WO2012138115A2 - 금속 섬유를 포함하는 전극 구조체를 갖는 전지 및 상기 전극 구조의 제조 방법 - Google Patents
금속 섬유를 포함하는 전극 구조체를 갖는 전지 및 상기 전극 구조의 제조 방법 Download PDFInfo
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- WO2012138115A2 WO2012138115A2 PCT/KR2012/002517 KR2012002517W WO2012138115A2 WO 2012138115 A2 WO2012138115 A2 WO 2012138115A2 KR 2012002517 W KR2012002517 W KR 2012002517W WO 2012138115 A2 WO2012138115 A2 WO 2012138115A2
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- metal fibers
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/806—Nonwoven fibrous fabric containing only fibres
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4234—Metal fibres
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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
- 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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
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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
- H01M4/626—Metals
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
Definitions
- the present invention relates to battery technology, and more particularly, to a battery having an electrode structure using metal fibers and a method of manufacturing the electrode structure.
- the battery is divided into a primary battery that can be used once for a certain life and a secondary battery that can be repeatedly used through recharging.
- a raw material of the battery lithium is the lightest of the metals known in nature, the lowest standard reduction potential, has the advantage of high energy density at the time of battery manufacturing, as well as high voltage. Accordingly, research on primary batteries and secondary batteries using lithium has attracted much attention.
- Lithium primary batteries are primarily used for mains and backup power supplies in portable electronic devices.
- Lithium secondary batteries range from batteries for small devices such as mobile phones, notebook PCs, and mobile displays to medium and large batteries for electric and hybrid vehicles. The field of application is gradually expanding.
- These batteries need to have high energy density, good charge / discharge rate, charge / discharge efficiency and cycle characteristics while being basically small in weight and volume, and have high stability and economy.
- the technical problem to be solved by the present invention is to provide a battery having an electrode structure having not only high energy density but also excellent charge / discharge efficiency, charge / discharge rate and cycle characteristics, and which is easy to change shape and adjust capacity. .
- Another technical problem to be solved by the present invention is to provide a manufacturing method which can easily manufacture a battery having the above-described advantages.
- the conductive network formed by one or more metal fibers; And a particle composition comprising an electrically active material in the form of particles bound to the conductive network.
- the metal fibers are bonded to each other by only physically contacting each other at random, and the conductive network may have a nonwoven structure.
- the particle composition may further include any one or both of a conductive material, a binder, and porous ceramic particles.
- the binder may be provided in the form of a point binder between the metal fibers and the first electrical active material and between the first electrical active materials.
- the metal fibers may have a thickness in the range of 1 ⁇ m to 200 ⁇ m. Preferably, the metal fibers may have a thickness in the range of 2 ⁇ m to 20 ⁇ m.
- the metal fibers may comprise any one or combination of stainless steel, aluminum, nickel, titanium and copper or alloys thereof. Further, in some embodiments, the size of the electrically active materials may be determined such that the ratio (s / d) of the average size (s) of the electrically active materials in the form of particles to the average thickness (d) of the metal fibers is from 0.01 to 10. Can be.
- a method of manufacturing an electrode structure including providing one or more metal fibers forming a conductive network; Providing a particle composition comprising electrical active materials in particle form; Mixing the metal fibers with the particle compositions; And compressing the mixed metal fibers and the particle compositions.
- the metal fibers may be randomly arranged in the form of a fibrous layer having a nonwoven structure.
- the particle composition may be provided in the solvent-free dry powder on the metal fibers.
- the mixing may be performed by spraying the particle composition in the conductive network.
- the particle composition includes external additives selected from any one or a combination of binder particles, conductive material particles, and porous ceramic particles mixed with the electrically active materials in the form of particles, wherein the external additives and the electrically active material
- the mixing of these may be carried out through a dry mixing process.
- providing the one or more metal fibers may include precoating a binder on the surface of the metal fibers.
- the particle composition may include external additives selected from any one or a combination of conductive material particles and porous ceramic particles mixed with the electrical active materials in the form of particles, and the external additive and the Mixing can be performed through a dry mixing process.
- the particle composition comprises an external additive selected from any one or a combination of conductive material particles and porous ceramic particles mixed with the electrically active materials in the form of particles, wherein the conductive material particles and the A binder is precoated on the surface of any one or both of the porous ceramic particles, and the mixing of the external additive and the electrical active materials may be performed through a dry mixing process.
- the manufacturing method of the electrode structure may further include the step of heating or ultraviolet irradiation at the same time as the pressing step.
- a metal fiber having the excellent electrical, mechanical and thermal properties of the metal but also combines the flexibility and organization of the fiber, reducing the contact resistance and increase the contact area between the current collector structure and the electrical active material
- the effect can not only improve the energy density of the battery, but also improve the charge / discharge rate, charge / discharge efficiency, and cycle characteristics of the battery.
- the conductive network provided by the metal fiber can buffer the volume change of the electrical active material due to charging and discharging, a next generation high efficiency Li intercalation material may be used as the electrical active material.
- the amount of separator required when manufacturing a battery by stacking electrodes can be reduced.
- the electrode can be made thick in the same cell volume, and a battery having excellent energy density per unit volume can be produced.
- the manufacturing method of the electrode structure having the above-described advantages is a small load on the environment, because a solvent such as water or an organic solvent is not used in the forming and mixing process of the particle composition except for the precoating process of the binder. .
- a separate drying process for removing the solvent in the slurry is not required, thereby simplifying the process, improving productivity, and simplifying the equipment.
- the solvent for the binder remains in the electrical active material, considering that the electrical active material may deteriorate, the mixing process using the solvent-free dry powder may improve the yield.
