WO2014098007A1 - Matière d'électrode, dispositif d'accumulation d'électricité pourvu d'une matière d'électrode et procédé de production d'une matière d'électrode - Google Patents

Matière d'électrode, dispositif d'accumulation d'électricité pourvu d'une matière d'électrode et procédé de production d'une matière d'électrode Download PDF

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WO2014098007A1
WO2014098007A1 PCT/JP2013/083568 JP2013083568W WO2014098007A1 WO 2014098007 A1 WO2014098007 A1 WO 2014098007A1 JP 2013083568 W JP2013083568 W JP 2013083568W WO 2014098007 A1 WO2014098007 A1 WO 2014098007A1
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electrode
electrode material
cobalt oxide
lithium cobalt
carbon material
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English (en)
Japanese (ja)
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智志 久保田
修一 石本
賢次 玉光
勝彦 直井
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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of 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
    • H01M4/36—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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 an electrode material in which an electrode active material is supported on a carbon material, a method for producing the electrode material, and an electricity storage device including the electrode material.
  • lithium cobalt oxide is used as the electrode active material.
  • Lithium ion secondary batteries that use non-aqueous electrolytes with high energy density are widely used as the power source for information devices such as mobile phones and laptop computers.
  • the performance of these information devices and the amount of information handled In order to cope with an increase in power consumption associated with an increase in the energy consumption, an improvement in the energy density of the lithium ion secondary battery is desired.
  • low-emission vehicles such as electric vehicles and hybrid vehicles that replace gasoline and teal vehicles. Expectations are increasing, and it is desired to develop a large lithium ion secondary battery having a high energy density as a motor drive power source for these low-pollution vehicles.
  • Patent Document 1 discloses a secondary battery using LiCoO 2 as a positive electrode active material and carbon as a negative electrode.
  • Patent Document 2 discloses a lithium ion secondary battery in which lithium cobaltate powder has a particle size distribution of 1 to 40 ⁇ m and a specific range such as an average particle size of 5 to 15 ⁇ m in order to improve charge / discharge characteristics such as rate characteristics. It is disclosed.
  • lithium cobaltate which is a positive electrode active material as described above
  • the output characteristics of lithium cobaltate are not always satisfactory.
  • lithium cobaltate is made into fine particles and the particle size distribution and particle size are in a specific range, so that deterioration of charge / discharge characteristics can be suppressed by a homogeneous electrolytic reaction.
  • the output characteristics have not been improved only by adjusting the particle size of the particles.
  • an object of the present invention is to provide an electrode material that provides a lithium ion secondary battery having good output characteristics even when lithium cobalt oxide is used as a positive electrode active material, an electricity storage device including the electrode material, and an electrode material. It is to provide a manufacturing method.
  • the present invention provides an electrode material in which a lithium cobalt oxide is supported on a carbon material, and the electrode material has an electrode density in a range of 2.5 g / cc or less.
  • an electricity storage device including an electrode formed using this electrode material is also one embodiment of the present invention.
  • the manufacturing method of this invention includes the following processes. (1) A precursor supporting step of supporting a precursor of lithium cobalt oxide on a carbon material by applying shear stress and centrifugal force to a reaction liquid containing a material source of lithium cobalt oxide and a carbon material; (2) A heat treatment step in which a precursor of lithium cobalt oxide supported on the carbon material is subjected to heat treatment to obtain a lithium cobalt oxide supported on the carbon material and nanonized. An electrode material having an electrode density of 2.5 g / cc or less is manufactured by the above steps (1) and (2).
  • the heat treatment step is preferably performed in an atmosphere containing oxygen.
  • 3 is a flowchart showing a manufacturing process of an electrode material in which LiCoO 2 is supported on a carbon material (KB) according to Example 1; Is a SEM ( ⁇ 10k) image of the electrode material was supported LiCoO 2 carbon material (KB) in Example 3. Is a SEM ( ⁇ 50k) image of the electrode material was supported LiCoO 2 carbon material (KB) in Example 3.
  • Electrode material The lithium cobalt oxide contained in the electrode material according to the present invention is a material capable of occluding and releasing lithium, and examples include LiCo 2 and LiCo1-yNiyO 2 (0.1 ⁇ y ⁇ 0.5). . These lithium cobalt oxides may contain some subcomponent elements (transition metals such as Ti, Nb, Sn, and Mg).
