁇ 4 nm and an average length in the range of > 25 nm to ⁇ 35 nm.
  • the nanoparticles for the electrode material are sphere-shaped nanoparticles.
  • the term "sphere-shaped nanoparticles" refers to nanosized spherical structures, particularly nanospheres and nanodots.
  • sphere-shaped nanoparticles have an average diameter in the range of > 2 nm and ⁇ 100 nm, preferably an average diameter in the range of > 5 nm to ⁇ 50 nm, more preferably an average diameter in the range of > 7 nm to ⁇ 25 nm.
  • the nanoparticles for the electrode material are titanium dioxide nanoparticles.
  • titanium dioxide has a polymorph selected from the group comprising rutile, anatase, brookite and titanium dioxide (B).
  • the polymorph of titanium dioxide is anatase.
  • the nanoparticles are lithium titanate nanoparticles.
  • the lithium titanate has a formula Li x Ti y 0 4 , wherein 0.8 ⁇ x ⁇ 1.4 and wherein 1.6 ⁇ y ⁇ 2.2, preferably the lithium titanate is I ⁇ TisO ⁇ .
  • the nanoparticles are silicon or silicon oxide nanoparticles, wherein preferably the silicon oxide has a formula SiO x , wherein 0 ⁇ x ⁇ 1.8.
  • the nanoparticles are transition metal oxide nanoparticles.
  • the transition metal oxide is selected from the group comprising transition metal oxides of the formula MO x wherein the transition metal M is selected from the group comprising Sn, Zn, Cu, Co, Ni, Mn, and Fe, and x is in the range of > 1 to ⁇ 2, and mixtures thereof, and transition metal oxides comprising at least one transition metal oxide of MO x , Fe 3 0 4 , Mn 3 0 4 , Co 3 0 4 , and mixtures thereof.
  • Transition metal oxides of the formula MO x wherein the transition metal M is selected from the group comprising Sn, Zn, Cu, Co, Ni, Mn, and Fe, and x is in the range of > 1 to ⁇ 2, are for example ZnO, CuO, CoO, Fe 3 0 4 , Mn 3 0 4 , Co 3 0 4 , and Sn0 2 .
  • Transition metal oxides of the formula MO x wherein the transition metal M is selected from the group comprising Sn, Zn, Cu, Co, Ni, Mn, and Fe, and x is in the range of > 1 to ⁇ 2 for example are oxides of the formula Cu x Sni_ x O wherein 0 ⁇ x ⁇ 1, ZnCo 2 0 4 , CoFe 2 0 4 , and ZnFe 2 0 4 .
  • Transition metal oxides comprising at least one transition metal oxide of MO x , Fe 3 0 4 , Mn 3 0 4 , and Co 3 0 4 are for example MgCo 2 0 4 and CdFe 2 0 4 .
  • a carbonization of the monocarboxylic acid coating of the nanoparticles a carbon-based coating layer can be formed on the surface of the nanoparticles.
  • the nanoparticle-carbon- composite can comprise a carbonaceous coating.
  • the nanoparticle-carbon- composite can comprise a carbon-based coating layer on the surface of the nanoparticles.
  • the carbonized nanoparticles for example carbonized Ti0 2 -nanorods, preferably comprise a weight ratio of nanoparticle to carbon, for example Ti0 2 /C, in the range of > 50 : 50 to ⁇ 98 : 2, more preferably in the range of > 75 : 25 to ⁇ 90 : 10, and most preferred in a weight ratio of 85: 15.
  • Another aspect of the invention refers to the use of nanoparticle-carbon-composite prepared by the method according to the invention as electrode material for electrochemical energy storage devices, particularly as active material for electrodes used in lithium and lithium ion batteries.
  • the carbonized nanoparticles comprise a carbonaceous coating.
  • Further possible applications for electrochemical energy storage devices for example are hybrid supercapacitors, for example comprising activated carbon as cathode and Ti0 2 as anode.
  • FIG. 1 A powder X-ray diffraction (XRD) pattern of the carbonized Ti0 2 -nanorods (Ti0 2 - NRs/C) after thermal treatment at 350°C in air.
  • the anatase Ti0 2 reference ICSD 172914 is shown in the bottom.
  • FIG. 1 Voltammograms of a Ti0 2 -nanorods electrode.
  • the scan rate was 0.05 mV sec "1 .
  • the voltammograms of cycles 1 to 5 are shown in figures a) to c). a) Between 3.0 V and 1.2 V. The cut-off potential was 1.2 V. b) Between 3.0 V and 1.0 V. The cut-off potential was 1.0 V. c) Between 3.0 V and 0.1 V. The cut-off potential was 0.1 V. The voltammograms were taken after one day rest after assembling.
  • FIG. 3 HRSEM images of aTi0 2 -nanorod electrodes a) pristine and b) after 50 cycles.
  • the cut-off voltage was 1.0 V.
  • Figure 4 Galvanostatic charge discharge tests at different C rates. The lower cut-off potential was 1.2 V.
  • OLEA oleic acid
  • NRs oleic acid capped anatase Ti0 2 nanorods
  • Technical grade oleic acid was degassed and titanium tetraisopropoxide (TTIP) was added under nitrogen flow at 100°C to the degassed oleic acid.
  • TTIP titanium tetraisopropoxide
  • the anhydrous environment prevented the titanium tetraisopropoxide from premature hydrolysis.
  • TMAO trimethylamine-N-oxide
  • the oleic acid-capped anatase Ti0 2 -nanorods obtained in example 1 were mixed with Super P conductive carbon (TIMCAL) in a 90: 10 Ti0 2 /C-weight ratio in CH 2 C1 2 .
  • the mixture was then homogenized using a planetary ball mill (Vario-Planetary Mill Pulverisette 4, Fritsch) set at 800 rpm for 3 hours.
  • the composite was allowed to dry overnight at ambient temperature (20 ⁇ 2°C) and then was heat-treated at 350°C in air for 12 hours by placing the sample in a quartz boat, which was subsequently placed in a tubular furnace and heated up by 3°C/minute.
