WO2013047832A1 - Composite oxyde métallique et nanotubes de carbone, son procédé de fabrication et électrode et élément électrochimique l'utilisant - Google Patents

Composite oxyde métallique et nanotubes de carbone, son procédé de fabrication et électrode et élément électrochimique l'utilisant Download PDF

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WO2013047832A1
WO2013047832A1 PCT/JP2012/075233 JP2012075233W WO2013047832A1 WO 2013047832 A1 WO2013047832 A1 WO 2013047832A1 JP 2012075233 W JP2012075233 W JP 2012075233W WO 2013047832 A1 WO2013047832 A1 WO 2013047832A1
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metal oxide
carbon nanotubes
composite
dispersed
dispersed carbon
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PCT/JP2012/075233
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English (en)
Japanese (ja)
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勝彦 直井
俊造 末松
大輔 堀井
和子 直井
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日本ケミコン株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 composite of a metal oxide active material and a carbon nanotube, a manufacturing method thereof, an electrode and an electrochemical device using the composite.
  • lithium titanate whose oxidation-reduction potential is higher than the reduction potential of the electrolytic solution, has been studied.
  • lithium titanate has a problem of low output characteristics.
  • it is a composite of lithium titanate nanoparticles and a carbon material it is difficult to reduce the carbon content, and it is difficult to improve the capacity characteristics.
  • the present invention has been proposed in order to solve the above-mentioned problems of the prior art, and its object is to provide an electrode or an electrochemical element that achieves output characteristics and high energy density.
  • An object of the present invention is to provide a composite of an oxide active material and a carbon nanotube, and a method for producing the same.
  • Another object of the present invention is to provide an electrode and an electrochemical device using the composite.
  • the composite of the metal oxide and the carbon nanotube of the present invention is produced by applying shear stress and centrifugal force to the carbon nanotube and the reaction product containing the reaction inhibitor in the rotating reactor. And a metal oxide nanoparticle supported in a highly dispersed manner on the dispersed carbon nanotube, and the bundle is at least partially dissociated by colliding jets of a solution containing the carbon nanotube with the carbon nanotube. It is characterized by being dispersed.
  • An electrode formed by molding a composite of the metal oxide and the carbon nanotube using a binder is also an embodiment of the present invention.
  • An electrochemical element using the electrode is also an embodiment of the present invention.
  • a method for producing a composite of a metal oxide and a carbon nanotube is also an embodiment of the present invention.
  • a large-capacity charge / discharge characteristic can be exhibited by performing a pretreatment step on the carbon nanotubes.
  • the composite of the metal oxide active material and the carbon nanotube according to the present embodiment is (1) As a pretreatment step, carbon nanotubes (hereinafter referred to as CNT) are dispersed by “ultra-high pressure dispersion treatment”. (2) As a UC treatment process, metal oxide nanoparticles are added to CNTs (dispersed carbon nanotubes) dispersed by “ultracentrifugal treatment”, and ultracentrifugal treatment (Ultra-) is one of the mechanochemical reactions. Centrifugal force processing method (hereinafter referred to as UC processing) (1) The product obtained in the processing step (2) is vacuum dried and then fired.
  • CNT carbon nanotubes
  • ultra- ultracentrifugal treatment
  • the pre-treatment step for dispersing CNTs by “ultra-high pressure dispersion treatment” includes (a) mixing step, (b) stirring step, and (c) ultra-high pressure dispersion treatment. And (d) a concentration and drying step.
  • each step (a) to (e) will be described in detail.
  • (a) Mixing step In the mixing step, CNT and a solvent are mixed to produce a mixed solvent.
  • the existing method can be used for the mixing method of CNT and a solvent.
  • a homogenizer described later can be used.
  • the ratio of CNT to solvent is preferably 0.5 to 1 g of CNT per 1 l of solvent.
  • CNT used in this example is a material in which a six-membered ring network (graphene sheet) made of carbon is formed into a single-layer or multilayer coaxial tube.