  • any carbon material having conductivity can be used without any particular limitation.
  • Examples include carbon black such as ketjen black (hereinafter referred to as KB), acetylene black and channel black, fullerene, carbon nanotube, carbon nanofiber (hereinafter referred to as CNF), amorphous carbon, carbon fiber, natural graphite, artificial graphite, Examples thereof include graphitized ketjen black, activated carbon, and mesoporous carbon.
  • vapor grown carbon fiber can be used.
  • the carbon material may be used alone or in combination of two or more.
  • a fibrous carbon material and a spherical carbon material are used in combination in order to improve output characteristics. It is preferable to do. It is preferable that at least a part of the carbon material is a carbon nanotube or a carbon nanofiber. This is because a highly conductive electrode material can be obtained.
  • the particle diameter of the carbon material is preferably in the range of 10 nm to 300 nm, more preferably in the range of 10 to 100 nm, and particularly preferably in the range of 10 to 50 nm.
  • the lithium cobalt oxide is supported on the carbon material as nanoparticles.
  • the nanoparticle has nano-level primary particles. Nanoparticles are those having a diameter of 5 to 500 nm or less in a lump such as a circle, ellipse or polygon.
  • the lithium cobalt oxide has a lithium cobalt oxide primary particle size of 110 to 500 nm (large particles) and a particle size of less than 5 to 110 nm.
  • Lithium cobalt oxide (small particles) is supported on a carbon material. Small particles may be supported on the surface of large particles.
  • the size of the lithium cobalt oxide nanoparticles of the present invention is 5 to 500 nm, and large particles and small particles are distributed and mixed therein. That is, the particle size distribution is polydispersed. Large particles are distributed so that the particle size distribution has a maximum value in the range of 110 to 500 nm, and small particles have a maximum particle size distribution in the range of 5 to 110 nm. Distributed.
  • the lithium cobalt oxide having different particle size distribution is supported on the carbon material as the primary particles of the lithium cobalt oxide, whereby the density of the electrode layer can be increased and the capacity can be increased.
  • the particle size of the primary particles is a value obtained by observing the electrode material with an SEM, selecting randomly large particles and small particles, and measuring the particle size. In Examples described later, the particle diameter of the nanoparticles was determined by this method.
  • lithium cobalt oxide is contained in an amount of 60 wt% or more in the electrode material, and the carbon material is contained in 40 wt% or less.
  • a high energy density electrode material can be obtained by blending lithium cobalt oxide in a proportion of 70 wt% or more and a carbon material in a proportion of 30 wt% or less.
  • the carbon material a spherical carbon material and a fibrous carbon material may be mixed.
  • the capacity can be improved by mixing spherical KB and fibrous CNF.
  • This electrode material is obtained as a powder, and the electrode material powder is kneaded with a predetermined solvent and a binder to form an electrode that stores electrical energy.
  • This electrode can be used for an electrochemical capacitor or a battery using an electrolytic solution containing lithium. That is, an electrode made of this secondary battery or capacitor electrode material can occlude and desorb lithium ions and operates as a positive electrode.
  • An example of a manufacturing process of an electrode material in which lithium cobalt oxide is supported on the carbon material of the present embodiment includes the following steps a) to c).
  • a heat treatment step including a step of heat-treating a precursor of lithium cobalt oxide supported on the carbon material to obtain a nano cobaltized lithium cobalt oxide supported on the carbon material.
  • supported lithium cobalt oxide on the obtained carbon material is the range of 2.5 g / cc or less.
  • (A) Adjustment Step In the adjustment step, at least one compound containing a metal that is a material source of lithium cobalt oxide (hereinafter referred to as “material source”) and a carbon material are added to a solvent, and a material source is added. Is dissolved in a solvent to obtain a reaction solution.
  • material source a material source of lithium cobalt oxide
  • any liquid that does not adversely affect the reaction can be used without particular limitation, and water, methanol, ethanol, isopropyl alcohol, and the like can be preferably used. Two or more solvents may be mixed and used.
  • Examples of the compound containing a metal which is a material source of lithium cobalt oxide include the following.
  • Lithium source Lithium hydroxide (LiOH.H 2 O) can be used.
  • lithium compounds such as lithium acetate, lithium carbonate, and lithium nitrate can be used.
  • Cobalt source Cobalt acetate (Co (CH 3 COO) 2 .4H 2 O) can be used.