- FIG. 1A-1C illustrate electrode structures in accordance with various embodiments of the present invention.
- FIG. 2 is a flowchart illustrating a method of manufacturing an electrode structure, according to an exemplary embodiment.
- 3A to 3D are diagrams sequentially showing the results according to the flowchart of FIG. 2.
- 4A and 4B are cross-sectional views illustrating electrode structures in accordance with other embodiments of the present invention.
- FIG. 5A is an exploded view illustrating a battery using an electrode structure according to an exemplary embodiment of the present invention
- FIG. 5B is a cross-sectional view schematically illustrating a method of stacking electrode structures.
- first, second, etc. are used herein to describe various members, parts, regions, layers, and / or parts, these members, parts, regions, layers, and / or parts are defined by these terms. It is obvious that not. These terms are only used to distinguish one member, part, region, layer or portion from another region, layer or portion. Thus, the first member, part, region, layer or portion, which will be discussed below, may refer to the second member, component, region, layer or portion without departing from the teachings of the present invention.
- the metal fiber is a fiber body of a metal such as stainless steel, aluminum, nickel, titanium and copper or alloys thereof, and extends continuously with a substantially uniform thickness over a full length range of substantially 1 ⁇ m or more. It is an integrated metal body.
- the metal fibers have the heat resistance, plasticity and electrical conductivity of the metals, and at the same time have the advantage that the fiber-specific weaving and nonwoven processing process is possible.
- the present invention relates to features and advantages of applying such metal fiber advantages to the electrode structure of a cell.
- the metal fibers may be prepared by maintaining a metal or alloy in a molten state in a vessel, and quenching and solidifying the molten metal through the injection hole of the vessel by using a pressurization device such as a compressed gas or a piston. .
- the metal fibers can be produced by a known focus drawing method. By controlling the number, size and / or emergence of the injected molten metal, the thickness, uniformity, structure such as nonwoven fabric and aspect ratio of the metal fibers can be controlled.
- the metal fibers constituting the battery of the present invention may be manufactured by other known manufacturing methods as well as the above-described manufacturing method, and the present invention is not limited thereto.
- the term 'separation membrane' as used herein includes a separator generally used in a liquid electrolyte battery using a liquid electrolyte having a small affinity with the separator.
- the 'membrane' as used herein includes an intrinsic solid polymer electrolyte and / or a gel solid polymer electrolyte in which the electrolyte is strongly bound to the separator, so that the electrolyte and the separator are recognized as the same. Therefore, the separator should be defined in the meaning as defined herein.
- FIG. 1A-1C illustrate electrode structures 100, 200, 300 in accordance with various embodiments of the present invention.
- the electrode structures 100, 200, 300 include one or more metal fibers 10 and an electrical active material 20.
- the metal fibers 10 may be plastic due to the ductility and malleability of the metal.
- the metal fibers 10 may be plural and segmented to have a suitable length. The number of metal fibers 10 may be appropriately selected depending on the size and capacity of the battery.
- the metal fibers 10 may have a thickness in the range of 1 ⁇ m to 200 ⁇ m. When the thickness of the metal fibers 10 is 1 ⁇ m or less, not only the forming of the metal fibers 10 having uniform physical properties is difficult, but also the artificial of the metal fibers 10 for forming a conductive network as described below. Arrays can be difficult.
- the metal fibers 10 may have a thickness of 2 ⁇ m to 20 ⁇ m. This translates to a 4 ⁇ 10 5 (1 / m) to 2 ⁇ 10 6 (1 / m) ratio of surface area / volume per unit length (eg 4 / diameter if it has a circular cross section).
- a conventional current collector using a foil has a thickness of approximately 20 ⁇ m.
- using a metal fiber having a thickness of 2 ⁇ m to 20 ⁇ m compared to a conventional current collector using a 20 ⁇ m thick foil may increase the surface area from about 4 to 40 times. Therefore, for the current collector of the same weight, the surface area can be maximized by using the current collector in the form of metal fiber rather than the current collector in the form of foil.
- the surface area of the current collector may be easily adjusted through the thickness control of the metal fibers.
- the surface area of the current collector means the surface area of the conductive network per electrode volume of the metal fibers 10 forming a reaction interface with the electrically active material 20 and the electrolyte solution 30, respectively, and thus maximizes this, thereby having a very high energy density cell. Can be formed.
- the average length of the metal fibers 10 may have a length in the range of 5 mm to 1000 mm, in which case the average aspect ratio of the metal fibers 10 is in the range of 25 to 10 6 .
- the metal fibers 10 are segmented to have a length on the order of 5 cm to 8 cm and used in the electrode structure. In reality, using a material other than a metal material, it is difficult to obtain a fiber structure having an aspect ratio of 10 3 or more and having flexible characteristics and excellent conductivity.
- the electrically active material 20 bound to the conductive network may be sintered by heat treatment, in which case the electrically active material 20 may be more strongly bonded to the metal fibers 10. have. This sintering process is not possible with the conventional electrode structure using the conductive polymer fibers described above.
- the conductive network of the present invention made of metal fibers may not have chemical bonds due to sintering, and may have a structure in which the metal fibers are only in physical contact.
- the inventors have observed that conductive networks in which metal fibers are only in physical contact and do not have chemical bonds have less performance degradation due to frequent charging and discharging. This is presumably because the conductive network can respond more flexibly to the volume expansion following charge and discharge when the metal fibers are simply in physical contact with each other than when they are in chemical bonds with each other.
- the metal fibers 10 shown in FIGS. 1A-1C is generally in a straight and bent form, as another embodiment of the present invention, the metal fibers 10 may have other shapes such as curls or spirals. It may be molded to have a regular and / or irregular shape.
