WO2013080988A1 - Collecteur pour électrodes, électrode pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux - Google Patents

Collecteur pour électrodes, électrode pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux Download PDF

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WO2013080988A1
WO2013080988A1 PCT/JP2012/080695 JP2012080695W WO2013080988A1 WO 2013080988 A1 WO2013080988 A1 WO 2013080988A1 JP 2012080695 W JP2012080695 W JP 2012080695W WO 2013080988 A1 WO2013080988 A1 WO 2013080988A1
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Prior art keywords
electrode
current collector
active material
surface area
layer
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PCT/JP2012/080695
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English (en)
Japanese (ja)
Inventor
俊夫 谷
健作 篠崎
鈴木　昭利
耕二 幡谷
直文 徳原
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古河電気工業株式会社
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Priority to JP2013516862A priority Critical patent/JP5437536B2/ja
Publication of WO2013080988A1 publication Critical patent/WO2013080988A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • 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 chargeable / dischargeable non-aqueous electrolyte secondary battery such as a lithium ion secondary battery, an electrode used in the secondary battery, and a current collector as a component of the electrode.
  • the lithium ion secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • the negative electrode is formed by applying carbon particles as a negative electrode active material layer to the surface of a negative electrode current collector made of a copper foil having a smooth surface, and further pressing it.
  • Lithium ion secondary batteries are currently used in mobile phones, notebook computers and the like.
  • An aluminum foil is used for the positive electrode current collector of this lithium ion secondary battery, and a copper foil subjected to rust prevention treatment is mainly used for the negative electrode current collector.
  • the electrolytic copper foil having a small difference in surface roughness between the glossy surface and the rough surface as described above is manufactured by adding an organic or inorganic compound or ionic species to an electrolytic solution for depositing copper.
  • an organic or inorganic compound or ionic species for example, a method for producing an electrolytic copper foil using an electrolytic solution to which an organic compound, chloride ion, low molecular weight glue and high molecular polysaccharide are added is disclosed (see Patent Document 2).
  • the electrolytic copper foil manufactured by such a manufacturing method is coated with a slurry containing carbon-based active material particles and the like on the surface of the copper foil, and after drying, is further pressed into a negative electrode.
  • An electrode (negative electrode) for a lithium ion secondary battery for the purpose of increasing the capacity is obtained by depositing, for example, silicon on an amorphous silicon thin film or microcrystalline silicon thin film on a current collector such as a copper foil by CVD or sputtering. As it is deposited and formed. Since the thin film layer of the active material prepared by such a method is in close contact with the current collector, it has been found that it exhibits good charge / discharge cycle characteristics (see Patent Document 4).
  • the volume of the active material layer expands and contracts during charge and discharge. That is, when the lithium ions are occluded during charging, the volume expands by about 4 times at the maximum, and the lithium ions are released and contracted during discharging. Thereby, the phenomenon in which the active material is pulverized and peeled from the current collector is observed. Further, since the active material layer is in close contact with the current collector, there is a problem that a large stress is applied to the current collector when the volume of the active material layer expands and contracts due to repeated charge and discharge.
  • the current collector When an electrode with such large expansion and contraction is accommodated in a battery and repeatedly charged and discharged many times, the current collector also expands and contracts, so that the current collector is wrinkled. In order to allow wrinkles, it is necessary to make room for the volume occupied by the electrode in the battery, but this causes a problem that the energy density (or charge / discharge capacity) per volume decreases.
  • the present invention has been made in view of the above-described problems, and an object of the present invention is to provide lithium ion secondary batteries using a negative electrode in which an active material having a high specific capacity such as silicon or tin is deposited on a current collector.
  • an active material having a high specific capacity such as silicon or tin is deposited on a current collector.
  • generation of wrinkles on the current collector, breakage of the current collector, or peeling between the current collector and the active material layer is suppressed, and the adhesion between the active material and the current collector is high, and the performance is stable for a long time. It is to provide a lithium ion secondary battery capable of maintaining the above.
  • the surface of the current collector for electrodes has any one or more of a chromate treatment layer, a benzotriazole treatment layer, a silane coupling treatment layer, a nickel treatment layer, a zinc treatment layer, and a tin treatment layer.
  • the electrode current collector has a tensile strength of 450 MPa or more, a breaking elongation of 3% or more, a breaking elongation of 3% or more after heating at 180 ° C. for 5 minutes, and after heating at 300 ° C. for 1 hour.
  • the current collector for an electrode according to (1) or (2) which has a tensile strength of 300 MPa or more.
  • a nonaqueous electrolyte secondary battery in which an active material-containing layer is formed by applying a slurry containing an electrode active material and an aqueous binder to the electrode current collector according to (1).
