WO2019177409A1 - Électrode de batterie secondaire, et son procédé de production - Google Patents

Électrode de batterie secondaire, et son procédé de production Download PDF

Info

Publication number
WO2019177409A1
WO2019177409A1 PCT/KR2019/003006 KR2019003006W WO2019177409A1 WO 2019177409 A1 WO2019177409 A1 WO 2019177409A1 KR 2019003006 W KR2019003006 W KR 2019003006W WO 2019177409 A1 WO2019177409 A1 WO 2019177409A1
Authority
WO
WIPO (PCT)
Prior art keywords
active material
electrode
secondary battery
film
manufacturing
Prior art date
Application number
PCT/KR2019/003006
Other languages
English (en)
Korean (ko)
Inventor
이종혁
윤덕영
강희경
Original Assignee
에스케이이노베이션 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020190029127A external-priority patent/KR20190109284A/ko
Application filed by 에스케이이노베이션 주식회사 filed Critical 에스케이이노베이션 주식회사
Priority to CN201980014936.0A priority Critical patent/CN111788722A/zh
Priority to US16/980,615 priority patent/US20210020898A1/en
Priority to JP2020545111A priority patent/JP2021515963A/ja
Priority to EP19768601.7A priority patent/EP3767711A4/fr
Publication of WO2019177409A1 publication Critical patent/WO2019177409A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a secondary battery electrode and a manufacturing method thereof.
  • nickel-metal hydride secondary batteries are mainly used as a power source of electric vehicles, but lithium secondary batteries have a higher power density (more than three times that of nickel-metal hydride secondary batteries), have a long cycle life, and have low self-discharge rates. Research into using the battery as the main power source of the electric vehicle has been actively conducted.
  • An object of the present invention is to provide a method for manufacturing a novel secondary battery electrode capable of high-loading, high mixture density.
  • Another object of the present invention is to provide a method for manufacturing a new secondary battery electrode capable of implementing a binder-free electrode, in which the active material layer does not contain a binder.
  • Another object of the present invention is to provide a method of manufacturing a new secondary battery electrode that can reduce the cost by a more simplified process and can mass-produce a uniform quality electrode.
  • Another object of the present invention is to provide an active material film capable of implementing a high-loading, high-density electrode, a secondary battery electrode including the same, and a secondary battery including the same.
  • a method of manufacturing an electrode for a secondary battery according to the present invention includes: cutting a bulk of an active material to prepare an active material film; And a binding step of integrating a current collector and the active material film.
  • the method of manufacturing an electrode for a secondary battery according to an embodiment of the present invention may further include a bulk manufacturing step of manufacturing an active material bulk using a raw material including a particulate electrode active material before cutting.
  • the electrode active material may be a negative electrode active material or a positive electrode active material.
  • the bulk of the active material may be free standing.
  • the active material bulk may be a molded or sintered body.
  • the bulk manufacturing step includes a molding step of manufacturing a molded body by compression molding the raw material; Or a sintering step of manufacturing a sintered body by heat-treating the molded body prepared in the molding step and the molding step.
  • the raw material may further include an additive selected from at least one of a binder, a conductive material, a carbon precursor, and a pore former.
  • the conductive material may include particles, fibers, nanostructures, or mixtures of one or two or more materials selected from conductive carbon, conductive polymers, and metals.
  • the conductive nanostructure may be selected from one or two or more from nanowires, nanotubes, nanoplates, nanoribbons, nanoparticles, and nanorods.
  • the carbon precursor may be selected from one or more of coke, pitch, thermosetting and thermoplastic resin.
  • the particulate particles are the core of the electrode active material; Shell of heterogeneous material; may be a core-shell structure.
  • the heterogeneous material may include a second electrode active material, a precursor of the second electrode active material, a conductive material, a binder, a carbon precursor, or a mixture thereof.
  • the raw material may contain two or more kinds of electrode active materials different in composition, crystal structure, particle shape, mechanical properties or physical properties.
  • the porosity of the active material film may be controlled by the porosity of the bulk of the active material.
  • the electrode active material in the active material bulk has an orientation, the orientation of the electrode active material in the active material film based on the thickness direction of the active material film by the cutting direction of the cutting step Can be controlled.
  • the binding step may include forming an adhesive layer on at least one surface of the surface of the current collector and the surface of the active material film; And laminating the current collector and the active material film to be in contact with the adhesive layer therebetween.
  • the binding step may include forming a metal film on one surface of the active material film.
  • the adhesive layer may be conductive.
  • the negative electrode active material is a graphite graphite; Non-graphitizable carbon; Natural graphite; Artificial graphite; Carbon nanotubes; Graphene; silicon; Sn alloys; Si alloys; Oxides of one or more elements selected from Sn, Si, Ti, Ni, Fe and Li; Or mixtures thereof.
  • the positive electrode active material is a lithium-metal oxide of a layered structure; Spinel structure lithium-metal oxides; Lithium-metal phosphate of olivine structure; Or mixtures thereof.
  • the active material may contain natural graphite, artificial graphite, or a mixture thereof.
  • the active material may include a plate shape or a flake shape.
  • the bulk manufacturing step by pressing the raw material containing the composite particles of the core-shell structure of the electrode active material core-carbon precursor shell with a particulate electrode active material Preparing a molded body; And pyrolyzing the carbon precursor of the shell with carbon by heat treating the molded body.
  • the bulk manufacturing step comprises the steps of preparing a molded body by press molding a raw material including a particulate electrode active material and a carbon precursor; And pyrolysing the carbon precursor to carbon by heat treating the molded body.
  • the molded body may be produced by one-way, two-way or isodirectional compression molding.
  • the step of surface treatment of at least one surface of the active material film may be further performed.
  • the surface treatment may include surface roughness control.
  • the present invention includes an electrode for secondary batteries manufactured by the above-described manufacturing method.
  • Lithium secondary battery (I) is a positive electrode; cathode; And a separator interposed between the anode and the cathode; And an electrolyte solution, wherein the electrode selected from at least one of the positive electrode and the negative electrode may include an active material film containing an electrode active material, a current collector, and an adhesive for attaching the active material film to the current collector.
  • Lithium secondary battery (II) according to another embodiment of the present invention is a positive electrode; cathode; And a separator interposed between the anode and the cathode; And an electrolyte solution, wherein the active material film included in the electrode selected from at least one of the positive electrode and the negative electrode may be a binder-free film containing no organic binder.
  • the active material film may be a free standing film.
  • the active material located on the surface of the active material film may be cut particles.
  • the active material film may be a cut film cut from a molded or sintered body containing the electrode active material.
  • the active material film may have an orientation of the electrode active material in the active material film based on the thickness direction of the active material film.
  • the active material film may be formed between the particle neck of the electrode active material.
  • the active material film may not contain an organic binder.
  • the active material film has an absolute value of the difference between the porosity in the surface region and the porosity in the central region based on the cross section in the thickness direction. Divided by 10% or less.
  • the active material film may further include one or more selected from pyrolytic carbon and a conductive material.
  • the apparent porosity of the active material film may be 10 to 45%.
  • the active material film may include pyrolytic carbon for binding the particles of the electrode active material and the particles of the electrode active material.
  • the adhesive may include a resin having a curing ability.
  • the adhesive may include a conductive component selected from at least one conductive resin, conductive particles, and conductive nanostructures.
  • the electrode active material may be a negative electrode active material or a positive electrode active material.
  • the present invention includes a lithium secondary battery module including the lithium secondary battery described above.
  • the present invention includes a device that is powered by the above-described lithium secondary battery.
  • the present invention includes an active material membrane for an electrolyte based secondary battery.
  • the active material film according to an aspect of the present invention is an active material film for a secondary battery provided with an electrolyte, and may be an active material film for a secondary battery containing an electrode active material and capable of free-standing.
  • the active material film according to another embodiment of the present invention is an active material film for a secondary battery provided with an electrolyte, and may be a binder-free active material film containing an electrode active material and not containing an organic binder.
  • the active material film according to the embodiment of the present invention may be in a state in which a neck formed between the electrode active material particles is formed.
  • the electrode active material in the active material film may have an orientation based on the thickness direction of the active material film.
  • the active material film according to an embodiment of the present invention may further include at least one selected from a conductive material and pyrolytic carbon.
  • a ratio obtained by dividing the absolute value of the difference between the porosity in the surface region and the porosity in the central region by the porosity in the central region may be 10% or less based on the thickness direction cross section.
  • the active material film according to one embodiment of the present invention may further include one or more selected from pyrolytic carbon and a conductive material.
  • the apparent porosity of the active material membrane may be 10 to 45%.
  • the present invention includes an electrolyte-based secondary battery electrode.
  • the secondary battery electrode according to the present invention is an electrolyte-based secondary battery electrode, and includes a binder-free active material film containing an electrode active material and no organic binder.
  • the secondary battery electrode according to the present invention is an electrolyte-based secondary battery electrode, and may be an electrode containing an electrode active material and having an active material film bound to at least one surface of a current collector by an adhesive.
  • the active material film may be a free standing film.
  • the active material film may further include one or more selected from a conductive material and pyrolytic carbon.
  • the active material film may be in a state in which a neck formed between particles of the electrode active material is formed.
  • the present invention includes a secondary battery including the electrode described above.
  • the secondary battery electrode is manufactured by an extremely simple process of cutting-attaching an active material bulk, process construction is easy and inexpensive, and precise and high process control is also achieved. Unnecessary, there is an advantage of excellent commerciality.
  • the method of manufacturing a secondary battery electrode according to an embodiment of the present invention based on the cut-attach process of the bulk of the active material, by applying a process of slicing (slicing) instead of the coating process by applying a slurry as in the conventional process
  • a process of slicing slicing
  • the conductive substrate is shaken according to the control of the drying air flow, or the thickness variation according to the drying conditions of the edge and the center during drying after coating under high loading conditions, and therefore subsequent rolling process
  • the method for manufacturing a secondary battery electrode according to an embodiment of the present invention as a large amount of active material film is prepared on the basis of a bulk, by a simple process called a cut-attach process, it is possible to mass-produce an electrode of extremely uniform quality And, there is an advantage that can be produced in a large amount of electrodes of extremely uniform quality.
  • an electrode for a secondary battery in the method of manufacturing an electrode for a secondary battery according to an embodiment of the present invention, as the active material bulk, which is a free-standing molded body or a sintered body, is cut to prepare an active material film, a binder-free active material film may be prepared, and the thickness of the active material film There is no substantial restriction on the active material film in the form of a thick film is possible, there is an advantage that the production of an electrode having a high loading and high mixture density.
  • the method of manufacturing an electrode for a secondary battery is made of an active material itself, made of a conductive material and an active material, made of an active material and pyrolytic carbon, or made of an active material, a conductive material, and pyrolytic carbon.
  • the preparation of the active material bulk is possible.
  • the electrolyte solution can stably penetrate even if the thickness of the active material film is increased, so that the thickness of the film is substantially unlimited.
