CN103503200A - Electrode for lithium-ion batteries - Google Patents

Electrode for lithium-ion batteries Download PDF

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Publication number
CN103503200A
CN103503200A CN201280022076.3A CN201280022076A CN103503200A CN 103503200 A CN103503200 A CN 103503200A CN 201280022076 A CN201280022076 A CN 201280022076A CN 103503200 A CN103503200 A CN 103503200A
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China
Prior art keywords
lithium
substrate
separator
electrode
lansi
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CN201280022076.3A
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Chinese (zh)
Inventor
蒂姆·谢弗
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LI TEC VERMOEGENSVERWALTUNGS GmbH
Li Tec Battery GmbH
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LI TEC VERMOEGENSVERWALTUNGS GmbH
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/12—Electroforming by electrophoresis
    • C25D1/14—Electroforming by electrophoresis of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/02—Electrophoretic coating characterised by the process with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/12—Electrophoretic coating characterised by the process characterised by the article coated
    • C25D13/16—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/20—Pretreatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • H01M4/0457—Electrochemical coating; Electrochemical impregnation from dispersions or suspensions; Electrophoresis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • General Chemical & Material Sciences (AREA)
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  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Ceramic Engineering (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

A method for producing an electrode for a lithium-ion battery, having the step (ii): (ii) electrophoretic deposition of ceramic particles from an aqueous suspension containing the ceramic particles onto a substrate.

Description

Electrode for lithium ion battery
At this, mode by reference is incorporated to the application to the full content of application DE102011100724 with priority.
The present invention relates to the method for a kind of manufacture for the electrode of lithium ion battery.The invention still further relates to a kind of electrode of manufacturing according to the method, and the lithium ion battery with kind electrode.
Electrode for lithium ion battery can form by applying the suitable conductive substrates manufacture with active material.Being called as such material of active material or material can discharge or absorb lithium ion and maybe can embed lithium.For example aluminium or copper (paper tinsel) are suitable substrates.
Coating process is such as extrusion molding or rolling process etc. are arranged.At this moment substrate is extruded and/or rolls together with the active material that will apply, and active material exists with form of suspension usually.Be fixed on after the suspension drying in substrate and just obtain electrode.The active material of using for the transport point of lithium ion or lithium can be nano level.Because nanoparticle surface is relatively large, thereby therefore make by active material, be convenient to matter transportation raising conductivity.
Task of the present invention is to provide a kind of electrode for lithium ion battery, and the conductivity of this electrode is able to further raising.
This task is achieved by electrophoresis, and it has step (ii):
(ii) will be from the ceramic particle electrophoretic deposition in waterborne suspension to substrate, described waterborne suspension has ceramic particle.
Therefore, a first aspect of the present invention relates to the method for manufacturing for the electrode of lithium ion battery, the method have step (ii) ':
(ii) ' will be from the ceramic particle electrophoretic deposition in waterborne suspension to substrate, described ceramic particle can transport lithium ion or embed lithium, and described waterborne suspension has ceramic particle.
Term " electrode " is positive electrode and the negative electrode of middle finger lithium ion battery hereinafter.
Term " positive electrode " is the such electrode of middle finger hereinafter, if battery is linked on electrical appliance, for example, while linking on electro-motor, can absorb the electrode of electronics.Under this condition, it is negative electrode.
Term " negative electrode " is the such electrode of middle finger hereinafter, when work, can provide the electrode of electronics.Under this condition, it is anode.
Hereinafter, term " lithium ion battery " can synonymously be used with " lithium rechargeable battery ".This term also comprises term " lithium battery ", " lithium-ions battery " and " lithium-ion cell ".Lithium-ions battery generally forms by single lithium-ion cell is connected in series or in parallel.This means, term " lithium ion battery " is the collective concept use as Essential Terms in above-mentioned prior art.
Term " electrophoresis " refers to the migration of charged particle material by being used as carrier material in electric field hereinafter.
Term " electrophoretic deposition " refers to that in category of the present invention ceramic particle arrives substrate by electrophoretic migration, and is deposited in substrate.
