WO2012133599A1 - Composé de manganèse et complexe de carbone, son procédé de production et élément électrochimique mettant en œuvre ledit complexe - Google Patents

Composé de manganèse et complexe de carbone, son procédé de production et élément électrochimique mettant en œuvre ledit complexe Download PDF

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WO2012133599A1
WO2012133599A1 PCT/JP2012/058273 JP2012058273W WO2012133599A1 WO 2012133599 A1 WO2012133599 A1 WO 2012133599A1 JP 2012058273 W JP2012058273 W JP 2012058273W WO 2012133599 A1 WO2012133599 A1 WO 2012133599A1
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composite
manganese
manganese compound
carbon
complex
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English (en)
Japanese (ja)
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勝彦 直井
吉幸 五十嵐
和子 直井
賢次 玉光
修一 石本
大介 米倉
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国立大学法人東京農工大学
有限会社ケー・アンド・ダブル
日本ケミコン株式会社
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Priority to JP2013507705A priority Critical patent/JP5916021B2/ja
Publication of WO2012133599A1 publication Critical patent/WO2012133599A1/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
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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 manganese compound and carbon, a method for producing the composite, an electrode using the composite, and an electrochemical element.
  • the inventions described in these patent documents are dispersed and supported on carbon by a method (generally called mechanochemical reaction) that promotes a chemical reaction by applying shear stress and centrifugal force to a reactant in a rotating reactor.
  • Lithium titanate is obtained.
  • titanium alkoxide and lithium acetate which are starting materials of lithium titanate, carbon such as carbon nanotube and ketjen black, acetic acid, and the like are used as the reactant.
  • Electrodes using carbon carrying lithium titanate nanoparticles described in these patent documents exhibit excellent output characteristics, but recently, in this type of electrode, the output characteristics have been further improved and the electric conductivity has been improved. There is a demand to improve. It is also desired to use a manganese compound that is more readily available instead of lithium titanate.
  • the present invention has been proposed to solve the above-described problems of the prior art, and its object is to provide an electrode or an electrochemical device that can achieve output characteristics and high energy density.
  • the object is to provide a composite of a compound and carbon, 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 present invention is characterized by comprising a manganese compound having a sub-nano-sized tunnel structure of 2 to 8 mm and carbon.
  • the manganese oxide is a ramsdellite type manganese oxide having a 1 ⁇ 2 tunnel structure and / or a cryptomelan type manganese oxide having a 2 ⁇ 2 tunnel structure.
  • the complex contains either MnOOH or Mn 3 O 4 .
  • the carbon is ketchin black.
  • the manganese oxide includes a todorokite type manganese oxide having a 3 ⁇ 3 tunnel structure.
  • the present invention relates to a method for producing a composite of a manganese compound and carbon, wherein a solution containing a manganese compound as a starting material and carbon powder is reacted by applying shear stress and centrifugal force in a rotating reaction vessel. It has the 1st composite process which produces
  • a large-capacity charge / discharge characteristic can be expressed by a composite of a manganese compound having a tunnel structure and carbon.
  • 6 is a graph showing a charging curve at the 10th cycle of the composites of Examples 1 to 4 and Comparative Examples 1 and 2 of the present invention.
  • 4 is a graph showing the results of crystal structure analysis by XRD performed on the composites of Examples 1 to 3 of the present invention.
  • 4 is a graph showing the results of crystal structure analysis by XRD performed on the composites of Examples 1 to 3 of the present invention.
  • 4 is a graph showing the results of crystal structure analysis by XRD performed on the composites of Examples 1 to 3 of the present invention.
  • 4 is a graph showing the results of crystal structure analysis by XRD performed on the composites of Examples 1 to 3 of the present invention.
  • FIG. 1 is a block diagram showing a work procedure of the present embodiment.
  • the manganese compound and carbon powder composite according to the present embodiment is prepared by using an ultracentrifugal force treatment (Ultra-Centrifugal force), which is one of mechanochemical reactions, in an aqueous solution. processing method: hereinafter referred to as UC treatment), and the product is washed and filtered, and then heat treated.
  • Ultra-Centrifugal force Ultracentrifugal force treatment
  • the composite of this embodiment has a sub-nano-sized tunnel structure.
  • This tunnel structure is a collection of a plurality of octahedral manganese oxide tubes.
  • the tunnel portion is provided with a cavity corresponding to 1 to 3 manganese compounds.
  • Specific examples of the sub-nano-sized tunnel structure include a manganese compound having ramsdellite, which is a 1 ⁇ 2 tunnel structure, cryptomelane, which is a 2 ⁇ 2 tunnel structure, or cryptomelane, which is a 3 ⁇ 3 tunnel structure.