  • the particulate electrode active material in the bulk of the active material is highly filled or sintered with each other by the pressure or pressure and heat of the molding process, there is an advantage that it is possible to produce an electrode having a high loading and high mixture density.
  • the method for manufacturing a secondary battery electrode according to an embodiment of the present invention can control the orientation direction of the electrode active material particles in the film of the active material film in the cutting direction of the bulk of the active material, so that the improvement of the electrolyte impregnation rate, output characteristics, and rate characteristics is possible. have.
  • the method of manufacturing an electrode for a secondary battery according to an embodiment of the present invention has an advantage that an active pore network has a uniform (designed) open pore network regardless of its thickness, so that the electrolyte solution is uniformly and stably impregnated with the electrolyte.
  • the secondary battery may be a binder-free film containing no organic binder, which is an independent member, so that high loading and high mixture density may be easily formed, and high energy density battery design may be easily implemented.
  • a binder-free film containing no organic binder which is an independent member, so that high loading and high mixture density may be easily formed, and high energy density battery design may be easily implemented.
  • the secondary battery according to an embodiment of the present invention has an advantage of uniformly and stably impregnating an electrolyte solution (and lithium ions) even in the form of a thick thick film by an orientation of an active material film or a structure bound by an interparticle neck as an independent member. have.
  • FIG. 1 is a cross-sectional view showing a cross section of an active material bulk that is a molded article according to an embodiment of the present invention.
  • FIG. 2 is a view showing a process for producing an active material film by cutting the bulk of the active material according to an embodiment of the present invention
  • FIG. 3 is a view showing the binding state of two electrode active material particles adjacent to each other in the bulk of the active material is a sintered body, according to an embodiment of the present invention
  • FIG. 4 is a cross-sectional view showing a cross section of an active material film according to an embodiment of the present invention.
  • FIG. 5 is another cross-sectional view showing a cross section of an active material film according to an embodiment of the present invention.
  • FIG. 6 is a cross-sectional view showing a cross section of an electrode according to an embodiment of the present invention.
  • FIG. 8 is a scanning electron microscope photograph of an active material film prepared according to an embodiment of the present invention.
  • the active material bulk is a three-dimensionally independent three-dimensionally alone containing an electrode active material, which can maintain its own shape and support its own weight. It may refer to a three-dimensional solid state in a free-standing state.
  • the bulk may refer to a size having one dimension (width, length or width) exceeding at least the design thickness based on at least the design thickness of the active material layer of the desired electrode. More specifically, the bulk is at least 5 times, substantially 10 times or more based on the thickness of the active material region of the electrode to be manufactured, the size of the three-dimensional solid dimension along at least one axis based on three axes perpendicular to each other It may mean having a size. In addition, it may mean that each dimension of the three-dimensional solid body along each of the other two axes has a size corresponding to or larger than the width or length of the active material region of the electrode to be manufactured, but is not necessarily limited thereto.
  • bulk may refer to a three-dimensional solid body having a weight that exceeds at least the design weight based on the design weight of the active material layer of the desired electrode. More specifically, it may mean a three-dimensional solid having a weight of 10 times or more, substantially 50 times or more based on the design weight (weight of one active material layer of the intended electrode), but is not necessarily limited thereto.
  • a free-standable membrane is a membrane reference having a width of 1 cm, a length of 5 cm, and a thickness corresponding to the active material area design thickness of the secondary battery of interest, with a hollow center, a flat bottom, and flat bilateral pillars.
  • a method of manufacturing an electrode for a secondary battery according to the present invention includes: cutting a bulk of an active material to prepare an active material film; And a binding step of integrating a current collector and the active material film.
  • the method of manufacturing an electrode for a secondary battery may further include a bulk manufacturing step of manufacturing an active material bulk using a raw material including a particulate electrode active material before cutting. That is, a method of manufacturing a secondary battery electrode according to an embodiment of the present invention a) manufacturing a bulk of the active material (bulk) using a raw material containing a particulate electrode active material (bulk manufacturing step); b) cutting the bulk of the active material to prepare an active material film (cutting step); And c) integrating a current collector and the active material film (binding step).
  • the bulk of the active material may be a molded or sintered body.
  • step a) may include a molding step of manufacturing a molded article by compression molding a raw material.
  • a molding step of compression molding the raw material to produce a molded body a molding step of compression molding the raw material to produce a molded body;
  • the manufacturing method of the electrode according to the present invention deviates from the conventional slurry-based process of coating and pressing the slurry containing the active material in the current collector, bulking the active material using a raw material containing a particulate electrode active material After the preparation of the active material, the bulk of the active material may be cut to prepare an active material film corresponding to the active material layer on the current collector in a conventional slurry-based process, and an active material film prepared independently of the current collector may be bonded to the current collector to prepare an electrode.
  • Conventional electrode production methods such as slurry application, drying and rolling include the properties of the slurry itself, such as viscosity and dispersibility of the slurry in the fluidized state, the specific application method or the physical (mechanical) properties of the material contained in the slurry, and the drying conditions of the applied film. This directly affects the structure of the active material layer.
  • the manufacturing technique of the electrode using the active material slurry is highly dependent on the dynamic element, and as the structure of the active material layer is determined, precise control of the active material layer is very difficult in reality, and it is difficult to ensure structural uniformity in a large area. Furthermore, there is also a thickness constraint of the active material layer which can be produced by the coating process. In addition, when the thickness of the electrode needs to be increased, the drying time is increased in the drying process, so the process parameters such as the length of the drying furnace should be changed, and thus there is a problem in that a construction of a new process facility is required.
  • the method of manufacturing the electrode according to the present invention is not slurry-based, by cutting the bulk of the active material having a pre-designed material, pore structure and porosity to prepare an independent active material film, and then to produce the electrode by binding the prepared active material film to the current collector As a result, the structure of the active material film can be precisely and reproducibly controlled.
  • the electrode manufacturing method according to the present invention is capable of producing a large amount of the active material film by cutting the bulk of the active material, as the active material film is prepared on the basis of the solid bulk of the active material rather than a liquid-based slurry, a large amount of active material film of uniform quality There is an advantage to produce.
  • the electrode manufacturing method according to the present invention can be easily controlled by the simple method of controlling the thickness of the film cut from the bulk of the active material, the thickness of the active material region provided on the current collector.
  • the thickness of the active material region provided on the current collector is not substantially constrained as the pores through which the electrolyte and the like penetrate are kept uniform and constant.
  • the electrode is based on a highly multi-step process such as slurry mixing, coating, drying, pressing, and slitting. Are manufactured.
  • the electrode active material slurry is prepared by gradually increasing the concentration (solid content concentration) from a low concentration to a high concentration, it is difficult to control the slurry concentration in consideration of dispersion and sedimentation reduction characteristics. It's tricky.
  • the production process of the slurry such as the recovery device of the organic solvent must be provided separately, and the manufacturing process is complicated and the process equipment and management is difficult.
  • the manufacturing method of the electrode according to the present invention is not based on the slurry, and based on the bulk of the active material, the organic solvent recovery apparatus (step) is unnecessary or minimized, and the remarkably simple process of preparing, cutting and attaching the bulk of the active material
  • the manufacturing of the electrode is possible by the process, which can significantly reduce the cost for process equipment and management.
  • the pore structure is unintentionally collapsed during the rolling of the active material layer, there is a problem that it is difficult to substantially realize the high density and the maintenance of the pores at the same time.
  • the manufacturing method according to the present invention as the pore structure and the porosity of the bulk of the active material having a physically (mechanically) stable strength is still maintained in the cut film (active material film), both the densification and the maintenance of the pores impregnated with the electrolyte solution There is an advantage that can be implemented.
  • the pore structure of the active material membrane may be controlled by only adjusting the pore structure of the active material bulk, and the porosity of the active material membrane may be controlled by the porosity of the active material bulk.
  • Method of manufacturing an electrode according to an embodiment of the present invention is an electrode for an electrolyte-based secondary battery, advantageously an electrode for an electrolyte-based lithium secondary battery, more advantageously an anode; cathode; And a separator interposed between the anode and the cathode; And it may be a method for producing a lithium secondary battery electrode comprising an electrolyte solution.
  • one problem to be solved by the present invention is to provide a method of manufacturing an electrode capable of high-loading and / or high-mixing while allowing an electrolyte solution to penetrate smoothly in an electrode provided in a lithium secondary battery including an electrolyte solution.
  • the electrode manufacturing method according to an embodiment of the present invention may include a method of manufacturing a negative electrode or a method of manufacturing a positive electrode according to the type of electrode active material.
  • the manufacturing method of the electrode according to an example may correspond to the manufacturing method of the negative electrode.
  • the particulate electrode active material included in the raw material is a positive electrode active material
  • a method of manufacturing an electrode according to an example may correspond to a method of manufacturing a positive electrode. Therefore, the manufacturing method of the electrode according to the present invention should not be construed as being limited to the manufacturing method of the positive electrode or the negative electrode.
  • the step of preparing the active material bulk using a raw material containing a particulate electrode active material, the pre-standable active material using a raw material containing a particulate electrode active material It may be a step of preparing the bulk.
  • the preparation of the active material bulk may be a step in which the active material bulk is physically integrated from a raw material including a particulate electrode active material by pressure (for a molded article) or application of pressure and heat (for a sintered body).
  • the raw material may include a particulate electrode active material, and the particulate particles may be spherical, flake (flake), aggregated, amorphous, plate, rod, crystalline (crystalline form consisting of thermodynamically stable crystal faces), polyhedron or these It may be a mixed form of, but is not limited thereto.
  • the electrode active material contained in a raw material is 1 type of electrode active material; Or two or more electrode active materials having different compositions, crystal structures, particle shapes, mechanical properties, or physical properties.
  • the different crystal structures also include cases of homogeneous or more having different crystal structures in the same composition.
  • different particle shapes include meanings of different particle shapes of different materials as well as different particle shapes of one material. For example, there may be mentioned primary particles or crystalline particles of one material, secondary particles of the same material, and flake particles of the same material as spherical particles of one material. It is presented to assist, but is not limited to.
  • the mechanical properties may include one or more selected properties such as hardness, strength, toughness, and ductility