Simultaneously, when electrophoresis, by between two electrodes separated from one another, applying electrical potential difference, produce electric field, wherein charged particle moves between these two electrodes.
The application electrophoresis deposits to the ceramic particle from waterborne suspension in substrate, and this is known on principle.JP2002042791 discloses with spacer and electrode and has manufactured bilayer.The ceramic material that wherein can form spacer is from suspension, and this suspension comprises ceramic material, and it is by electrophoretic deposition on the electrode in being immersed in suspension.Thereby form the electrode with the spacer be deposited thereon.
The method of the invention is characterised in that, step does not comprise the formation of spacer in (ii).
Term " ceramic particle " refers to inorganic material or the inorganic compound of particle form hereinafter.Preferential use such particle, under the lithium ion battery condition of work because its chemical property can absorb the particle that also can again discharge lithium ion or lithium.Such material is also referred to as " active material " for electrode in the prior art.
In the method according to the invention, ceramic particle can be used as active material, and it is usually used in negative electrode.
Used in one embodiment particle, it is the lithium transition-metal with olivine structural.Therefore, in one embodiment, phosphate has LiXPO 4total molecular formula, wherein X=Mn, Fe, Co or Ni, or their combination.
Mixture or the mixed oxide that can use in another embodiment LiMn2O4, cobalt acid lithium, lithium nickelate or be formed by two or more these oxides.In one embodiment, these oxides have spinel structure.
Also can use the mixture formed by two or more above-mentioned substances.
Preferably, the ceramic particle in suspension is used as nano particle.
Nano particle can be taked any form, and it can be rough spherical in shape or elongated.
In one embodiment, particle has the particle size that is less than 15 μ m of measuring as the D95 value.Particle size is preferably and is less than 10 μ m.
In another embodiment, particle have as the D95 value, measure at 0.005 μ m to the particle size between 10 μ m, or there is the particle size that is less than 10 μ m as the measurement of D95 value, wherein the D50 value is that 4 μ m ± 2 μ m and D10 value are less than 1.5 μ m.
The value of appointment is by being used static laser light scattering (laser diffraction, laser diffractometry) to measure, and these methods are known in the prior art.
Also possible in addition, particle comprises for improving the carbon of conductivity.Can prepare by known method by such particle, for example, by carbon coating compound (such as acrylic acid or ethylene glycol).Particle is by pyrolysis subsequently, for example pyrolysis at the temperature of 2500 ℃.
Suitable ceramic particle for negative electrode preferably comprises lithium-metal oxide as lithium-titanium oxide.Other suitable material is graphite, Delanium, carbon black, mesocarbon, doping carbon, fullerene, niobium pentaoxide, ashbury metal, titanium dioxide, tin ash and/or silicon, or the mixture be comprised of two or more these materials.
Term " suspension " hereinafter with term " emulsion ", " dispersant ", " colloid " or " slurry " synonymously used.Suspension is preferably waterborne suspension.
Also possible that, in suspension with an organic solvent.Suitable organic solvent is preferably the mixture of ethanol, isopropyl alcohol, acetone or dimethyl formamide or these solvents.
Suspension also can contain adhesive in one embodiment.Adhesive contributes to particle is fixed in substrate.Suitable adhesive is known in the prior art.Can preferably use polymer adhesive, it is preferably polyvinylidene fluoride, poly(ethylene oxide), polyethylene, polypropylene, polytetrafluoroethylene, polyacrylate, ethene-(propylene-diene monomers)-copolymer (EPDM) and their mixture and copolymer.
Suspension also can comprise acid or alkali, dispersing aid, polyelectrolyte and the surface reactive material for adjusting the pH value.Can regulate stability and the electrophoretic mobility of suspension with this, namely the migration velocity of ceramic particle in electric field.
Suspension can for example mix the component of using according to the method preparation of conventional use in ceramic technology, preferably mixed grinding or stirring component.In addition, also can improve mixing by ultrasonic processing.
Term " substrate " refers to this material in category of the present invention, on it by electrophoretic deposition the material of ceramic particle.
In one embodiment, substrate has ceramic material, especially is suitable for the ceramic material of separator.
In one embodiment, substrate is metal.Suitable metal is preferably aluminium or copper.
