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WO2018110133A1 - Électrode de batterie secondaire - Google Patents

Électrode de batterie secondaire Download PDF

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Publication number
WO2018110133A1
WO2018110133A1 PCT/JP2017/039685 JP2017039685W WO2018110133A1 WO 2018110133 A1 WO2018110133 A1 WO 2018110133A1 JP 2017039685 W JP2017039685 W JP 2017039685W WO 2018110133 A1 WO2018110133 A1 WO 2018110133A1
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WIPO (PCT)
Prior art keywords
electrode
secondary battery
conductive agent
agent
positive electrode
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English (en)
Japanese (ja)
Inventor
克 上田
純 川治
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Hitachi Ltd
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Hitachi Ltd
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Priority to CN201780075754.5A priority Critical patent/CN110121799B/zh
Priority to JP2018556242A priority patent/JP6916815B2/ja
Publication of WO2018110133A1 publication Critical patent/WO2018110133A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers

Definitions

  • the present invention relates to an electrode for a secondary battery, a secondary battery, and a method for producing them.
  • Lithium ion secondary batteries capable of realizing high voltage and high energy density are used in a wide range of applications from in-vehicle use such as electric vehicles and hybrid vehicles to personal computers and portable communication devices.
  • the central issue in the research and development of lithium ion secondary batteries is to further improve the energy density and improve the safety and reliability of the battery itself.
  • development of solid electrolyte membranes having high lithium ion conductivity has been vigorously advanced.
  • a typical example of the solid electrolyte is a solid electrolyte using an oxide or sulfide-based ceramic having lithium ion conductivity. This is characterized by high fire resistance because it does not contain the electrolyte itself.
  • electrode material particles having an average particle diameter of Da, solid particles having an average particle diameter of Db, and an ionic liquid are dispersed in a liquid medium to obtain a dispersion, and the dispersion is placed on a support.
  • a method is disclosed.
  • acetylene black is used in the electrode material particles.
  • the surface potential of the conductive material such as acetylene black is negative, lithium ions in the ionic liquid are adsorbed on the conductive material, and the secondary material is secondary. The ionic conductivity of the battery electrode may be reduced.
  • An object of the present invention is to improve the ionic conductivity of an electrode for a secondary battery.
  • a secondary battery that includes an electrode active material, an electrode conductive agent, and an ionic conductive material, the ionic conductive material is held by the electrode conductive agent, a coating is formed on the surface of the electrode conductive agent, and the surface potential of the electrode conductive agent is positive Electrode.
  • the ionic conductivity of the secondary battery electrode can be improved. Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.
  • a lithium ion secondary battery will be described as an example of an all-solid battery, but the technical idea of the present invention is not only a lithium ion secondary battery, but also a sodium ion secondary battery, a magnesium ion secondary battery, The present invention can also be applied to an aluminum ion secondary battery.
  • FIG. 1 is a cross-sectional view of a secondary battery according to an embodiment of the present invention.
  • the all-solid battery 100 includes a positive electrode 70, a negative electrode 80, a battery case 30, and a solid electrolyte layer 50.
  • the battery case 30 accommodates the solid electrolyte layer 50, the positive electrode 70, and the negative electrode 80.
  • the material of the battery case 30 can be selected from materials that are corrosion resistant to non-aqueous electrolytes, such as aluminum, stainless steel, and nickel-plated steel.
  • an electrode body composed of the positive electrode 70, the solid electrolyte layer 50, and the negative electrode 80 is laminated.
  • the positive electrode 70 includes the positive electrode current collector 10 and the positive electrode mixture layer 40.
  • a positive electrode mixture layer 40 is formed on both surfaces of the positive electrode current collector 10.
  • the negative electrode 80 includes a negative electrode current collector 20 and a negative electrode mixture layer 60. Negative electrode mixture layers 60 are formed on both surfaces of the negative electrode current collector 20.