  • Electrode. (9) A non-aqueous electrolyte 2 characterized in that an active material-containing layer is formed by applying a slurry containing an electrode active material and an organic solvent binder to the electrode current collector described in (2).
  • Secondary battery electrode. (10) The electrode for a nonaqueous electrolyte secondary battery according to (8) or (9), wherein the electrode active material contains silicon, tin, or carbon.
  • an electrode using a water-based binder is inferior in adhesion between a copper foil and an electrode coating film and has a shorter charge / discharge cycle life than an organic solvent-based binder.
  • the present invention swelling and peeling of the interface with the aqueous binder-using electrode can be prevented, and the cycle life is improved.
  • the adhesion is improved and the cycle life is extended by specifying a large interface real surface area.
  • FIG. 3 is a cross-sectional view showing a nonaqueous electrolyte secondary battery 11. The plot which shows the capacity
  • the current collectors for electrodes according to the first embodiment are current collectors 1, 4, and 7 shown in FIGS. 1 (a), 1 (b), and 1 (c).
  • the current collectors 1, 4, and 7 form the active material-containing layers 2, 5, and 8 by applying a slurry containing an electrode active material or a conductive additive and an aqueous binder.
  • the surface of the current collectors 1, 4, 7 on which the active material containing layers 2, 5, 8 are formed is measured with a resolution in the roughness (Z-axis) direction of 0.05 ⁇ m, the actual surface area is the unit plane area
  • the surface area ratio divided by is 1.1 to 4.0.
  • the actual surface area is a surface area including the surface area of minute irregularities on the surface.
  • the actual surface area of the surface of the electrode current collector is measured by measuring the surface of the minute compartment and image analysis using an ultra-deep shape measurement laser microscope. For example, in a laser microscope using a pinhole confocal optical scanning method, it is roughly based on the following measurement analysis. Laser scanning measurement is performed on the position of a point having a number determined by the resolution of the apparatus in an XY plane having a specific vertical and horizontal screen width at a specified magnification at a certain height position in the Z-axis direction. This is moved in the Z-axis direction for each designated resolution, and XY in-plane measurement is repeatedly performed. After each plane data is captured, the three-dimensional representation is calculated.
  • the observation magnification is several hundred times to 20,000 times
  • the planar laser scanning accuracy is from 1024 ⁇ 768 pixels to 2048 ⁇ 1536 pixels
  • the Z-axis direction linear scale resolution is 10 nm (0.01 ⁇ m) to 0.5 nm. (0.0005 ⁇ m) is possible and these values depend on the device.
  • the unit plane area is a geometric area in the measured range ignoring surface irregularities.
  • the surface area ratio is a value obtained by dividing the actual surface area by the unit plane area. The surface area ratio becomes closer to the minimum value of 1 as the surface has no irregularities and the surface has a higher smoothness. Higher surface area ratio means more uneven surface.
  • problems such as uneven shapes, changes in actual thickness due to uneven shapes, changes in slurry application amount, electrode thickness, and the like are also derived.
  • current concentration occurs at the time of charging / discharging, and the current density increases, so that a side reaction occurs at the interface. This may cause an obstacle such as a decomposition reaction of the electrolyte component.
  • a particularly severe example is the combined effect of water and surface convexity.
  • the treatment is performed so as not to include the aqueous solvent in the electrolytic solution in principle, but water, hydrogen fluoride ions, and the like are often contained on the order of ppm.
  • As charging / discharging is repeated there is a high possibility that it gradually increases due to side reactions and the like.
  • water may remain in the aqueous binder electrode coating film depending on the drying conditions.
  • the surface convex shape is strong, these trace amounts of moisture and the like cause reductive decomposition due to high current density at the negative electrode surface or the copper foil interface.
  • the hydrogen gas generated at this time causes swelling of the electrode coating film and peeling from the current collector.
  • the ten-point average roughness Rz is desirably 2.0 ⁇ m or less.
  • the lower limit is about Rz 1.0 ⁇ m. That is, the surface roughness Rz of the current collectors 1, 4, and 7 shown in FIGS. 1A, 1B, and 1C as the electrode current collector according to the first embodiment is 1.0 to It has a feature of 2.0 ⁇ m.
  • the current collector is preferably thin, and therefore, it is preferably a metal foil such as a copper foil or an aluminum foil, particularly an electrolytic copper foil or a rolled copper foil in the case of a copper foil.
  • the thickness of the current collector is preferably about 8 ⁇ m for the thin and about 20 ⁇ m for the thick depending on the battery application. This is because if the thickness is 8 ⁇ m or less, the strength of the foil cannot be maintained, and breakage occurs when the active material expands or contracts. On the other hand, when the thickness exceeds 20 ⁇ m, the battery characteristics can be satisfied, but the battery itself is large and heavy.