In another embodiment, substrate also can form or comprise carbon by carbon.
Step substrate (ii) can form by the form of paper tinsel.In other embodiments, substrate can exist by the form of line or fiber.Described line also can exist by the form of nano wire and carbon nano-tube.
In one embodiment, metal is with the form of sheet metal, with the form of paper tinsel or with the form of line, is used.
In another embodiment, carbon and/or ceramic material are used with the form of fiber.
In one embodiment, substrate is used as an electrode in electrophoresis method.Substrate simultaneously can optionally be electrically connected to, and makes electronegative or positively charged ceramic particle to precipitate or to be deposited thereon.
Can dry substrate after (ii) depositing in substrate by ceramic particle according to step, for example by heating, make substrate drying.And then substrate is coated with and is covered with ceramic particle, the electrode so just can be used as in lithium ion battery is used.
In one embodiment, in electrophoresis the composition of the voltage applied between electrode and/or suspension used to select to make step (ii) in brine electrolysis simultaneously.
Therefore, the feature of the method also be step (ii) in brine electrolysis simultaneously.
In one embodiment, the voltage applied during electrophoresis will increase always, until the electrolysis of water occurs.This point generally can form and identify well from the bubble occurred.
Can promote electrolysis by acid adding in suspension.Suitable acid is preferably acetic acid.
The bubble occurred during electrolysis forms in the ceramic particle layer that can on purpose be used for depositing in substrate and forms pore.The ABC that relevant pore forms principle is described in DE102008012586A1.Be surprised to find, electrode constructed in accordance particularly can improve the conductivity of commonly used in lithium ion battery and electrode that manufacture by conventional method due to the formation of pore.
In another execution mode of the method according to this invention, the method also has step (i) before (ii) in step:
(i) pattern generation on substrate surface.
The space structure of term " pattern " on category middle finger substrate surface of the present invention.
By pattern generation on substrate surface, make the surface of substrate further enlarge and/or contribute to the formation in directed hole.These measures can be used to further improve conductivity.
In one embodiment, can form net-like pattern by the application net to substrate.
In another embodiment, can form net-like pattern or other pattern by applied metal line or polymer fiber to substrate.
In one embodiment, nano wire can be applied in substrate.
The metal that term " nano wire " is elongated at category middle finger of the present invention, semimetal or connection semiconductor, it has the diameter of scope in 0.0001 millimeter.
In one embodiment, nano wire comprises carbon nano-tube or is comprised of carbon nano-tube.
The manufacture method of nano wire is known.According to known method, as spin-coating method or knife coating, nano wire can be applied in substrate.
In another embodiment, on substrate surface, the formation of pattern can realize by method known in photoetching technique.Than formula, can be electron beam lithography and ion photoetching or laser lithography.
In another embodiment, after performing step (ii), the demoulding (entformen) is wanted in the particle of deposition and substrate, and described particle exists with layer form in substrate.
In the present embodiment, described method is characterised in that, it has step (iii):
The (iii) particle of deposition and the demoulding of substrate.
Term " demoulding " refers to that in category of the present invention the particle of deposition and substrate will be separated from each other.
In one embodiment, in the method step of the demoulding (iii) according to step, special expectation is, in the time will preparing the active material of special porous, active material more easily enters lithium ion due to its porosity and associated larger surface, thereby further improves conductivity.
Preferably use in the present embodiment substrate, its form with the line that is interlaced with one another or the form of fiber exist.Then according to step, after ceramic particle (ii) deposition, obtaining the compound that the ceramic particle layer forms, line or fiber have wherein been embedded.
In one embodiment, the demoulding (iii) according to step, be about to the particle separation of substrate and deposition, by thermal effect and/or chemical effect, undertaken.
Term " thermal effect " refers to pyrolytic reaction and heat scission reaction in category of the present invention.
In one embodiment, the compound consisted of ceramic particle and substrate will be heated to substrate and decompose, and catabolite is separated at least in part or fully from compound.At this moment the pottery produced has a plurality of pores or passage, preferably is attached to the previous position of substrate.