- the metal fibers 10 having the straight, bent, or other regular and / or irregular shape described above are electrically connected to each other through physical contact or chemical bonds within the electrode structures 100, 200, and 300.
- Form a conductive network is formed by bending or bending one or more metal fibers 10 to be tangled and contacted or bonded to each other, thereby having a porosity therein and being mechanically strong, and having flexibility due to the fiber properties.
- the metal fibers 10 may comprise any one or combination of stainless steel, aluminum, nickel, titanium and copper or alloys thereof.
- the metal fibers 10 may be made of aluminum or an alloy thereof, which does not oxidize in a high potential region.
- anode cathode
- copper, stainless steel, nickel or alloys thereof which are electrochemically inert at low operating potentials can be used.
- metals described above are exemplary, and other suitable metal materials may be used that may be stable without oxidation and reduction at each electrode.
- it may be made of two or more different kinds of metals, respectively, and an additional process such as heat treatment or sintering forms an intermetallic compound therebetween, whereby chemical bonding between the metal fibers It may be achieved as described above.
- An electrically active material 20 is bound within the conductive network provided by the metal fibers 10 described above.
- the size and porosity of the pores in the conductive network formed by the metal fibers 10 may be appropriately adjusted so that the electrically active material 20 is strongly bound to the conductive network. Control of the pore size and porosity may be performed by adjusting the mixing weight ratio with the electrical active material 20 in the entire electrode structure 10 of the metal fibers 10.
- the mixed weight ratio of the metal fibers 10 in the electrode structure 100 may be adjusted by increasing the number or length of the metal fibers 10.
- the size and porosity of the pores in the electrode structure 100 as described below, by using the plasticity of the metal fibers 10, the mixture of the metal fibers 10 and the electrical active material 20 and the roll press
- mechanical compression using the same pressurizer it may be adjusted appropriately.
- the conductive network having a nonwoven structure is mechanically more robust, and at the same time, the electrical active materials 20 are strongly bound to the conductive network, thereby increasing the energy density of the electrode.
- the electrically active material 20 may be particles having an average size of 0.1 ⁇ m to 100 ⁇ m.
- the electrical active material 20 may have a particle size distribution in a predetermined range, and if necessary, the electrical active material 20 may have a particle size distribution controlled through a classification process. In some embodiments, the electrically active material 20 may have an average size of 0.1 ⁇ m to 15 ⁇ m.
- the size s of the micronized electrical active material 20 bound thereto is determined by the metal latent fibers ( It is preferable to correspond to the thickness d of 10). In this case, the electrically active materials 20 can be well bound within the conductive network.
- the ratio (s / d) of the average size s of the electrically active materials 20 in the form of particles to the thickness d of the metal fibers 10 may be 0.01 to 10.
- the ratio is less than 0.01, the electrical active materials 20 are easily dropped into the electrolyte 30, and when the ratio is 10 or more, the volume expansion mitigation by the conductive network and the improvement of electrical conductivity may be weakened.
- the electrical active materials 20 in the form of particles By miniaturizing the electrical active materials 20 in the form of particles, deterioration of the battery due to the stress change of the electrical active materials generated during the oxidation / reduction cycle of the battery, particularly the anode active materials may be suppressed or reduced.
- the metal fibers 10 pass between the electrically active materials 20 in the form of particles, the electrode structures 100, 200, and 300 may absorb mechanical stress caused by a redox reaction, and thus The irreversibility of charging and discharging that may be caused can be alleviated, thereby reducing the capacity reduction caused by the use of the battery.
- a Li-ion battery which is a representative secondary battery, it may experience a volume expansion of 100% or more during lithiation according to an electrical active material constituting a high capacity anode.
- the expansion and contraction of the anode may be repeated, resulting in cracking of the anode.
- the conventional electrode structure in which the active material is coated on the current collector such cracking prevents the electric active material from making electrical contact with the current collector anymore, or the electrical conductivity between the electric active materials is reduced, so that the capacity is drastically reduced, The irreversibility increases, and stability problems can result.
- the conductive network may play the same role as the current collector, and pores formed by the metal fibers 10 and the electrical active material 20 are electrically charged and discharged.
- the electrically active materials 20 By buffering the volume change of the active material 20, not only cracking occurs in the electrically active material 20, but also because the electrically active materials 20 in the form of particles are still bound to the metal fibers 10, the electrically active materials 20.
- the problem of reduction in electrical conductivity which may occur when the 20s are separated from each other is solved, thereby improving the charge and discharge reversibility of the battery.
- nanoscale structure such as nanowire, nanotube or nanorod, which is less vulnerable to volume change and cracking mechanism
- these structures are inherently suitable for application to small capacity battery structures, they are difficult to apply to high capacity batteries requiring large volumes, and complex manufacturing processes such as catalytic reactions during their production are difficult.
- a difficult process such as a vacuum deposition process is involved to apply the electrically active material to the nanoscale electrode.
- the electrically active material 20 in the form of particles bound in the conductive network may be appropriately selected depending on the polarity of the electrode structure and whether it is a primary battery or a secondary battery.
- the cathode active material is a two-component or more oxide including lithium, nickel, cobalt, chromium, magnesium, strontium, vanadium, lanthanum, cerium, iron, cadmium, lead, titanium, molybdenum or manganese. ), Phosphate, sulfide, fluoride or combinations thereof.
- the cathode type electrical active material comprises at least two or more of cobalt, copper, nickel, manganese, titanium and molybdenum suitable for lithium secondary batteries, and includes O, F, S, P, and combinations thereof.
- At least one non-metallic element selected from the group consisting of, for example, may be a compound of three or more components such as Li [Ni, Mn, Co] O 2 .