  • physical properties include one of electrical conductivity, thermal conductivity, thermal expansion rate, and specific gravity. It may include the characteristic selected above.
  • the electrode active material contained in the raw material may be a negative electrode active material, and the negative electrode active material may be used as long as it is a material commonly used for the negative electrode of the secondary battery.
  • the negative electrode active material is digraphitizable carbon; Non-graphitizable carbon; Natural graphite; Artificial graphite; Carbon nanotubes; Graphene; silicon; Sn alloys; Si alloys; Oxides of one or more elements selected from Sn, Si, Ti, Ni, Fe and Li (eg, Sn oxide, Si oxide, Ti oxide, Ni oxide, Fe oxide (FeO) and lithium-titanium oxide (LiTiO 2 , Li 4 Ti 5 O 12 ); or a mixture thereof, but is not limited thereto.
  • the electrode active material contained in the raw material may be a positive electrode active material
  • the positive electrode active material may be used as long as it is a material capable of reversible insertion / removal of ions (for example, lithium ions) involved in charging and discharging.
  • the electrode material used for the anode may be sufficient.
  • the cathode active material may be at least one selected from cobalt, manganese, nickel, and at least one of a composite oxide of lithium.
  • a composite oxide of lithium examples include the following compounds. Li x Mn 1 - y M y A 2 , LixMn 1 - y M y O 2 - z X z , Li x Mn 2 O 4 - z X z , Li x Mn 2 -y MyM ' z A 4 , Li x Co 1 - y M y A 2 , Li x Co 1 - y M y O 2 - z X z , Li x Ni 1 - y M y A 2 , Li x Ni 1 - y M y O 2 - z X z , Li x Ni 1 - y M y A 2 , Li x Ni 1 - y M y O 2 - z X z , Li x Ni 1
  • the positive electrode active material may be a lithium-metal oxide having a layered structure; Spinel structure lithium-metal oxides; Lithium-metal phosphate of olivine structure; Or mixtures thereof.
  • the phosphate-based material of the olivine structure may include LiMPO 4 (M is Fe, Co, Mn) and the like, but is not limited thereto.
  • particulate particles may include core-shell structured composite particles as well as particles such as primary particles (crystalline particles), aggregated particles (secondary particles), amorphous particles, spherical particles, flake particles, acicular particles, and the like. Can be.
  • the particulate particles are the core of the electrode active material; It may be a composite particle of the core-shell structure of the shell of the heterogeneous material, the heterogeneous material of the shell is the second electrode active material, the precursor of the electrode active material, the conductive material, the precursor of the conductive material, the binder (first binder) or a mixture thereof It may include.
  • the shell may include a precursor of an electrode active material or a precursor of a conductive material
  • the synthesis or conversion of the material may also be performed during the heat application process for bulking. That is, since the production of the conductive material or the electrode active material may be made in-situ during the bulking of the raw material by heat application, the core of the electrode active material; and the precursor of the electrode active material or the precursor of the conductive material; Composite particles of a shell of the same precursor can be used in particulate form.
  • the bulking of the raw material and the material conversion of the precursor may be simultaneously performed, but if necessary, a separate heat application may be performed before or after the bulking of the molding or sintering furnace.
  • the precursor of the electrode active material may be a precursor of an electrode active material that is the same as the core, or may be a precursor of an electrode active material different from the core (heterogeneous).
  • the shell of the composite particle may be a conductive material or a precursor of the conductive material.
  • the conductive material can be used as long as it is a material known as a conductive material that is commonly incorporated into the active material slurry in order to improve the electrical conductivity of the electrode active material layer.
  • Specific examples of the conductive material include carbon black, acetylene black, ketjen black, channel black, farnes black, lamp black, thermal black, carbon nanotubes, carbon fibers (including VGCF) and exfoliated graphite or these Conductive carbon bodies such as mixtures thereof, but is not limited thereto.
  • the precursor of the conductive material may be a material known as a carbon precursor.
  • the precursor of the conductive material may include a carbon precursor that is converted to carbon by pyrolysis.
  • the carbon precursor may be at least one selected from coke, pitch, thermosetting resin and thermoplastic resin.
  • the coke may include petroleum or coal tar pitch derived cokes, and the pitch may include petroleum pitch, coal pitch or mixtures thereof.
  • the pitch may include an isotropic pitch, mesophase pitch, or a mixture thereof.
  • the resin used as the carbon precursor may be a thermosetting resin, a thermoplastic resin or a mixture thereof.
  • the thermosetting resin may be an epoxy resin, a polyester resin, a phenol resin, an alkyd (unsaturated polyester) resin, a polyimide resin, a vinyl ester resin, a polyurethane resin, a polyisocyanurate resin, or a mixture thereof, and the like.
  • the resin is polyethylene resin, polypropylene resin, polyvinyl alcohol resin, polyvinylidene chloride resin, polyethylene terephthalate resin, polyester resin, polystyrene resin, polymethyl methacrylate resin, polyvinyl chloride resin, ABS (Acrylonitrile Butadien Stylene) Resins, polyamide resins, polycarbonate resins, polyoxymethylene resins, acrylic resins, polyvinylsulfide resins, polyetheretherketone resins, polytetrafluoroethylene resins, or mixtures thereof, but are not limited thereto.
  • the insertion of ions (eg lithium ions) involved in charging and discharging may also occur in the carbon (pyrolysis carbon) converted from the carbon precursor, and furthermore, the carbon precursor is converted into carbon It may also serve to bind and bind the electrode active material in the form of particles.
  • the carbon precursor should not be construed as being limited only to the precursor of the conductive material, and may not be interpreted as a precursor of the binder and / or the electrode active material.
  • the binder may include an organic binder, and the organic binder may be a polymer commonly used for electrodes of lithium secondary batteries for binding between active materials and between an active material and a current collector.
  • the binder may be polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-trichloroethylene copolymer, polymethyl methacrylate, polyacrylonitrile, polyvinyl Pyrrolidone, polyvinylacetate, polyethylene-vinyl acetate copolymer, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethyl pullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, cya Noethyl sucrose, pullulan, carboxyl methyl cellulose
  • the active material bulk contains a binder (organic binder) derived from the shell of the composite particles, or the shell of the composite particles.
  • the contained binder (organic binder) may contain carbon remaining after carbonization or pyrolysis.
  • the active material bulk manufacturing step by pressing the raw material containing the composite particles of the core-shell structure of the electrode active material core-carbon precursor shell with a particulate electrode active material to form a molded body Manufacturing step; And pyrolyzing the carbon precursor of the shell with carbon by heat-treating the molded body.
  • the electrode active material core may be a positive electrode active material or a negative electrode active material.
  • the raw material may further include an additive selected from at least one of a binder (second binder), a conductive material, a carbon precursor, and a pore-forming agent together with the above-mentioned particulate electrode active material.
  • the raw material when the raw material includes a binder, or when a more even and rapid mixing of materials is required, the raw material may further include a solvent for dissolving the binder (second binder) contained as an additive or a dispersion medium for dispersing the raw material.
  • the binder (second binder) contained in the raw material as an additive may be an aqueous organic binder and / or a non-aqueous organic binder used in a conventional secondary battery.
  • the non-aqueous binder is vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile, polymethyl methacrylate (polymethylmethacrylate) ), Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM ), Sulfonated ethylene propylene terpolymer (EPDM), polytetrafluoroethylene (PTFE), polyvinylidene fluoride
  • the active material bulk may contain a binder added as an additive, or the binder added as an additive may contain carbon remaining after carbonization or pyrolysis.
  • the conductive material is not particularly limited as long as it can be generally used to improve the conductivity of the active material layer in the secondary battery field.
  • the particles may include particles, fibers, nanostructures, or mixtures thereof of one or more materials selected from conductive carbon, conductive polymers, and metals.
  • one or more materials selected from conductive carbon, conductive polymers, and metals include artificial graphite, natural graphite, soft carbon, hard carbon, carbon black, acetylene black, ketjen black, denka black, thermal black. , Channel black, aluminum, tin, bismuth, silicon, antimony, nickel, copper, titanium, vanadium, chromium, manganese, iron, cobalt, zinc, molybdenum, tungsten, silver, gold, lanthanum, ruthenium, platinum, iridium, titanium oxide , Zinc oxide, potassium titanate, carbon fluoride, polyaniline, polythiophene, polyacetylene, polypyrrole or combinations thereof.
  • the conductive material may be particles (including amorphous particles), plate, rod, wire (fiber), or a mixture thereof, of the aforementioned conductive material, and together with or in place of the conductive material described above. It may include nanostructures.
  • the nanostructures may be selected from one or two or more from nanowires, nanotubes, nanoplatelets, nanoribbons, nanoparticles and nanorods. Such nanostructures can ensure uniform and excellent electrical conductivity in all directions of the bulk of the active material (and active material film) by a network of nanostructures.
  • the conductive material serves to improve the electrical conductivity of the bulk of the active material and the active material film, and active material particles when melt bonding (including partial melting) of the conductive material occurs by a heat treatment process or a separate energy application process for producing a sintered body. It may also play the role of a binder that binds the liver.
  • Pore formers may be decomposed or dissolved away during bulking of the raw materials or after bulking.
  • the pore-forming agent can be used as long as the carbon yield is 40% or less, specifically, a polymer having a carbon yield of 1 to 20%.
  • the carbonization yield of the polymer may be a carbonization yield based on 900 °C carbonization conditions in the N 2 reducing gas atmosphere of 99.99% or more purity.
  • the pore-forming agent may be a polymer having a carbon yield of 40% or less, specifically, a carbon yield of 1-20%, and a content of fixed carbon in residual carbon of 99% by weight or more.
  • Specific examples of the pore-forming agent for forming residual pores in the bulk of the active material include, but are not limited to, polystyrene, polyvinyl alcohol, polyvinyl chloride, epoxy resin, phenol resin, polypropylene, or a mixture thereof.
  • the pore former may be spherical to fibrous, but is not limited thereto.
  • the carbon precursor contained in the raw material as an additive may include at least one selected from coke, pitch, thermosetting resin, and thermoplastic resin.
  • the coke may include petroleum or coal tar pitch derived cokes, and the pitch may include petroleum pitch, coal pitch or mixtures thereof.
  • the pitch may include an isotropic pitch, mesophase pitch, or a mixture thereof.
  • the resin used as the carbon precursor may be a thermosetting resin, a thermoplastic resin or a mixture thereof.
  • the thermosetting resin may be an epoxy resin, a polyester resin, a phenol resin, an alkyd (unsaturated polyester) resin, a polyimide resin, a vinyl ester resin, a polyurethane resin, a polyisocyanurate resin, or a mixture thereof, and the like.
  • the resin is polyethylene resin, polypropylene resin, polyvinyl alcohol resin, polyvinylidene chloride resin, polyethylene terephthalate resin, polyester resin, polystyrene resin, polymethyl methacrylate resin, polyvinyl chloride resin, ABS (Acrylonitrile Butadien Stylene) Resins, polyamide resins, polycarbonate resins, polyoxymethylene resins, acrylic resins, polyvinylsulfide resins, polyetheretherketone resins, polytetrafluoroethylene resins, or mixtures thereof, but are not limited thereto.
  • the carbonization yield of the resin used as the carbon precursor may be 10% or more, specifically 30 to 90%, and more specifically 40 to 90%.
  • the carbon precursor when using a carbon-based resin precursor having a carbon yield of 40% or less, the carbon precursor may also serve as a pore-forming agent.
  • carbon (pyrolysis carbon) generated by pyrolysis of the carbon precursor may play a role of a conductive material and a binder binding between the active material, and may also play a role of an active material involved in charge and discharge reactions. .
  • pyrolytic carbon is not limited to carbon derived from a carbon precursor, but also includes residual carbon derived from an additive such as a pore-forming agent or an organic binder by a heat treatment for producing a sintered body or a heat treatment process performed independently if necessary.
  • an additive such as a pore-forming agent or an organic binder by a heat treatment for producing a sintered body or a heat treatment process performed independently if necessary.
  • the active material bulk manufacturing step may include pressing a raw material including a particulate electrode active material and a carbon precursor to prepare a molded article; And pyrolysing the carbon precursor to carbon by heat treating the molded body.
  • the electrode active material core may be a positive electrode active material or a negative electrode active material.
  • the type and content of the additive contained in the raw material can of course be adjusted.