  • the active material-containing layer can be formed by being deposited on one side or both sides of the current collector. If not limited to the water-based binder, it is generally preferable that the surface roughness Rz of the surface of the current collector forming the active material-containing layer is 1.0 to 5 ⁇ m. When the active material-containing layer is formed on both surfaces of the current collector, the surface roughness Rz on both sides of the current collector is 1.0 to 5 ⁇ m, and the difference between the front and back surfaces is 3 ⁇ m or less. preferable. Generally, when the value of Rz is below the lower limit, the adhesion due to the anchor effect with the active material is poor.
  • the current collector is a copper foil
  • a surface roughening treatment may be performed, and the surface roughening treatment has a particle size of 0.1 to 3 ⁇ m and copper or copper containing Cu as a main component. It is preferable that the fine particles of the alloy be applied to the surface.
  • a roughening treatment layer in which the roughened particles are fixed to the surface of the copper foil by copper plating is formed using the alloy fine particles made of copper or a copper alloy containing Cu as a main component as the roughened particles. This is because the adhesion between the roughened particles and the untreated copper foil is improved, and the roughness can be easily adjusted by controlling the crystal grain size of the roughened particles. Thereby, the applicability
  • the main component means containing 50% by mass or more.
  • the current collector is an aluminum foil
  • the surface of the electrode current collector preferably has one or more of a chromate treatment layer, a benzotriazole treatment layer, a silane coupling treatment layer, a nickel treatment layer, a zinc treatment layer, and a tin treatment layer.
  • the chromate treatment layer is a passive layer obtained on the surface by immersing the current collector in an aqueous solution such as chromate or dichromate or by performing electrolytic treatment.
  • the benzotriazole-treated layer is a layer generated on the current collector surface by immersing the current collector in a benzotriazole aqueous solution.
  • the silane coupling treatment layer is a layer obtained by immersing the surface of the current collector with a silane coupling agent solution.
  • the nickel treatment layer is a nickel layer obtained by performing nickel plating or the like on the current collector surface.
  • the zinc treatment layer is a zinc layer obtained by galvanizing the surface of the current collector.
  • the tin treatment layer is a tin layer obtained by performing tin plating or the like on the current collector surface. Any of the plating treatments can be performed according to a conventional method, and a thin layer of 1 ⁇ m or less that does not inhibit high conductivity is desirable.
  • a negative electrode current collector for a lithium ion battery has a drying step during the manufacturing process. If this drying is insufficient, the characteristics of the battery deteriorate.
  • the copper foil as the current collector is softened by heat in the drying process, distortion due to partial elongation occurs, the electrode manufacturing process does not meet the electrode design specifications, and in extreme cases, the foil breaks. Therefore, it is preferable that the elongation at break after heating at 180 ° C. for 5 minutes is also 3% or more.
  • the battery can be obtained by using an organic solvent-based binder that has high heat resistance that brings a large volume change and stress strain due to expansion and contraction to the current collector foil and excellent mechanical strength such as elastic modulus.
  • the characteristics may also be improved.
  • a heat-resistant copper foil is used for the current collector foil, and a foil having a tensile strength of 300 MPa or more after heating at 300 ° C. for 1 hour is preferable.
  • the tensile strength and the elongation rate are values measured by a method defined in Japanese Industrial Standard (JIS K 6251).
  • the surface roughness Rz is a ten-point average roughness defined in Japanese Industrial Standard (JIS B 0601-1994), for example, a value measured by a surface roughness meter.
  • coating the slurry containing an electrode active material or a conductive support agent, and a water-system binder to the electrode collectors 1, 4, and 7 which concern on 1st Embodiment. 3, 6, and 9 are excellent in cycle characteristics and have a long life.
  • the electrode current collectors according to the second embodiment are current collectors 1, 4, and 7 shown in FIGS. 1 (a), (b), and (c).
  • each of the surface area is 2500 ⁇ 17500 ⁇ m 2 / 2500 ⁇ m 2.
  • the second embodiment is the same as the first embodiment except that the surface area ratio obtained by dividing the actual surface area by the unit plane area is different and that the binder contained in the slurry used is an organic solvent-based binder. It has the composition of. Since the binder is organic solvent-based, there is less moisture film remaining than water-based binders, and there is less gas generation due to reductive decomposition like water-based binders, so there is a need to suppress the surface area ratio compared to water-based binders. Low. Therefore, the current collector surface can be set to an optimum surface area ratio excellent in electrode coating film adhesion and battery electrode characteristics.