- the anode active material may be, for example, a carbon-based material such as low crystalline carbon or high crystalline carbon.
- the low crystalline carbon may be, for example, soft carbon or hard carbon.
- the high crystalline carbon may include, for example, natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch based carbon fiber, and carbon microspheres. carbon microbeads, mesophase pitches, hot calcined carbon such as petroleum or coal tar pitch derived cokes. This is exemplary and other carbon-based materials of diamonds and carbines may be applied.
- the anode active material is, as a non-carbon-based active material, sodium, or other oxides, carbides, nitrides, sulfides, phosphides, selenides, suitable for NaS cells. And at least one of teleniumide. Or monomagnetic fields such as silicon, germanium, tin, lead, antimony, bismuth, zinc, aluminum, iron and cadmium, intermetallic compounds having high lithium ion occlusion and release capability for high capacity of the cathode Or non-carbon based active materials such as oxide based materials may be used.
- next-generation high-efficiency Li intercalation materials such as silicon (Si), bismuth (Bi), tin (Sn), and aluminum
- Si silicon
- Bi bismuth
- Sn tin
- aluminum aluminum
- An electrical active material containing a metal-based or an intermetallic compound having a high volumetric high volume change such as (Al) or an alloy thereof may be used.
- a binder 40 may be externally attached so that the electrically active materials 20 in the form of particles are strongly bound to the conductive network.
- the binder is, for example, vinylidene fluoride-hexafluoropropylene copolymer (PVdF-co-HFP), polyvinylidene fluoride (PVdF), polyacrylonitrile, polymethylmethacryl Polymethylmethacrylate, polytetrafluoroethylene (PTFE), styrenebutadiene rubber (SBR), polyimide, polyurethane-based polymers, polyester-based polymers, and ethylene-propylene-diene copolymers (ethylene-propylene -diene copolymer (EPDM) may be a polymeric material.
- PVdF-co-HFP vinylidene fluoride-hexafluoropropylene copolymer
- PVdF polyvinylidene fluoride
- SBR styrenebutadiene rubber
- the binder may be another polymer material having conductivity, petroleum pitch, coal tar.
- the present invention is not limited by these examples, and may be a material having stability while having a predetermined binding force in an electrochemical environment without dissolving in an electrolyte.
- the binders 40a and 40b may be added at a weight ratio of about 0.5 to 5% based on the total mixed weight of the electrical active material 10 and the binders 40a and 40b. Since the binders 40a and 40b generally use an organic solvent or water as a dispersion medium in terms of the manufacturing process, it takes time for drying them and remains in the electrically active material even after drying, thereby degrading the cycle characteristics of the battery. have. In addition, since the binders 40a and 40b are insulators, their use is preferably limited. In the electrode structure 200 according to the present embodiment, since the electrically active material 20 in the form of particles is strongly bound in the conductive network, the use of the binder 40 may be minimized. In addition, when using the binder (40a, 40b) it is possible to minimize the use of the binder (40a, 40b) due to the mechanical fixing force of the conductive network.
- the binder 40 is between the electrical active material 20 in the form of particles 40a and between the electrical active material 20 and the metal fibers 10.
- 40b may exist in the form of point binding, and the point binding is preferable because the internal resistance of the electrode structure 200 can be minimized. A method of manufacturing various electrode structures for inducing the point binding will be described later.
- the conductive material 50 in the case of the electrically active material 20, in particular, the cathode active material, the conductive material 50, as shown in FIG. 1C, together with the electrically active material 20 and the binders 40a and 40b described above in the electrode structure 200. May be further externalized.
- the conductive material 50 may be uniformly mixed with the electrical active material 20 and provided in the electrode structure 200.
- the conductive material 50 may be added in a weight ratio of about 1% to 15% based on the total amount of the electrically active material 20 and the conductive material 50 mixed.
- the conductive material 50 may be, for example, fine carbon such as carbon black, acetylene black, ketjen black and ultra fine graphite particles, nano metal particle paste, or indium tin oxide (ITO) paste or carbon nano tube. It may also be a nanostructure having a large specific surface area, such as low resistance.
- the conductive material 50 since the metal fibers 10 having a fine size corresponding to the active material 20 may play the same role as the conductive material 50, the conductive material 50 There is an advantage that can suppress the increase in manufacturing cost due to the addition of).
- porous ceramic particles may be further externalized in the electrode structure described above.
- the porous ceramic particles may include, for example, porous silica.
- the porous ceramic particles facilitate the impregnation of the electrolyte solution 30 into the electrode structures 100, 200, and 300.
- the electrode structure including the same has improved capacity and energy density and improved charge and discharge efficiency.
- SLI lighting and ignition
- a battery including the electrode structure may be integrated into a product having flexible characteristics such as clothes and a bag.
- a battery including the electrode structure may be provided on the rear surface of the flexible display substrate, so that a degree of freedom of a place and a space where the battery is disposed may be extended.
- FIG. 2 is a flowchart illustrating a method of manufacturing an electrode structure according to an exemplary embodiment of the present invention
- FIGS. 3A to 3D are diagrams sequentially illustrating the results of the flowchart of FIG. 2.
- the above-described metal fibers are prepared (S100).
- the metal fibers may be a plurality of segments segmented to have a predetermined length. In some embodiments, the metal fibers may be segmented to have a length of about 5 cm to 8 cm to form an electrode structure of nonwoven structure.
- the metal fibers 10 may be randomly deployed on a suitable support plane. In this case, the metal fibers 10 may be laminated in a single layer or a thickness of several to several hundred layers, and thus the first fiber layer 10L1 may be provided.