  • the positive electrode current collector 10 and the negative electrode current collector 20 protrude outside the battery case 30, and the plurality of protruding positive electrode current collectors 10 and the plurality of negative electrode current collectors 20 are bonded together by, for example, ultrasonic bonding. As a result, a parallel connection is formed in the all solid state battery 100.
  • FIG. 2 is a cross-sectional view of a secondary battery according to an embodiment of the present invention.
  • FIG. 2 includes a plurality of positive electrode mixture layers 40, negative electrode mixture layers 60, and solid electrolyte layers 50. Outermost positive electrode mixture layer 40 and negative electrode mixture layer 60 in bipolar all solid state battery 200 in the figure are connected to positive electrode current collector 10 and negative electrode current collector 20. Further, an interconnector 90 as a current collector is disposed between the positive electrode mixture layer 40 and the negative electrode mixture layer 60 that are adjacent to each other in the battery case 30. The interconnector 90 has high electronic conductivity, no ionic conductivity, and the surface in contact with the negative electrode mixture layer 60 and the positive electrode mixture layer 40 does not exhibit a redox reaction depending on the respective potentials. Can be mentioned.
  • Materials that can be used for the interconnector 90 include materials that can be used for the following positive electrode current collector 10 and negative electrode current collector 20. Specific examples include aluminum foil and SUS foil. Alternatively, the positive electrode current collector 10 and the negative electrode current collector 20 can be bonded together by clad molding and electron conductive slurry.
  • FIG. 3 is a cross-sectional view of a main part of the secondary battery according to the embodiment of the present invention.
  • the positive electrode mixture layer 40 includes a positive electrode active material 42, a positive electrode conductive agent 43, a positive electrode binder for binding them, arbitrary inorganic particles 51, and an ionic conductive material 52.
  • the negative electrode mixture layer 60 includes a negative electrode active material 62, a negative electrode conductive agent 63, a negative electrode binder for binding them, arbitrary inorganic particles 51, and an ionic conductive material 52.
  • the solid electrolyte layer 50 has an electrolyte binder 53 and a solid electrolyte 55.
  • the solid electrolyte 55 includes inorganic particles 51 and an ion conductive material 52.
  • the positive electrode 70 and the negative electrode 80 are electrodes (secondary battery electrodes), the positive electrode conductive agent 43 or the negative electrode conductive agent 63 is an electrode conductive material, the positive electrode binder or the negative electrode binder is an electrode binder, and the positive electrode active material 42 or the negative electrode active material 62 is an electrode active material.
  • the positive electrode active material 42 or the negative electrode active material 62 is an electrode active material.
  • Electrode binder As the electrode binder, styrene-butadiene rubber, carboxymethyl cellulose, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), poly (vinylidene fluoride-co-hexafluoropropylene) copolymer (PVdF-HFP) ) And mixtures thereof, but are not limited thereto.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVdF-HFP poly (vinylidene fluoride-co-hexafluoropropylene) copolymer
  • a lithium composite oxide containing a transition metal is preferable, and specific examples include LiCoO 2 , LiNiO 2 , LiMn 2 O 4 , LiMnO 3 , LiMn 2 O 3 , LiMnO 2 , Li 4.
  • Li 2 Mn 3 MO 8 Fe, Co, Ni, Cu, Zn
  • Electrode conductive agent manufactured from conductive fibers (for example, vapor-grown carbon, carbon nanotubes, pitch (byproducts such as petroleum, coal, coal tar, etc.) and carbonized at high temperature, and acrylic fibers. Carbon fiber etc.) are preferably used.
  • the electrode conductive agent is a material having a lower electrical resistivity than the electrode active material, and does not oxidize and dissolve at the charge / discharge potential of the electrode (usually 2.5 to 4.5 V in the case of the positive electrode 70). May be used.