  • Active material containing layers 2, 5, 8 are formed by applying a slurry containing an electrode active material or a conductive additive and an organic solvent binder to the electrode current collectors 1, 4, 7 according to the second embodiment.
  • the electrodes 3, 6, and 9 have excellent cycle characteristics and a long life.
  • FIG. 1 (a) is a current collector in which the surface of an untreated copper foil is subjected to rust prevention treatment and smooth plating treatment.
  • FIG.1 (b) is the electrical power collector which performed the roughening process by the etching by a chemical agent or alternating current etching on the surface of untreated copper foil.
  • a current collector 7 shown in FIG. 1 (c) is a current collector that has been subjected to a roughening treatment for forming a bump-shaped copper layer containing copper alloy fine particles 10 on the surface.
  • DSA insoluble anode
  • a titanium cathode drum provided opposite to the anode.
  • Copper is deposited on the surface of the cathode drum by applying a direct current between the two electrodes while rotating the cathode drum at a constant speed. The deposited copper is peeled off from the surface of the cathode drum and continuously wound up to produce an electrolytic copper foil.
  • the untreated copper foil used for the copper foil for a lithium ion secondary battery electrode of the present invention comprises, for example, a compound having a mercapto group, a chloride ion, a low molecular weight glue having a molecular weight of 10,000 or less, and a high molecular weight polymer. It can be produced by adding saccharides. For example, MPS (sodium 3-mercapto-1-propanesulfonate), HEC (hydroxyethyl cellulose), and glue can be mentioned.
  • the surface in contact with the titanium cathode drum is generally a glossy surface (hereinafter referred to as S surface), and the surface in contact with the electrolytic solution is generally defined as a mat surface (hereinafter referred to as M surface).
  • the electrolytic copper foil before the roughening treatment in the present invention is preferably a double-sided smooth or glossy foil, and the surface Rz of both surfaces is preferably as low as 2.5 ⁇ m or less, and a foil having a small difference in front and back is suitable.
  • the electrolytic copper foil produced by the conventional printed circuit application technology has ridges and valleys on the M surface, and the surface roughness of the foil thickness of 18 ⁇ m or less is about 2.2 to 5.0 ⁇ m.
  • the electrolytic plating method is a method of roughening the surface by forming a thin film layer having irregularities on the surface of the untreated electrolytic copper foil. Even if the untreated foil conforms to the above surface roughness, a part of which has been subjected to a functional surface treatment in addition to a rust prevention treatment such as a chromate treatment or a silane coupling treatment can be used. Moreover, in order to reduce surface roughness, unevenness, and surface area ratio, it is possible to perform smooth plating treatment.
  • a roughening treatment layer which is a plating film mainly composed of copper such as copper or copper alloy is formed on the surface of the untreated electrolytic copper foil by an electrodeposition method.
  • the electrolytic plating method the following method is preferable. First, an untreated electrolytic copper foil is immersed in a copper plating electrolytic solution having a particle diameter of 0.1 to 3 ⁇ m and added with copper or copper alloy fine particles containing Cu as a main component. Fine particles are imparted to the surface of the untreated electrolytic copper foil to form a coarse powdery copper plating layer. Next, capsule plating is performed on the grainy copper plating layer so as not to impair the uneven shape. Thereby, a substantially smooth plating layer is deposited, and the granular copper is used as a so-called bumpy copper layer. The surface on which the bumpy copper layer is formed becomes a rough surface.
  • a roughening method by plating used in a copper foil for printed circuits disclosed in a patent document may be used. That is, after a granular copper plating layer is formed by so-called “bake plating”, capsule plating is performed on the granular copper plating layer so as not to impair the uneven shape. As a result, a substantially smooth plating layer is deposited to make the powdered copper into a so-called bumpy copper layer. The surface on which the bumpy copper layer is formed becomes a rough surface.
  • etching with chemicals such as formic acid or hydrochloric acid or roughening treatment by alternating current etching may be used, and it can also be applied to aluminum foil and each alloy foil.
  • the non-aqueous electrolyte secondary battery electrodes 3, 6, and 7 according to the first and second embodiments are arranged in the first and second embodiments.
  • the active material containing layers 2, 5, 8 are formed by applying a slurry containing an electrode active material or a conductive additive and an aqueous binder to the electrode current collectors 1, 4, 7 according to the embodiment.
  • the active material in the present invention is a material that occludes / releases lithium, and includes an active material that occludes lithium by alloying.
  • an active material include carbon, silicon, germanium, tin, lead, zinc, magnesium, sodium, aluminum, potassium, indium, and antimony.
  • silicon and tin are preferably used because of their high theoretical capacity. Therefore, the active material-containing layer used in the present invention is preferably a layer containing silicon or tin as a main component, and particularly preferably a layer containing silicon as a main component.