- the metal fibers 10 may be deformed by tapping the randomly deployed metal fibers 10 with a rod, which causes the metal fibers 10 to intertwine to form a nonwoven structure. can do.
- the metal fibers 10 in the first fiber layer 10L1 are in physical contact with each other to form a rather sparse conductive network.
- a suitable heat treatment may ensure chemical bonding between the metal fibers 10.
- the heat treatment may be performed, for example, at 100 ° C. to 1200 ° C.
- the metal fibers 10 may first be uniformly pre-coated with the electrical active material using a binder. To this end, the mixed composition of the micronized electrical active material particles and the binder is dispersed with a suitable solvent, and then the metal active material 10 is immersed in the resultant, and the solvent is removed by a drying process to coat the electrical active material. Metal fibers can be obtained.
- the electrical active material to be precoated may be another kind of active material having the same or chemical affinity as the electrical active material 20 to be infiltrated in the conductive network.
- the precoat layer may include another metal or metal oxide coating having corrosion resistance.
- a particle composition including an electrical active material to be subjected to a battery reaction is prepared (S200).
- the electrical active material is in the form of particles, and as described above, the electrical active material 20 may be particles having a size of 0.1 ⁇ m to 100 ⁇ m.
- an external additive selected from any one or a combination of two or more selected from a binder, a conductive material, and porous ceramic particles may be included.
- the particle composition may be provided by a dry mixing process as follows. For example, first, the electrically active materials in the form of particles and a predetermined amount of conductive material particles are rotated at high speed by using a mixer to form an intermediate mixed particle composition. Thereafter, solid binder particles may be added to the dry intermediate mixed composition, and then rotated at a high speed using a mixer to complete the particle composition.
- the intermediate mixed particle composition and the final particle composition thus obtained by the mixing step are solvent-free dry powders mixed without depending on the solvent.
- the binder particles may first be introduced into a mixer together with the electrical active material and rotated at high speed to form an intermediate mixed particle composition. Thereafter, a conductive material may be added to the intermediate mixed particle composition, and then mixed again to provide the particle composition. As another example, the binder particles and the conductive material particles may be added to the electrical active material at the same time, and rotated at a high speed using a mixer to form the particle composition. Likewise, in this case, both the intermediate mixed particle composition and the final particle composition obtained are solvent-free dry powders.
- the porous ceramic particles When the porous ceramic particles are externally attached to the particle composition, the porous ceramic particles may be mixed with the electrically active material particles together with or separately from any one of other materials, that is, binder particles and conductive materials. For example, after the electrical active material particles, the binder particles and the conductive material particles are mixed to form an intermediate mixed particle composition, the porous ceramic particles may be further added and mixed with the resultant to form a final particle composition. Also in this case, the finally obtained particle composition is a solvent-free dry powder.
- the binder is provided in the form of particles.
- the binder may optionally be provided pre-coated on the surface of at least one of metal fibers, conductive particles, or porous ceramic particles.
- the metal fibers are immersed in a solution in which the binder is dissolved or dispersed, and after the predetermined time has elapsed, the metal fibers are again taken out and dried using a dryer or the like, thereby obtaining a metal fiber precoated with the binder.
- the solvent after immersing the metal fibers in a solution in which the binder is dissolved or dispersed, the solvent may be dried while stirring the solution to obtain a metal fiber precoated with the binder.
- any one or both of the conductive material particles and the porous ceramic particles are placed in a solution in which the binder is dissolved or dispersed, and the solvent is dried while stirring the solution to prevent the binder from being coated on the surface.
- porous ceramic particles can be obtained.
- the environmental load is smaller than that of the conventional manufacturing process in which a large amount of the binder and the active material are mixed in a solvent to form a slurry.
- the step of externalizing the binder particles in the above-described forming process of the particle composition may be omitted.
- the binder when the binder is provided pre-coated with metal fibers or external additives such as conductive particles and porous ceramic particles, the distribution state and content of the binder in the entire electrode composition may be reasonably limited.
- there may be an attempt to precoat the binder on the electrically active material particles but only by heating at a low temperature at which the binder is melted in the crimping process described later, the point binding cannot be induced, The amount of addition may increase and the electrical performance of the battery may deteriorate.
- the precoating process is preferably performed only on the surface of the metal fibers, the conductive material particles or the porous ceramic particles, and is not precoated on the electrically active material particles.
- the binder is precoated.
- the metal fibers 10 and the electrical active materials 20 as shown in FIG. 1B, which may be generally held in position and undergoes a swelling and shrinking process with slight heat supplied during the electrode fabrication process.
- the point binders 40a and 40b may be induced between the field 20 and the conductive materials 50 and further between the electrical active materials 20. Since the binder does not contribute to the electrical properties except to exhibit lithium ion conductivity, it is preferable to minimize the application thereof in the electrode structure.
- the metal fibers and the particle compositions are mixed (S300).
- the metal fibers 10 are provided in the form of a first fiber layer 10L1, preferably in the form of a metal nonwoven, the metal fibers may be sprayed onto the first fiber layer 10L1, as shown in FIG. 3B.
- the particle compositions can be mixed.
- the results shown in FIG. 3B show that the particle compositions 20L invade the interior of the first fiber layer 10L1 and overflow, leaving the particle compositions on the first fiber layer 10L1.
- This result shown in FIG. 3B is exemplary only, and the present invention is not limited thereto.
- the particle compositions may be mixed only by the amount completely infiltrated into the first fibrous layer 10L1.
- the particle composition after spraying the particle composition on the upper side of the first fiber layer 10L 1 , the particle composition is further sprayed on the bottom side of the first fiber layer 10L1 exposed by flipping it over to the first fiber layer 10L 1 .