  • FIG. 2 to 4 are diagrams showing the shape of the manganese compound of the present embodiment.
  • FIG. 2 shows the structure of 1 ⁇ 2 ramsdelite.
  • Ramsdellite is a tube formed of a manganese compound, and has a tunnel structure of (one manganese compound) ⁇ (two manganese compounds) inside the tube.
  • FIG. 3 shows the structure of 2 ⁇ 2 cryptomelan.
  • Cryptomeran is a tube formed of a manganese compound, and has a tunnel structure of (two manganese compounds) ⁇ (two manganese compounds) inside the tube.
  • FIG. 4 shows the structure of 3 ⁇ 3 cryptomelane.
  • Cryptomelene is a tube formed of a manganese compound, and has a tunnel structure of (3 manganese compounds) ⁇ (3 manganese compounds) inside the tube.
  • One side of the tunnel structure of each manganese oxide is 2.732 mm ⁇ 4.680 mm with 1 ⁇ 2 MnO 2 ramsdelite and 4.711 mm ⁇ 4.711 mm with 2 ⁇ 2 MnO 2 cryptomelane. . Therefore, the range suitable as one side of the tunnel of the manganese oxide of this embodiment is a range of 2 to 8 mm.
  • This tunnel structure causes surface adsorption to the tunnel structure at a high potential during charging and discharging. If the tunnel diameter is outside the range of 2 to 8 mm, surface adsorption to the tunnel structure does not occur efficiently, and charge / discharge capacity is reduced.
  • the UC process used in the embodiment 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.
  • Ultra-high pressure dispersion treatment In the ultra-high pressure dispersion 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 a mixed solution of carbon material pressurized by a high-pressure pump is sprayed from each nozzle to cause a frontal collision in the chamber. Thereby, the bundle of carbon materials having a fiber structure can be pulverized, dispersed and homogenized. As an example, the treatment is performed at a pressure and concentration of 200 MPa, 3 Pass, 0.5 g / l.
  • manganese compounds As the manganese compound used in the present embodiment, a manganese compound having a valence of manganese of 2 ⁇ x ⁇ 4 and a manganese compound having 4 ⁇ x ⁇ 7 are used. Each manganese compound may be an anhydride or a hydrate.
  • Manganese compounds having a valence of manganese of 2 ⁇ x ⁇ 4 are used as starting materials. Specifically, the following divalent manganese compounds can be used as manganese compounds having a valence of manganese of 2 ⁇ x ⁇ 4.
  • Manganese acetate Mn (CH 3 CO 2 ) 2 Manganese acetate tetrahydrate Mn (OAc) 2 ⁇ 4H 2 O
  • Manganese formate Mn (COO) 2
  • Manganese oxalate MnC 2 O 4
  • Manganese tartrate MnC 4 H 4 O 6
  • Manganese oleate Mn (C 17 H 33 COO) 2
  • Manganese chloride MnCl 2
  • Manganese fluoride MnF 2
  • Manganese iodide MnI 2
  • Manganese hydroxide Mn (OH) 2
  • Manganese sulfide MnS
  • Manganese carbonate MnCO 3
  • Manganese perchlorate Mn (ClO 4 ) 2
  • Manganese sulfate MnSO 4
  • Manganese nitrate Mn (NO 3 ) 2
  • Manganese phosphate Mn
  • a manganese compound having a valence of manganese of 4 ⁇ x ⁇ 7 is used as a material to be further compounded with respect to the complex of the intermediate product that has undergone the complexing process when the UC process is performed a plurality of times.
  • the following 7-valent manganese compounds can be used as manganese compounds having a valence of manganese of 4 ⁇ x ⁇ 7.
  • Calcium permanganate Ca (MnO 4 ) 2
  • Carbon particles By adding predetermined carbon particles in the course of the reaction, a complex of a manganese compound and carbon particles can be obtained. That is, a manganese compound is introduced into the inner cylinder of the reactor, and the inner cylinder is swirled to mix and disperse the carbon particles. Further, the manganese compound is added and mixed while the inner cylinder is swung. By heating this after completion of the reaction, a complex of manganese compound having a sub-nanosize tunnel structure and carbon can be formed.
  • carbon particles having a hollow shell-like structure can be used.
  • CNT carbon nanotubes
  • CNF carbon nanofibers
  • KB ketjen black
  • solvent As the solvent, alcohols, water, or a mixed solvent 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.