  • TGA Thermogravimetric analysis
  • XRD powder X-ray diffraction
  • Ti0 2 -nanorods electrodes The Ti0 2 -nanorods-carbon-composite (Ti0 2 -NRs/C composite) was mixed with PVDF-HFP copolymer (Kynarflex 2801, Arkema), as the binder, in an 88: 12 weight ratio. No additional carbon was used for the electrode preparation. N-methylpyrrolidone (Aldrich) was used as the solvent. The dry composition of the slurry was 75 wt.-% Ti0 2 -nanorods, 13 wt.-% carbon and 12 wt.-% PVDF-HFP.
  • the slurry was homogenized using planetary ball milling at 800 rpm for 1 hour (Vario-Planetary Mill Pulverisette 4, Fritsch). The resulting slurry was then casted on dendritic copper foil (Schlenk) by using a laboratory doctor blade, with a wet film thickness of 120 ⁇ .
  • the electrodes were dried in air for 1 hour at 80°C then 12 hours at ambient temperature (20 ⁇ 2°C). Disk electrodes of 12 mm diameter were then punched and dried for 12 hours at 120°C under vacuum.
  • the active material mass loading was comprised between 1.5 and 1.7 mg cm "2 . The active material mass loading was determined by weighting the electrodes, in a dry room or a glove box at room temperature, then the weight was divided by the area of the coated copper foil.
  • the cells were assembled in an MBraun glove box with oxygen and water contents below 0.5 ppm.
  • Galvanostatic cycling and cyclic voltammetry were performed in three different potential ranges ranging from 3.0 V (cathodic limit) and either 0.1, 1.0 and 1.2 V (anodic limit).
  • cyclic voltammetry a scan rate of 0.05 mV sec "1 was applied.
  • HRSEM high resolution scanning electron microscope
  • Cyclic voltammetry was carried out with different cathodic potential limits, namely 0.1, 1.0 and 1.2 V.
  • the anodic limit was in all experiments set to 3.0 V.
  • the recorded voltammograms during the initial 5 cycles are shown in Figure 2 a) - c). All three figures show the
  • anatase Ti0 2 For micrometer-sized anatase Ti0 2 only this peak couple is observed, which corresponds to the Li insertion/extraction processes into the Ti0 2 host structure. During lithium insertion, anatase Ti0 2 undergoes a separation in two phases, the Li-poor Lio. 0 iTi0 2 phase (space group with maintained anatase structure and tetragonal symmetry, and the Li-rich
  • Lio.55Ti0 2 phase space group Imma
  • lithium titanate structure and orthorhombic symmetry These two phases coexist up to a Li mol fraction of 0.55.
  • a second phase transformation Lio.ssTiC ⁇ - ⁇ LiTi0 2
  • LiTi0 2 space group: I4]/amd
  • the appearance of this new phase is confirmed by the peak couple seen in Figures 2 a) and b) at 1.45 V and 1.8 V, respectively for the lithium insertion and extraction processes. This peak couple is never observed in micro-sized particles.
  • Electrolyte decomposition was already observed during the voltammetric test performed with a cathodic limit of 1.0 V as confirmed by high resolution scanning electron microscope HRSEM analysis of a pristine and a cycled electrode, as can be seen in Figure 3.
  • the comparison of these two HRSEM images of Figure 3a) and Figure 3b) shows that a Solid Electrolyte Interphase (SEI) film was formed on the cycled electrode.
  • Solid Electrolyte Interphase denotes an electrodeposited layer originating from the decomposition products of the electrolyte.
  • an SEI passivates the electrode, preventing further decomposition of the electrolyte, while allowing the transport of lithium ions to the active material.
  • the delivered capacity at 1C rate was as high as 210 mAh g "1 with a faradic efficiency higher than 99%.
  • the electrodes still delivered high reversible capacities, namely 194 mAh g "1 at 2C, 165 mAh g "1 at 5C (this capacity
  • the Figure 4b shows the performance of a Ti0 2 -nanorods electrode subjected to continuous charge/discharge tests at different rates within 3.0 V and 1.2 V cut-off limits.
  • the overall stability of delivered capacity upon cycling at different rates demonstrates the highly stable cyclability of the investigated nanorods for a potential range of 1.2 to 3.0 V.
  • the high reversibility of the lithium insertion/extraction processes in the Ti0 2 -nanorods electrode after the first cycle is demonstrated by the recovery of the delivered specific capacity when the discharge/charge rate is set back to 1C.
  • the electrochemically investigations show that dispersed anatase Ti0 2 -nanorods prepared by low-temperature synthesis using capping with oleic acid, led to improved high rate performance and cycling stability of the synthesized nanorods.
  • the Ti0 2 -nanorods based electrodes showed very good results in terms of combined reversible capacity, long-term cycle performance, and safety, while the operative potential window was within the electrochemical stability window of common electrolytes.
  • the Ti0 2 -nanorods appear as an appealing anode material candidate for the realization of safe, high performance, large electrochemical energy storage devices that are strongly required for the development of sustainable electric vehicles and effective use of renewable energies.