- the uniformity of the particle composition to be infiltrated can be improved. If necessary, during the mixing step (S300), a vibration having a suitable frequency and strength may be applied to promote uniform invasion of the particle composition between the pores between the metal fibers.
- the second fibrous layer 10L2 may be further provided on the resultant, as shown in FIG. 3C.
- the second fibrous layer 10L 2 may be formed, for example, in a similar manner to the first fibrous layer 10L 1 .
- the thickness of the second fiber layer 10L 2 may be a single layer or a size of several to several hundred layers.
- the metal fibers 10 may be deformed by tapping the randomly deployed metal fibers 10 with a rod, whereby the metal fibers 10 may be entangled with each other to form a nonwoven structure.
- a plurality of fiber layers, as shown in Fig. 3d (10L 1, 10L 2, 10L 3) of the step and to this mixture the electrically active material in the fiber layer electrically active material layer forming (20L 1, 20L 2 ) May be performed alternately a plurality of times.
- FIG. 3D three fiber layers 10L 1 , 10L 2 , 10L 3 and two electrical active material layers 20L 1 , 20L 2 are alternately stacked, but this is merely illustrative and the present invention is limited thereto. It doesn't happen.
- two fibrous layers and one electrically active material layer may be alternately stacked, and four or more fibrous layers and three or more electrically active material layers may be alternately stacked.
- the structure 400 in which the metal fibers and the particle compositions are mixed is compressed (S400).
- the structure 400 may have a plate-like structure having a predetermined thickness.
- the pressing step S400 may be performed by using a roll press to increase the capacitance density of the electrode and to increase the adhesion between the conductive network and the electrical active material.
- energy for melting the binder may be applied to the resultant during the pressing step S400.
- the energy may be heat and / or ultraviolet radiation.
- the energy may be appropriately selected depending on the type of binder, but typically, the heating step may be performed at a relatively low temperature, for example, 50 ° C to 400 ° C, preferably 150 ° C to 300 ° C.
- the surface of the structure 400 may be pressed by pressing in the direction of an arrow, thereby adjoining adjacent fibrous layers, for example, the first fibrous layer 10L 1 and the second fibrous layer 10L 2.
- a conductive network can be formed over the entire volume of the structure 400 by the metal fibers belonging to the second fibrous layer 10L 2 and the second fibrous layer 10L 3 intertwined with the fibers of the other layer to make physical contact with each other.
- the particle composition is only mixed in the form of a solvent-free dry powder and in the form of a slurry. Is not provided. That is, in the above embodiments, the electrically active material is invaded in the form of dried particles without solvent in the conductive network of metal fibers.
- the load on the environment is small.
- a separate drying step for removing the solvent in the slurry is not necessary, so that the process can be simplified, the productivity can be improved, and the equipment can be simplified.
- the electrical active material may be deteriorated, so that the above-described mixing process using the solvent-free dry powder improves the yield.
- 4A and 4B are cross-sectional views illustrating electrode structures 400A and 400B according to other embodiments of the present invention.
- the conductive layer CL may be provided on one surface of the electrode structures 100 and 200 of the nonwoven structure obtained through the above-described manufacturing method. Since the metal fibers in the electrode structures 100 and 200 of the nonwoven structure can function as current collectors, the conductive layer CL can be applied as a tab for battery assembly.
- the conductive layer CL may be attached to the electrode structure 100 having a nonwoven structure using the conductive adhesive layer AL, for example, a metal paste.
- the conductive layer CL may be formed by a reaction layer or a bonding layer BL formed by chemical bonding or solid solution between the electrode structure 200 having the nonwoven fabric structure and the conductive layer CL. It may be coupled to the electrode structure 200.
- the conductive layer CL may be a thin metal foil such as stainless steel, aluminum, and copper.
- FIG. 5A is an exploded view illustrating a battery 1000 using an electrode structure according to an exemplary embodiment of the present invention
- FIG. 5B is a cross-sectional view schematically illustrating a method of stacking electrode structures.
- the battery 1000 may be a general cylindrical battery.
- the electrode structures 100a and 100b having different polarities as the cathode and the anode may be alternately wound with each other.
- Tabs 100T such as a conductive layer (CL in FIGS. 4A and 4B) may be coupled to one end of the electrode structures 100a and 100b, respectively.
- a separator 500 may be disposed between the electrode structures 100a and 100b to insulate the electrode structures 100a and 100b having different polarities. If at least one or both of these different polarity electrode structures 100a, 100b is not coated with a current collector such as a conventional metal foil, ion exchange between these electrode structures 100a, 100b during charge and discharge Can be done in both directions. For example, in a lithium ion battery, if the first electrode structures 100a are a negative electrode, the second electrode structures 100b are a positive electrode, and a conventional current collector is not applied to the positive electrode structure 100b, The pair of cathode structures 100a may share the anode structure 100b therebetween.
- a current collector such as a conventional metal foil
- lithium ions of negative electrode structures 100a move to both surfaces of positive electrode structure 100b to emit energy, as indicated by arrows A1 and A2. It becomes possible. Even in charging, lithium ions move in both directions, contributing to cell chemistry.
- the thicker the electrical active material layer the lower the capacitance.
- the thickness of the positive electrode current collector is thick, for example, even if it has twice the thickness of the electrical active material layer of the conventional electrode structure, the cell has an equivalent or larger electrical capacity.
- the number of separators to be used can be reduced as compared with the case of using a conventional electrode, there is an advantage that can provide a battery having a high energy density.
- the separator 500 applied to such a battery may be, for example, a polymer microporous membrane, a woven fabric, a nonwoven fabric, a ceramic, an intrinsic solid polymer electrolyte membrane, a gel solid polymer electrolyte membrane, or a combination thereof.