  • a composite of a manganese compound having a sub-nanosize tunnel structure and carbon particles is obtained by a mechanochemical reaction, and the composite is heated in a vacuum to promote the tunnel structure of the manganese compound. , To improve the capacity and output characteristics of electrodes and electrochemical devices using this composite.
  • heating is performed in a temperature range of 100 ° C. to 200 ° C. in a vacuum.
  • aggregation of the manganese compound can be prevented, and a manganese oxide having a tunnel structure can be obtained.
  • the temperature during the heat treatment is 100 ° C. or lower, amorphous manganese oxide is formed, and tunnel structure manganese oxide is not generated.
  • the temperature at the time of heat treatment exceeds 200 ° C., the aggregation of particles proceeds, the diameter of the tunnel structure decreases, the tunnel structure collapses, and the charge / discharge capacity decreases.
  • Electrode The composite of manganese compound and carbon particles obtained by the present invention is kneaded with a binder, molded, and can be used as an electrode of an electrochemical element, that is, an electrode for storing electrical energy, the electrode having high output characteristics, Shows high capacity characteristics.
  • Such an electrode is an electrode formed by adding polyvinylidene fluoride (PVdF) as a binder to a composite of a manganese compound and carbon particles and forming a film on a copper current collector.
  • PVdF polyvinylidene fluoride
  • Li metal for the counter electrode of this electrode and using 1.0 MLiPF 6 / EC DEC (1: 1) as the electrolyte, a coin cell can be obtained.
  • FIG. 8 shows the state of the surface of the composite by HR-TEM before charge and discharge and at the 10th cycle when the composite is used as an electrode.
  • no polymer is present around the manganese oxide before the first cycle charge.
  • the electrolyte around the electrode becomes a polymer and is stabilized.
  • the UC-treated carbon particles are taken into the polymer as a graphene layer.
  • the polymer layer undergoes a redox reaction while maintaining the polymer layer stabilized in the first cycle.
  • a part of this polymer layer undergoes a reversible reaction during charge / discharge, but is generally stabilized. That is, after the polymer layer is stabilized through a charge / discharge cycle, the growth is suppressed and a certain shape is maintained.
  • composition ratio In the composite of manganese oxide and carbon particles, the composition ratio of manganese oxide and carbon particles is 70:30 to 12:88, preferably 65:35 to 12:88. This is because if the amount of manganese oxide is larger than this range, the composite is not refined and the graphene layer is not distributed in the polymer.
  • 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.
  • the electrode of the present invention can occlude and desorb metal ions, and operates as a negative electrode and a positive electrode. Therefore, an electrochemical capacitor and a battery can be configured by using an electrolytic solution containing metal ions and using activated carbon, carbon or metal oxides that occlude and desorb metal ions as a counter electrode.
  • manganese acetate tetrahydrate (Mn (OAc) 2 ⁇ 4H 2 O) was used as the manganese compound with manganese valence of 2 ⁇ x ⁇ 4 as shown in FIG.
  • Potassium permanganate (KMnO 4 ) was used as a manganese compound having a number 4 ⁇ x ⁇ 7.
  • composites of Examples 1 to 4 and Comparative Examples 1 and 2 were prepared by changing the addition amounts of Mn (OAc) 2 .4H 2 O and KMnO 4 to 500 mg of KB, and the characteristics of the composites Compared.
  • Examples 1 to 4 and Comparative Examples 1 and 2 were synthesized as follows. (1) Add 20mL of distilled water to Mn (OAc) 2 ⁇ 4H 2 O and apply ultrasonic treatment for 5 minutes. (2) After sonication, 500 mg of KB and 15 mL of distilled water are added and subjected to UC treatment for 5 minutes to produce a first complex which is an intermediate product. (3) Add 10mL of distilled water to KMnO 4 and apply ultrasonic treatment for 5 minutes. (4) Add 10 mL of distilled water to the first composite subjected to the above treatment and KMnO 4 and perform UC treatment for 3 minutes. (5) Further, after washing and filtration, the first vacuum drying at 100 ° C for 12 hours and the second vacuum drying at 130 ° C for 12 hours to synthesize the final product manganese compound and KB complex did.
  • PVdF Polyvinylidene fluoride
  • a film was formed on a copper current collector to produce an electrode.
  • Li metal was used, and 1.0MLiPF 6 / EC DEC (1: 1) was used as an electrolytic solution to produce a 2032 coin cell.
  • the coin cell was charged and discharged at a current density of 200 mAg ⁇ 1 and 0.0 to 2.5 V, and the charge / discharge characteristics were evaluated.