Abstract

La présente invention concerne un procédé de fabrication d'un matériau d'électrode, notamment pour des batteries au lithium et au lithium-ion, comprenant les étapes suivantes : a) fourniture de nanoparticules de dioxyde de titane, de titanate de lithium, de silicium, d'oxyde de silicium ou d'un oxyde métallique de transition, enduites d'un acide monocarboxylique ayant une longueur de chaîne de 7 à 26 atomes de carbone ; b) traitement thermique des nanoparticules enduites d'acide monocarboxylique de l'étape a) pour la carbonisation du revêtement d'acide monocarboxylique.
PCT/EP2011/059148 2011-06-01 2011-06-01 Matériau d'électrode pour batteries au lithium et au lithium-ion WO2012163426A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/EP2011/059148 WO2012163426A1 (fr) 2011-06-01 2011-06-01 Matériau d'électrode pour batteries au lithium et au lithium-ion
EP11725660.2A EP2715843A1 (fr) 2011-06-01 2011-06-01 Matériau d'électrode pour batteries au lithium et au lithium-ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2011/059148 WO2012163426A1 (fr) 2011-06-01 2011-06-01 Matériau d'électrode pour batteries au lithium et au lithium-ion

Publications (1)

Publication Number Publication Date
WO2012163426A1 true WO2012163426A1 (fr) 2012-12-06

Family

ID=44627078

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/059148 WO2012163426A1 (fr) 2011-06-01 2011-06-01 Matériau d'électrode pour batteries au lithium et au lithium-ion

Country Status (2)