- the intrinsic solid polymer electrolyte membrane may include, for example, a linear polymer material or a crosslinked polymer material.
- the gel polymer electrolyte membrane may be, for example, a combination of any one of a plasticizer-containing polymer containing a salt, a filler-containing polymer, or a pure polymer.
- the solid electrolyte layer is, for example, polyethylene, polypropylene, polyimide, polysulfone, polyurethane, polyvinyl chloride, polystyrene, polyethylene oxide, polypropylene oxide, polybutadiene, cellulose, carboxymethyl cellulose, nylon, polyacryl Ronitrile, polyvinylidene fluoride, polytetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene, copolymer of vinylidene fluoride and trifluoroethylene, vinylidene fluoride and tetrafluoroethylene Copolymers of polymethyl acrylate, polyethyl acrylate, polyethyl acrylate, polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyvinylacetate, and polyvinyl alcohol Made of any one or a combination thereof It may include a polymer matrix, additive
- the materials listed with respect to the above-described separator 500 are exemplary, and as the separator 500, the shape change is easy, and the mechanical strength is excellent, so that no deformation or tear of the electrode structures 100a and 100b is caused. Materials that have suitable electronic insulation and yet have good ion conductivity can be selected.
- the separator 500 may be a single layer film or a multilayer film, and the multilayer film may be a laminate of the same monolayer film or a stack of monolayer films formed of different materials.
- the laminate may have a structure including a ceramic coating film on the surface of a polymer electrolyte film such as polyolefin.
- the thickness of the separator 500 may be 10 ⁇ m to 300 ⁇ m, preferably 10 ⁇ m to 40 ⁇ m, and more preferably 10 ⁇ m to 25 ⁇ m in consideration of durability, shutdown function, and battery safety.
- the battery 1000 is electrically connected to the external electrode terminals 600 and 700 through the conductive tabs 100T coupled to the electrode structures 100a and 100b, respectively.
- a suitable aqueous electrolyte comprising salts such as potassium hydroxide (KOH), potassium bromide (KBr), potassium chloride (KCL), zinc chloride (ZnCl 2 ), and sulfuric acid (H 2 SO 4 ).
- KOH potassium hydroxide
- KCL potassium chloride
- ZnCl 2 zinc chloride
- SO 4 sulfuric acid
- the battery 1000 may be completed by being absorbed by the 100a and 100b and / or the separator 500.
- a suitable battery management system for controlling stability and / or power supply characteristics during use of the battery 1000 may additionally be combined.
- the electrode structures made of the above-described metal fibers are easy to change in shape because of their fibrous properties, and because the active material layer and the conductive network are substantially uniformly mixed in the entire volume of the electrode structure, the thickness of the electrode structures is reduced. It will be appreciated that even with increasing the volume, there is no deterioration in battery performance exhibited in the conventional battery structure obtained by coating the active material layer on the metal foil, and the volume can be variously selected.
- the fibrous electrode structure can be deformed three-dimensionally by methods such as stacking and bending and winding, in addition to the winding type as shown in FIG. It can have various volumes and shapes that are integrated into pouches, or textile products such as clothes and bags.
- the aforementioned electrode structures can be applied to either or both of the cathode and anode electrodes in one cell.
- a metal fiber having the excellent electrical, mechanical and thermal properties of the metal but also combines the flexibility and organization of the fiber, reducing the contact resistance and increase the contact area between the current collector structure and the electrical active material
- the effect can provide a battery in which the energy density is improved, the charge / discharge speed, the charge / discharge efficiency and cycle characteristics are improved in the energy density of the battery.
- the amount of separator required when manufacturing a battery by stacking electrodes can be reduced.
- the electrode can be made thick in the same cell volume, and a battery having excellent energy density per unit volume can be produced.
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Abstract
Description
Claims (18)
- 하나 이상의 금속 섬유들에 의해 형성된 도전성 네트워크; 및상기 도전성 네트워크에 속박된 입자 형태의 전기적 활물질을 포함하는 입자 조성물을 포함하는 전극 구조체를 갖는 전지.
- 제 1 항에 있어서,상기 금속 섬유들은 랜덤하게 서로 물리적으로만 접촉하여 서로 결합되고, 상기 도전성 네트워크는 부직포 구조를 갖는 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 제 1 항에 있어서,상기 입자 조성물은 도전재, 결착재 및 다공성 세라믹 입자 중 어느 하나 또는 이들 모두를 더 포함하는 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 제 3 항에 있어서,상기 결착재는 상기 금속 섬유들과 상기 제 1 전기적 활물질 사이, 및 상기 제 1 전기적 활물질들 사이에 점 결착 형태로 제공되는 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 제 1 항에 있어서,상기 금속 섬유들은 1 ㎛ 내지 200 ㎛ 범위 내의 두께를 갖는 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 제 1 항에 있어서,상기 금속 섬유들은 2 ㎛ 내지 20 ㎛ 범위 내의 두께를 갖는 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 제 1 항에 있어서,상기 금속 섬유들은 스테인레스강, 알루미늄, 니켈, 티타늄 및 구리 또는 이들의 합금 중 어느 하나 또는 이들의 조합을 포함하는 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 제 1 항에 있어서,상기 금속 섬유들의 평균 두께(d)에 대한 상기 입자 형태의 상기 전기적 활물질들의 평균 크기(s)의 비(s/d)는 0.01 내지 10 인 것을 특징으로 하는 전극 구조체를 갖는 전지.