  • FIGS. 12 and 13 are diagrams showing the charge / discharge characteristics of electrodes using the composites of Examples 1 to 4 and Comparative Examples 1 and 2.
  • FIG. FIG. 12 is a diagram showing a discharge curve at the 10th cycle.
  • FIG. 13 is a diagram showing a charging curve at the 10th cycle.
  • the discharge capacity of Comparative Example 2 in which the composition ratio of the complex of manganese compound and KB is 0: 100 is about 680 mAhg ⁇ 1 .
  • the charging capacity per composite of Comparative Example 2 is 586 mAhg- 1 .
  • Comparative Example 1 in which the composition ratio of the manganese compound and KB is 90:10 it can be seen that the charge / discharge capacity per complex is lower than the value in Comparative Example 2.
  • the charge capacity per composite of Examples 1 to 3 having a composition ratio in the range of 29:71 to 65:35 exceeds the value of Comparative Example 2.
  • Example 4 where the composition ratio of the manganese compound and KB is 12:88 it can be seen that the charge / discharge capacity per complex shows the same value as that of Comparative Example 2.
  • the charge / discharge capacity per composite is improved by adjusting the amount of the manganese compound and KB so that the composition ratio of the manganese compound and KB is 12:88 to 65:35. .
  • Crystal structure analysis by XRD 14 to 16 are diagrams showing the results of crystal structure analysis by XRD (X-ray powder diffraction method) performed on the composites of Examples 1 to 3.
  • FIG. 1 A diagram showing the results of crystal structure analysis by XRD (X-ray powder diffraction method) performed on the composites of Examples 1 to 3.
  • FIG. 1 A diagram showing the results of crystal structure analysis by XRD (X-ray powder diffraction method) performed on the composites of Examples 1 to 3.
  • FIG. 14 shows a 2 ⁇ 2 MnO 2 cryptomelane peak in Example 1. This is because the amount of potassium contained in the manganese source is increased by increasing the amount of manganese compound relative to KB. This is because the crystal structure of the composite is reduced.
  • Example 3 the peak of 1 ⁇ 2 MnO 2 ramsdelite is observed in Example 3. This is because the amount of potassium contained in the manganese source is increased by reducing the amount of manganese compound relative to KB. This is because the crystal structure of the composite is reduced. Further, as shown in FIG. 16, in Example 2, the crystal structure of the composite is a polymorph of two crystal structures. This difference in crystal structure between 2 ⁇ 2 MnO 2 cryptomelan and 1 ⁇ 2 MnO 2 ramsdellite is due to the difference in potassium of the manganese source. Due to the template effect of potassium as the manganese source, a composite of a manganese compound having a porous structure and carbon is formed.
  • Mn 3 O 4 is present in the crystal structures of Examples 2 and 3 .
  • MnOOH is present in the crystal structure of Example 3. That is, from the measurement result of FIG. 17, it is desirable that the complex having the crystal structure of this example includes any one of MnOOH and Mn 3 O 4 .
  • FIG. 18 is a diagram showing the state of the surface of the composite by HR-TEM during charge and discharge in the first cycle when the composite of Example 2 is used as an electrode, and the capacity and potential per composite. .
  • FIG. 17 it can be seen that manganese oxide is acicular and no film is formed around it when the potential is 2.5 V to 0.7 V during the first cycle discharge.
  • FIG. 18 by continuing the discharge from 0.7 V to 0 V, the formation of a remarkable polymer layer is observed on the surface of the composite when it reaches 0 V.
  • FIG. 18 it can be seen that a part of the polymer layer undergoes a reversible reaction by charging from 0 V to 2.5 V.
  • FIG. 19 is a graph showing the capacity developed during charge / discharge at the 10th cycle in the composites of Examples 1 to 3 and Comparative Example. In each of the examples and comparative examples, capacity development occurs because different reactions become main in the high potential region, the plateau region, and the low potential region.
  • FIG. 20 is a diagram showing the discharge cycle characteristics of the composite. From FIG. 20, in all the composites of Examples 1 to 4, the charge capacity per composite is larger than that of Comparative Example 1 even when the number of cycles exceeds 100. In particular, in Example 1, it turns out that charging / discharging capacity
  • the composite obtained by the present invention can be kneaded and molded with a binder to form an electrode for an electrochemical element, that is, an electrode for storing electrical energy.
  • This electrode can be used as a lithium ion secondary battery. It can form by providing the composite_body
  • a conductive material such as platinum, gold, nickel, aluminum, titanium, steel, or carbon can be used.