Country Link
EP (1) EP2715843A1 (fr)
WO (1) WO2012163426A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103022464A (zh) * 2013-01-23 2013-04-03 西南大学 MnCuZnFe2O4锂离子电池阳极材料的制备方法
CN103066262A (zh) * 2013-01-10 2013-04-24 西南大学 Mn0.5-xCuxZn0.5Fe2O4锂离子电池阳极材料的制备方法
CN103682268A (zh) * 2013-12-04 2014-03-26 上海纳米技术及应用国家工程研究中心有限公司 一种碳、钛酸锂双层包覆的硅负极材料的制备方法
CN103904332A (zh) * 2014-02-19 2014-07-02 上海璞泰来新材料技术有限公司 一种钛酸锂负极材料及其制备方法以及应用这种钛酸锂负极材料的锂离子电池
CN104332625A (zh) * 2014-08-27 2015-02-04 山东大学 动力锂电池用铁酸钴-氮掺碳复合负极材料及制备方法
CN105098168A (zh) * 2015-09-18 2015-11-25 孟红琳 一种动力型锂电池负极材料的制备方法
CN105206819A (zh) * 2014-05-30 2015-12-30 河南科隆新能源有限公司 一种锂离子电池负极浆料以及负极浆料的制备方法和负极极片的制备方法
CN105449193A (zh) * 2015-11-24 2016-03-30 桂林理工大学 P123辅助制备高性能铁酸锌电极材料的方法
CN106115803A (zh) * 2016-07-05 2016-11-16 西京学院 一种Co3O4纳米点水相法合成方法
CN106340403A (zh) * 2016-09-30 2017-01-18 江苏大学 一种钴酸锌纳米线或纳米带电极材料的制备方法及其用途
CN104465117B (zh) * 2014-11-08 2017-03-29 安徽师范大学 一种钴酸锌@二氧化锰核壳异质结构纳米管阵列材料、制备方法及其应用
WO2017197675A1 (fr) * 2016-05-20 2017-11-23 山东玉皇新能源科技有限公司 Matériau modifié au titanate de lithium et son procédé de fabrication
CN107705994A (zh) * 2017-09-06 2018-02-16 济南大学 一种ZnFe2O4掺氮碳纳米纤维复合电极材料及其制备方法
US10044037B2 (en) 2015-03-02 2018-08-07 Dun Chi Manufacturing a lead-acid battery that includes a composite that includes lead oxide and a nanomaterial
CN108539183A (zh) * 2018-05-14 2018-09-14 山东玉皇新能源科技有限公司 钛酸锂复合材料及其制备方法与锂离子电池负极材料和锂离子电池
CN109742342A (zh) * 2018-12-20 2019-05-10 桂林理工大学 一种制备高性能氧化锌/铁酸锌复合电极材料的方法
CN110364708A (zh) * 2019-06-28 2019-10-22 陕西科技大学 四氧化三锰-二氧化锡/四氧化三钴复合材料的制备方法
CN110993938A (zh) * 2019-12-21 2020-04-10 河南电池研究院有限公司 一种锂离子电池用铁基复合氧化物负极材料及其制备方法
US10770605B2 (en) * 2017-04-20 2020-09-08 King Abdulaziz University Photodiode with spinel oxide photoactive layer
CN111943285A (zh) * 2020-08-19 2020-11-17 浙江帕瓦新能源股份有限公司 一种纳米富锂锰基正极材料及其前驱体、基材以及制备方法
CN112952071A (zh) * 2021-04-08 2021-06-11 合肥国轩高科动力能源有限公司 一种多孔导电陶瓷复合硅负极材料及其制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108686665B (zh) * 2018-05-10 2022-04-15 南昌航空大学 一种纳米棒铁酸锌原位复合片层二氧化钛光催化材料的制备方法
CN109301209B (zh) * 2018-09-27 2022-03-18 三峡大学 一种二氧化钛改性磷/碳复合负极材料的制备方法
CN111180663A (zh) * 2018-11-13 2020-05-19 北方奥钛纳米技术有限公司 负极材料及其制备方法、负极片和锂离子电池
CN113036090A (zh) * 2021-03-15 2021-06-25 上海大学 一种氧化物修饰三元正极材料及其制备方法、二次电池

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060188431A1 (en) * 2004-12-03 2006-08-24 Daocheng Pan Method for preparing organic ligand-capped titanium dioxide nanocrystals
WO2011056150A2 (fr) * 2009-11-05 2011-05-12 National University Of Singapore Dioxyde de titane cristallin mésoporeux et son utilisation dans les dispositifs électrochimiques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060188431A1 (en) * 2004-12-03 2006-08-24 Daocheng Pan Method for preparing organic ligand-capped titanium dioxide nanocrystals
WO2011056150A2 (fr) * 2009-11-05 2011-05-12 National University Of Singapore Dioxyde de titane cristallin mésoporeux et son utilisation dans les dispositifs électrochimiques