  • CNT includes single-wall single-wall nanotubes (hereinafter referred to as SWCNT) and multi-wall multi-wall nanotubes (hereinafter referred to as MWCNT).
  • SWCNT single-wall single-wall nanotubes
  • MWCNT multi-wall multi-wall nanotubes
  • the bundle diameter is 0.05 ⁇ m or less, there is an inconvenience that the interaction between the CNTs increases and reaggregation occurs.
  • the bundle diameter is more than 1 ⁇ m, there is a problem that the rate characteristics of the obtained composite electrode deteriorate.
  • solvent mixed with CNTs alcohols, water, and mixed solvents thereof can be used.
  • a mixed solvent in which acetic acid and lithium acetate are dissolved in a mixture of isopropanol and water can be used.
  • ammonium persulfate can be used as a solvent.
  • the stirring step is a step of stirring the mixed solvent that has passed through the mixing step to uniformly disperse the CNTs in the solvent and pulverizing the CNTs.
  • a homogenizer is used and stirred under the conditions of 2000 rpm and 30 minutes.
  • Homogenizer is a kind of generator. This homogenizer is composed of a drive unit, a fixed outer blade, and a rotating inner blade, and performs a series of homogenization from high speed dispersion to fine crushing to homogenization.
  • (c) Ultra-high pressure dispersion treatment process In the ultra-high pressure dispersion treatment process, a known method generally called jet mixing is used. That is, a pair of nozzles are provided at positions facing each other on the inner wall of the cylindrical chamber, and the mixed solvent pressurized by the high-pressure pump is ejected from each nozzle to cause a frontal collision in the chamber. Thereby, the bundle of CNT can be pulverized and dispersed and homogenized. As an example, the treatment is performed at a pressure and concentration of 200 MPa, 3 Pass, 0.5 g / l.
  • FIG. 2 is a view showing the state of SWCNT when jet mixing is performed on an aggregate of 2 ⁇ m SWCNT and when it is not performed. From this figure, the bundle diameter of the agglomerates is increased by jet mixing. It can be seen that the thickness is 1 ⁇ m (50 nm).
  • FIG. 3 is a view showing the state of SWCNT when jet mixing is performed on an aggregate of 2 ⁇ m SWCNT and when it is not performed. From this figure, the bundle diameter of the agglomerates is increased by jet mixing. It can be seen that the thickness is 0.05 ⁇ m (25 nm).
  • concentration and drying step the highly dispersed solution obtained by the ultra-high pressure treatment is concentrated and dried.
  • concentration a known method can be used.
  • the metal alkoxide used in this example is preferably a titanium alkoxide, and a metal alkoxide having a reaction rate constant of 10 ⁇ 5 mol ⁇ 1 sec ⁇ 1 or more is preferred.
  • metals include tin, zirconia, and cesium.
  • lithium compound As the lithium compound, lithium acetate (CH3COOLi, manufactured by Wako Pure Chemical Industries, Ltd., special grade) can be used. As a lithium source other than lithium acetate, lithium hydroxide, lithium sulfate, or the like can be used.
  • the lithium compound solution was prepared by dissolving lithium acetate in a mixed solution of distilled water, acetic acid and isopropyl alcohol.
  • reaction inhibitor When, for example, titanium alkoxide is used as the metal alkoxide, there is a problem that the reaction is too fast and titanium oxide is formed when producing lithium titanate, so that lithium titanate cannot be produced.
  • a predetermined compound that forms a complex with the metal alkoxide as a reaction inhibitor, it is possible to suppress the chemical reaction from being accelerated too much.
  • substances that can form a complex with a metal alkoxide include acetic acid, carboxylic acids such as citric acid, succinic acid, formic acid, lactic acid, tartaric acid, fumaric acid, succinic acid, propionic acid, and repuric acid, and aminopolyesters such as EDTA.