  • the raw material may contain 1 to 30 parts by weight, specifically, 1 to 20 parts by weight of the conductive material based on 100 parts by weight of the electrode active material, but is not limited thereto.
  • the raw material may contain 0.5 to 10 parts by weight of the binder based on 100 parts by weight of the electrode active material, but is not limited thereto.
  • the raw material may contain 1 to 30 parts by weight, specifically, 1 to 25 parts by weight of the carbon precursor based on 100 parts by weight of the electrode active material, but is not limited thereto.
  • the raw material may contain 1 to 20 parts by weight of the pore-forming agent based on 100 parts by weight of the electrode active material, but is not necessarily limited thereto.
  • the raw material may not contain a conductive material, a binder, a carbon precursor, and / or a pore-forming agent.
  • the bulk of the active material may be made of an electrode active material.
  • the raw material may further contain a dispersion medium for the solvent or dispersion of the binder to the carbon precursor, of course, the present invention is not limited by the use or the specific content of the solvent or dispersion medium.
  • a solvent or a dispersion medium may be used, and in the case of dry mixing, a solvent or a dispersion medium may not be used.
  • the solvent (aqueous solvent or organic solvent) contained in the raw material may be any aqueous solvent or organic solvent that is commonly used in the production of a positive electrode or negative electrode active material slurry in the secondary battery field.
  • the aqueous solvent may include a solvent including water, isopropyl alcohol, propanol, methanol, ethanol and the like
  • the organic solvent may be acetone, N-methyl-2-pyrrolidone (NMP), dimethylformamide, dimethyl Acetamide, chloroform, dichloromethane, trichloroethylene, normal hexane, N, N-dimethylaminopropylamine, ethylene oxide, tetrahydrofuran, or a mixed solvent thereof, and the like, but are not limited thereto.
  • the active material bulk may be a molded body manufactured by applying a physical force to the raw material, or may be a sintered body manufactured by applying heat to the molded body.
  • the molded body may be plastically deformed and bound to each other and have a constant strength
  • the sintered body may be bound to integral water by sintering and may have a constant strength
  • the active material bulk which is a molded or sintered body
  • the active material bulk may be a binder-free active material bulk containing no organic binder, and thus an active material film and a binder-free active material film may be prepared.
  • this is an example possible by the manufacturing method according to an embodiment of the present invention for producing an active material film which is a molded body or a sintered body and then cut it, and the present invention is a binder-free active material bulk binder-free active material film It is not limited to.
  • the step of preparing the active material bulk may be prepared by one-way, two-way, or isodirectional compression molding of the raw material.
  • the bulk manufacturing step of the active material, which is a molded body may include mixing raw materials; And pressing (compressing) molding the mixed raw materials.
  • the mixing of the raw materials may be dry or wet mixing. Dry mixing may be performed by mixing the particulate electrode active material with an additive such as a carbon precursor or the like without using a solvent (or a dispersion medium).
  • a solvent or a dispersion medium is used, but unlike a conventional active material slurry manufacturing process, the mixing is performed in a state where the solid content is very high (for example, solid content of 60% by weight or more, concrete weight of 70% by weight or more). It can be carried out, it is possible to significantly reduce the amount of the aqueous solvent to the organic solvent used as a solvent or a dispersion medium.
  • a drying step may be further carried out to volatilize the solvent (or dispersion medium) before or after molding.
  • Compression molding is performed by inserting a mixed raw material into a mold having an internal receiving space corresponding to a three-dimensional solid shape and size of a desired bulk, and then compressing the raw material by uniaxial pressing, biaxial pressing, or isostatic pressing. It can be performed by applying.
  • the pressure applied during molding may be properly adjusted in consideration of the type of material contained in the raw material, the sintering characteristics, and the designed porosity.
  • the molding may be performed at a pressure of 10 to 120 MPa, but is not limited thereto.
  • the active material bulk which is a molded article, may contain a material capable of plastically deforming the electrode active material, in particular, a negative electrode active material, substantially one or more carbon-based negative electrode active material selected from natural graphite and artificial graphite.
  • a material capable of plastically deforming the electrode active material in particular, a negative electrode active material, substantially one or more carbon-based negative electrode active material selected from natural graphite and artificial graphite.
  • the electrode active material is plastically deformed by compression and pressed in the pressure application direction, that is, its shape is deformed into pressed particles, and the orientation of the electrode active material is formed in the active material bulk by the pressed particles (electrode active material particles). Can be.
  • the orientation of the electrode active material is advantageous because it can improve the charge and discharge rate characteristics of the electrode.
  • the bulk of the active material is a molded article, it is preferable to prepare the molded article by uniaxial pressurization or biaxial pressurization after inputting the mixed raw material into the mold.
  • the present invention should not be construed as being limited only to the orientation caused by plastic deformation.
  • the orientation may be already formed in the process of adding and packing the raw material into the mold for molding and liquid kneading in the bulk manufacturing step. In this state, a magnetic field may be applied to control the orientation.
  • the flaky graphite-based active material may be oriented in a direction perpendicular to the compressive force for forming, and spherical natural graphite undergoes plastic deformation and It can be oriented in the vertical direction.
  • FIG. 1 is a material that can plastically deform an electrode active material, in particular, a carbon-based negative electrode active material, a molded body 200 manufactured by compression molding the raw material 100 containing the carbon-based negative electrode active material particles 110 before molding and It is a figure which shows the pressed particle 210 of the carbon-based negative electrode active material in the molded object 200.
  • the pressed particles 210 in which the carbon-based negative electrode active material particles 110 are deformed in a predetermined direction by compression molding may be formed, and the molded particles 200 may be formed by the pressed particles.
  • the orientation of the electrode active material particles (shown by the arrow in FIG. 1) may be formed.
  • the manufacturing method after the active material bulk is manufactured, according to the cutting direction for cutting the active material bulk having the orientation of the electrode active material, as the active material film is cut and attached to the current collector,
  • the orientation in the thickness direction of the active material film (the orientation direction of the electrode active material particles) can be controlled.
  • the orientation of such an electrode active material film is substantially difficult to realize in the conventional slurry-based electrode manufacturing technique of coating and rolling slurry. This is because when the plastic deformation (permanent deformation) of the active material occurs as the rolling is performed after the active material slurry is applied to the current collector, the orientation of the plastically deformed electrode active material particles is the interface direction between the current collector and the active material layer (active material). This is because it is limited to the direction parallel to the in-plane direction of the layer surface).
  • the thickness direction of the active material film 300 is referred to.
  • the orientation direction of the electrode active material may be controlled.
  • the active material film The thickness direction of 300 and the orientation direction of the active material particles (pressed particles) are substantially parallel, so that the impregnation of the electrolyte through the space between the particles and the particles and the diffusion of ions involved in charge and discharge, such as lithium ions, are more smoothly performed. Can be done.
  • the active material bulk may be a sintered body
  • an active material bulk which is a sintered body
  • the manufacturing method according to an embodiment of the present invention comprises the steps of preparing a molded body by putting the raw material into the mold and molding; Producing a sintered body by applying heat to the molded body; may include.
  • the molded article manufacturing step and the sintered body manufacturing step may be performed at the same time. That is, the sintered compact may be manufactured by simultaneously applying heat and physical force to the raw material.
  • Specific examples of applying mechanical force (physical force) together with heat include hot press sintering and the like.
  • the application of heat may be performed by heat treatment using a conventional furnace, but is not limited thereto, and may be performed using any method known to be used to manufacture a sintered body such as spark plasma sintering (SPS).
  • the atmosphere may be controlled in consideration of the type of the specific electrode active material during heat treatment (application of heat).
  • heat treatment may be performed in a non-oxidizing atmosphere such as nitrogen and argon.
  • the heat treatment may be performed in an oxygen-containing atmosphere such as an atmosphere. Can be performed.
  • the electrode active material of the raw material in the production of the active material bulk which is a sintered body may be a positive electrode active material or a negative electrode active material.
  • the electrode active material of the raw material may include a positive electrode active material or a non-carbon negative electrode active material.
  • the sintered body may be in a state in which grain boundaries or necks are formed between the electrode active material particles by heat application (specifically, for example, heat treatment) and the particulate electrode active material is integrally bound (fused).
  • the sintered compact may be in a state in which active material particles are bound to each other by pyrolysis carbon (pyrolysis carbon derived from a carbon precursor).
  • the active material bulk may be a sintered body in which electrode active material particles of a raw material form a neck and are bound to each other.
  • FIG. 3 illustrates active material particles 210 bound to each other by a neck (shown by an arrow in FIG. 3) based on two electrode active material particles 110 adjacent to each other in a raw material.
  • the sintering process is divided into an initial stage, a middle stage, and a final stage, and an initial stage of sintering is a stage in which a neck is formed between the particles.
  • the initial stage of sintering may correspond to a stage of sintering shrinkage of about 3-10% (vol%), specifically 3-7%.
  • the pores in the molded body are substantially mostly open pores, and mainly a mass transfer (diffusion) occurs at the contact point of the particles and the particles, and the particles and the particles are connected to each other by a neck. Accordingly, when the sintered body is a product of the initial stage of sintering in which the neck between the electrode active material particles is formed, it contains a large amount of open pores while having a mechanical (physical) strength that enables stable handling and process performance during cutting, conveying, and attaching processes.
  • the sintered body is not limited to the state connected to the neck between the electrode active material particles, and can not be interpreted.
  • heat to the molded body or the raw material specifically, thermal energy capable of moving a substance, and heat treatment of substantially 300 ° C. or more It can be interpreted as a product obtained by performing a heat treatment more substantially 500 ° C. or more and even more substantially 600 ° C. or more.
  • the negative electrode active material is a material that is difficult to plastically deform, such as hard carbon or soft carbon, or a material such as natural graphite that can be plastically changed if necessary, particulate electrode active material (hard carbon, soft carbon, natural graphite, etc.)
  • the bulk of the active material in the form of a sintered compact can be prepared by applying heat to convert the carbon precursor into carbon.
  • the sintered body may be in a state where particulate electrode active materials are bound by at least carbon (pyrolysis carbon) converted from a carbon precursor.
  • the active material bulk may include particulate active material and pyrolytic carbon binding the particulate active material
  • the active material film prepared from such active material bulk may also include pyrolytic carbon binding between the particulate active material and the electrode active material particles.
  • a free-standable sintered body may be manufactured by grain boundaries between electrode active material particles, neck formation, or binding by carbon (pyrolysis carbon) converted from a carbon precursor.
  • the active material bulk may be a binder-free sintered body, and the active material film prepared by cutting it may also be a binder-free film containing no binder.
  • the binder-free may be interpreted as containing no organic binder.
  • the weight loss rate is less than 2%, substantially less than 1%, and more substantially, It may mean that the weight loss does not occur within 0.5%, more substantially within the error range.
  • Carbon derived from the carbon precursor specifically, pyrolytic carbon may serve as a conductive material to improve conductivity, bind a particulate active material, and may also function as an active material capable of inserting lithium.
  • the binder-free may be interpreted as an organic binder-free
  • the binder-free active material bulk may mean a molded or sintered body containing no organic binder.