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
EUN YI KIM ET AL: "Controlled growth of TiO2 nanorods capped with carboxylate groups by the solvothermal process", JOURNAL OF MATERIALS SCIENCE, KLUWER ACADEMIC PUBLISHERS, BO, vol. 45, no. 14, 10 April 2010 (2010-04-10), pages 3895 - 3900, XP019821620, ISSN: 1573-4803 *
LIN Z ET AL: "One-step synthesis of Li4Ti5O12/C anode material with high performance for lithium-ion batteries", SOLID STATE IONICS, NORTH HOLLAND PUB. COMPANY. AMSTERDAM; NL, NL, vol. 181, no. 8-10, 29 March 2010 (2010-03-29), pages 412 - 415, XP026960722, ISSN: 0167-2738, [retrieved on 20100218] *
SHYAMAL K. DAS ET AL: "Influence of Mesoporosity and Carbon Electronic Wiring on Electrochemical Performance of Anatase Titania", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 158, no. 6, 13 April 2011 (2011-04-13), pages A705 - A710, XP055015701, ISSN: 0013-4651, DOI: 10.1149/1.3574028 *

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103066262A (zh) * 2013-01-10 2013-04-24 西南大学 Mn0.5-xCuxZn0.5Fe2O4锂离子电池阳极材料的制备方法
CN103022464A (zh) * 2013-01-23 2013-04-03 西南大学 MnCuZnFe2O4锂离子电池阳极材料的制备方法
CN103682268A (zh) * 2013-12-04 2014-03-26 上海纳米技术及应用国家工程研究中心有限公司 一种碳、钛酸锂双层包覆的硅负极材料的制备方法
CN103904332B (zh) * 2014-02-19 2016-02-24 上海璞泰来新能源科技股份有限公司 一种钛酸锂负极材料及其制备方法以及应用这种钛酸锂负极材料的锂离子电池
CN103904332A (zh) * 2014-02-19 2014-07-02 上海璞泰来新材料技术有限公司 一种钛酸锂负极材料及其制备方法以及应用这种钛酸锂负极材料的锂离子电池
CN105206819A (zh) * 2014-05-30 2015-12-30 河南科隆新能源有限公司 一种锂离子电池负极浆料以及负极浆料的制备方法和负极极片的制备方法
CN104332625A (zh) * 2014-08-27 2015-02-04 山东大学 动力锂电池用铁酸钴-氮掺碳复合负极材料及制备方法
CN104465117B (zh) * 2014-11-08 2017-03-29 安徽师范大学 一种钴酸锌@二氧化锰核壳异质结构纳米管阵列材料、制备方法及其应用
US10050269B2 (en) 2015-03-02 2018-08-14 Dun Chi Manufacturing a lead-acid battery that includes a composite that includes lead oxide and a nanomaterial
US10044037B2 (en) 2015-03-02 2018-08-07 Dun Chi Manufacturing a lead-acid battery that includes a composite that includes lead oxide and a nanomaterial
CN105098168A (zh) * 2015-09-18 2015-11-25 孟红琳 一种动力型锂电池负极材料的制备方法
CN105449193B (zh) * 2015-11-24 2017-12-12 桂林理工大学 P123辅助制备高性能铁酸锌电极材料的方法
CN105449193A (zh) * 2015-11-24 2016-03-30 桂林理工大学 P123辅助制备高性能铁酸锌电极材料的方法
WO2017197675A1 (fr) * 2016-05-20 2017-11-23 山东玉皇新能源科技有限公司 Matériau modifié au titanate de lithium et son procédé de fabrication
CN106115803A (zh) * 2016-07-05 2016-11-16 西京学院 一种Co3O4纳米点水相法合成方法
CN106340403A (zh) * 2016-09-30 2017-01-18 江苏大学 一种钴酸锌纳米线或纳米带电极材料的制备方法及其用途
US10770605B2 (en) * 2017-04-20 2020-09-08 King Abdulaziz University Photodiode with spinel oxide photoactive layer
US10923612B2 (en) 2017-04-20 2021-02-16 King Abdulaziz University Photodiode having quantum dot light absorption layer
US10892369B2 (en) 2017-04-20 2021-01-12 King Abdulaziz University Photodiode having an aluminum metal ohmic contact and a spinel oxide layer
CN107705994A (zh) * 2017-09-06 2018-02-16 济南大学 一种ZnFe2O4掺氮碳纳米纤维复合电极材料及其制备方法
CN108539183A (zh) * 2018-05-14 2018-09-14 山东玉皇新能源科技有限公司 钛酸锂复合材料及其制备方法与锂离子电池负极材料和锂离子电池
CN109742342A (zh) * 2018-12-20 2019-05-10 桂林理工大学 一种制备高性能氧化锌/铁酸锌复合电极材料的方法
CN110364708A (zh) * 2019-06-28 2019-10-22 陕西科技大学 四氧化三锰-二氧化锡/四氧化三钴复合材料的制备方法
CN110993938A (zh) * 2019-12-21 2020-04-10 河南电池研究院有限公司 一种锂离子电池用铁基复合氧化物负极材料及其制备方法
CN111943285A (zh) * 2020-08-19 2020-11-17 浙江帕瓦新能源股份有限公司 一种纳米富锂锰基正极材料及其前驱体、基材以及制备方法
CN111943285B (zh) * 2020-08-19 2022-10-14 浙江帕瓦新能源股份有限公司 一种纳米富锂锰基正极材料及其前驱体、基材以及制备方法
CN112952071A (zh) * 2021-04-08 2021-06-11 合肥国轩高科动力能源有限公司 一种多孔导电陶瓷复合硅负极材料及其制备方法

