WO2013069083A1 - Batterie entièrement solide - Google Patents

Batterie entièrement solide Download PDF

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Publication number
WO2013069083A1
WO2013069083A1 PCT/JP2011/075614 JP2011075614W WO2013069083A1 WO 2013069083 A1 WO2013069083 A1 WO 2013069083A1 JP 2011075614 W JP2011075614 W JP 2011075614W WO 2013069083 A1 WO2013069083 A1 WO 2013069083A1
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active material
electrode active
positive electrode
solid electrolyte
average particle
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PCT/JP2011/075614
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English (en)
Japanese (ja)
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達哉 古賀
元 長谷川
杉浦　功一
敬介 大森
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トヨタ自動車株式会社
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Priority to PCT/JP2011/075614 priority Critical patent/WO2013069083A1/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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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 all solid state battery having low battery resistance and high capacity.
  • lithium secondary batteries have high electromotive force and high energy density, they are widely used in the fields of information-related equipment and communication equipment.
  • development of electric vehicles and hybrid vehicles has been urgently caused by environmental problems and resource problems, and lithium secondary batteries are also being studied as power sources for these.
  • lithium secondary batteries currently on the market use an electrolyte containing a flammable organic solvent, they are equipped with a safety device that prevents the temperature rise during short-circuiting and in terms of structure and materials for short-circuit prevention. Improvement is needed.
  • an all-solid lithium secondary battery in which the electrolyte solution is changed to a solid electrolyte layer to make the battery all solid does not use a flammable organic solvent in the battery, so the safety device can be simplified and manufactured. It is considered to be excellent in cost and productivity.
  • Such an all-solid battery generally has a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer.
  • Patent Document 1 includes a positive electrode active material that is at least one of LiCoO 2 and LiNiO 2 and a sulfide solid electrolyte material, and the average particle size of the positive electrode active material is in the range of 1 to 5 ⁇ m.
  • a positive electrode layer forming material in which the volume fraction of the active material is in the range of 37 to 42 vol% is disclosed. This technique aims to improve lithium ion conductivity while maintaining good electron conductivity.
  • the proportion of the positive electrode active material contained in the positive electrode active material layer is preferably higher.
  • the present invention has been made in view of the above circumstances, and a main object of the present invention is to provide an all solid state battery having low battery resistance and high capacity.
  • a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer are all included.
  • the positive electrode active material layer contains a positive electrode active material and a solid electrolyte material, and the ratio of the positive electrode active material to the total of the positive electrode active material and the solid electrolyte material is greater than 50% by volume,
  • an all-solid battery characterized in that an average particle diameter ratio of the positive electrode active material to a solid electrolyte material is 0.9 or more.
  • the battery resistance is low and the capacity is reduced.
  • a high all-solid-state battery can be obtained.
  • the positive electrode active material preferably has an average particle size of 20 ⁇ m or less, and the solid electrolyte material preferably has an average particle size of 18 ⁇ m or less. This is because lower resistance and higher capacity can be achieved.
  • an average particle diameter of the positive electrode active material is 5 ⁇ m or less and an average particle diameter of the solid electrolyte material is 3 ⁇ m or less. This is because the contact area (reaction area) between the positive electrode active material and the solid electrolyte material can be increased, and further reduction in resistance and increase in capacity can be achieved.
  • the solid electrolyte material preferably has an average particle size of 0.8 ⁇ m or more. This is because a decrease in ionic conductivity due to an increase in grain boundary resistance can be suppressed.
  • the average particle size ratio of the positive electrode active material to the solid electrolyte material is preferably 1.6 or more.
  • FIG. 3 is a result of battery capacity evaluation for the batteries obtained in Examples 1 to 4 and Comparative Examples 1 to 5.
  • FIG. 3 is a result of battery resistance evaluation (1C discharge) for the batteries obtained in Examples 1 to 4 and Comparative Examples 1 to 5.
  • FIG. 3 shows the results of battery capacity evaluation for the batteries obtained in Examples 5 to 9 and Comparative Example 6.
  • FIG. 6 is a result of battery resistance evaluation (1C discharge) for the batteries obtained in Examples 5 to 9 and Comparative Example 6.