  • the binder-free sintered compact includes a sintered compact composed of an active material; A sintered body made of an active material and residual carbon (residual carbon by organic binder decomposition, etc.); A sintered body made of an active material and a conductive material; A sintered body composed of an active material, a conductive material and residual carbon; A sintered body made of an active material and carbon derived from a carbon precursor; A sintered body consisting of an active material, carbon precursor-derived carbon, and residual carbon; A sintered body made of an active material, a conductive material, and carbon derived from a carbon precursor; Or an sintered body made of an active material, a conductive material, carbon precursor-derived carbon, and residual carbon.
  • the active material film may be a binder-free film containing no organic binder.
  • the active material film that is a binder-free film may be made of an electrode active material, made of an electrode active material and a conductive material, or made of carbon which binds to the electrode active material.
  • the binder-free active material film can be manufactured by the manufacturing method structure of this invention, and if necessary, the active material film of this invention can contain an organic binder,
  • this invention is an active material film containing an organic binder, It should not be interpreted as excluding the bulk of the active material containing the organic binder.
  • the molded body before sintering may contain an organic binder, of course, the organic binder may be burned out during the sintering process and a binder-free sintered body may be manufactured.
  • the organic binder may or may not leave residual carbon depending on the process atmosphere during burn-out. If the process atmosphere is an oxidizing atmosphere, it may not leave residual carbon, and only serves to assist the active material particles to achieve physical integration before sintering.
  • the burnout atmosphere is a non-oxidizing atmosphere, the organic binder may serve to coat carbon on the surface of the active material particles or bind particles and particles with residual carbon while leaving residual carbon.
  • the raw material further contains an additive which is a binder together with the particulate electrode active material, an electrode active material which is hard to be plastically deformed, for example, a non-carbon-based negative electrode active material, a hard carbon or soft carbon, a positive electrode active material, and the like, and the active material bulk Of course it can also be prepared.
  • an electrode active material which is hard to be plastically deformed, for example, a non-carbon-based negative electrode active material, a hard carbon or soft carbon, a positive electrode active material, and the like, and the active material bulk Of course it can also be prepared.
  • the raw material further contains an additive which is a conductive material together with the particulate electrode active material
  • an additive which is a conductive material together with the particulate electrode active material
  • the bulk of the active material in which the conductive material is uniformly dispersed and contained, in particular, when the conductive material includes the nanostructure, the network of the nanostructure It is possible to manufacture the bulk of the active material in which the continuous current movement path is formed.
  • the conductive material contained in the bulk of the active material may be deformed, compressed, softened or partially melted by a pressure or pressure and heat applied for bulking, and may be in a state of being bound between the conductive materials and the electrode active material.
  • the particulate electrode active material is a composite particle having a core-shell structure
  • the composite particle itself may be used, and the core-shell structure may be used during the mixing of raw materials using the core particles (electrode active material particles) and the materials of the shell.
  • the composite particles can be made.
  • the electrode active material is a carbon-based negative electrode active material
  • the raw material including the core-shell composite particles of the carbon-based negative electrode active material core-carbon precursor shell is molded to prepare a molded body, and then the carbon precursor of the shell through heat treatment.
  • the bulk of the active material can be prepared by converting to carbon.
  • Bulk of the active material may be prepared by converting a carbon precursor in a state into carbon.
  • the carbon precursor may serve as a binder in the shaped body.
  • the active materials may be bound to each other and provide a conductive path, and the carbon-based active material bulk made of a carbon-based material may be advantageous.
  • the carbon-based active material bulk can be produced using low-cost plate-shaped graphite instead of expensive spherical graphite as the carbon-based electrode active material.
  • the flaky graphite is oriented in a direction parallel to the current collector by rolling, charging and discharging due to a phenomenon in which electrolyte impregnation becomes difficult or speed is slow in the direction perpendicular to the electrode There is a problem that the rate characteristic is lowered.
  • the flaky graphite in the electrode current collector can be adjusted to have the orientation in the vertical direction impregnated with the electrolyte This can be facilitated and the battery reaction speed can be improved.
  • the porosity can be adjusted by using a pore-forming agent and / or a common-coated structure, or by using a molding pressure or the like, while aligning, and thus, it is possible to solve problems in the use of conventional flaky graphite, which is commercially advantageous.
  • the pore-forming structure is a concept that is distinguished from the pore-forming agent, and is not plate-shaped, but is an active material particle having an average particle diameter of at least 1/2 or less than plate-graphite. When small, it may mean an active material which is located between the plate graphite particles and the surface of the particles to serve to space the surface and the surface. Specific examples are hard carbon, soft carbon, granulated artificial graphite, amorphous particle form If the well-known anode active material, such as artificial graphite, MCMB (mesocarbon microbead), spherical natural graphite, Li 4 Ti 5 O 12 is possible.
  • anode active material such as artificial graphite, MCMB (mesocarbon microbead), spherical natural graphite, Li 4 Ti 5 O 12 is possible.
  • the plate graphite is packed by pressure molding, whereby a molded article having an orientation in the particle unit can be produced.
  • the molding strength can be improved.
  • the heat treatment may convert the carbon-based precursor into carbon (pyrolysis) to improve the electrical conductivity of the bulk of the active material, and optionally, further convert the negative electrode active material by selectively performing a graphitization heat treatment.
  • the pyrolysis may be carried out under conventionally known conditions in consideration of the specific material of the carbon-based precursor, and the graphitization treatment may also be performed under the conventionally known conditions used for graphitizing carbon. For example, pyrolysis may be performed at a temperature of 600 to 1500 ° C., and graphitization may be performed at a temperature of 2800 ° C. or more, but is not limited thereto.
  • the manufacturing method comprises the steps of molding a raw material containing the active material and the carbon precursor, or a raw material containing the active material, the carbon precursor and the conductive material to produce a molded article; And heat-treating the molded body to produce a sintered body.
  • thermal decomposition of the carbon precursor may occur simultaneously during the heat treatment for sintering.
  • to heat the sintered body for more complete pyrolysis to prepare a secondary sintered body in which the carbon-based precursor is pyrolyzed into carbon may be further performed.
  • the step of heat-treating the sintered body or the secondary sintered body to produce a sintered body graphitized pyrolytic carbon may be further performed.
  • the apparent porosity of the bulk of the active material is a molded or sintered body may be 10 to 45%, specifically, may be 15 to 40%.
  • the apparent porosity of the active material film may be 10 to 45%, specifically 15 to 40%.
  • the active material film may have substantially the same porosity as the bulk of the active material.
  • the composition of the bulk of the active material (and the active material film) may vary depending on the type or content of the additive contained in the raw material.
  • the active material film may contain 1 to 30 parts by weight, specifically 1 to 20 parts by weight of the conductive material, based on 100 parts by weight of the electrode active material. It is not necessarily limited thereto.
  • the active material film may contain 0.5 to 30 parts by weight of pyrolyzed carbon, specifically, 1 to 25 parts by weight of pyrolyzed carbon based on 100 parts by weight of the electrode active material. However, it is not necessarily limited thereto.
  • a processing step of cutting and / or grinding the active material bulk may be further performed in order to process to a desired dimension such as chamfering or rectangular parallelepiped.
  • Cutting of the prepared active material bulk may be performed using a method commonly used to cut semiconductor ingots used for conventional semiconductor wafer manufacture, such as wire saws, laser cutting, and the like. It is not limited by the specific cutting method of an active material bulk.
  • the thickness of the active material film is controlled by the cutting width of the bulk of the active material, there is no limitation in the thickness of the active material film to be produced, and an active material film in the form of a thick film having a thickness of 200 ⁇ m or more, which is difficult to be produced by slurry coating technology, can also be easily manufactured.
  • the present invention is not limited by the thickness of the active material film, of course, the thickness of the active material film can be appropriately adjusted according to the use of the active material secondary battery.
  • the thickness of the active material film may range from several tens of micrometers order to several millimeters order, more specifically, 10 ⁇ m to 500 ⁇ m, but is not limited thereto.
  • FIG. 4 is a cross-sectional view of an active material film 300 prepared by cutting an active material bulk that is a molded body
  • FIG. 5 is a cross-sectional view of an active material film 300 prepared by cutting an active material bulk that is a sintered body.
  • the active material film or the bulk of the active material is made of the electrode active material is illustrated.
  • the active material bulk is an additive such as a conductive material, a carbon-based precursor and / or a binder, and the like. Of course, it may further include.
  • the active material located on the surface of the active material film may be cut particulates.
  • the cut surface of the cut particles may be parallel to the surface of the active material film 300.
  • the surface of the active material film 300 may include the cut surfaces of the cut particles.
  • the cut particulates refer to a shape of the electrode active material particles (inner particles) positioned at an inner center of the active material bulk, and the inner particles are cut along an arbitrary plane. can do.
  • the cut particulates are located at the inner center of the bulk of the active material, and the shape of the electrode active material particles (inner particles) in the state of being bound to each other is used as a reference, and the inside of the cut particles is formed along an arbitrary plane. It may mean a shape in which the particles are cut off.
  • the active material bulk is a sintered body, it is advantageous that the active material bulk is a sintered body at the initial stage of sintering in which a neck between electrode active material particles 110 contained as a raw material is formed.
  • the bulk of the active material when the bulk of the active material is a sintered body, it may mean a shape in which the electrode active material particles 110 contained in the raw material are cut along an arbitrary plane based on the shape of the electrode active material particles 110 contained in the raw material.
  • the cut particles In the cut-out shape based on the electrode active material particles contained as a raw material, the cut particles should not be interpreted strictly as cut particles of the electrode active material particles 110 contained as raw materials.
  • the concave curvature neck region may be properly considered in the cut shape. .
  • the manufacturing method further includes the step of surface treatment of at least one surface of the active material film after cutting the bulk of the active material to prepare the active material film and before integration or after the active material film and the current collector are integrated. can do.
  • Such surface treatment may include surface roughness control.
  • the surface treatment step may be a treatment of reducing the surface roughness of at least one surface of the active material film relative to the surface of the active material film before treatment, or a process of relatively increasing the surface roughness of at least one surface of the active material film, The surface roughness of one surface of the film may be reduced and the surface roughness of the other surface may be increased.
  • An example of a treatment for reducing surface roughness may be surface polishing, and one example of a treatment for increasing surface roughness may include surface etching, mechanical scratch, and the like.
  • the surface etching may include plasma etching, partial oxidation of the surface area when the active material film includes a carbon-based electrode active material, but the present invention is not limited thereto.
  • the surface roughness of the inorganic film or the carbon-based film may be increased or decreased. Any surface treatment method conventionally used for the purpose may be used.
  • a step (binding step) of integrating the current collector and the active material film may be performed.
  • integration may mean a state in which the current collector and the active material film are directly bound, or a state in which the current collector and the active material film are attached to each other.