  • cobalt compounds such as cobalt nitrate, cobalt sulfate, and cobalt chloride can also be used.
  • the precursor supporting step is a step of supporting a precursor of lithium cobalt oxide on the surface of the carbon material.
  • the reactor shown in FIG. 2 is swirled to apply a shear stress and a centrifugal force to the reaction solution (hereinafter referred to as “UC treatment”). Load the source.
  • the reaction vessel comprises 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 turning.
  • the reaction solution is introduced into the inner cylinder 2 of the reactor, and the inner cylinder 2 is turned so that the cobalt source and the carbon material, which are the reactants in the inner cylinder 2 by the centrifugal force, pass through the through-hole 2-1 of the inner cylinder. And moves to the inner wall 1-3 of the outer cylinder.
  • the reaction product collides with the inner wall 1-3 of the outer cylinder by the centrifugal force of the inner cylinder 2, and forms a thin film and slides up to the upper part of the inner wall 1-3.
  • both the shear stress between the inner wall 1-3 and the centrifugal force from the inner cylinder are simultaneously applied to the reactant, and a large mechanical energy is applied to the thin-film reactant.
  • This mechanical energy seems to be converted into chemical energy required for the reaction, so-called activation energy, but the reaction proceeds in a short time.
  • shear stress and centrifugal force are applied to the cobalt source and the carbon material to adsorb at least a part of the cobalt source to the carbon material.
  • 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 required to produce this thin film is 1500 N (kgms -2) or more, preferably 60000N (kgms -2) or more, more preferably 270000N (kgms -2) or more.
  • a lithium source is further added to the reaction solution, and a second UC treatment is performed to cause a mechanochemical reaction to generate a precursor of lithium cobalt oxide on the carbon material.
  • alkali metal hydroxide lithium hydroxide, sodium hydroxide, etc.
  • the cobalt source reacts to become a hydroxide, and the loading efficiency on the carbon material is improved.
  • the lithium source can be contained in the reaction solution and subjected to the UC treatment.
  • the lithium source may be mixed during the heat treatment step described later.
  • the mixing process of the lithium source can be simultaneously performed by the UC process, it is preferable to mix together at the precursor supporting step.
  • the heat treatment step is a step of synthesizing and crystallizing a precursor of lithium cobalt oxide supported on a carbon material.
  • a hydrothermal synthesis method which is a method for synthesizing a compound and growing a crystal in the presence of high-pressure steam, can be used.
  • This hydrothermal synthesis is carried out in saturated steam by charging the aqueous raw material solution into an autoclave, heating it under pressure.
  • the heating temperature is usually 110 to 300 ° C. although it depends on the type of metal salt used as a raw material. Pressurization is simultaneously performed by heating in a closed container.
  • the internal pressure of the autoclave is generally determined by the temperature, but it may be positively pressurized and is preferably about 1.1 to 84.8 atm.
  • a lithium cobalt oxide precursor is synthesized and crystallized.
  • a carbon material oxidizes and disappears when the temperature exceeds 300 ° C. in an atmosphere containing oxygen.
  • the precursor of lithium cobalt oxide can be synthesized and crystallized at 300 ° C. or lower, and thus can be performed in an atmosphere containing oxygen. This is particularly effective in lithium cobalt oxide that requires oxygen in the heat treatment step.
  • it is possible to synthesize and crystallize a lithium cobalt oxide precursor at a relatively low temperature of 300 ° C. or lower even a nano-level small precursor dispersed and supported on a carbon material by UC treatment can be crystallized. Thus, lithium cobalt oxide dispersed and supported on a carbon material as nanoparticles can be generated.
  • the carbon material does not disappear at a heating temperature of 110 to 300 ° C., which is a heating temperature in the hydrothermal synthesis method, and lithium cobalt oxide is dispersed and supported as nanoparticles on the surface of the carbon material.
  • an organic solvent such as alcohols (ethanol, methanol, isopropyl alcohol, etc.) or a mixed solution of these organic solvents and water is used in addition to water as a solvent to be charged into the autoclave. It can also be used.
  • the heat treatment step is performed at a relatively low temperature of 110 to 300 ° C. Therefore, even a lithium cobalt oxide precursor made of a thermodynamically unstable material can be crystallized. Similarly, a crystal having a small particle size that is more susceptible to heat than one having a large particle size can be crystallized at a low temperature.