  • the active material in the present invention can be used regardless of crystal, amorphous or microcrystal. Further, it is possible to use a form in which a part of the active material is an alloy, a form in which an alloy is attached to a single substance, or a form in which both the simple substance and the alloy are mixed with a slurry and then mixed and mixed.
  • a single element of the active material cobalt, nickel, calcium, scandium, copper, silver, gold, iron, titanium, vanadium, chromium, manganese, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, barium ,
  • An alloy form with a metal selected from barium, rhodium, ruthenium and yttrium is desirable.
  • These include a first phase of a single active material and a solid solution, and a second phase that is a compound of an active material element and other elements, in which both phases are joined.
  • the form containing the active material element includes primary particles and secondary particles obtained by granulating the primary particles, and those having a particle size of about 0.01 to 10 ⁇ m are used. Furthermore, a form in which the surface of these active materials is coated with a conductive material, or subjected to hydrophilicity, hydrophobicity treatment, non-aggregation dispersion treatment, or the like may be used. Preferable examples include an amorphous carbon coat that prevents a decrease in conductivity due to surface oxidation of silicon. From the electrochemical theoretical specific capacity, silicon or a silicon-silicon alloy or the above-described carbon-coated form is preferably used.
  • a silicon-based active material form partially incorporating oxygen is also used. This is because the silicon oxide form having oxygen relaxes the volume expansion due to electrochemical alloying of lithium ions, so that the active material silicon can be prevented from being broken and pulverized. From the same reason and the further stability of charge / discharge characteristics, it is excellent as an electrode battery containing an active material in which a carbon-based active material is mixed with silicon or tin.
  • the active material-containing layer in the present invention is formed by applying an active material or a conductive additive into a slurry form together with a binder and a solvent, and applying, drying and pressing the surface of the current collector (copper foil).
  • an aqueous binder or an organic solvent binder can be used as the binder. Further, when using an aqueous binder, an aqueous solvent can be used as a solvent, and when using an organic solvent binder, an organic solvent can be used as a solvent.
  • water-based binder a water-based binder in which a polymer represented by styrene-butadiene copolymer (SBR), latex, and polyacrylate is dispersed in water can be used.
  • SBR styrene-butadiene copolymer
  • latex latex
  • polyacrylate polyacrylate
  • the organic solvent binder polyvinylidene fluoride, epoxy resin, polyamideimide, polybenzimidazole, and polyimide can be used. It is preferable that the coating film obtained by drying or baking and curing these organic solvent binders has a tensile strength of 150 MPa or more, a tensile elastic modulus of 2 GPa or more, and an elongation of 20% or more.
  • a metal-based active material having a high electrochemical specific capacity such as silicon the volume expands greatly due to electrochemical alloying (charging) of lithium and the volume is increased by dealloying (discharging). Shrink.
  • the binder or polymer forming the coating film matrix has a characteristic that is difficult to be plastically deformed by stress.
  • lithium may be occluded or added in advance.
  • Lithium may be added when forming the active material-containing layer. That is, an active material-containing layer containing lithium is formed on the current collector surface in advance. Moreover, after forming an active material content layer, you may occlude or add lithium to an active material content layer. Examples of the method for inserting or adding lithium into the active material-containing layer include a method for electrochemically inserting or adding lithium.
  • a lithium ion secondary battery of the present invention comprises a negative electrode comprising the lithium ion secondary battery electrode of the present invention, a positive electrode using a material that absorbs and releases lithium as an active material, and a nonaqueous electrolyte.
  • the non-aqueous electrolyte secondary battery 11 which is a lithium ion secondary battery of the present invention includes a positive electrode 13 and a negative electrode 12 which are connected to a separator-negative electrode-separator-positive electrode via a separator 15. Laminated in order.
  • the positive electrode 13 is wound so as to be on the inner side to constitute an electrode plate group, which is inserted into the battery can 19.
  • the positive electrode 13 is connected to the positive electrode terminal 25 via the positive electrode lead 21, and the negative electrode 12 is connected to the battery can 19 via the negative electrode lead 23. Therefore, the chemical energy generated inside the nonaqueous electrolyte secondary battery 11 can be taken out as electric energy.
  • the battery 17 is filled with the electrolyte 17 so as to cover the electrode plate group. Then, it can manufacture by attaching the sealing body 27 to the upper end (opening part) of the battery can 19 via a cyclic
  • the sealing body 27 is composed of a circular lid plate and the positive electrode terminal 25 on the upper portion thereof, and has a structure in which a safety valve mechanism is built therein.
  • the nonaqueous electrolyte used in the lithium ion secondary battery of the present invention is an electrolyte in which a solute is dissolved in a solvent.