  • a metal film may be directly formed on the active material film, thereby integrating the same.
  • the active material film is a film cut out of the active material bulk, specifically, the structure in which the film is free-standable, the active material film can act as a substrate (substrate).
  • the metal film may be any method conventionally used to form a conventional electrode or metal film, such as metal deposition (including chemical and physical vapor deposition), conductive ink application, and heat treatment.
  • the binding step may include: c1) forming an adhesive layer on at least one of the surface of the current collector and the surface of the active material film; And c2) laminating the current collector and the active material film to be in contact with each other with the adhesive layer therebetween.
  • the adhesive layer may be formed on one surface of the current collector, one surface of the active material film, or one surface of the current collector and one surface of the active material film.
  • the adhesive layer may be formed by applying an adhesive to at least one of the surface of the current collector and the surface of the active material film when the adhesive is a fluid phase.
  • the application of the adhesive may be carried out by an application method commonly used for the application of liquid or dispersion phases. For example, dip coating, spin coating, casting, bar coating, gravure coating, blade coating and roll coating, spray, Screen printing, inkjet printing, electrostatic printing, micro-contact printing, imprinting, gravure printing, offset-reverse offset printing, etc. can be performed by one or more application methods selected.
  • the coating may be performed by surface coating, line coating, point coating, etc.
  • the adhesive may be formed by attaching an adhesive film to at least one of the surface of the current collector and the surface of the active material film. At this time, the coating amount of the adhesive may be 0.1 to 1mg / cm 2 level, but is not limited thereto.
  • the active material film may be attached to the current collector by laminating the current collector and the active material film in contact with each other with the adhesive layer therebetween.
  • At least one of heat, light, and pressure may be applied when laminating the current collector and the active material film for uniform adhesion, curing of the adhesive, strengthening of the binding force, or rapid binding.
  • heat may be applied and pressure may be applied together with the heat.
  • hot pressing and the like may be used, and the pressure during hot pressing may be applied by pressing in a surface pressure method or a linear pressure method, but the present invention is not limited thereto.
  • the active material film may be bound to at least one surface of the current collector, that is, one surface of the current collector or each of two opposite surfaces of the current collector.
  • the active material film When the active material film is to be attached to each of two opposite surfaces of the current collector, the active material film is attached to one of two opposite surfaces of the current collector through steps c1) to c2), and then the other one of the two opposite surfaces.
  • the active material film may be attached to the active material film again through steps c1) to c2, and the active material film may be attached to each of two opposite surfaces of the current collector.
  • step c1) an adhesive layer is formed such that each of two opposing surfaces of the current collector contacts the active material film with the adhesive layer interposed therebetween, and in step c2), the adhesive layer and the active material film are stacked to form a sandwich structure around the current collector.
  • the active material film can be attached to each of two opposite surfaces of the current collector.
  • the active material film of the electrode may be a free-standing film, and may be a cut film cut from a molded body as shown in FIG. 4, or a cut film cut from a sintered body as shown in FIG. 5.
  • FIG. 6 is a cross-sectional view illustrating a cross section of an electrode, and includes an electrode active material 210 and conductive particles 220 on two opposite surfaces of the current collector 500 by an adhesive layer 400. It is a figure which shows the attached example.
  • the active material film 300 of FIG. 6 may be plastically deformed into a particle form in which the electrode active material which is plastically deformable is pressed by press molding and the orientation of the electrode active material particles are formed, or the electrode active material of the flake shape is press molded and packed in one direction. It is an example which shows the cut film cut
  • the active material film is a film in which a neck between electrode active material particles is formed, that is, a cut film cut from the sintered body of the initial sintering step, the surface pores opened by the continuous gap between the particles and the particles are similarly opened. And the pore channel across the thickness of the active material film is uniformly formed so that the electrolyte solution (and lithium ions) can penetrate stably and uniformly regardless of the thickness of the film.
  • the adhesive layer 400 may include a resin having curability.
  • having curability means the ability to lose fluidity and harden by chemical change, drying (volatile removal of solvent) or solidification.
  • the hardenability of the resin having a hardenability may include hardening by phase transformation (solidification) from a liquid phase (melted phase) to hard phase, hardening due to volatilization of the solvent, and / or hardening by chemical change.
  • the resin having a curing ability is one of a resin (resin solution), a thermoplastic resin (resin having a solidification ability by melting-solidification), a photocurable resin, a thermosetting resin, and a chemical curable resin in a state dissolved in a solvent. Or two or more selected resins.
  • the thermoplastic resin may be used in any known resin in which melting (or softening) occurs upon application to heat.
  • the thermoplastic resin may be a polyamide resin, a polyester resin (eg, an aromatic polyester resin such as polyethylene terephthalate), a polyacetal resin, a polycarbonate resin, a polyphenylene ether resin, or a polysulfide resin.
  • Polysulfone resin, polyether ketone resin, polyolefin resin, polystyrene resin and the like but is not limited thereto.
  • the thermoplastic resins may be used alone or in combination of two or more thereof.
  • the active material film may be bound to the current collector by melting (or softening) and cooling the thermoplastic resin by applying heat to a laminate laminated so that the current collector and the active material film are in contact with the adhesive layer therebetween. have. At this time, the pressure may be applied together with the heat to improve the binding force and to achieve a uniform binding.
  • the active material film may be bound to the current collector by laminating the current collector and the active material film so as to be in contact with each other with a coating film of the resin solution therebetween, and volatilizing removing the solvent of the resin solution.
  • the resin dissolved in the resin solution when using the resin solution may include the above-described binder material (aqueous binder and / or non-aqueous binder) as an example of the additive.
  • the adhesive layer may comprise a thermosetting, photocurable and / or chemically curable resin.
  • the adhesive layer may contain a thermosetting resin and / or a chemical curable resin.
  • thermosetting resin or the chemical curable resin may be any resin known to be thermally or chemically cured, and examples thereof include epoxy resins, unsaturated polyester resins, vinyl ester resins, acrylic resins, phenol resins, urea resins, melamine resins, aniline Resins, polyimide resins, bismaleimide resins, and the like, but are not limited thereto.
  • Curable resin may be used individually or in combination of 2 or more types.
  • the adhesive layer contains a thermosetting resin or a chemical curable resin, it is of course possible to further contain a curing agent or a curing accelerator known to be used for the resin.
  • the adhesive layer can be conductive or nonconductive.
  • the adhesive layer may include a non-conductive resin having the above-described hardenability.
  • the adhesive layer may include a conductive component selected from one or more of conductive resins, conductive particles, and conductive nanostructures.
  • a conductive component may be mixed with a resin solution or a resin melt and applied together with the resin.
  • the adhesive layer when the adhesive layer is conductive, the adhesive layer may include one or more components selected from conductive particles and conductive nanostructures, together with the non-conductive resin having the above-described hardenability.
  • the adhesive layer when the adhesive layer is conductive, the adhesive layer may include a conductive resin.
  • the conductive resin may have at least a curing ability (ie, curing by drying) according to the volatilization of the solvent, but is not limited thereto, and may have heat or chemical curing ability or solidify (phase transformation of melt-solidification) by a functional group. Of course, it may have a curing ability by.
  • the adhesive layer when the adhesive layer is conductive, the adhesive layer may include, together with the conductive resin, one or more components selected from conductive particles and conductive nanostructures.
  • the adhesive layer may include a resin matrix, and the resin matrix may be a conductive adhesive layer which is a conductive resin having curability.
  • the adhesive layer may include a resin matrix, and the resin matrix may be a non-conductive resin, and may be a conductive adhesive layer including a dispersed phase selected from the conductive particles and the conductive nanostructures, which are disposed in the resin matrix.
  • the conductive particles of the adhesive layer are one or more selected from conductive resin particles, particles of metal, coreshell particles of a nonconductive core-conductive shell (shell or metal shell of conductive resin) and coreshell particles of a conductive core-nonconductive shell. It may include particles, but is not limited thereto.
  • the conductive nanostructures of the adhesive layer may be metal nanowires such as silver nanowires; Conductive nanotubes such as carbon nanotubes; Metal nanoplates such as gold nanoplates and silver nanoplates; Two-dimensional carbon bodies such as graphene, metal nanorods such as silver nanorods, etc .; Or a mixture thereof, but is not limited thereto.
  • the conductive resin of the adhesive layer is polyacetylene, polypyrrole, PEDOT: PSS (poly (3,4-ethylenedioxythiophene) poly (styrenesulfonate)), polyanilne, P3MT (poly (3-methylthiophene)), Or a mixed resin thereof, but is not limited thereto.
  • the conductive or non-conductive adhesive layer is a conventional non-conductive film (NCF; non-contuctive film), anisotropic conductive film (ACF) used for bonding in packaging fields, such as flip chip connection or chip mounting of conventional electronic components Film), a conductive film (CF) or a laminated film thereof; or an anisotropic conductive paste (ACP), a conductive paste (Conductive Paste) or a non-conductive paste (NCP) Membrane; but is not limited thereto.
  • NCF non-conductive film
  • ACF anisotropic conductive film
  • ACP anisotropic conductive paste
  • Conductive Paste Conductive Paste
  • NCP non-conductive paste
  • the current collector 500 is commonly used in the secondary battery field and may be used as long as it has a material having high conductivity without causing chemical change during battery operation.
  • the current collector may be copper, stainless steel, aluminum, nickel, titanium, calcined carbon, graphene, carbon nanotube, or carbon, nickel, titanium, silver, graphene, carbon nanotube on the surface of aluminum or stainless steel. And the like may be used as surface treated.
  • the current collector may be in the form of a foam, film, mesh, felt or porous film.
  • the current collector may have a surface irregularities formed on its surface. In the case of the current collector having the surface irregularities including the protruding structure, the binding area may increase, and the binding force between the active material film and the current collector may be increased, and charge transfer may occur more easily.
  • the present invention includes an electrode for secondary batteries manufactured by the above-described manufacturing method.
  • the secondary battery is an electrolyte-based secondary battery, specifically, a positive electrode; cathode; And a separator interposed between the anode and the cathode; And it may be a secondary battery containing an electrolyte.
  • the secondary battery includes a lithium secondary battery.
  • the present invention includes a lithium secondary battery including the secondary battery electrode manufactured by the above-described manufacturing method.
  • the secondary battery electrode manufactured by the above-described manufacturing method in the secondary battery may be a positive electrode, a negative electrode or a positive electrode and a negative electrode.
  • the present invention provides an electrode for a secondary battery.
  • the secondary battery electrode according to the present invention may include an active material film containing an electrode active material, a current collector and an adhesive for attaching the active material film to the current collector.
  • the electrode may have a structure of a current collector-adhesive layer (adhesive layer) -active material film, and the active material film may be an electrode bound to each side of the current collector or both sides of the current collector by an adhesive layer (adhesive layer).
  • the secondary battery electrode according to the present invention includes an active material film containing an electrode active material, and the active material film may be a binder-free film containing no organic binder.
  • the secondary battery electrode according to the present invention includes an active material film containing an electrode active material, the active material film may be a free standing film.
  • the secondary battery is an electrolyte-based secondary battery, specifically, a positive electrode; cathode; And a separator interposed between the anode and the cathode; And it may be a secondary battery including an electrolyte, the secondary battery includes a lithium secondary battery.