  • FIG. 6 is a result of battery resistance evaluation (10C discharge) for the batteries obtained in Examples 5 to 9 and Comparative Example 6.
  • An all solid state battery of the present invention is an all solid state battery having a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer.
  • the positive electrode active material layer contains a positive electrode active material and a solid electrolyte material, and the ratio of the positive electrode active material to the total of the positive electrode active material and the solid electrolyte material is greater than 50% by volume.
  • the average particle size ratio of the positive electrode active material is 0.9 or more.
  • FIG. 1 is a schematic sectional view showing an example of the all solid state battery of the present invention.
  • An all-solid battery 10 in FIG. 1 includes a positive electrode active material layer 1, a negative electrode active material layer 2, a solid electrolyte layer 3 formed between the positive electrode active material layer 1 and the negative electrode active material layer 2, and a solid electrolyte layer 3.
  • the positive electrode active material layer 1 contains a positive electrode active material (for example, an oxide active material) and a solid electrolyte material (for example, a sulfide solid electrolyte material), and the volume ratio of the positive electrode active material and the positive electrode active material with respect to the solid electrolyte material.
  • the average particle size ratio is in a specific range.
  • the battery resistance is low and the capacity is reduced.
  • a high all-solid-state battery can be obtained. That is, in the positive electrode active material layer, when the volume ratio of the positive electrode active material is higher than the volume ratio of the solid electrolyte material, the average particle size ratio is adjusted to a specific value or more to increase the capacity of the all solid state battery. Can be planned.
  • the positive electrode active material has a volume ratio of 40 vol%, the positive electrode active material has an average particle diameter of 4 ⁇ m, and the sulfide solid electrolyte material has an average particle diameter of 7 ⁇ m.
  • an active material layer is described, in this case, if only the volume ratio of the positive electrode active material is simply increased, there is a problem that battery resistance increases and capacity decreases. The reason is considered as follows.
  • the ion conduction path in a positive electrode active material layer is ensured by making the said average particle diameter ratio more than a specific value.
  • the battery resistance decreases and the capacity increases.
  • the contact area of a positive electrode active material and a solid electrolyte material becomes large by making the said average particle diameter ratio more than a specific value.
  • the reaction points at which metal ions are inserted into and desorbed from the positive electrode active material increase, the battery resistance decreases, and the capacity increases.
  • the all solid state battery of the present invention will be described for each configuration.
  • the positive electrode active material layer in the present invention is a layer containing at least a positive electrode active material and a solid electrolyte material.
  • the ratio of the positive electrode active material to the total of the positive electrode active material and the solid electrolyte material is usually larger than 50% by volume, preferably 55% by volume or more, and preferably 60% by volume or more. It is more preferable. This is because if the volume ratio is too small, the energy density may not be sufficiently improved.
  • the ratio is not particularly limited, but is preferably 95% by volume or less, more preferably 90% by volume or less, and still more preferably 85% by volume or less. This is because if the volume ratio is too large, the ion conduction path may not be sufficiently secured.
  • the average particle size ratio of the positive electrode active material to the solid electrolyte material is usually 0.9 or more, preferably 1 or more, and preferably 1.6 or more. More preferred. This is because if the average particle size ratio is too small, the ion conduction path and the contact area between the two may not be sufficiently secured.
  • the average particle diameter ratio is not particularly limited, but is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less, for example. If the average particle size ratio is too large, the contact area between the two may decrease due to the large particle size of the positive electrode active material, or the grain boundary due to the small particle size of the solid electrolyte material. This is because the resistance may increase.
  • the average particle size ratio can be calculated by dividing the average particle size of the positive electrode active material by the average particle size of the solid electrolyte material.
  • the average and particle size is usually refers to the average particle diameter D 50 was measured with a particle size distribution measurement, a value calculated by a scanning electron microscope (SEM) may be an average particle diameter.