  • the electrode material produced by this manufacturing method maintains lithium cobalt oxide as nanoparticles.
  • a battery using the electrode material as an electrode material for a lithium secondary battery or an electrical storage device such as an electrochemical capacitor achieves higher input / output and higher capacity.
  • the electrode material according to the present invention is an electrode material in which lithium cobalt oxide is supported on a carbon material, and the electrode density is increased to a range of 2.5 g / cc or less. Good results are obtained in energy density and output characteristics. In general, it is thought that increasing the electrode density increases the electrode capacity, resulting in an increase in energy density and output characteristics. However, an electrode material in which a lithium cobalt oxide is supported on a carbon material is used to increase the electrode capacity. Even if an electrode having a high density was prepared, the energy density and the rate characteristics were not improved, but it deteriorated.
  • the electrode material in which fine nano-level lithium cobalt oxide is supported on the carbon material as in the present invention has a high energy density by making the electrode density within a specific density range, and the output characteristics Gives good results. If the electrode density is less than 1.2 g / cc, the electrode density is not sufficient, and good energy density and output characteristics are not obtained. Therefore, the range of the electrode density of the present invention is preferably 1.2 g / cc or more and 2.5 g / cc or less.
  • electrode density refers to an electrode material in which lithium cobalt oxide is supported on a carbon material, N-methylpyrrolidone as a specific solvent, and polyvinylidene fluoride as a binder.
  • a slurry in which the solvent was 50 and the binder was formed at a weight ratio of 5 was applied onto an aluminum foil and dried to create an electrode layer on the aluminum foil, and the mass per unit volume of the electrode layer And Specifically, in the thickness region (volume) of the electrode layer at 1 cm 2 of the electrode layer, a value obtained by dividing the weight of the solid content including the electrode material by the volume.
  • the solid content includes polyvinylidene fluoride.
  • the electrode density of the electrode material according to the present invention is a change in the particle diameter of lithium cobalt oxide and the blending ratio of lithium cobalt oxide and carbon material (wt%), treatment conditions for hydrothermal synthesis, Other electrode materials obtained can be adjusted by performing ball milling or not.
  • the electrode material of this invention is suitable for the positive electrode of a lithium ion secondary battery. Accordingly, the present invention also provides a lithium ion secondary comprising a positive electrode having an electrode layer containing the electrode material of the present invention, a negative electrode, and a separator holding a non-aqueous electrolyte disposed between the negative electrode and the positive electrode. Provide batteries.
  • An electrode layer for the positive electrode is obtained by dispersing an electrode material in which a lithium cobalt oxide is supported on the carbon material of the present invention in a solvent (N-methylpyrrolidone, isopropyl alcohol, etc.) in which a binder is dissolved, if necessary.
  • the obtained dispersion can be prepared by coating on a current collector by a doctor blade method or the like and drying. Further, the obtained dispersion may be formed into a predetermined shape and may be pressure-bonded on the current collector.
  • a mixed material layer can also be formed by using a mixed solvent in which a metal oxide or a carbon material is further mixed and dispersed in the electrode material and binder-containing solvent of the present invention.
  • a conductive material such as platinum, gold, nickel, aluminum, titanium, steel, or carbon can be used.
  • shape of the current collector 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.
  • 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 electrode layer is not sufficient, and if it is 30% by mass or more, the discharge capacity of the negative electrode is reduced and internal resistance becomes excessive.
  • a negative electrode provided with an electrode layer containing a known negative electrode active material can be used without any particular limitation.
  • the negative electrode active material include Fe 2 O 3 , MnO, MnO 2 , Mn 2 O 3 , Mn 3 O 4 , CoO, Co 3 O 4 , NiO, Ni 2 O 3 , TiO, TiO 2 , SnO, SnO 2 , oxides such as SiO 2 , RuO 2 , WO, WO 2 , ZnO, metals such as Sn, Si, Al, Zn, composite oxides such as LiVO 2 , Li 3 VO 4 , Li 4 Ti 5 O 12 , Examples thereof include nitrides such as Li 2.6 Co 0.4 N, Ge 3 N 4 , Zn 3 N 2 , and Cu 3 N.
  • the electrode layer for the negative electrode is dispersed on the current collector by the doctor blade method or the like by dispersing the negative electrode electrode material and the conductive agent in a solvent in which a binder is dissolved as necessary. It can be created by drying. Further, the obtained dispersion may be formed into a predetermined shape and may be pressure-bonded on the current collector.