  • the active material film may have a uniform porosity in the thickness direction of the film, and the active material film has substantially the same porosity and pore structure regardless of the position in the thickness direction. Can be.
  • the porosity may be substantially the same between the surface area and the central area of the film based on the cross section of the active material film.
  • the uniform porosity is based on the cross section of the active material film, and the ratio of the difference between the porosity (P1) in the surface region and the porosity (P2) in the center region (the absolute value of P1-P2) divided by the porosity in the center region is 10%. Or less, substantially less than or equal to 8%, more substantially less than or equal to 5%, for example, substantially the same.
  • substantially identical means identical within a measurement error.
  • the porosity of the cross section of the active material film may be an area occupied by pores per unit area of the cross section of the thickness in the thickness cross section across the center of the active material film.
  • the surface area may mean an area up to 0.2t 0 from the surface based on the thickness (t 0 ) of the active material film, and the center area is based on the center (center line, virtual line of 0.5t 0 ) of the thickness cross section. This may mean an area up to 0.1t 0 (an area of 0.4t 0 to 0.6t 0 ) as the upper and lower portions, respectively.
  • the porosity of the surface region may refer to the porosity at each of the two surfaces as well as at any one of the two surfaces facing each other.
  • the porosity based on the thickness cross section can be calculated using a cross-sectional observation image such as a scanning electron microscope.
  • the electrode active material, the active material film or the current collector is similar to or the same as described above in the method of manufacturing a secondary battery electrode
  • the adhesive is the adhesive layer described in the method of manufacturing a secondary battery electrode Similar to the material of. Accordingly, the secondary battery electrode according to the present invention includes all the contents described in the above-described method for producing a secondary battery electrode.
  • the present invention includes a secondary battery, specifically, a lithium secondary battery including the secondary battery electrode.
  • the present invention includes a lithium secondary battery.
  • Lithium secondary battery according to the present invention is a positive electrode; cathode; And a separator interposed between the anode and the cathode; And an electrolyte solution, wherein the electrode selected from at least one of the positive electrode and the negative electrode may include an active material film containing an electrode active material attached to at least one surface of the current collector by an adhesive.
  • the positive electrode may be an active material film containing a positive electrode active material attached to at least one surface of the current collector by an adhesive. That is, a lithium secondary battery according to an embodiment of the present invention includes a positive electrode having an active material film containing a positive electrode active material attached to at least one surface of the current collector by an adhesive; cathode; And a separator interposed between the anode and the cathode; And an electrolyte solution.
  • the negative electrode may include a negative electrode active material layer positioned on the current collector, the negative electrode active material of the negative electrode active material layer may be a material commonly used for the negative electrode of a lithium secondary battery, and the negative electrode active material may be a lithium intercalable material. It is enough.
  • the negative electrode active material is lithium (metal lithium), digraphitizable carbon, non-graphitizable carbon, graphite, silicon, Sn alloy, Si alloy, Sn oxide, Si oxide, Ti oxide, Ni oxide, Fe oxide ( FeO) and lithium-titanium oxide (LiTiO 2 , Li 4 Ti 5 O 12 ) and the like may be one or more selected materials.
  • the negative electrode may be an active material film containing a negative electrode active material attached to at least one surface of the current collector by an adhesive. That is, a lithium secondary battery according to an embodiment of the present invention is a positive electrode; An anode in which an active material film containing an anode active material is attached to at least one surface of the current collector by an adhesive; And a separator interposed between the anode and the cathode; And an electrolyte solution.
  • the positive electrode may include a positive electrode active material layer positioned on the current collector, and the positive electrode active material of the positive electrode active material layer may be used as long as it is a material capable of reversible insertion / removal of lithium ions, and used for a positive electrode of a conventional lithium secondary battery.
  • Any electrode material may be used.
  • the cathode active material may be an oxide having a layer structure represented by LiCoO 2 , an oxide having a spinel structure represented by LiMn 2 O 4 , or a phosphate material having an olivine structure represented by LiFePO 4 .
  • a lithium secondary battery is a positive electrode having an active material film containing a positive electrode active material attached to at least one surface of the current collector by an adhesive; An anode in which an active material film containing an anode active material is attached to at least one surface of the current collector by an adhesive; A separator interposed between the positive electrode and the negative electrode; And an electrolyte solution.
  • the electrode active material, the active material film or the current collector is similar to or the same as described above in the method of manufacturing a secondary battery electrode
  • the adhesive is the adhesive layer described in the method of manufacturing a secondary battery electrode. Similar to the material of. Accordingly, the lithium secondary battery according to the present invention includes all the contents described in the above-described method for manufacturing the electrode for secondary batteries.
  • the separator may be a microporous membrane in which lithium ions are permeable in a conventional lithium secondary battery and electrically insulate the positive electrode and the negative electrode.
  • the separator is a porous polymer film, such as a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ytterin / hexene copolymer and ethylene / methacrylate copolymer, etc. It may be a single or a laminate thereof, or a conventional porous nonwoven fabric, for example, a non-woven fabric of high melting glass fibers, polyethylene terephthalate fibers and the like can be used, but is not limited thereto.
  • the separator may serve to separate the positive electrode and the negative electrode by simply positioned between the positive electrode and the negative electrode as in a conventional lithium secondary battery.
  • the separator may be in a state of being bound (attached) to at least one electrode of the positive electrode and the negative electrode.
  • the electrolyte may be any conventional non-aqueous electrolyte that smoothly conducts ions involved in charging and discharging the battery in a conventional lithium secondary battery.
  • the non-aqueous electrolyte may include a non-aqueous solvent and a lithium salt.
  • the lithium salt contained in the electrolyte is a lithium cation and NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, PF 6 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, ( CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (FSO 2) 2 N -, CF 3 CF 2 (CF 3) 2 CO -, (CF 3 SO 2) 2 CH -, (SF 5) 3 C -, (CF 3 SO 2) 3 C -, CF 3 (CF 2) 7 SO 3 -, CF 3 CO 2 -, CH 3 CO 2 -, SCN -, and (CF 3 CF 2 SO 2) 2 N - providing an anion selected at least one from It may be a salt.
  • the solvent of the electrolyte is ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, Dimethyl carbonate, diethyl carbonate, di (2,2,2-trifluoroethyl) carbonate, dipropyl carbonate, dibutyl carbonate, ethylmethyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, methylpropyl carbonate , Ethylpropyl carbonate, 2,2,2-trifluoroethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, dimethyl ether, diethyl ether, di Propyl ether, methylethyl ether, methylpropyl ether, ethylpropyl ether, methyl acetate, ethyl acetate, prop
  • a lithium secondary battery may be manufactured by manufacturing an electrode assembly including a separator interposed between a positive electrode and a negative electrode, inserting the prepared electrode assembly into a case, and injecting and sealing an electrolyte. .
  • the electrode assembly impregnated in the electrolyte may be prepared by charging and sealing the case.
  • the battery case may be one commonly used in the lithium secondary battery field.
  • a cylindrical, square, pouch or coin type may be mentioned, but the present invention may not be limited by the spherical shape of the battery case.
  • the present invention includes the above-described secondary battery, for example, a lithium secondary battery as a unit battery cell, and a battery module in which unit battery cells are connected in series and / or in parallel.
  • the present invention includes a device that is powered by the above-described secondary battery, for example, a lithium secondary battery.
  • a lithium secondary battery for example, a lithium secondary battery.
  • Specific examples include, but are not limited to, electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, power storage systems, and the like.
  • FIG. 7 is an optical picture of observing an active material film (3cmx5cmx280 ⁇ m) prepared according to an embodiment of the present invention.
  • the active material film of FIG. 7 is manufactured by bulking an active material by molding and sintering, and then cut to a thickness of 280 ⁇ m using an electric saw.
  • molding is performed by putting a mixture of artificial graphite: pitch mixed at a weight ratio of 8: 2 into a molding mold and compressing the first molding, and then pressing the first molded article by cold isostatic pressing (CIP) secondarily. It became.
  • Sintering was carried out in a nitrogen-molded atmosphere of less than 50ppm oxygen temperature to 700 °C at 2 °C / min speed, the first heat treatment at 700 °C 60 minutes, and then again at 700 °C to 1200 °C 3 °C / min rate
  • Bulk active material was prepared by secondary heat treatment at 1200 ° C. for 60 minutes.
  • the apparent porosity of the prepared active material bulk and the active material film was substantially the same, and was 19.8%.
  • FIG. 8 (a) is a scanning electron microscope photograph of the surface of the prepared active material film
  • FIG. 8 (b) is a scanning electron microscope photograph of a thickness cross section of the prepared active material film.
  • the active material film is prepared by cutting the bulk of the active material having already uniform properties, it can be seen that the active material film has an open pore structure having substantially the same porosity in the surface and thickness cross-section of the active material film.
  • the pore area was measured by observing the surface area and the center area in the thickness cross section of the prepared active material film, it was confirmed that they had substantially the same porosity.
  • FIG. 9 is an optical photograph of a cathode obtained by attaching the active material films of FIGS. 7 and 8 to a Cu foil as a current collector.
  • the mirrored surface was attached to the current collector, and a copper paste (65 wt% of 30 nm copper nanoparticles and styrene-butadiene rubber 8) was used as a conductive adhesive. Weight percent)).
  • Table 1 summarizes the characteristics of the secondary battery manufactured using the negative electrode of FIG. 8.
  • Comparative Examples (1 and 2) were prepared using a conventional slurry method of coating, drying, and rolling a negative electrode slurry, using graphite as an active material and an organic binder / active material weight ratio (%) of 3.1.
  • graphite as an active material
  • organic binder / active material weight ratio (%) of 3.1 As a result of the secondary battery provided, it is an example produced by varying the thickness of the active material layer.
  • lithium metal (3.2cmx5.2cmx2mm) was used as the positive electrode, and the battery was formed between the negative electrode and the positive electrode plate through a separator (polyethylene, 25 ⁇ m thick), and the tab portion of the positive electrode and the tab portion of the negative electrode were Each was welded.
  • the welded anode / separator / cathode combination was placed in a pouch, and the tabbed portion was included in the sealing portion to seal three surfaces except the electrolyte injection surface. After pouring the electrolyte into the remaining part and sealing the remaining side, it was impregnated for 12 hours or more.
  • 1M LiPF 6 solution was used as a mixed solvent of ethylene carbonate (EC) / ethyl methyl carbonate (EMC) / diethylene carbonate (DEC) (25/45/30; volume ratio) as the electrolyte.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Une électrode de batterie secondaire selon la présente invention comprend : une étape de tranchage pour produire un film de matériau actif par tranchage d'un volume de matériau actif en vrac ; et une étape de liaison pour combiner un collecteur de courant et le film de matériau actif. Un procédé de production d'une électrode de batterie secondaire selon la présente invention produit un film de matériau actif par tranchage d'un volume de matériau actif, qui est un corps moulé ou une pastille autoportant(e), permettant ainsi de produire un film de matériau actif exempt de liant, et il n'existe pas de restrictions réelles pour l'épaisseur du film de matériau actif, un film de matériau actif épais peut être produit, et ainsi des électrodes ayant une charge élevée et une densité composite élevée peuvent être produites.
PCT/KR2019/003006 2018-03-15 2019-03-15 Électrode de batterie secondaire, et son procédé de production WO2019177409A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201980014936.0A CN111788722A (zh) 2018-03-15 2019-03-15 二次电池用电极及其制造方法
US16/980,615 US20210020898A1 (en) 2018-03-15 2019-03-15 Secondary battery electrode, and method for producing same
JP2020545111A JP2021515963A (ja) 2018-03-15 2019-03-15 二次電池用電極およびその製造方法
EP19768601.7A EP3767711A4 (fr) 2018-03-15 2019-03-15 Électrode de batterie secondaire, et son procédé de production