  • SEM scanning electron microscope
  • the average particle diameter of the positive electrode active material is not particularly limited, but is preferably, for example, 20 ⁇ m or less, more preferably 10 ⁇ m or less, and further preferably 5 ⁇ m or less. This is because if the average particle diameter of the positive electrode active material is too large, there is a possibility that a sufficient contact area between the positive electrode active material and the solid electrolyte material cannot be secured. In particular, when the average particle diameter of the positive electrode active material is 5 ⁇ m or less, as will be described in Examples described later, an all-solid battery capable of increasing discharge capacity and capable of high-rate discharge can be obtained.
  • the average particle size of the positive electrode active material is, for example, preferably 0.1 ⁇ m or more, and more preferably 2 ⁇ m or more. This is because if the average particle diameter of the positive electrode active material is too small, the grain boundaries increase and the grain boundary resistance increases.
  • the average particle size of the solid electrolyte material is not particularly limited, but is preferably, for example, 18 ⁇ m or less, more preferably 8 ⁇ m or less, and further preferably 3 ⁇ m or less. This is because if the average particle size of the solid electrolyte material is too large, there is a possibility that a sufficient contact area between the solid electrolyte material and the positive electrode active material cannot be secured. In particular, when the average particle size of the solid electrolyte material is 3 ⁇ m or less, as will be described later in Examples, the discharge capacity is increased, and an all-solid battery capable of high rate discharge can be obtained.
  • the average particle size of the solid electrolyte material is preferably 0.01 ⁇ m or more, for example, preferably 0.1 ⁇ m or more, and more preferably 0.8 ⁇ m or more. This is because the grain boundary resistance may increase if the average particle size of the solid electrolyte material is too small.
  • the positive electrode active material in this invention is not specifically limited, For example, an oxide active material and a sulfide active material can be mentioned.
  • a rock salt layer type such as LiCoO 2 , LiMnO 2 , LiNiO 2 , LiVO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 Active material, spinel type active material such as LiMn 2 O 4 and Li (Ni 0.5 Mn 1.5 ) O 4 , reverse spinel type active material such as LiNiVO 4 and LiCoVO 4 , LiFePO 4 , LiMnPO 4 , LiCoPO 4 , olivine active material LiNiPO 4 etc., can be cited Li 2 FeSiO 4, Li 2 MnSiO Si -containing active material such as 4.
  • an oxide active material a rock salt layer shape in which a part of transition metal is substituted with a different metal, such as LiNi 0.8 Co (0.2-x) Al x O 2 (0 ⁇ x ⁇ 0.2).
  • Type active material Li 1 + x Mn 2-xy M y O 4 (M is at least one of Al, Mg, Co, Fe, Ni, Zn, and 0 ⁇ x + y ⁇ 2).
  • a spinel active material whose part is replaced with a different metal, or lithium titanate such as Li 4 Ti 5 O 12 may be used.
  • examples of the sulfide active material include copper chevrel, iron sulfide, cobalt sulfide, nickel sulfide and the like.
  • a coat layer is preferably formed on the surface of the positive electrode active material. This is because, for example, the generation of the high resistance layer due to the reaction between the oxide active material and the sulfide solid electrolyte material can be suppressed.
  • the material for the coating layer include an oxide material having ion conductivity.
  • lithium niobate LiNbO 3
  • lithium titanate for example, Li 4 Ti 5 O 12
  • lithium phosphate Li 3 PO 4
  • LATP for example Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3
  • LAGP for example Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3
  • Li 2 WO 4 Li 2 ZrO 3
  • Li 4 SiO 4 Li 2 CO 3 , Li 2 BO 2 and the like.
  • metal oxides such as ZrO 2 , Al 2 O 3 , HgO, WO 3 , BaTiO 3 , and Pb (Zr, Ti) O 3 are present on the surface of the positive electrode active material. You may do it. This is because the resistance can be further reduced.
  • the solid electrolyte material in the present invention is not particularly limited, and examples thereof include a sulfide solid electrolyte material and an oxide solid electrolyte material.
  • the sulfide solid electrolyte material is preferable in that it has a higher ion conductivity than the oxide solid electrolyte material, and the oxide solid electrolyte material has higher chemical stability than the sulfide solid electrolyte material. This is preferable.