  • the description of the current collector and binder for the positive electrode also applies to the negative electrode.
  • the conductive agent carbon powder such as carbon black, natural graphite, and artificial graphite can be used.
  • a polyolefin fiber nonwoven fabric or a glass fiber nonwoven fabric is preferably used.
  • an electrolytic solution in which an electrolyte is dissolved in a non-aqueous solvent is used, and a known non-aqueous electrolytic solution can be used without any particular limitation.
  • Examples of the solvent for the non-aqueous electrolyte include electrochemically stable ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methyl sulfolane, ⁇ -butyrolactone, acetonitrile, and dimethoxyethane, N-methyl-2-pyrrolidone, dimethylformamide or a mixture thereof can be preferably 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 (CF 3 SO 2) 2, LiCF 3 SO 3, LiC (SO 2 CF 3) 3, LiN (SO 2 C 2 F 5) 2, LiAsF 6, LiSbF 6 Or a mixture thereof can be preferably used.
  • a solute of the nonaqueous electrolytic solution a quaternary ammonium salt or a quaternary phosphonium salt having a quaternary ammonium cation or a quaternary phosphonium cation can be used in addition to a salt that generates lithium ions.
  • Example 1 As shown in FIG. 3, first, a reaction liquid prepared by mixing ketjen black (KB), Co (CH 3 COO) 2 .4H 2 O, which is a cobalt source as a material source, and distilled water is prepared (adjusted). Then, the reaction solution was subjected to UC treatment for 5 minutes at a rotational speed of 50 m / s. The reaction solution that had been subjected to the UC treatment was added with LiHO.H 2 O as a lithium source, and further subjected to a UC treatment for 5 minutes at a rotational speed of 50 m / s. In this UC process, a centrifugal force of 66000 N (kgms ⁇ 2 ) is applied.
  • the first and second UC processes correspond to a precursor supporting process in which a LiCoO 2 precursor by UC process is supported on a carbon material.
  • the obtained solution is filtered and dried, further rapidly heated to 250 ° C. in an oxidizing atmosphere such as the air, and kept for 1 hour to perform a preheating treatment.
  • H 2 O the precursor prepared by the pre-heating treatment, and H 2 O 2 are added to the autoclave, hydrothermal synthesis is performed, and the mixture is held at 250 ° C. for 6 hours, and LiCoO 2 is supported on the KB.
  • An electrode material was obtained. The pressure at this time is 39.2 atmospheres. This hydrothermal synthesis corresponds to the heat treatment process. At this time, adjustment is made so that LiCoO 2 in the electrode material is 80 wt% and KB is 20 wt%.
  • an electrode material in which LiCoO 2 is supported on the obtained KB is used together with polyvinylidene fluoride (PVDF) as a binder and N-methylpyrrolidone (NMP) as a solvent (LiCoO 2 / KB / PVDF / NMP). 80: 20: 5: 50 / wt%) was dispersed to prepare an electrode slurry. This electrode slurry was put into a SUS mesh welded on a SUS plate and dried to form an electrode layer having an electrode thickness of 10 ⁇ m. E. It was.
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • a value obtained by dividing the weight of the solid content in the thickness region (volume) at 1 cm 3 of this electrode layer by the volume was measured and shown as an electrode density in Table 1 (the electrode density shown in the following examples and comparative examples is the method) ).
  • a separator and a counter electrode C. are formed on the electrode layer.
  • E. In addition, a Li foil was placed as a reference electrode, and a 1M LiPF6 ethylene carbonate / diethyl carbonate 1: 1 solution was infiltrated as an electrolyte solution to obtain a battery cell.
  • Example 2 to Example 5 In Examples 2 to 5, in the electrode material in which LiCoO 2 was supported on the KB prepared in Example 1, the treatment temperature and treatment time of hydrothermal synthesis were changed, and the electrode materials having the electrode densities shown in Table 1 were obtained. Was made. Using the electrode material, batteries of Examples 2 to 5 were produced. In Examples 2 to 5, adjustment is made so that LiCoO 2 in the electrode material is 80 wt% and KB is 20 wt%.