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20180030070 2018-03-15
KR10-2018-0030070 2018-03-15
KR10-2019-0029127 2019-03-14
KR1020190029127A KR20190109284A (ko) 2018-03-15 2019-03-14 이차전지용 전극 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2019177409A1 true WO2019177409A1 (fr) 2019-09-19

Family

ID=67907978

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2019/003006 WO2019177409A1 (fr) 2018-03-15 2019-03-15 Électrode de batterie secondaire, et son procédé de production

Country Status (1)

Country Link
WO (1) WO2019177409A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6007588A (en) * 1998-02-17 1999-12-28 Valence Technology, Inc. Methods for coating current collector with polymeric adhesives
KR20050027224A (ko) * 2002-06-26 2005-03-18 산요덴키가부시키가이샤 리튬 2차 전지용 부극 및 리튬 2차 전지
US20050271798A1 (en) * 2004-04-02 2005-12-08 Maxwell Technologies, Inc. Electrode formation by lamination of particles onto a current collector
KR20080098261A (ko) * 2007-05-04 2008-11-07 한국과학기술연구원 나노파이버 네트워크 구조의 음극 활물질을 구비한이차전지용 음극 및 이를 이용한 이차전지와, 이차전지용음극 활물질의 제조방법
KR20130043932A (ko) * 2011-10-21 2013-05-02 삼성전기주식회사 전기 이중층 캐패시터
KR101572082B1 (ko) 2013-12-24 2015-11-26 주식회사 엘지화학 고용량 리튬 전이금속 산화물과 그것을 포함하고 있는 리튬 이차전지
KR101608635B1 (ko) 2013-07-31 2016-04-05 주식회사 엘지화학 고용량의 이차전지용 음극

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6007588A (en) * 1998-02-17 1999-12-28 Valence Technology, Inc. Methods for coating current collector with polymeric adhesives
KR20050027224A (ko) * 2002-06-26 2005-03-18 산요덴키가부시키가이샤 리튬 2차 전지용 부극 및 리튬 2차 전지
US20050271798A1 (en) * 2004-04-02 2005-12-08 Maxwell Technologies, Inc. Electrode formation by lamination of particles onto a current collector
KR20080098261A (ko) * 2007-05-04 2008-11-07 한국과학기술연구원 나노파이버 네트워크 구조의 음극 활물질을 구비한이차전지용 음극 및 이를 이용한 이차전지와, 이차전지용음극 활물질의 제조방법
KR20130043932A (ko) * 2011-10-21 2013-05-02 삼성전기주식회사 전기 이중층 캐패시터
KR101608635B1 (ko) 2013-07-31 2016-04-05 주식회사 엘지화학 고용량의 이차전지용 음극
KR101572082B1 (ko) 2013-12-24 2015-11-26 주식회사 엘지화학 고용량 리튬 전이금속 산화물과 그것을 포함하고 있는 리튬 이차전지

Similar Documents

Publication Publication Date Title
WO2017135794A1 (fr) Matière active d'électrode négative et batterie secondaire la comprenant
WO2011068389A2 (fr) Poudre d'oxyde de nanocomposite multicomposant et procédé de préparation de celle-ci, procédé de fabrication d'une électrode utilisant celle-ci, batterie à film mince munie de l'électrode et procédé de fabrication de la batterie
KR20190109284A (ko) 이차전지용 전극 및 이의 제조방법
WO2018105970A1 (fr) Électrolyte non aqueux et batterie secondaire au lithium le comprenant
WO2019194613A1 (fr) Matériau actif de cathode, procédé de préparation de matériau actif de cathode, cathode comprenant un matériau actif de cathode, et batterie secondaire comprenant une cathode
WO2018117752A1 (fr) Matériau actif d'électrode négative et électrode négative comprenant ledit matériau destinés à un dispositif électrochimique
WO2022103091A1 (fr) Film mince poreux en nanofibres d'aramide, procédé pour sa fabrication et batterie rechargeable le comprenant
WO2016200223A1 (fr) Mélange d'électrode positive et batterie rechargeable le comprenant
WO2019177355A1 (fr) Composite oxyde de cérium-carbone-soufre, son procédé de préparation, et électrode positive et batterie au lithium-soufre comprenant ladite électrode positive
WO2021066494A1 (fr) Électrode et batterie secondaire la comprenant
WO2019168352A1 (fr) Matériau actif d'anode, son procédé de préparation, et batterie secondaire au lithium et d'anode, qui comprennent un matériau actif d'anode
WO2023282684A1 (fr) Anode pour batterie secondaire au lithium, procédé de fabrication d'anode pour batterie secondaire au lithium et batterie secondaire au lithium comprenant une anode
WO2017209556A1 (fr) Matériau actif de cathode, procédé permettant de préparer ce dernier, cathode comprenant ce dernier et batterie rechargeable au lithium comprenant ce dernier
WO2017095151A1 (fr) Cathode pour batterie secondaire et batterie secondaire comprenant celle-ci
WO2021086098A1 (fr) Matériau actif d'anode, son procédé de préparation, et anode et batterie secondairele comprenant
WO2021251663A1 (fr) Anode et batterie secondaire la comprenant
WO2020141953A1 (fr) Matériau actif d'anode pour batterie secondaire, électrode le comprenant, et procédé destiné à le fabriquer
WO2019177409A1 (fr) Électrode de batterie secondaire, et son procédé de production
WO2023059015A1 (fr) Composition d'électrode négative, électrode négative pour batterie secondaire au lithium la comprenant, batterie secondaire au lithium comprenant une électrode négative, et procédé de préparation de composition d'électrode négative
WO2019147093A1 (fr) Matériau conducteur, bouillie de formation d'électrode le comprenant, électrode et batterie secondaire au lithium fabriquée au moyen de celui-ci
WO2019103526A1 (fr) Composition de bouillie de cathode pour accumulateur, et cathode pour accumulateur et accumulateur produits à l'aide de celle-ci
WO2022050664A1 (fr) Matériau actif d'électrode positive, électrode positive comprenant le matériau actif d'électrode positive, et batterie secondaire comprenant l'électrode positive
WO2021118144A1 (fr) Matériau actif d'anode, son procédé de préparation, et anode et batterie secondaire comprenant chacune celui-ci
WO2023158272A1 (fr) Séparateur pour accumulateur lithium-soufre et accumulateur lithium-soufre le comprenant
WO2023121218A1 (fr) Procédé de pré-lithiation pour électrode négative pour batterie secondaire au lithium, électrode négative pour batterie secondaire au lithium, et batterie secondaire au lithium comprenant une électrode négative

Legal Events

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

Ref document number: 19768601

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2020545111

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2019768601

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2019768601

Country of ref document: EP

Effective date: 20201015