The fiber consisted of carbon is specially adapted to this execution mode.It can use with fabric or liner form.By selecting fiber thickness, except being included into ceramic pore by brine electrolysis, other pore or passage with definite diameter also is included in pottery.
In this case, especially can use organic polymer fiber.Substrate containing " carbon " refers to especially " organic polymer ", i.e. carbonaceous material in category of the present invention.In one embodiment, use polyester fiber or polyolefine fiber.
In another embodiment, according to step, the demoulding (iii) can start by chemical effect.
Term " chemical effect " refers in category of the present invention, and substrate and reactant reaction, until it partially or even wholly separates from compound.
Metallic substrates, preferably metal wire, be particularly suitable for present embodiment.Due to the impact of acid (its can with metal reaction), substrate can be separated from compound.Also can form pore or passage simultaneously.
The active material for electrode of producing like this can be applied to substrate according to conventional method, and this substrate is for the electrode of lithium ion battery.
According to second aspect, the present invention relates to a kind of electrode for lithium ion battery, wherein electrode can be according to made according to the method for the present invention.
According to the third aspect, the present invention relates to a kind of lithium ion battery, it comprises according to electrode made according to the method for the present invention; Or comprise according to electrode of the present invention.
Term " electrode " is the restriction that there is no numerical value in category of the present invention.This term also means that battery can comprise a plurality of electrodes, preferably includes two electrodes.
In one embodiment, battery has separator.
Term " separator " is a kind of material of middle finger hereinafter, and it is separated from each other the positive electrode of lithium ion battery and negative electrode.
For the separator of battery, must allow lithium ion to see through, in order to guarantee the ion transfer of the lithium ion that carries out between positive electrode and negative electrode.On the other hand, separator must completely cut off electronics.
In one embodiment, separator comprises the Wei Lansi (Vlies) be comprised of the nonwoven polymer fiber, and it is non-conductive.This Wei Lansi particularly forms by the weaving method manufacture with follow-up process of setting.
An execution mode of lithium ion battery is characterised in that, it comprises separator, and this separator comprises the Wei Lansi be comprised of the nonwoven polymer fiber, and Wei Lansi is applied by electrodeless material by one-sided or bilateral ground.
Term " Wei Lansi " is synonymously used as " non-union ", " looped fabric " or " felted thing " with term hereinafter.Also use term " non-interweaving " to replace term " nonwoven ".
Preferably, the group that polymer fiber selects free polymer to form, it comprises polyacrylonitrile, polyolefin, polyester, polyimides, Polyetherimide, polysulfones, polyamide, polyethers.Suitable polyolefin is for example polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride.
Preferred polyester is PETG.
The Wei Lansi comprised in separator in category of the present invention preferably one-sided or bilateral ground by the inorganic material coating of ionic conduction.Term " coating " also refers in category of the present invention, not only is coated on the one or both sides of Wei Lansi but also in the inorganic material of the ionic conduction of the inside of Wei Lansi.
The inorganic material of ionic conduction is ionic conduction in the temperature range from-40 ℃ to 200 ℃, for lithium ion, is ionic conduction.Apply material therefor and be at least one compound at least one the group of oxide, phosphate, sulfate, titanate, silicate, alumino-silicate in element zirconium, aluminium, silicon or lithium.
In a preferred implementation, ion conductive material comprises aluminium oxide or zirconia or aluminium oxide and zirconia, or consisting of.
In one embodiment, use a kind of separator in battery according to the present invention, it is comprised of the carrier that allows at least in part material permeance, this separator be non-electron conduction or be only very poor ground electron conduction.Be coated with inorganic material at least one side of this carrier.To use organic material as the carrier that allows at least in part material permeance, it is constituted as nonwoven Wei Lansi.Organic material forms with the form of polymer fiber, and preferably the polymer fiber with PETG (PET) forms.Wei Lansi is applied by the inorganic material of ionic conduction, and it is ionic conduction in the temperature range from-40 ℃ to 200 ℃ preferably.The inorganic ions electric conducting material preferably comprises at least one compound at least one the group of oxide, phosphate, sulfate, titanate, silicate, alumino-silicate had in element zirconium, aluminium or lithium, particularly preferably comprises titanium dioxide white.Preferably, the inorganic ions electric conducting material comprises having the particle that maximum gauge is less than 100nm.