  • Examples include complexing agents represented by amino alcohols such as carboxylic acid and triethanolamine.
  • the UC process used in the present invention is a process using a mechanochemical reaction.
  • This mechanochemical reaction is a process of a chemical reaction, and a chemical reaction is promoted by applying a shear stress and a centrifugal force to the reactants in a rotating reactor in the process of a rotating reaction.
  • This reaction method can be performed, for example, using a reactor as shown in FIG.
  • the reactor includes an outer cylinder 1 having a cough plate 1-2 at an opening and an inner cylinder 2 having a through hole 2-1 and swirling.
  • the reactant inside the inner cylinder moves to the inner wall 1-3 of the outer cylinder through the through hole of the inner cylinder by the centrifugal force.
  • the reaction product collides with the inner wall of the outer cylinder by the centrifugal force of the inner cylinder, and forms a thin film and slides up to the upper part of the inner wall.
  • the thickness of the thin film is 5 mm or less, preferably 2.5 mm or less, more preferably 1.0 mm or less.
  • the thickness of the thin film can be set according to the width of the dam plate and the amount of the reaction solution.
  • the centrifugal force applied to the reactants in the inner cylinder necessary for the present invention is 1500 N (kgms -2) or more, preferably 60000N (kgms -2) or more, more preferably 270000N (kgms -2) or more.
  • lithium titanate be highly dispersed and supported on CNTs by a two-step UC process. That is, as the first UC treatment, CNT, titanium alkoxide, and isopropyl alcohol are charged into the inner cylinder of the reactor, and the inner cylinder is turned to obtain a mixed solution in which CNT and titanium alkoxide are uniformly dispersed.
  • the precursor of the lithium titanate is uniformly dispersed and supported on the CNT, and the aggregation of the lithium titanate nanoparticles is caused. Prevented and improved output characteristics.
  • CNTs in which a lithium titanate precursor is dispersed and supported can also be generated by a one-step UC treatment.
  • CNT, titanium alkoxide, reaction inhibitor, and water are put into the inner cylinder of the reactor, and the inner cylinder is swirled to mix and disperse them and proceed with hydrolysis and condensation reaction, Promote chemical reactions.
  • CNTs in which a lithium titanate precursor is dispersed and supported can be obtained.
  • the precursor of lithium titanate obtained by UC treatment was highly dispersed and supported on CNTs.
  • the CNTs are heated in the range of 300 ° C. to 900 ° C. in a vacuum or nitrogen gas. Thereby, aggregation of lithium titanate particles is prevented, and the capacity and output characteristics of an electrode or an electrochemical element using the electrode material of the present embodiment are improved.
  • Electrode The composite powder in which the metal oxide nanoparticles obtained by this embodiment are highly dispersed and supported on carbon nanotubes is dissolved in isopropyl alcohol, and CNT is added and stirred to prepare a slurry. The slurry is filtered to form a sheet. This sheet can be rolled and molded to form an electrode of an electrochemical element, that is, an electrode for storing electrical energy, and the electrode exhibits high output characteristics and high capacity characteristics.
  • lithium titanate has been described above, similar effects can be obtained with metal oxides such as lithium iron phosphate.
  • a lithium source such as lithium acetate, an iron source such as iron acetate, a phosphorus source such as phosphoric acid and citric acid as a complexing agent are used, and no reaction inhibitor is used.
  • Electrochemical element An electrochemical element that can use this electrode is an electrochemical capacitor or a battery that uses an electrolytic solution containing a metal ion such as lithium or magnesium. That is, the electrode of the present invention can occlude and desorb metal ions, and operates as a negative electrode and a positive electrode.
  • the electrode of the present invention is laminated by sandwiching a separator between an electrode such as activated carbon as a counter electrode, carbon or metal oxide that occludes and desorbs metal ions, and uses an electrolytic solution containing metal ions.
  • Chemical capacitors and batteries can be configured.
  • the rate characteristics were compared according to the type of CNT.