  • the solid electrolyte material in the present invention may be an amorphous material or a crystalline material. The amorphous material can be obtained, for example, by applying a mechanical milling method or a melt quenching method to the raw material composition.
  • the crystalline material can be obtained, for example, by applying a solid phase method to the raw material composition.
  • a material (glass ceramic) obtained by heat-treating an amorphous material at a temperature equal to or higher than the crystallization temperature may be used as the solid electrolyte material.
  • Examples of the sulfide solid electrolyte material having Li ion conductivity include Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —LiI, Li 2 S—P 2 S 5 —LiCl, and Li 2 S.
  • Li 2 S-P 2 S 5 -LiBr Li 2 S-P 2 S 5 -Li 2 O, Li 2 S-P 2 S 5 -Li 2 O-LiI, Li 2 S-SiS 2, Li 2 S-SiS 2 - LiI, Li 2 S—SiS 2 —LiBr, Li 2 S—SiS 2 —LiCl, Li 2 S—SiS 2 —B 2 S 3 —LiI, Li 2 S—SiS 2 —P 2 S 5 —LiI, Li 2 S-B 2 S 3, Li 2 S-P 2 S 5 -Z m S n ( however, m, n is the number of positive .Z is, Ge, Zn, one of Ga.), Li 2 S- GeS 2, Li 2 S-SiS 2 -Li 3 PO 4, Li 2 S- iS 2 -Li x MO y (provided that, x, y is a positive number .M is, P, Si,
  • examples of the oxide solid electrolyte material having Li ion conductivity include Li 2 O—B 2 O 3 —P 2 O 5 , Li 2 O—SiO 2 , LiLaTaO (eg, Li 5 La 3 Ta 2 O 12).
  • LiLaZrO eg, Li 7 La 3 Zr 2 O 12
  • LiBaLaTaO eg, Li 6 BaLa 2 Ta 2 O 12
  • Li 1 + x Si x P 1-x O 4 (0 ⁇ x ⁇ 1, eg, Li 3.6 Si 0.6 P 0.4 O 4
  • Li 1 + x Al x Ge 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 2)
  • Li 1 + x Al x Ti 2-x (PO 4 ) 3 (0 ⁇ x ⁇ 2)
  • LiI and Li 3 N can be used as other solid electrolyte materials.
  • the sulfide solid electrolyte material is a raw material composition containing Li 2 S and a sulfide of A (A is at least one of P, Si, Ge, Al, and B). It is preferable to use it.
  • the raw material composition may further contain a halogen compound.
  • the sulfide of A include P 2 S 3 , P 2 S 5 , SiS 2 , GeS 2 , Al 2 S 3 , B 2 S 3 and the like.
  • the halogen compound include LiF, LiPF 6 , LiCl, LiBr, LiI, and the like, and LiI is preferable.
  • the sulfide solid electrolyte material has an ortho-composition anion structure (PS 4 3- structure, SiS 4 4- structure, GeS 4 4- structure, AlS 3 3- structure, BS 3 3- structure) as a main component. It is preferable to have. This is because a sulfide solid electrolyte material having high chemical stability can be obtained.
  • the ratio of the anion structure of the ortho composition is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, based on the total anion structure in the ion conductor, 90 mol % Or more is particularly preferable.
  • the ratio of the anion structure of the ortho composition can be determined by Raman spectroscopy, NMR, XPS, or the like.
  • ortho generally refers to one having the highest degree of hydration among oxo acids obtained by hydrating the same oxide.
  • the crystal composition in which Li 2 S is added most in the sulfide is called the ortho composition.
  • Li 3 PS 4 corresponds to the ortho composition
  • Li 2 S—Al 2 S 3 system Li 3 AlS 3 corresponds to the ortho composition
  • Li 3 BS 3 corresponds to the ortho composition
  • Li 4 SiS 4 corresponds to the ortho composition
  • Li 4 GeS 4 corresponds to the ortho composition. Applicable.
  • the raw material composition is, when containing Li 2 S and P 2 S 5, the proportion of Li 2 S to the total of Li 2 S and P 2 S 5 is preferably in the range of 70 mol% ⁇ 80 mol% 72 mol% to 78 mol% is more preferable, and 74 mol% to 76 mol% is more preferable.