  • corrosion resistant metals such as titanium and gold
  • carbides such as SiC and WC
  • nitrides such as Si3N4 and BN
  • a carbon material having a high specific surface area for example, carbon black or activated carbon
  • an ionic conductive material 52 is included in the electrode. At this time, similarly to the inorganic particles 51, the ionic conductive material 52 is supported on the electrode conductive agent, whereby a semi-solid semi-solid electrolyte is formed.
  • the treatment of keeping the surface of the electrode conductive agent at a positive potential is performed. Since the surface of the electrode conductive agent such as carbon has a negative potential, lithium ions having a positive charge are adsorbed on the surface of the electrode conductive agent. Since the adsorbed lithium ions can no longer contribute to charge transport, the ionic conductivity inside the electrode decreases as a result. On the other hand, if the surface of the electrode conductive agent is a positive potential, lithium ion adsorption to the surface of the electrode conductive agent is suppressed, so that a decrease in ion conduction inside the electrode can be suppressed.
  • a surface treatment agent is introduced.
  • the coating agent is formed on the entire surface or part of the electrode conductive agent.
  • surface treatment agents include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, aminophenyltrimethoxysilane, 3-aminophenyltrimethoxysilane, and m-aminophenyl.
  • a surface treatment agent at least one of an amino group and a phosphine group is introduced onto the surface of the electrode conductive agent.
  • 3-aminopropyltriethoxysilane 3-aminopropyltri (methoxyethoxy) silane, diphenylphosphinoethyldimethylethoxysilane. Since these materials have a relatively small molecular weight of about 200 to 300, the functional groups are likely to perform thermal motion and can improve the diffusion of lithium ions. Further, since the surface treatment agent is composed of short side chains such as methyl group and ethyl group, a large number of functional groups can be imparted to the surface of the electrode conductive agent, and the surface potential can be kept higher. If the surface of the electrode conductive agent is kept at a positive potential, it may be modified with other known functional groups.
  • an electrode electrically conductive agent in combination of multiple types among surface treating agents.
  • a plurality of types of conductive materials may be used in combination as the electrode conductive agent, but at least one of the conductive materials needs to be surface-modified with a surface treatment agent.
  • the type of functional group on the surface of the electrode conductive agent can be confirmed by optical measurement such as XPS.
  • the average from the functional groups on the surface of the electrode conductive agent 0.3nm of Li ion density 1.50 nm -3 or less, even 1.10 nm -3 or less and further is 0.90 nm -3 or less.
  • the number of functional groups on the surface of the electrode conductive agent is preferably 0.01 or more and 5 or less, more preferably 0.6 or more and 2.4 or less per square nanometer.
  • the number of functional groups on the surface of the electrode conductive agent is determined by measuring the coverage from infrared spectroscopy, XPS spectrum analysis, etc., and multiplying it by the specific surface area of the electrode conductive agent.
  • the coating agent may be formed on the entire surface or part of the electrode conductive agent by coating the surface with a metal oxide or the like so that the surface potential of the electrode conductive agent becomes positive.
  • the surface area of the coating agent occupying the electrode conductive agent is preferably 30% or more and 70% or less of the total surface area of the electrode conductive agent so that the electronic conductivity of the electrode conductive agent is not reduced by the coating.
  • the surface area of the electrode conductive agent can be obtained from infrared spectroscopy, XPS spectrum analysis, or the like.
  • the positive electrode current collector 10 is preferably a low-resistance conductor having heat resistance that can withstand the heating during the secondary battery manufacturing process and the operating temperature of the secondary battery, but is not limited thereto.
  • metal foil thinness of 10 ⁇ m or more and 100 ⁇ m or less
  • perforated metal foil thinness of 10 ⁇ m or more and 100 ⁇ m or less, pore diameter of 0.1 mm or more and 10 mm or less
  • species aluminum, stainless steel, titanium, a noble metal (for example, gold, silver, platinum) etc. can be used.