The commodity that this type of separator for example has German Evonik AG company to sell are by name separator.The method of producing this type of separator is known in the prior art, for example from EP1017476B1, WO2004/021477, WO2004/021499, learns.
Hereinafter will summarize to the advantage of the particularly preferred execution mode of applied separator in battery according to the present invention and the battery of particularly seeing from security standpoint.
In principle, be used in excessive pore and hole in the separator in secondary cell and may cause internal short-circuit.Battery therefore may be with a kind of very rapidly self discharge of reaction of danger.Now large electric current may occur, so that the monocell of the battery that connected in the worst case even may explode.Because this reason, separator can play vital effect for the fail safe of high-performance or high-octane lithium ion battery or fail safe lack.
Polymer spacer starts to block any by the current delivery of electrolyte by a certain temperature (so-called " shutdown temperature ", generally 120 ℃ of left and right) usually.This is to occur like this, at this temperature, destroys the pore structure of separator and all holes are sealed to realize.Thus, no longer including ion can be transmitted, thereby suppresses to cause the hazardous reaction of blast.If this monocell, because external environment condition is persistently overheating, will surpass so-called " puncturing temperature " in the time of about 150 ℃ to 180 ℃.From this temperature, for traditional separator, this separator can melt, and therefore shrinks.Direct contact between two electrodes now can occur on the many positions in the monocell of battery and therefore cause large-area internal short-circuit.This can cause uncontrolled reaction, and this reaction finally may cause the blast of battery, or the pressure produced need reduce by pressure relief valve (rupture diaphragm), usually when on fire, must so do.
Comprise Wei Lansi and the inorganic coating formed by the non-woven polymer fiber according to the separator used in battery of the present invention; while also therefore these pores being sealed in the pore that by high temperature, the polymer architecture of carrier material is melted and infiltrates inorganic material, may cause shutting down (closing).Yet not there will be and puncture (interruption) when using this separator, this is to have guaranteed separator and can not melt fully due to inorganic particle.Therefore guaranteed not exist the wherein operation conditions of possibility occurrence of large-area short circuit.Pass through used Wei Lansi (it has the combination of specially suitable thickness and porosity) technology, can produce separator, this separator can meet heavy-duty battery, the particularly requirement of high-performance lithium battery to separator.By come (pottery) coating of production porous will realize that made separator has extra high porosity by particle size by exactly determined oxide particle simultaneously, wherein pore is still enough little sees through separator in order to stop " lithium whisker " undesirably to extend.
Because the porosity of separator is high and its thickness is little so also possible that, separator is fully or at least almost entirely by electrolyte-impregnated, cause and do not there will be dead angle in the regional of separator, then not there will be dead angle at the monocell of battery in definite winding or layer, wherein in described dead angle without electrolyte.This point is achieved like this especially, and, by keeping the particle size of oxide particle, the separator obtained is without closed pore or almost without closed pore, and wherein electrolyte can not infiltrate in the pore of described closure.The present invention's separator used also has the following advantages, and on the inorganic surfaces of spacer material, partly deposits the anion of conducting salt, and it has caused the improvement of decomposing and has therefore caused the better ionic conductivity in high galvanic areas.The not uncorrelated advantage of another of separator is to have extraordinary wetability (Benetzbarkeit).Soak and realize very fastly because the hydrophily of ceramic coating makes with electrolyte, this has equally also caused the improvement of conductivity.
The separator that battery according to the present invention is used (it comprise flexible, with the Wei Lansi that is present in the porous, inorganic coating in the upper and Wei Lansi of Wei Lansi, wherein the material of Wei Lansi is selected from polymer fiber nonwoven, dielectric), it is characterized in that, the thickness of Wei Lansi is less than 30 μ m, and its porosity surpasses 50%(and is preferably 50% to 97%) and there is the pore radius that at least 50% hole wherein has the pore radius of 75 μ m to 150 μ m and distribute.
