EP2715843A1 - Electrode material for lithium and lithium ion batteries - Google Patents
Electrode material for lithium and lithium ion batteriesInfo
- Publication number
- EP2715843A1 EP2715843A1 EP11725660.2A EP11725660A EP2715843A1 EP 2715843 A1 EP2715843 A1 EP 2715843A1 EP 11725660 A EP11725660 A EP 11725660A EP 2715843 A1 EP2715843 A1 EP 2715843A1
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- EP
- European Patent Office
- Prior art keywords
- range
- acid
- nanoparticles
- lithium
- carbon
- Prior art date
- Legal status (The legal status 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 status listed.)
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- 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
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- 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
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- 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
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- 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
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- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- 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
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- 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
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- 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
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- 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
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- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- 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
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- 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
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- 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.
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