  • ⁇ Positive electrode 70> A positive electrode slurry in which a positive electrode active material 42, a positive electrode conductive agent 43, a positive electrode binder, and an organic solvent are mixed is attached to the positive electrode current collector 10 by a doctor blade method, a dipping method, or a spray method, and then the organic solvent is dried. Then, the positive electrode 70 can be produced by pressure forming with a roll press. In addition, a plurality of positive electrode mixture layers 40 can be laminated on the positive electrode current collector 10 by performing a plurality of times from application to drying.
  • the positive electrode active material and the active material contain a solid electrolyte 55 and function as a conduction path for lithium ions in the positive electrode.
  • ⁇ Negative electrode active material 62 As a material of the negative electrode active material 62, for example, a carbon-based material (for example, graphite, graphitizable carbon material, amorphous carbon material), a conductive polymer material (for example, polyacene, polyparaphenylene, polyaniline, polyacetylene), A lithium composite oxide (eg, lithium titanate: Li 4 Ti 5 O 12 ), metal lithium, or a metal alloyed with lithium (eg, aluminum, silicon, tin) can be used, but is not limited thereto.
  • a carbon-based material for example, graphite, graphitizable carbon material, amorphous carbon material
  • a conductive polymer material for example, polyacene, polyparaphenylene, polyaniline, polyacetylene
  • a lithium composite oxide eg, lithium titanate: Li 4 Ti 5 O 12
  • metal lithium or a metal alloyed with lithium (eg, aluminum, silicon, tin) can be used, but
  • the negative electrode current collector 20 is desirably a low-resistance conductor having heat resistance capable of withstanding the heating during the secondary battery manufacturing process and the operating temperature of the secondary battery.
  • metal foil thickness of 10 ⁇ m or more and 100 ⁇ m or less
  • perforated metal foil thickness of 10 ⁇ m or more and 100 ⁇ m or less, pore diameter of 0.1 mm or more and 10 mm or less
  • expanded metal foamed metal plate, glassy carbon plate and the like.
  • a metal seed species, copper, stainless steel, titanium, nickel, a noble metal (for example, gold, silver, platinum) etc. can be used.
  • ⁇ Negative electrode 80> A negative electrode slurry obtained by mixing a negative electrode active material 62, a negative electrode conductive agent 63, and an organic solvent containing a small amount of water is used as a reverse roll method, direct roll method, blade method, knife method, extrusion method, curtain method, gravure method, bar After making it adhere to the negative electrode current collector 20 and the negative electrode surface of the interconnector 90 by a method, a dip method, a squeeze method, a spray method, etc., the organic solvent is dried, and a negative electrode is produced by pressure forming with a roll press. be able to.
  • a plurality of negative electrode mixture layers 60 can be laminated on the negative electrode current collector 20 and the interconnector 90 by performing a plurality of times from application to drying.
  • the solid electrolyte 55 includes inorganic particles 51 and an ion conductive material 52. By supporting the ion conductive material 52 on the inorganic particles 51, a semi-solid solid electrolyte 55 (semi-solid electrolyte) is formed.
  • Examples of the method for producing the solid electrolyte 55 include the following methods.
  • the ionic conductive material 52 and the inorganic particles 51 are mixed at a specific volume ratio, and an organic solvent such as methanol is added and mixed to prepare a slurry of the solid electrolyte 55. Thereafter, the slurry is spread on a petri dish, and the organic solvent is distilled off to obtain a solid electrolyte 55 powder.
  • the volume fraction of the ionic conductive material 52 is 30 volumes. % To 90% by volume is preferable.
  • the volume fraction of the ionic conductive material 52 is lower than the range, the lithium ion conductivity is lowered.
  • the volume ratio is higher than the range, the ionic conductive material 52 that is not held on the surface of the inorganic particles 51 is increased, resulting in a semi-solid electrolyte. It becomes difficult to maintain the shape.
  • the inorganic particles 51 are preferably insulating particles, insoluble in an organic solvent such as an ionic liquid or glyme, and having no electrical conductivity.