Particularly preferably be, separator has Wei Lansi, and its thickness is from 5 μ m to 30 μ m, and preferred thickness is that 10 μ m are to 20 μ m.Particularly importantly as top given pore radius as far as possible uniformly, distribute.In Wei Lansi, more uniform pore radius distributes and has been caused by the specific dimensions of best definite oxide particle the separator porosity of optimizing.The thickness of substrate greatly affects the characteristic of separator, and this is because be immersed in the flexibility of the separator in electrolyte and the thickness that sheet resistance all depends on substrate.Realize low especially separator resistance in using electrolytical application due to the thickness young pathbreaker.Separator itself has very high resistance, because itself must have insulating properties.Thin separator allows to improve packaging density in cell stack in addition, so that can store more substantial energy in identical volume.
Wei Lansi preferably has 60% to 90% porosity, is particularly preferably 70% to 90%.The volume (100%) that wherein porosity is defined as Wei Lansi deducts the volume of the blue silk fiber of dimension, in the volume of Wei Lansi, there is no the part of packing material.
Therefore the volume of Wei Lansi can be calculated by the size of Wei Lansi.The volume of fiber calculates according to the weight of the observed Wei Lansi measured and the thickness of polymer fiber.The high porosity of substrate also can make separator have higher porosity, can realize thus absorbing more electrolyte with separator.In order to obtain the separator with insulation characterisitic, it is as the polymer fiber for Wei Lansi as top defined nonconducting polymer fiber that preferably includes, and it preferably is selected from polyacrylonitrile (PAN), polyester (for example PETG (PET)) and/or polyolefin (PO) (for example polypropylene (PP) or polyethylene (PE)) or these polyolefinic mixtures.
The polymer fiber of Wei Lansi preferably has from the diameter of 0.1 μ m to 10 μ m, is particularly preferably the diameter of 1 μ m to 4 μ m.
The surface weight of particularly preferred flexible Wei Lansi is less than 20g/m 2, be preferably 5g/m 2to 10g/m 2.
Preferably, Wei Lansi is flexible and has the thickness that is less than 30 μ m.
Separator is included in Wei Lansi above or porous, ceramic coating electric insulation in Wei Lansi.Preferably, be arranged in the oxide particle that upper or porous, inorganic coating Wei Lansi of Wei Lansi has element lithium, aluminium, silicon and/or zirconium, its average particle size particle size be 0.5 μ m to 7 μ m, be preferably 1 μ m to 5 μ m, be particularly preferably 1.5 μ m to 3 μ m.
Particularly preferably be, separator comprises the porous, inorganic coating that is arranged in the upper or Wei Lansi of Wei Lansi, and it comprises alumina particle.Preferably, the average particle size particle size that alumina particle has be 0.5 μ m to 7 μ m, be preferably 1 μ m to 5 μ m and be particularly preferably 1.5 μ m to 3 μ m.In one embodiment, alumina particle comes bonding with the oxide of element Zr or Si.
In order to obtain high as far as possible porosity, the percentage by weight of all particles is preferably more than 50% and particularly preferably in more than 80%, and this percentage by weight is in the limits of above-mentioned average particle size particle size.As described above, maximum particle size be preferably Wei Lansi thickness used 1/3 to 1/5 and be particularly preferably and be less than or equal to 1/10 of Wei Lansi thickness used.
Preferably, the porosity that separator has is 30% to 80%, is preferably 40% to 75%, is particularly preferably 45% to 70%.Wherein, porosity refers to accessible pore, i.e. open pore.Wherein, porosity can determine or can draw from volume and the density calculation of used material by known mercury injection method, and condition is to suppose open pore is only arranged.The feature of the separator used according to battery of the present invention also is, its tensile strength that can have is at least 1N/cm, is preferably at least 3N/cm, is particularly preferably 3N/cm to 10N/cm.Preferably, separator bending with no damage is until any radius of 100mm, preferably until 50mm and particularly preferably until 1mm.
The advantage that the high-tensile of separator and good flexible have is, can adapt to the variation of the electrode geometry occurred when the battery charging and discharging by separator, and it does not caused to damage.Flexible also has advantages of such, uses separator can produce commercially standardized takeup type monocell.In these monocells, the layer of the electrode/separator of modular size is each other in spirally reeling and contacting.