- 도전성 네트워크를 형성하는 하나 이상의 금속 섬유들을 제공하는 단계;입자 형태의 전기적 활물질들을 포함하는 입자 조성물을 제공하는 단계;상기 금속 섬유들과 상기 입자 조성물들을 혼합하는 단계; 및혼합된 상기 금속 섬유들과 상기 입자 조성물들을 압착하는 단계를 포함하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 금속 섬유들은 랜덤하게 배열되어 부직포 구조를 갖는 섬유층 형태로 제공되는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 10 항에 있어서, 상기 혼합하는 단계에서,상기 입자 조성물은 상기 섬유층 상에 무용매 건식 분체 상으로 제공되는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 혼합하는 단계는 상기 도전성 네트워크 내에 상기 입자 조성물을 뿌림으로써 수행되는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 입자 조성물은, 상기 입자 형태의 전기적 활물질들과 함께 혼합되는 결착재 입자, 도전재 입자 및 다공성 세라믹 입자 중 어느 하나 또는 이들의 조합으로부터 선택된 외첨제들을 포함하며,상기 외첨제들과 상기 전기적 활물질들의 상기 혼합은 건식 믹싱 공정을 통해 수행되는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 하나 이상의 금속 섬유들을 제공하는 단계는 상기 금속 섬유들의 표면 상에 결착재를 프리코팅하는 단계를 포함하는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 입자 조성물은, 상기 입자 형태의 전기적 활물질들과 함께 혼합되는 도전재 입자 및 다공성 세라믹 입자 중 어느 하나 또는 이들의 조합으로부터 선택된 외첨제들을 포함하고,상기 외첨제와 상기 전기적 활물질들의 상기 혼합은 건식 믹싱 공정을 통해 수행되는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 입자 조성물은, 상기 입자 형태의 전기적 활물질들과 함께 혼합되는 도전재 입자 및 다공성 세라믹 입자 중 어느 하나 또는 이들의 조합으로부터 선택된 외첨제들을 포함하고, 상기 도전재 입자 및 상기 다공성 세라믹 입자 중 어느 하나 또는 이들 모두의 표면 상에는 결착재가 프리코팅되며,상기 외첨제와 상기 전기적 활물질들의 상기 혼합은 건식 믹싱 공정을 통해 수행되는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 압착하는 단계와 동시에 가열 또는 자외선 조사를 하는 단계를 더 포함하는 것을 특징으로 하는 전극 구조체의 제조 방법.
- 제 9 항에 있어서,상기 가열은, 50℃ 내지 400℃ 에서 수행되는 것을 특징으로 하는 전극 구조체의 제조 방법.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280017338.7A CN103620828B (zh) | 2011-04-06 | 2012-04-04 | 具有含金属纤维电极结构体的电池及电极结构体制备方法 |
JP2014503593A JP6053751B2 (ja) | 2011-04-06 | 2012-04-04 | 金属繊維を含む電極構造体を有する電池、及び前記電極構造体の製造方法 |
US14/110,180 US9929409B2 (en) | 2011-04-06 | 2012-04-04 | Battery having electrode structure including metal fiber and preparation method of electrode structure |
ES12768144T ES2719268T3 (es) | 2011-04-06 | 2012-04-04 | Batería que tiene una estructura de electrodo que incluye fibra metálica y procedimiento de preparación de la estructura de electrodo |
EP12768144.3A EP2696399B1 (en) | 2011-04-06 | 2012-04-04 | Battery having electrode structure including metal fiber and preparation method of electrode structure |
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KR1020110031917A KR101806547B1 (ko) | 2011-04-06 | 2011-04-06 | 금속 섬유를 포함하는 전극 구조체를 갖는 전지 및 상기 전극 구조의 제조 방법 |
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US (1) | US9929409B2 (ko) |
EP (1) | EP2696399B1 (ko) |
JP (1) | JP6053751B2 (ko) |
KR (1) | KR101806547B1 (ko) |
CN (1) | CN103620828B (ko) |
ES (1) | ES2719268T3 (ko) |
WO (1) | WO2012138115A2 (ko) |
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- 2012-04-04 EP EP12768144.3A patent/EP2696399B1/en not_active Not-in-force
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Cited By (5)
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CN105493323A (zh) * | 2013-06-24 | 2016-04-13 | Jenax股份有限公司 | 二次电池用集电体及利用其的电极 |
CN104701567A (zh) * | 2013-12-10 | 2015-06-10 | 三星Sdi株式会社 | 可再充电电池及其制造方法 |
EP2884559A1 (en) * | 2013-12-10 | 2015-06-17 | Samsung SDI Co., Ltd. | Rechargeable battery and manufacturing method of the same |
US9905816B2 (en) | 2013-12-10 | 2018-02-27 | Samsung Sdi Co., Ltd. | Rechargeable battery and manufacturing method of the same |
CN113571755A (zh) * | 2013-12-10 | 2021-10-29 | 三星Sdi株式会社 | 可再充电电池及其制造方法 |
Also Published As
Publication number | Publication date |
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JP2014510386A (ja) | 2014-04-24 |
EP2696399A4 (en) | 2014-10-01 |
EP2696399A2 (en) | 2014-02-12 |
CN103620828A (zh) | 2014-03-05 |
JP6053751B2 (ja) | 2016-12-27 |
KR101806547B1 (ko) | 2018-01-10 |
US20140030605A1 (en) | 2014-01-30 |
CN103620828B (zh) | 2017-01-25 |
US9929409B2 (en) | 2018-03-27 |
KR20120114117A (ko) | 2012-10-16 |
WO2012138115A3 (ko) | 2013-01-10 |
EP2696399B1 (en) | 2019-01-16 |
ES2719268T3 (es) | 2019-07-09 |
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