  • oxide nanoparticles such as SiO 2 , Al 2 O 3 , CeO 2 , ZrO 2 , BaTiO 3 , ZnO, TiO 2 are preferable, such as Li 7 La 3 Zr 2 O 12 and Li x La 1-x TiO 3. Those having lithium ion conductivity can also be preferably used.
  • the surface of the nanoparticles may be modified with a known functional group such as a hydroxy group, a carboxyl group, or an amino group, and hexamethyldisilazane, trimethylethoxysilane, trimethylmethoxy may be used as the silane coupling agent.
  • a known hydrophobic treatment may be performed with silane, trimethylsilyl chloride, methyltriethoxysilane, dimethyldiethoxysilane, decyltrimethoxysilane, or the like.
  • other known metal oxide particles may be used.
  • the average particle size of the primary particles of the inorganic particles 51 is preferably 1 nm or more and 10 ⁇ m or less. If the average particle diameter is larger than the above range, the inorganic particles 51 cannot appropriately hold a sufficient amount of the organic solvent, and it may be difficult to form a semi-solid electrolyte. On the other hand, if the average particle diameter is smaller than the above range, the inter-surface force between the inorganic particles 51 is increased, and the particles are likely to aggregate, making it difficult to form a semi-solid electrolyte.
  • the average particle size of the primary particles of the inorganic particles 51 is more preferably 1 nm to 50 nm, and still more preferably 1 nm to 10 nm.
  • the average particle size of the inorganic particles 51 is an average particle size that can be measured using a known particle size distribution measuring apparatus using a laser scattering method.
  • SiO 2 particles average particle size: 7 nm, zeta potential: about ⁇ 20 mV
  • a highly heat-resistant quasi-solid electrolyte can be obtained.
  • ⁇ -Al 2 O 3 particles (average particle size: 5 nm, zeta potential: about ⁇ 5 mV) are used as the inorganic particles 51, it is possible to increase the number of times of charge and discharge of the secondary battery. Although the exact reason is unclear, it is considered that precipitation of lithium dendrite on the negative electrode side during the charge / discharge cycle can be suppressed by using alumina particles having high reduction resistance.
  • the ionic conductive material 52 is an ionic liquid or a mixture of glymes and lithium salts that exhibit similar properties to the ionic liquid.
  • the ionic liquid a known ionic liquid that functions as an electrolyte can be used. From the viewpoint of ionic conductivity (conductivity), N, N-diethyl-N-methyl-N- (2-methoxyethyl) is particularly preferable. Ammonium bis (trifluoromethanesulfonyl) imide (DEME-TFSI) can be preferably used.
  • DEME-TFSI Ammonium bis (trifluoromethanesulfonyl) imide
  • Glymes (R—O (CH 2 CH 2 O) n—R ′ (R and R ′ are saturated hydrocarbons, n is an integer), a generic name for symmetric glycol diethers) are similar to ionic liquids Known glymes exhibiting properties can be used, but from the viewpoint of ion conductivity (conductivity), tetraglyme (tetraethylene dimethyl glycol, G4), triglyme (triethylene glycol dimethyl ether, G3), pentag lime (penta Ethylene glycol dimethyl ether (G5) and hexaglyme (hexaethylene glycol dimethyl ether, G6) can be preferably used.
  • lithium salt LiPF 6, LiBF 4, LiClO 4, LiCF 3 SO 3, LiCF 3 CO 2, LiAsF 6, LiSbF 6, lithium bis oxalate borate (LiBOB), and lithium imide salt (e.g., lithium Bis (fluorosulfonyl) imide, LiFSI) or the like can be preferably used.
  • lithium imide salt e.g., lithium Bis (fluorosulfonyl) imide, LiFSI
  • LiFSI lithium bis oxalate borate
  • the mixed molar ratio of the lithium salt to the ambient temperature molten salt or the organic solvent is preferably 0.1 or more and 10 or less. If the lithium salt ratio is higher than the range, it is difficult to dissolve the lithium salt. If the lithium salt ratio is lower than the range, the lithium carrier in the electrolyte is reduced, so the secondary battery has a low output, and the cycle of the secondary battery The characteristics are also degraded.