  • the solvent for the nonaqueous electrolyte is not particularly limited as long as it is a solvent used for lithium ion secondary batteries.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, and vinylene carbonate, dimethyl carbonate, and diethyl carbonate.
  • chain carbonates such as methyl ethyl carbonate.
  • a mixed solvent of a cyclic carbonate and a chain carbonate is used.
  • a mixed solvent of the above cyclic carbonate and an ether solvent such as 1,2-dimethoxyethane or 1,2-diethoxyethane, or a chain ester such as ⁇ -butyrolactone, sulfolane, or methyl acetate may be used. Good.
  • the solute of the nonaqueous electrolyte is not particularly limited as long as it is a solute used for a lithium ion secondary battery.
  • LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (CF 3 SO 2 ) 3 , LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 examples thereof include LiClO 4 , Li 2 B 10 Cl 10 , and Li 2 B 12 Cl 12 .
  • LiXFy (wherein X is P, As, Sb, B, Bi, Al, Ga, or In, y is 6 when X is P, As, or Sb, and X is B, Bi, Al) , Ga or the y when in is 4.), lithium perfluoroalkyl sulfonic acid imide LiN (C m F 2m + 1 SO 2) (C n F 2n + 1 SO 2) (wherein,, m and n Are each independently an integer of 1 to 4.) or lithium perfluoroalkylsulfonic acid methide LiC (C p F 2p + 1 SO 2 ) (C q F 2q + 1 SO 2 ) (C r F 2r + 1 SO 2 ) (wherein p, q and r are each independently an integer of 1 to 4).
  • a mixed solute of LiPF 6 and LiN (C 2 F 5 SO 2 ) 2 is particularly preferably used.
  • a gel polymer electrolyte obtained by impregnating a polymer electrolyte such as polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride with an electrolytic solution, or an inorganic solid electrolyte such as LiI or Li 3 N can be used.
  • a polymer electrolyte such as polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride
  • an electrolytic solution or an inorganic solid electrolyte such as LiI or Li 3 N
  • the electrolyte of the lithium ion secondary battery of the present invention is limited as long as the Li compound as a solute that develops ionic conductivity and the solvent that dissolves and retains it are not decomposed by the voltage at the time of charging, discharging or storing the battery. Can be used.
  • lithium-containing transition metal oxides such as LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 2 , LiCo 0.5 Ni 0.5 O 2 , LiNi 0.7 Co 0.2 Mn 0.1 O 2
  • metal oxides such as MnO 2 that do not contain lithium
  • any substance that can electrochemically alloy lithium can be used without limitation.
  • the interfacial adhesion and the like are not impaired even after repeated charge and discharge, and an electrode that can achieve a high cycle life.
  • a secondary battery can be provided.
  • the thickness is a value measured with a micrometer, and the tensile strength and elongation at break are values measured using a tensile tester (Model 1122 manufactured by Instron).
  • the surface roughness Rz was measured with a stylus type surface roughness meter (SE-3C type manufactured by Kosaka Laboratory).
  • Granular plating conditions Copper sulfate 80g / L Sulfuric acid 110-160g / L Additive * Appropriate amount Liquid temperature 30-60 °C Current density 10-50A / dm 2 Treatment time 2 to 20 seconds * Additive: Fine particles of copper alloy having a particle size of 0.1 to 3 ⁇ m.
  • Dense copper plating (capsule plating) conditions Copper sulfate 200g / L Sulfuric acid 90 ⁇ 130g / L Liquid temperature 30-60 °C Current density 10-30A / dm 2 Processing time 2-20 seconds
  • the surface roughness Rz, actual surface area, and surface area ratio of the copper foil after the roughening treatment were measured.
  • the surface roughness Rz was measured by the method described above.
  • the actual surface area was measured using an ultra-deep shape measuring laser microscope VK-8500 manufactured by KEYENCE.
  • the surface area ratio was obtained by dividing the actual surface area by the unit plane area.
  • the measurement was performed at an observation magnification of 2,000 and a 50 ⁇ m square micro-plane (area 2500 ⁇ m 2 ) was measured.
  • the planar laser scanning was performed at 1024 ⁇ 768 pixels (800,000 points) and the resolution in the roughness (Z-axis) direction was 0.05 ⁇ m.
  • Each in-plane data was three-dimensionally aggregated for each Z-axis position, and the actual surface area was calculated by image analysis processing. However, the actual surface area and the surface area ratio in the example table are described with respect to a value (100 ⁇ m square, 10000 ⁇ m 2 ) multiplied by 4 for easy understanding.
  • Electrode (negative electrode) Working electrodes were prepared using the prepared roughened electrolytic copper foil as a current collector, and the electrode characteristics were evaluated.