  • Comparative Example 1 In order to further increase the electrode density, the electrode material in which LiCoO 2 was supported on KB prepared in Example 1 was examined by changing the treatment temperature and treatment time of hydrothermal synthesis. It was difficult to produce an electrode material having an electrode density of / cc. Instead, the electrode material in which LiCoO 2 was supported on the KB prepared in Example 1 was further ball milled to increase the electrode density, and the electrode material having an increased electrode density shown in Table 1 was obtained. It was. And the battery of the comparative example 1 was created using this electrode material. The battery of Comparative Example 1 was prepared by using the same method as in Example 1 except that the electrode material subjected to densification treatment was used for the electrode layer by a ball mill.
  • the rate characteristic indicates the maintenance rate (%) of the energy density of 10C with respect to the energy density of 0.1C.
  • the battery cell using the electrode material of Comparative Example 1 has a 10C compared to the battery cell using the electrode material of Examples 1 to 5 despite the high electrode density.
  • the energy density was remarkably small, and the rate characteristics were also low.
  • the battery cell using the electrode material of Example 1 has extremely good energy density and rate characteristics, and has an energy density exceeding 200 Wh / L even in Example 1 where the electrode density is low. It was.
  • FIG. 4 shows an SEM image ( ⁇ 10 k) of an electrode material in which LiCoO 2 is supported on a carbon material (KB) before electrode preparation in Example 3.
  • FIG. 5 further shows an SEM image ( ⁇ 50 k) of the electrode material in Example 3.
  • Example 3 fine nanoparticles can be seen. Further, in FIG. 5 was observed by increasing the magnification, when observing the electrode material of Example 3, a relatively particle size large LiCoO 2 particles (particle diameter 110 ⁇ 500 nm), relatively particle size small LiCoO 2 particles (Particle diameter 5 to less than 110 nm) is supported. Some of the LiCoO 2 particles having a relatively small particle diameter are supported on the surface of the LiCoO 2 particles having a large particle diameter. It can be seen that these LiCoO 2 particles are highly dispersed at the nano level.
  • Example 6 The conditions other than the ratio of the carbon material in the electrode material of Example 3 were the same, and CNF was mixed as a carbon material in addition to KB.
  • electrode materials were obtained by changing the blending ratio of LiCoO 2 and carbon materials (KB and CNF), and batteries of Examples 6 to 8 were made using these electrode materials.
  • the ratios of LiCoO 2 , KB, and CNF in the electrode materials of Examples 6 to 8 at this time are as shown in Table 2.
  • the batteries of Examples 6 to 8 were evaluated for energy density and rate characteristics at a 10 C rate, and the results are shown in Table 2.
  • the rate characteristic indicates the maintenance rate (%) of the energy density of 10C with respect to the energy density of 0.1C.
  • the batteries of Examples 6 to 8 all had an energy density at 10 C rate exceeding 200 Wh / L, and the rate characteristics had good values. Especially, the energy density of the battery cells of Example 7 and Example 8 in which 70% by weight or more of LiCoO 2 was blended was extremely good. Moreover, it became a result that the capacity

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  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de production d'une matière d'électrode ayant des caractéristiques de sortie améliorées, et un dispositif d'accumulation d'électricité doté de la matière d'électrode. Selon l'invention, le procédé de production d'une matière d'électrode par lequel on charge une matière carbonée d'oxyde de cobalt et de lithium, fait appel : à une étape de préparation au cours de laquelle on prépare un liquide de réaction contenant la matière carbonée et des sources de matière d'oxyde de cobalt et de lithium ; une étape de charge de précurseur au cours de laquelle on charge la matière carbonée d'un précurseur d'oxyde de cobalt et de lithium par application d'une contrainte de cisaillement et d'une force centrifuge au liquide de réaction ; et une étape de traitement thermique au cours de laquelle on applique un traitement thermique à la matière carbonée chargée du précurseur, obtenant ainsi de l'oxyde de cobalt et de lithium à une échelle nanométrique. Les caractéristiques de sortie sont améliorées par fixation de la densité d'électrode de la matière d'électrode ainsi obtenue à 2,5 g/cc au maximum.
PCT/JP2013/083568 2012-12-21 2013-12-16 Matière d'électrode, dispositif d'accumulation d'électricité pourvu d'une matière d'électrode et procédé de production d'une matière d'électrode WO2014098007A1 (fr)

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JP2012-280281 2012-12-21
JP2012280281A JP6253884B2 (ja) 2012-12-21 2012-12-21 電極層、該電極層を備えた蓄電デバイス及び電極層の製造方法

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* Cited by examiner, † Cited by third party
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