  • the raw material composition is, when containing Li 2 S and Al 2 S 3, which is the same when containing Li 2 S and B 2 S 3.
  • the raw material composition is, when containing Li 2 S and SiS 2, the ratio of Li 2 S to the total of Li 2 S and SiS 2 is in the range of 62.5mol% ⁇ 70.9mol% Is more preferable, within the range of 63 mol% to 70 mol%, more preferably within the range of 64 mol% to 68 mol%.
  • the raw material composition contains Li 2 S and GeS 2 .
  • the proportion of the halogen compound in the raw material composition is preferably in the range of 1 mol% to 60 mol%, and preferably in the range of 5 mol% to 40 mol%. More preferably, it is more preferably in the range of 10 mol% to 40 mol%.
  • the positive electrode active material layer in the present invention is a layer containing at least the positive electrode active material and the solid electrolyte material, and may contain only the positive electrode active material layer and the solid electrolyte material, and at least of the conductive material and the binder. One may be further contained.
  • the total ratio of the positive electrode active material and the solid electrolyte material in the positive electrode active material layer is, for example, 80% by weight or more, preferably 85% by weight or more, and more preferably 90% by weight or more. The total may be 100% by weight.
  • the positive electrode active material layer may further contain a conductive material.
  • a conductive material By adding a conductive material, the electronic conductivity of the positive electrode active material layer can be improved.
  • the conductive material include carbon materials such as acetylene black (AB), ketjen black (KB), vapor grown carbon fiber (VGCF), carbon nanotube (CNT), and carbon nanofiber (CNF). It can.
  • the positive electrode active material layer may further contain a binder. By adding a binder, flexibility can be imparted to the positive electrode active material layer. Examples of the binder include butylene rubber, styrene butadiene rubber (SBR), polyvinylidene fluoride (PVDF), and the like.
  • the thickness of the positive electrode active material layer varies depending on the type of the target battery, but is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
  • Negative electrode active material layer is a layer containing at least a negative electrode active material, and further contains at least one of a solid electrolyte material, a conductive material and a binder as necessary. Also good.
  • the negative electrode active material in this invention is not specifically limited, For example, a carbon active material, a metal active material, an oxide active material etc. can be mentioned.
  • the carbon active material include graphite such as mesocarbon microbeads (MCMB) and highly oriented graphite (HOPG), and amorphous carbon such as hard carbon and soft carbon.
  • the metal active material include In, Al, Si, Sn, and alloys containing at least one of these elements.
  • oxide active material may include, for example Nb 2 O 5, Li 4 Ti 5 O 12, SiO and the like.
  • Examples of the shape of the negative electrode active material include a particle shape and a film shape.
  • the average particle size of the particulate negative electrode active material is preferably in the range of 0.1 ⁇ m to 50 ⁇ m, for example.
  • the method for obtaining the average particle diameter is as described above.
  • the content of the negative electrode active material in the negative electrode active material layer is preferably in the range of, for example, 10% by weight to 99% by weight, and more preferably in the range of 20% by weight to 90% by weight.
  • the negative electrode active material layer preferably contains a solid electrolyte material, and more preferably contains a sulfide solid electrolyte material. This is because the ion conductivity in the negative electrode active material layer can be improved. In addition, since it is the same as that of the content described in said "1. positive electrode active material layer" about solid electrolyte material, description here is abbreviate
  • the content of the solid electrolyte material in the negative electrode active material layer is, for example, preferably in the range of 1% by weight to 90% by weight, and more preferably in the range of 10% by weight to 80% by weight.
  • the negative electrode active material layer may further contain a conductive material.
  • the negative electrode active material layer may further contain a binder.
  • the conductive material and the binder are the same as those described in “1. Cathode active material layer”, and are not described here.
  • the thickness of the negative electrode active material layer varies depending on the type of the target battery, but is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, for example.
  • Solid electrolyte layer in the present invention is a layer containing at least a solid electrolyte material.
  • the solid electrolyte material is the same as the contents described in “1. Positive electrode active material layer”, and therefore the description thereof is omitted here.