Also Published As

Publication number Publication date
EP2715843A1 (fr) 2014-04-09

Similar Documents

Publication Publication Date Title
EP2715843A1 (fr) Matériau d'électrode pour batteries au lithium et au lithium-ion
Zheng et al. High performance columnar-like Fe2O3@ carbon composite anode via yolk@ shell structural design
Roy et al. Nanostructured anode materials for lithium ion batteries
US9868105B2 (en) Spinel-type lithium titanium oxide/graphene composite and method of preparing the same
US9923206B2 (en) Encapsulated phthalocyanine particles, high-capacity cathode containing these particles, and rechargeable lithium cell containing such a cathode
Rai et al. Partially reduced Co3O4/graphene nanocomposite as an anode material for secondary lithium ion battery
Bresser et al. Percolating networks of TiO2 nanorods and carbon for high power lithium insertion electrodes
TWI627783B (zh) 鋰離子二次電池用電極材料、此電極材料的製造方法及鋰離子二次電池
Zhang et al. One-step thermolysis synthesis of two-dimensional ultrafine Fe 3 O 4 particles/carbon nanonetworks for high-performance lithium-ion batteries
JP5529286B2 (ja) ＬｉＦｅＰＯ４粉末の製造のための水熱方法
WO2012132387A1 (fr) Matière d'électrode, son procédé de fabrication, électrode, batterie secondaire et véhicule
Ko et al. Effect of PEDOT: PSS coating on manganese oxide nanowires for lithium ion battery anodes
Lee et al. Coating of sulfur particles with manganese oxide nanowires as a cathode material in lithium–sulfur batteries
Lim et al. Biomineralized Sn-based multiphasic nanostructures for Li-ion battery electrodes
CN109768228A (zh) 锂离子二次电池用电极材料、锂离子二次电池用电极及锂离子二次电池
EP2638581A2 (fr) Électrodes en v205 a densités de puissance et d énergie elevées
KR102036330B1 (ko) 이산화티타늄／그래핀 나노복합체 제조방법 및 이를 음극재로서 이용한 이차전지 제조방법
US20150214541A1 (en) Method for producing carbon-coated metal-doped zinc oxide articles and the use thereof
US20150171426A1 (en) POROUS AMORPHOUS GeOx AND ITS APPLICATION AS AN ANODE MATERIAL IN LI-ION BATTERIES
He et al. Template-assisted molten-salt synthesis of hierarchical lithium-rich layered oxide nanowires as high-rate and long-cycling cathode materials
Kim et al. Effect of N-doped carbon layer on Co3O4 nanowire-graphene composites as anode materials for lithium ion batteries
US20130337335A1 (en) Negative electrode material for a secondary battery and method for manufacturing same
US9882218B2 (en) Lithium secondary battery and method for producing same
Kozawa et al. Wet milling synthesis of NH4CoPO4· H2O platelets: formation reaction, growth mechanism, and conversion into high-voltage LiCoPO4 cathode for Li-ion batteries
Ayhan et al. Effect of Mn 3 O 4 nanoparticle composition and distribution on graphene as a potential hybrid anode material for lithium-ion batteries

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11725660

Country of ref document: EP

Kind code of ref document: A1

REEP Request for entry into the european phase

Ref document number: 2011725660

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011725660

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: DE