  • the mixing molar ratio is more preferably 0.5 or more and 5 or less, and further preferably 0.8 or more and 3 or less.
  • Electrolyte binder 53 As the electrolyte binder 53, a fluorine-based resin is preferably used. PVDF and PTFE are preferably used as the fluorine-based resin. By using PVDF or PTFE, the adhesion between the solid electrolyte layer 50 and the electrode current collector is improved, so that the battery performance is improved.
  • Solid electrolyte layer 50 There are a method of compression molding the powder of the solid electrolyte 55 into a pellet using a molding die or the like, and a method of adding and mixing the electrolyte binder 53 to the powder of the solid electrolyte 55 to form a sheet.
  • a highly flexible solid electrolyte layer 50 electrolyte sheet
  • the solid electrolyte layer 50 can be produced by adding and mixing a solution of a binder in which the electrolyte binder 53 is dissolved in the dispersion solvent to the solid electrolyte 55 and distilling off the dispersion solvent.
  • LiTFSI lithium bis (trifluorosulfonyl) imide
  • acetylene black average particle size 48 nm
  • PTFE binder
  • acetylene black is vacuum-dried at 120 ° C., and then acetylene black is dispersed in toluene and refluxed at 100 ° C. Further, 3-aminopropyltriethoxysilane is added as a surface treating agent to the mixed solution, and the mixture is refluxed for 6 hours while stirring uniformly. Thereafter, the reaction solution is collected, washed thoroughly with methanol, and the unreacted surface treatment agent is hydrolyzed with a water-methanol solution to obtain surface-modified acetylene black.
  • Example 2 The same as Example 1 except that diethylphosphotoethyltriethoxysilane was used as the surface treatment agent.
  • Example 2 The same as Example 1 except that 3-aminopropyltrimethoxysilane was used as the surface treatment agent.
  • Example 2 The same as Example 1 except that 4-aminobutyltriethoxysilane was used as the surface treatment agent.
  • Example 2 The same as Example 1 except that aminophenyltrimethoxysilane was used as the surface treatment agent.
  • Example 2 The same as Example 1 except that 3-aminopropyltri (methoxyethoxy) silane was used as the surface treatment agent.
  • Example 2 The same as Example 1 except that diphenylphosphinoethyldimethylethoxysilane was used as the surface treatment agent.
  • Example 2 The same as Example 1 except that the number of functional groups (functional group density) on the surface of the electrode conductive agent was 2.4 per square nanometer.
  • Example 1 is the same as Example 1 except that the surface of the electrode conductive agent is modified with a hydroxy group.
  • Comparative example 2 The same as Comparative Example 1, except that the number of functional groups on the surface of the electrode conductive agent was 4.8 per square nanometer.
  • FIG. 4 shows the results of Examples 1 to 8 and Comparative Examples 1 to 2.
  • Example 1 Example 2, Comparative Example 1, and Comparative Example 2
  • Li ions were measured in three regions with distances of 0.3, 0.9, and 1.5 nm from the functional group formed on the surface of the electrode conductive agent. The density is shown. Focusing on Example 1 and Example 2, it can be seen that the Li ion density decreases as the surface of the electrode conductive agent is approached, such as from 1.5 nm to 0.3 nm. In particular, compared to Comparative Example 1 and Comparative Example 2, the Li ion density on the electrode conductive agent surface (0.3 nm) is reduced to about 50%.