  • the silicon electrode is applied on a current collector by applying a silicon powder and acetylene black, an aqueous sodium carboxymethylcellulose solution and an aqueous dispersion SBR, which are kneaded and adjusted in a conventional manner, and dried. It was produced by pressing.
  • the silicon electrode is formed on a current collector on a silicon powder and acetylene black, a polyimide precursor (polyamic acid as an organic solvent binder), NMP (N-methyl-2-pyrrolidone, It was prepared by applying a kneaded and adjusted slurry as an organic solvent, drying and pressing.
  • a polyimide precursor polyamic acid as an organic solvent binder
  • NMP N-methyl-2-pyrrolidone
  • polyimides (1), (2), and (3) Three types are used as the polyimide, and the tensile strength as a coating film is (1) 400 MPa, (2) 170 MPa, (3) 125 MPa, and the coating film elastic modulus is Three types were used: (1) 8 GPa, (2) 3 GPa, (3) 1 GPa, and coating elongation percentages of (1) 50%, (2) 22%, and (3) 11%.
  • Polyimide (1) was used except that polyimide (2) was used in Example 32 and (3) was used in Example 33.
  • a three-electrode cell comprising a counter electrode, a test electrode, and a reference electrode was produced in a glove box under an argon gas atmosphere.
  • the cell was configured by hermetically assembling in a SUS container and injecting an electrolyte between the test electrode and the reference electrode.
  • an electrolytic solution an electrolytic solution in which at least 1 mol / liter of LiPF 6 was dissolved in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 3: 7 was used.
  • Lithium metal was used as the counter electrode and the reference electrode.
  • the capacity retention ratio is decreased as the surface area ratio is increased.
  • the current collector of Example 8 had a surface area ratio of 2.36 and was smaller than 4.0. Therefore, the capacity retention rate of the cycle test was as good as 44%.
  • the capacity retention rate decreased to 33%.
  • Comparative Example 1 having a surface area ratio of 4.21 had a capacity retention rate of 29%. That is, since the surface area ratio of 4.0 or more was not satisfied, the capacity retention ratio was 30%, which was greatly reduced.
  • the 10-point average surface roughness Rz was adjusted to be within a certain range (1.0 to 2.0 ⁇ m) on the surface on which the active material-containing layer was formed. .
  • the current collectors of Examples 14 to 33 have a surface area ratio of 1.0 to 7.0. Therefore, the capacity retention rate of the cycle test was 60% or more, which was better than that of the aqueous binder. Further, the capacity retention rate in the case of the electrode using the surface area ratio of the current collectors of Examples 19 to 29 in the range of 1.4 to 6.5 is 70% or more. According to the current collector electrodes having a surface area ratio of 2.0 to 4.0 in Examples 21 to 26, a maintenance ratio of 75% or more is obtained, and each is good.
  • Example 31 the type of polyimide used for the binder is different.
  • the polyimide used in Example 31 has the highest coating film strength (and elastic modulus or elongation).
  • the polyimide used in Example 32 has the next highest strength (supra).
  • the polyimide used in Example 33 has the properties of the coating film, the tensile strength is less than 150 MPa, the tensile elastic modulus is less than 2 GPa, and the elongation at break is less than 20%. Compared to the capacity maintenance rate. It has been found that the polyimide used for the binder is more effective for large volume changes accompanying high capacity charge / discharge of silicon or the like and has a higher capacity retention ratio as the strength and elastic modulus are higher.
  • organic solvent binders such as polyimide binders have a high capacity retention rate can be considered as follows.
  • the coating film does not easily contain moisture, so electrode side reactions between the electrode and the electrolyte solution are unlikely to occur, and gas generation is unlikely to occur. Even when the surface area ratio is large, a high capacity retention rate can be maintained.
  • the surface area ratio is too small, the adhesion between the current collector and the active material-containing layer that is a coating film is deteriorated, and the active material-containing layer is peeled off during repeated charging and discharging. Furthermore, since the adhesiveness is poor, it is difficult to secure a conductive path. Further, if the surface area ratio is too large, the expansion / contraction is too large, and it is considered that the active material-containing layer is peeled off or pulverized.
  • the capacity retention rate of Comparative Example 5 using untreated copper foil C (Table 2) having the smallest tensile strength after heating at 300 ° C. is less than 30%. Deteriorated. Since Example 29 using untreated foil A and Example 31 using untreated foil B have substantially the same Rz and the same polyimide used, they are suitable for comparison due to differences in untreated copper foil. The result of the capacity retention rate in the charge / discharge test is 71% of the untreated foil A (Example 29) as compared to 90% of the untreated foil B (Example 31). When using an organic solvent-based binder, the difference in the capacity retention ratio between Example 31 and Example 29 is not due to the effect of the surface area ratio on the capacity retention ratio.