  • the content of the solid electrolyte material in the solid electrolyte layer is, for example, preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
  • the solid electrolyte layer may contain a binder or may be composed only of a solid electrolyte material.
  • the thickness of the solid electrolyte layer varies greatly depending on the configuration of the battery. For example, the thickness is preferably in the range of 0.1 ⁇ m to 1000 ⁇ m, and more preferably in the range of 0.1 ⁇ m to 300 ⁇ m.
  • the all solid state battery of the present invention has at least the positive electrode active material layer, the negative electrode active material layer, and the solid electrolyte layer described above. Furthermore, it usually has a positive electrode current collector for collecting current of the positive electrode active material layer and a negative electrode current collector for collecting current of the negative electrode active material layer.
  • the material for the positive electrode current collector include SUS, nickel, chromium, gold, platinum, aluminum, iron, titanium, zinc, and carbon.
  • examples of the material for the negative electrode current collector include SUS, copper, nickel, iron, titanium, cobalt, zinc, and carbon.
  • the thickness and shape of the positive electrode current collector and the negative electrode current collector are preferably appropriately selected according to the use of the battery.
  • a general battery case can be used for the battery case used for this invention, For example, the battery case made from SUS, the battery case made from aluminum, an aluminum laminated foil etc. can be mentioned.
  • All-solid battery Examples of the all-solid battery of the present invention include an all-solid lithium battery, an all-solid sodium battery, an all-solid magnesium battery, an all-solid calcium battery, and the like. Among these, an all-solid lithium battery is preferable.
  • the all solid state battery of the present invention may be a primary battery or a secondary battery, but is preferably a secondary battery. This is because it can be repeatedly charged and discharged and is useful, for example, as an in-vehicle battery.
  • examples of the shape of the all solid state battery of the present invention include a coin type, a laminate type, a cylindrical type, and a square type.
  • the manufacturing method of the all-solid-state battery of this invention will not be specifically limited if it is a method which can obtain the all-solid-state battery mentioned above.
  • the present invention is not limited to the above embodiment.
  • the above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.
  • Example 1 Synthesis of sulfide solid electrolyte materials
  • lithium sulfide (Li 2 S), diphosphorus pentasulfide (P 2 S 5 ) and lithium iodide (LiI) were used as starting materials.
  • Li 2 S and P 2 S 5 were weighed so as to have a molar ratio of 75Li 2 S ⁇ 25P 2 S 5 (Li 3 PS 4 , ortho composition).
  • LiI was weighed so that the LiI ratio was 30 mol%.
  • sulfide glass ceramic sulfide glass ceramic.
  • the resulting sulfide solid electrolyte material, stainless steel mesh sieve was classified with an average particle diameter D 50 was obtained 6.7 .mu.m, 16.3, a sulfide solid electrolyte material 34.8Myuemu.
  • a composition prepared by dissolving equimolar LiOC 2 H 5 and Nb (OC 2 H 5 ) 5 in an ethanol solvent was prepared as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (manufactured by Nichia Corporation). ) was spray coated using a tumbling fluidized coating apparatus (SFP-01, manufactured by POWREC Co., Ltd.). Thereafter, the coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 was heat-treated at 350 ° C. under atmospheric pressure for 1 hour, and LiNbO 3 coated LiNi 1/3 Co 1/3. Mn 1/3 O 2 was obtained. The obtained positive electrode active material, stainless steel mesh sieve classified was used to adjust the average particle diameter D 50 at a predetermined value.
  • Examples 2 and 3 Comparative Examples 1 to 3
  • a battery was fabricated in the same manner as in Example 1 except that the conditions such as the average particle diameter of the positive electrode active material and the sulfide solid electrolyte material were changed as shown in Table 1.
  • Example 4 A battery was fabricated in the same manner as in Example 4 except that the conditions such as the average particle diameter of the positive electrode active material and the sulfide solid electrolyte material were changed as shown in Table 2.