  • any shape such as a film shape, a foil shape, a plate shape, a net shape, an expanded metal shape, and a cylindrical shape can be adopted.
  • the active material layer is formed using a mixed material obtained by adding a binder, a conductive material, or the like to the composite which is the electrode active of the present invention as necessary.
  • binder known binders such as polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, and carboxymethyl cellulose are used.
  • the binder content is preferably 1 to 30% by mass with respect to the total amount of the mixed material. If it is 1% by mass or less, the strength of the active material layer is not sufficient, and if it is 30% by mass or more, disadvantages such as a decrease in the discharge capacity of the negative electrode and an excessive internal resistance occur.
  • the conductive material carbon powder such as carbon black, natural graphite, and artificial graphite can be used.
  • a salt that generates lithium ions when dissolved in an organic electrolytic solution can be used without any particular limitation.
  • LiPF 6, LiBF 4, LiClO 4, LiN (CF3SO2) 2, LiCF 3 SO 3, LiC (SO 2 CF 3) 3, LiN (SO 2 C 2 F 5) 2, LiAsF 6, LiSbF 6, or their A mixture of these can be suitably used.
  • a quaternary ammonium salt or a quaternary phosphonium salt having a quaternary ammonium cation or a quaternary phosphonium cation can be used as a solute of the nonaqueous electrolytic solution.
  • cationic represented by R1R2R3R4N + or R1R2R3R4P + and, PF6 -, BF4 -, ClO4 -, N (CF3SO3) 2 -, CF3SO3 -, C (SO2CF3 ) 3 -, N (sO 2 C 2 F 5) 2-, salts consisting of anions consisting of AsF 6- or SbF 6-, or be suitably used a mixture thereof it can.
  • a known positive electrode active material can be used without particular limitation.
  • complex oxides of lithium and transition metals such as LiMn 2 O 4 , LiMnO 2 , LiV 3 O 5 , LiNiO 2 , LiCoO 2 , sulfides such as TiS 2 and MoS 2 , selenides such as NbSe 3 , Cr 3 Transition metal oxides such as O 8 , V 2 O 5 , V 5 O1 3 , VO 2 , Cr 2 O 5 , MnO 2 , TiO 2 , MoV 2 O 8 , polyfluorene, polythiophene, polyaniline, polyparaphenylene, etc.
  • the conductive polymer can be used.
  • the composite for the positive electrode can be formed using a mixed material in which the binder, the conductive material and the like exemplified for the negative electrode are added to the positive electrode active material as necessary.
  • the positive electrode active material and other additives as necessary are dispersed in a solvent in which a binder is dissolved, and the obtained dispersion is applied to the negative electrode by a doctor blade method or the like. It can be made by coating and drying.
  • a solvent may be added to the obtained mixed material as necessary to form into a predetermined shape, and may be pressure-bonded on the current collector.
  • the composite of the present invention is suitable not only as a lithium ion secondary battery but also as a negative electrode active material for a hybrid capacitor.
  • activated carbon, carbon nanotubes, mesoporous carbon, etc. are used as the positive electrode active material, and lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 are dissolved in non-aqueous solvents such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate.
  • non-aqueous solvents such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate.

Abstract

La présente invention concerne un composé de manganèse et un complexe de carbone permettant de former une électrode et un élément électrochimique qui présentent des caractéristiques de sortie et une densité d'énergie élevées. L'invention concerne en outre un procédé de production du composé de manganèse et du complexe de carbone. Le procédé de formation dudit complexe, qui comprend un composé de manganèse et du carbone présentant une structure tunnel de taille subnanométrique allant de 2 à 8 Å, comprend une première étape de formation de complexe à laquelle une poudre composite est produite par une réaction générée en appliquant une contrainte de cisaillement et une force centrifuge à une solution contenant une matière première à base de composé de manganèse et de poudre de carbone à l'intérieur d'une cuve de réaction rotative. De plus, le procédé de formation dudit complexe comprend une étape de chauffage à laquelle la poudre composite qui a subi l'étape de formation de complexe subit un traitement thermique sous vide. Ledit complexe contient un des éléments suivants : MnO, MnOOH ou Mn3O4. Par ailleurs, il est possible d'utiliser du noir de carbone Ketjen Black pour les particules de carbone.
PCT/JP2012/058273 2011-03-28 2012-03-29 Composé de manganèse et complexe de carbone, son procédé de production et élément électrochimique mettant en œuvre ledit complexe WO2012133599A1 (fr)

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CN112908729A (zh) * 2021-02-05 2021-06-04 广州金立电子有限公司 一种电容器的电极材料及其制备方法

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