  • the interfacial adhesion and the like are not impaired even after repeated charge and discharge, and an electrode that can achieve a high cycle life.
  • a secondary battery can be provided.

Abstract

L'invention vise à procurer une batterie secondaire à lithium-ion qui fait appel à une électrode négative obtenue par dépôt d'une matière active présentant une forte capacité spécifique comme le silicium sur un collecteur et susceptible de maintenir un comportement stable sur une période de temps prolongée. L'invention fait appel à un collecteur (1) pour électrodes sur lequel est appliquée une bouillie contenant une matière active d'électrode et un liant aqueux dans le but de former une couche (2) contenant la matière active, et qui est caractérisé en ce que le rapport d'aires entre l'aire effective et une unité d'aire plane est compris entre 1,1 et 4,0 dans une surface sur laquelle est formée la couche (2) contenant la matière active. En variante, l'invention fait appel à un collecteur (1) pour électrodes sur lequel est appliquée une bouillie contenant une matière active d'électrode et un liant à base de solvant organique dans le but de former une couche (2) contenant la matière active, et qui est caractérisé en ce que le rapport d'aires obtenu entre l'aire effective et une unité d'aire plane est compris entre 1,0 et 7,0 dans une surface sur laquelle est formée la couche (2) contenant la matière active.
PCT/JP2012/080695 2011-11-29 2012-11-28 Collecteur pour électrodes, électrode pour batteries secondaires à électrolyte non aqueux et batterie secondaire à électrolyte non aqueux WO2013080988A1 (fr)

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CN104282915A (zh) * 2013-07-07 2015-01-14 山东润峰集团新能源科技有限公司 一种锂离子电池多孔载体制作工艺
WO2015005067A1 (fr) * 2013-07-10 2015-01-15 日立金属株式会社 Collecteur pour accumulateurs lithium-ion et électrode positive pour accumulateurs lithium-ion
JP2018522378A (ja) * 2015-07-24 2018-08-09 エル エス エムトロン リミテッドＬＳ Ｍｔｒｏｎ Ｌｔｄ． リチウム二次電池用の電解銅箔及びこれを含むリチウム二次電池
JP2020057581A (ja) * 2018-10-01 2020-04-09 長春石油化學股▲分▼有限公司 リチウム二次電池の集電体用銅箔及びそれを含む負極
WO2022038056A1 (fr) 2020-08-20 2022-02-24 Covestro Deutschland Ag Formulations de polyol et procédé de production de mousses de pur/pir sur la base de ces formulations de polyol
WO2023276757A1 (fr) * 2021-06-30 2023-01-05 パナソニックＩｐマネジメント株式会社 Batterie secondaire au lithium
WO2023063673A1 (fr) * 2021-10-12 2023-04-20 주식회사 엘지에너지솔루션 Électrode négative pour batterie secondaire, et ensemble électrode de type feuille enroulée la comprenant
LU502546B1 (en) * 2022-07-21 2024-01-22 Circuit Foil Luxembourg Copper foil, secondary battery comprising the same and production method thereof

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CN104282915A (zh) * 2013-07-07 2015-01-14 山东润峰集团新能源科技有限公司 一种锂离子电池多孔载体制作工艺
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JP2018522378A (ja) * 2015-07-24 2018-08-09 エル エス エムトロン リミテッドＬＳ Ｍｔｒｏｎ Ｌｔｄ． リチウム二次電池用の電解銅箔及びこれを含むリチウム二次電池
JP2020057581A (ja) * 2018-10-01 2020-04-09 長春石油化學股▲分▼有限公司 リチウム二次電池の集電体用銅箔及びそれを含む負極
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WO2022038056A1 (fr) 2020-08-20 2022-02-24 Covestro Deutschland Ag Formulations de polyol et procédé de production de mousses de pur/pir sur la base de ces formulations de polyol
WO2023276757A1 (fr) * 2021-06-30 2023-01-05 パナソニックＩｐマネジメント株式会社 Batterie secondaire au lithium
WO2023063673A1 (fr) * 2021-10-12 2023-04-20 주식회사 엘지에너지솔루션 Électrode négative pour batterie secondaire, et ensemble électrode de type feuille enroulée la comprenant
LU502546B1 (en) * 2022-07-21 2024-01-22 Circuit Foil Luxembourg Copper foil, secondary battery comprising the same and production method thereof
WO2024018005A1 (fr) * 2022-07-21 2024-01-25 Circuit Foil Luxembourg Feuille de cuivre, batterie secondaire la comprenant et son procédé de production

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