In one embodiment, separator also can be set makes separator have the shape of recessed or protruding sponge or mat or has wire shaped or felt shape.Present embodiment is applicable to the change in volume in balancing battery very much.The technical staff knows corresponding manufacturing process.
In another embodiment, in separator, applied polymer Wei Lansi has other polymer.This polymer preferred arrangements is between separator and negative electrode and/or between separator and positive electrode, and it is preferably with the form of polymeric layer.
In one embodiment, separator is by the one-sided or this polymer-coated in bilateral ground.
Described polymer can be usingd the form of perforated membrane (as paper tinsel) and be existed, or exists to tie up blue filate formula, preferably to be existed by the non-blue filate formula of dimension that polymer fiber was formed that interweaves.
The group that these polymer preferably select free polyester, polyolefin, polyacrylonitriles, Merlon, polysulfones, polyether sulfone, polyvinylidene fluoride, polystyrene, Polyetherimide to form.
Above-mentioned other polymer is preferably polyolefin.Preferred polyolefin is polyethylene and polypropylene.
One or more layers that preferably use above-mentioned other polymer (preferred polyolefm) applies separator, and wherein polyolefin, preferably also as Wei Lansi, exists as the non-polymer fiber that interweaves.
Preferably, use the Wei Lansi consisted of PETG in separator, apply one or more layers of above-mentioned other polymer (preferred polyolefm) on it, polyolefin, preferably also as Wei Lansi, exists as the non-polymer fiber that interweaves.
Particularly preferably be the separator of above-mentioned Separion type, apply one or more layers of above-mentioned other polymer (preferred polyolefm) on it, polyolefin, preferably also as Wei Lansi, exists as the non-polymer fiber that interweaves.
With above-mentioned other polymer, preferably with polyolefin, apply, this can be by bonding, lamination, by chemical reaction, by welding or realizing by mechanical connection.Such polymer connects and manufacture method is learnt from EP1852926.
Preferably, the fibre diameter of PETG Wei Lansi is larger than the fibre diameter of above-mentioned other polymer Wei Lansi (preferred polyolefm Wei Lansi), separator by unilaterally or bilateral ground with it, apply.
Preferably, the pore diameter that the Wei Lansi made by PETG has is larger than the pore diameter of the Wei Lansi made by above-mentioned other polymer.
Preferably, the Wei Lansi that can use in separator is made by the nanofiber of used polymer, forms thus Wei Lansi, and it has high porosity in the situation that form less pore diameter.Can further reduce thus the danger of the reaction that is short-circuited.
Except PETG, also use polyolefin to guarantee to improve the fail safe of electrochemistry single cell because do not expect to occur or while crossing highland heating monocell polyolefinic pore can shrink and charge transport by separator is reduced or stops.If the temperature of electrochemistry single cell improves, make polyolefin start fusing, PETG has effectively suppressed the fusing of separator and has effectively suppressed thus the uncontrolled destruction to electrochemistry single cell.
In another embodiment, lithium ion battery comprises nonaqueous electrolyte.
Preferably, term " electrolyte " refers to liquid and conducting salt in category of the present invention.Preferably, liquid is the solvent of conducting salt.Preferably electrolyte exists as electrolyte solution.Suitable electrolyte is known in the prior art.
Suitable solvent is preferably inertia.Suitable solvent is preferably such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, carbonic acid methyl butyl ester, ethyl propyl carbonic acid ester, dipropyl carbonate, cyclopentanone, sulfolane, methyl-sulfoxide, 3-methyl isophthalic acid, 3-oxazolidine-2-ketone, gamma-butyrolacton, 1,2-diethoxymethane, oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, methyl acetate, ethyl acetate, nitromethane, 1, the 3-propane sultone (1, solvent 3Propansulton).
Ionic liquid also can be used as solvent in one embodiment.