  • Examples 1 to 8 and Comparative Examples 1 to 2 are compared, the adsorption amounts of Li ions of Examples 1 to 8 are the same as those of Comparative Examples 1 to 2. More specifically, since the average Li ion density of 0.3 nm from the functional group is 1.50 nm ⁇ 3 or less, Examples 1 to 8 are Li ions. It turns out that it is effective for adsorption

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Abstract

La présente invention améliore la conductance ionique d'une électrode de batterie secondaire. Ainsi, une électrode de batterie secondaire contenant un matériau actif d'électrode, un agent conducteur d'électrode et un matériau conducteur d'ions, où : le matériau conducteur d'ions est maintenu par l'agent conducteur d'électrode, un revêtement est formé sur la surface de l'agent conducteur d'électrode, et le potentiel de surface de l'agent conducteur d'électrode est positif; et les matériaux utilisés pour former le revêtement comprennent, par exemple, le 3-aminopropyltriéthoxysilane, le 3-aminopropyltriméthoxysilane , le 4-aminobutyltriéthoxysilane, l'aminophényltriméthoxysilane, le 3-aminophényltriméthoxysilane, le m-aminophényltriméthoxysilane, le p-aminophényltriméthoxysilane, le 3-aminopropyltri(méthoxyéthoxy)silane, le 11-aminoundécyltriéthoxysilane , et similaires.
PCT/JP2017/039685 2016-12-16 2017-11-02 Électrode de batterie secondaire Ceased WO2018110133A1 (fr)

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CN201780075754.5A CN110121799B (zh) 2016-12-16 2017-11-02 二次电池用电极、二次电池、它们的制造方法
JP2018556242A JP6916815B2 (ja) 2016-12-16 2017-11-02 二次電池用電極、二次電池、それらの製造方法

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KR20210114044A (ko) * 2019-02-19 2021-09-17 니뽄 도쿠슈 도교 가부시키가이샤 이온 전도체, 축전 디바이스, 및, 이온 전도체의 제조 방법
WO2022239525A1 (fr) * 2021-05-10 2022-11-17 パナソニックＩｐマネジメント株式会社 Batterie
JP2022180935A (ja) * 2021-05-25 2022-12-07 本田技研工業株式会社 固体電池及び固体電池の製造方法
WO2022255474A1 (fr) * 2021-06-04 2022-12-08 リファインホールディングス株式会社 Procédé de déshydratation pour élément de dispersion de matière carbonée et procédé de production d'élément de dispersion de matière carbonée
JP7804890B2 (ja) 2021-05-10 2026-01-23 パナソニックＩｐマネジメント株式会社 電池

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CN112670548A (zh) * 2020-06-12 2021-04-16 中国科学院物理研究所 双极型电池及其制造方法和应用
CN111816869A (zh) * 2020-08-07 2020-10-23 深圳先进技术研究院 负极材料、负极、钾离子电池及其制备方法
CN112768771B (zh) * 2021-01-27 2023-02-10 上海奥威科技开发有限公司 一种锂离子电解液及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003173770A (ja) * 2001-12-04 2003-06-20 Japan Storage Battery Co Ltd 非水電解質電池および非水電解質電池の製造法
WO2007111070A1 (fr) * 2006-03-29 2007-10-04 Nissan Chemical Industries, Ltd. Composition pour electrode de dispositif de stockage d'energie et procede de production de celle-ci
JP2013093171A (ja) * 2011-10-25 2013-05-16 Mitsubishi Chemicals Corp リチウム二次電池用正極およびそれを用いたリチウム二次電池
WO2014185344A1 (fr) * 2013-05-17 2014-11-20 日産自動車株式会社 Batterie secondaire à électrolyte non aqueux