  • the relationship between the average particle size ratio (A / B) and the discharge capacity is shown in FIG. As shown in FIG. 2, when the average particle size ratio (A / B) was 0.9 or more, the discharge capacity increased. Moreover, the relationship between average particle diameter ratio (A / B) and battery resistance is shown in FIG. As shown in FIG. 3, when the average particle size ratio (A / B) was 0.9 or more, the battery resistance decreased.
  • Example 5 The resulting sulfide solid electrolyte material in Example 1 (sulfide glass ceramics), stainless steel mesh sieve was classified with an average particle diameter D 50 was obtained 6.7 .mu.m, a sulfide solid electrolyte material of 16 [mu] m. Also, the sulfide solid electrolyte material obtained in Example 1 (sulfide glass ceramics), and pulverized in a ball mill, 0.8 [mu] m average particle diameter D 50, 1.5 [mu] m, 2.5 [mu] m sulfide solid electrolyte material Got.
  • a composition prepared by dissolving equimolar LiOC 2 H 5 and Nb (OC 2 H 5 ) 5 in an ethanol solvent was prepared as LiNi 1/3 Co 1/3 Mn 1/3 O 2 (manufactured by Nichia Corporation). ) was spray coated using a tumbling fluidized coating apparatus (SFP-01, manufactured by POWREC Co., Ltd.). Thereafter, the coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 was heat-treated at 350 ° C. under atmospheric pressure for 1 hour, and LiNbO 3 coated LiNi 1/3 Co 1/3. Mn 1/3 O 2 was obtained. The obtained positive electrode active material, stainless steel mesh sieve classified was used to adjust the average particle diameter D 50 at a predetermined value.
  • a conductive material (VGCF, Showa) Denko)
  • a binder 5% by weight heptane solution of butylene rubber binder
  • dehydrated heptane was added.
  • the PP container is stirred for 30 seconds with an ultrasonic dispersion apparatus (SMH, UH-50), and then the PP solution is stirred for 3 minutes with a shaker (Shiba Chemical Co., Ltd., TTM-1). Shake it.
  • SSH ultrasonic dispersion apparatus
  • the obtained composition was coated on a carbon coated Al foil (Showa Denko, SDX) by a blade method using an applicator. Then, it dried for 30 minutes on a 100 degreeC hotplate, and obtained the positive electrode.
  • a binder 5% by weight heptane solution of butylene rubber-based binder
  • dehydrated heptane were added.
  • the PP container is stirred for 30 seconds with an ultrasonic dispersing device (SMH, UH-50), and then the PP solution is stirred for 30 minutes with a shaker (Shiba Chemical Co., Ltd., TTM-1). Shake it.
  • the obtained composition was coated on Cu foil by a blade method using an applicator. Then, it dried for 30 minutes on a 100 degreeC hotplate, and obtained the negative electrode.
  • SSH ultrasonic dispersing device
  • the solid electrolyte layer is disposed in a mold of 1 cm 2, it was pressed under a pressure of 1 ton / cm 2.
  • the positive electrode was placed on one surface of the obtained solid electrolyte layer and pressed at a pressure of 1 ton / cm 2 .
  • the negative electrode was placed on the other surface of the solid electrolyte layer and pressed at a pressure of 4 ton / cm 2 to form a negative electrode active material layer.
  • a battery was produced using the obtained power generation element.
  • Example 6 A battery was fabricated in the same manner as in Example 5 except that the conditions such as the average particle diameter of the positive electrode active material and the sulfide solid electrolyte material were changed as shown in Table 3.
  • FIG. 4 shows the relationship between the average particle size ratio (A / B) and the discharge capacity. As shown in FIG. 4, when the average particle size ratio (A / B) is 0.9 or more, the discharge capacity is increased. In Examples 5 to 7, the discharge capacity was higher than that in Examples 8 and 9.
  • FIG. 5 shows the relationship between the average particle size ratio (A / B) and the battery resistance in 1C discharge. As shown in FIG. 5, when the average particle size ratio (A / B) was 0.9 or more, the battery resistance was low. In Examples 5 to 7, the battery resistance was further reduced as compared with Examples 8 and 9.