  • Examples and comparative examples used in the first characteristic comparison are as follows.
  • Example 1 In Example 1, as shown in FIG. 5, SWCNT is used as CNT, isopropyl alcohol is used as a solvent mixed with CNT in the pretreatment process, and the two-stage UC treatment is performed in the subsequent UC treatment process. did. (Example 2) In Example 2, as shown in FIG. 6, MWCNT is used as CNT, isopropyl alcohol is used as a solvent mixed with CNT in the pretreatment process, and the two-stage UC treatment is performed in the subsequent UC treatment process. did. (Comparative Example 1) In Comparative Example 1, SWCNT was used as the CNT, and only the two-stage UC treatment was performed without performing the ultra-high pressure dispersion treatment. (Comparative Example 2) In Comparative Example 2, MWCNT was used as the CNT, and only the two-stage UC treatment was performed without performing the ultra-high pressure dispersion treatment.
  • CNT of Example 1 (diameter 1 to 2 nm, length 0.01 to 0.1 mm, 400 m 2 / g), CNT of Example 2 (diameter 5 to 10 nm, length 0.01 to 0.02 mm, 250 m 2 / G) was weighed about 1 g and mixed in 2 L of isopropyl alcohol to prepare a mixed solvent. The mixed solvent is stirred using a homogenizer at 2000 rpm for 30 minutes.
  • this mixed solvent was sprayed from a pair of nozzles provided in the chamber at a pressure and concentration of 200 MPa, 3 Pass, 0.5 g / l, and the fluids collided with each other to prepare a CNT / isopropyl alcohol dispersion solution. .
  • the resulting dispersion was concentrated and dried.
  • a mixed solvent was prepared by dissolving 0.12 g of the CNT dispersion solutions of Examples 1 and 2 and Comparative Examples 1 and 2 and 1.77 g of tetrabutoxytitanium in 18.7 g of isopropyl alcohol. This mixed solvent was put into a swirl reactor, and the inner cylinder was swirled at 40 m / s for 300 seconds to apply high shear dispersion by applying shear stress and centrifugal force to the mixed solvent. A highly dispersed mixture of CNT and titanium as an intermediate product was obtained for each of the two.
  • a mixed solvent was prepared by dissolving 0.7 g of acetic acid and 0.34 g of lithium acetate in a mixture of 2.28 g of isopropyl alcohol and 0.93 g of water. This mixed solvent is put into a swirl reactor in which a mixture for each of the above-described Examples 1 and 2 and Comparative Examples 1 and 2 is formed, and the inner cylinder is swung for 300 seconds at 40 m / s. A thin film of the reaction product was formed on the inner wall of the material, and a chemical reaction was promoted by applying shear stress and centrifugal force to the reaction product to obtain a CNT having a highly dispersed precursor of lithium titanate as a final product. .
  • Example 1 and 2 and Comparative Examples 1 and 2 in which the precursor of lithium titanate was highly dispersed and supported on the CNTs after two-stage firing processes of 300 ° C. for 1 hour and 900 ° C. for 4 minutes Obtained.
  • the amount of titanium alkoxide and CNT charged into the swirl reactor was adjusted so that the weight ratio of lithium titanate and CNT was about 8: 2. did.
  • a lithium foil was opposed to the obtained electrode as a counter electrode through a separator, and an electrochemical cell was prepared using 1M LiBF 4 / PC as an electrolytic solution.
  • results as shown in FIGS. 7 and 8 were obtained.
  • FIG. 7 is a graph showing the rate characteristic evaluation of Example 1 and Comparative Example 1 using SWCNT as CNT.
  • FIG. 8 is a diagram showing rate characteristic evaluation of Example 2 and Comparative Example 2 using MWCNT as CNT. 7 and 8, it can be seen that both the SWCNT and the MWCNT have higher rate characteristics in the example in which the pretreatment process is performed than in the comparative example in which the CNT is not subjected to the pretreatment process.