WO2016038644A1 (fr) * 2014-09-10 2016-03-17 株式会社豊田自動織機 Électrode positive pour batteries secondaires au lithium-ion, procédé de fabrication de celle-ci et batterie secondaire au lithium-ion

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100576608C (zh) * 2007-05-22 2009-12-30 龚思源 一种锂离子电池正极材料磷酸铁锂的制备方法
JP2009193940A (ja) * 2008-02-18 2009-08-27 Toyota Motor Corp 電極体及びその製造方法、並びに、リチウムイオン二次電池
JP4948510B2 (ja) * 2008-12-02 2012-06-06 トヨタ自動車株式会社 全固体電池
JP2010146936A (ja) * 2008-12-22 2010-07-01 Toyota Motor Corp 全固体電池
CN102656723B (zh) * 2009-12-10 2014-09-24 丰田自动车株式会社 电池用电极的制造方法
WO2012008532A1 (fr) * 2010-07-16 2012-01-19 三菱化学株式会社 Cathode pour batterie secondaire au lithium et batterie secondaire au lithium utilisant cette dernière
CN104054200B (zh) * 2012-01-31 2017-02-22 独立行政法人产业技术综合研究所 锂离子电池正极用树脂组合物
JP6452814B2 (ja) * 2015-06-02 2019-01-16 富士フイルム株式会社 正極用材料、全固体二次電池用電極シートおよび全固体二次電池ならびに全固体二次電池用電極シートおよび全固体二次電池の製造方法
JP2017183591A (ja) * 2016-03-31 2017-10-05 株式会社キャタラー 蓄電デバイス用炭素材料及び電極並びに蓄電デバイス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003173770A (ja) * 2001-12-04 2003-06-20 Japan Storage Battery Co Ltd 非水電解質電池および非水電解質電池の製造法
WO2007111070A1 (fr) * 2006-03-29 2007-10-04 Nissan Chemical Industries, Ltd. Composition pour electrode de dispositif de stockage d'energie et procede de production de celle-ci
JP2013093171A (ja) * 2011-10-25 2013-05-16 Mitsubishi Chemicals Corp リチウム二次電池用正極およびそれを用いたリチウム二次電池
WO2014185344A1 (fr) * 2013-05-17 2014-11-20 日産自動車株式会社 Batterie secondaire à électrolyte non aqueux
WO2016038644A1 (fr) * 2014-09-10 2016-03-17 株式会社豊田自動織機 Électrode positive pour batteries secondaires au lithium-ion, procédé de fabrication de celle-ci et batterie secondaire au lithium-ion

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210114044A (ko) * 2019-02-19 2021-09-17 니뽄 도쿠슈 도교 가부시키가이샤 이온 전도체, 축전 디바이스, 및, 이온 전도체의 제조 방법
KR102567168B1 (ko) * 2019-02-19 2023-08-16 니테라 컴퍼니 리미티드 이온 전도체, 축전 디바이스, 및, 이온 전도체의 제조 방법
US12283656B2 (en) 2019-02-19 2025-04-22 Niterra Co., Ltd. Ion conductor, power storage device, and method for manufacturing ion conductor
WO2022239525A1 (fr) * 2021-05-10 2022-11-17 パナソニックＩｐマネジメント株式会社 Batterie
JPWO2022239525A1 (fr) * 2021-05-10 2022-11-17
JP7804890B2 (ja) 2021-05-10 2026-01-23 パナソニックＩｐマネジメント株式会社 電池
JP2022180935A (ja) * 2021-05-25 2022-12-07 本田技研工業株式会社 固体電池及び固体電池の製造方法
JP7691851B2 (ja) 2021-05-25 2025-06-12 本田技研工業株式会社 固体電池及び固体電池の製造方法
US12500234B2 (en) 2021-05-25 2025-12-16 Honda Motor Co., Ltd Solid-state battery and method of manufacturing solid-state battery
WO2022255474A1 (fr) * 2021-06-04 2022-12-08 リファインホールディングス株式会社 Procédé de déshydratation pour élément de dispersion de matière carbonée et procédé de production d'élément de dispersion de matière carbonée
JP2022186527A (ja) * 2021-06-04 2022-12-15 リファインホールディングス株式会社 炭素質材料分散体の脱水方法および炭素質材料分散体の製造方法
JP7239638B2 (ja) 2021-06-04 2023-03-14 リファインホールディングス株式会社 炭素質材料分散体の脱水方法および炭素質材料分散体の製造方法

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