Ionic liquid is known in the prior art.It comprises ion.Exemplify, spendable, special can be had glyoxaline cation, pyridylium, pyrrolidines cation, guanidine cation, uronium, thiocarbamide cation, piperidines cation, morpholine cation, sulfonium cation, ammonium cation with phosphonium cation by alkylating cation.Exemplify, spendable anion has halide anions, tetrafluoro boric acid salt anionic, trifluoroacetic acid salt anionic, trifluoromethyl sulfonic acid anion, hexafluorophosphoric acid salt anionic, phosphonate anion and p-methyl benzenesulfonic acid salt anionic.
The exemplary ionic liquid of mentioning has: two (trifyl) acid imides of N-methyl-N-propyl group piperidines, two (trimethyl fluoride sulfonyl) acid imides of N-methyl-N-butyl pyrrolidine, two (trimethyl fluoride sulfonyl) imines of N-butyl-N-trimethyl ammonium, triethyl group sulfonium-bis-(trimethyl fluoride sulfonyl) imines, N, N-diethyl-N-methyl-N-(2-methoxy ethyl) two (the trimethyl fluoride sulfonyl)-acid imides of ammonium.
Can use two or more in aforesaid liquid.
Preferred conducting salt is lithium salts, and it comprises inert anion and is nontoxic.Suitable lithium salts is preferably lithium hexafluoro phosphate, hexafluoroarsenate lithium, lithium-bis-(trifluoromethanesulp-onyl-onyl imide), trifluoromethayl sulfonic acid lithium, three (trifyl) lithium methide, LiBF4, lithium perchlorate, tetrachloro-lithium aluminate, two oxalyl lithium borate, difluoro oxalyl lithium borate and/or lithium chloride; And the mixture of one or more compositions in these salt.

Claims (15)

1. a manufacture is for the method for the electrode of lithium ion battery, and described method has step (ii):
(ii) will comprise described ceramic particle electrophoretic deposition in the waterborne suspension of ceramic particle to substrate.
2. method as claimed in claim 1, wherein said ceramic particle can transport lithium ion or embed lithium.
3. method as claimed in claim 1 or 2, step (ii) in brine electrolysis simultaneously.
4. the method according to any one of the preceding claims, it itself is porous at least partly that wherein said substrate comprises ceramic material or metal or carbon, particularly wherein said substrate.
5. the method according to any one of the preceding claims, wherein said substrate is configured to paper tinsel and/or metal wire and/or fiber.
6. the method according to any one of the preceding claims, it has step (i) before (ii) in step:
(i) pattern generation on substrate surface.
7. the method according to any one of the preceding claims, wherein said substrate comprises that nano wire or described substrate are nano wires.
8. method as claimed in claim 7, wherein said nano wire comprises carbon nano-tube or is comprised of carbon nano-tube.
9. the method according to any one of the preceding claims, it has step (iii):
(iii) by ceramic particle and the substrate demoulding of deposition.
10. method as claimed in claim 9, the wherein said demoulding is carried out by thermal effect and/or by chemical effect.
11. the method according to any one of the preceding claims, wherein said ceramic particle comprises that one or more or one or more in following material in following material form: LiMn2O4, cobalt acid lithium, lithium nickelate, LiFePO4, lithium manganese phosphate, cobalt phosphate lithium and LiNiPO, or the mixture formed by two or more these materials, or the mixing cpd formed by two or more these materials; Perhaps: lithium-titanium oxide, graphite, Delanium, carbon black, mesocarbon, doping carbon, fullerene, niobium pentaoxide, ashbury metal, titanium dioxide, tin ash and/or silicon, or the mixture formed by two or more these materials.
12. one kind that can manufacture according to as defined as any one in above-mentioned claim method, for the electrode of lithium ion battery.
13. the lithium ion battery with electrode as claimed in claim 12.
14. lithium ion battery as claimed in claim 13 also has separator, described separator has the Wei Lansi consisted of the non-polymer fiber that interweaves, described Wei Lansi unilaterally or bilateral ground with inorganic material, apply.
15., as lithium ion battery as described in claim 13 or 14, wherein said inorganic material comprises aluminium oxide or zirconia, or comprises aluminium oxide and zirconia.
CN201280022076.3A 2011-05-06 2012-03-30 Electrode for lithium-ion batteries Pending CN103503200A (en)

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