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Abstract

La présente invention concerne le procédé de fabrication d'un composite à partir d'un oxyde métallique et de nanotubes de carbone, un composite d'oxyde métallique et de carbone dans lequel un film carbonisé est formé sur la surface de l'oxyde métallique, et un procédé de fabrication de celui-ci. Tout d'abord, une étape de prétraitement est effectuée dans laquelle des courants-jets d'une solution contenant des nanotubes de carbone sont amenés à entrer en collision l'un avec l'autre de façon à au moins partiellement séparer et disperser des faisceaux de nanotubes de carbone. Ensuite, une étape de fabrication d'un premier composite est effectuée, dans laquelle les nanotubes de carbone qui ont subi l'étape de prétraitement et un alcoolate métallique qui est la matière de départ pour des nanoparticules d'oxyde métallique sont dispersés et mélangés par l'application d'une contrainte de cisaillement et d'une force centrifuge dans un récipient de réaction de filage. Ensuite, le composite est fabriqué par réalisation d'une étape dans laquelle une contrainte de cisaillement et une force centrifuge sont appliqués au premier composite et un réactif dans un récipient de réaction de filage pour former des nanoparticules d'oxyde métallique qui sont hautement dispersées et supportées sur les nanotubes de carbone dispersés.
PCT/JP2012/075233 2011-09-30 2012-09-28 Composite oxyde métallique et nanotubes de carbone, son procédé de fabrication et électrode et élément électrochimique l'utilisant WO2013047832A1 (fr)

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JP2019129142A (ja) * 2018-01-23 2019-08-01 ツィンファ ユニバーシティ 電池電極の製造方法
JP2019186188A (ja) * 2018-04-03 2019-10-24 ツィンファ ユニバーシティ 電池電極、電池電極の製造方法およびハイブリッドエネルギー貯蔵装置
CN111247095A (zh) * 2017-10-30 2020-06-05 霓达株式会社 碳纳米管分散液及其制造方法
JP7504291B2 (ja) 2022-03-07 2024-06-21 寧徳新能源科技有限公司 二次電池及び電子装置

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JP6271865B2 (ja) * 2013-05-24 2018-01-31 日本ケミコン株式会社 蓄電デバイスの電極材料の製造方法
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JP2015050170A (ja) * 2013-09-04 2015-03-16 日本ケミコン株式会社 電極材料、該電極材料を備えた蓄電デバイス及び電極材料の製造方法
JP2016072144A (ja) * 2014-09-30 2016-05-09 日本ケミコン株式会社 電極、電気化学デバイス及び電極の製造方法
CN110299516B (zh) * 2019-06-10 2022-05-10 天津大学 碳纳米管阵列负载钛酸锂柔性电极材料的制备方法
CN113785422A (zh) * 2019-10-04 2021-12-10 株式会社Lg新能源 电极和包括该电极的二次电池
JP7457228B1 (ja) 2023-06-30 2024-03-28 ａｒｔｉｅｎｃｅ株式会社 二次電池電極用複合物の製造方法

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CN105696090B (zh) * 2016-02-19 2018-04-17 江苏亿茂滤材有限公司 一种空气过滤碳纳米管纤维膜的制备方法
CN111247095A (zh) * 2017-10-30 2020-06-05 霓达株式会社 碳纳米管分散液及其制造方法
CN111247095B (zh) * 2017-10-30 2023-09-05 霓达株式会社 碳纳米管分散液及其制造方法
JP2019129142A (ja) * 2018-01-23 2019-08-01 ツィンファ ユニバーシティ 電池電極の製造方法
JP2019186188A (ja) * 2018-04-03 2019-10-24 ツィンファ ユニバーシティ 電池電極、電池電極の製造方法およびハイブリッドエネルギー貯蔵装置
JP7504291B2 (ja) 2022-03-07 2024-06-21 寧徳新能源科技有限公司 二次電池及び電子装置

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