  • FIG. 6 shows the relationship between the average particle size ratio (A / B) and the battery resistance in 10C discharge. As shown in FIG. 6 and Table 3, in Examples 8 and 9 and Comparative Example 6, the resistance was too high to be measured, whereas in Examples 5 to 7, the resistance was as low as measurable. there were.

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Abstract

La présente invention aborde le problème de fourniture d'une batterie entièrement solide qui a une faible résistance de batterie et une capacité élevée. La présente invention résout le problème décrit ci-dessus en fournissant une batterie entièrement solide, qui comprend une couche de matière active d'électrode positive, une couche de matière active d'électrode négative et une couche d'électrolyte solide qui est formée entre la couche de matière active d'électrode positive et la couche de matière active d'électrode négative, et qui est caractérisée en ce que : la couche de matière active d'électrode positive contient une matière active d'électrode positive et une matière d'électrolyte solide ; le rapport de la matière active d'électrode positive au total de la matière active d'électrode positive et de la matière d'électrolyte solide est supérieur à 50 % en volume ; et le rapport du diamètre moyen de particule de la matière active d'électrode positive par rapport à celui de la matière d'électrolyte solide n'est pas inférieur à 0,9.
PCT/JP2011/075614 2011-11-07 2011-11-07 Batterie entièrement solide WO2013069083A1 (fr)

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JP2013157195A (ja) * 2012-01-30 2013-08-15 Tdk Corp 無機全固体二次電池
US20150357644A1 (en) * 2014-06-04 2015-12-10 Quantumscape Corporation Electrode materials with mixed particle sizes
JPWO2015030053A1 (ja) * 2013-09-02 2017-03-02 三菱瓦斯化学株式会社 全固体電池および電極活物質の製造方法
WO2018145565A1 (fr) * 2017-02-09 2018-08-16 上海蔚来汽车有限公司 Matériau d'électrode positive composite destiné à être utilisé dans une batterie au lithium-ion à semi-conducteur et son procédé de préparation
JP2020015661A (ja) * 2018-07-24 2020-01-30 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド チオリン酸リチウム複合体材料のマイクロ波合成
CN114864885A (zh) * 2021-02-04 2022-08-05 丰田自动车株式会社 全固体电池

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JP2009238636A (ja) * 2008-03-27 2009-10-15 Toyota Motor Corp 正極層形成用材料
JP2010140725A (ja) * 2008-12-10 2010-06-24 Namics Corp リチウムイオン二次電池、及び、その製造方法
JP2011044249A (ja) * 2009-08-19 2011-03-03 Toyota Motor Corp 硫化物固体電解質材料

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JP2009094029A (ja) * 2007-10-12 2009-04-30 Ohara Inc 全固体型リチウム二次電池および全固体型リチウム二次電池用の電極
JP2009238636A (ja) * 2008-03-27 2009-10-15 Toyota Motor Corp 正極層形成用材料
JP2010140725A (ja) * 2008-12-10 2010-06-24 Namics Corp リチウムイオン二次電池、及び、その製造方法
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013157195A (ja) * 2012-01-30 2013-08-15 Tdk Corp 無機全固体二次電池
JPWO2015030053A1 (ja) * 2013-09-02 2017-03-02 三菱瓦斯化学株式会社 全固体電池および電極活物質の製造方法
EP3152795B1 (fr) 2014-06-04 2019-10-02 QuantumScape Corporation Matériaux d'électrode à tailles de particules mélangées
CN106605329A (zh) * 2014-06-04 2017-04-26 昆腾斯科普公司 具有混合粒度的电极材料
US9859560B2 (en) * 2014-06-04 2018-01-02 Quantumscape Corporation Electrode materials with mixed particle sizes
US20150357644A1 (en) * 2014-06-04 2015-12-10 Quantumscape Corporation Electrode materials with mixed particle sizes
KR20230012056A (ko) * 2014-06-04 2023-01-25 퀀텀스케이프 배터리, 인코포레이티드 혼합 입자 크기를 가진 전극 물질
KR102606710B1 (ko) 2014-06-04 2023-11-29 퀀텀스케이프 배터리, 인코포레이티드 혼합 입자 크기를 가진 전극 물질
KR20230164760A (ko) * 2014-06-04 2023-12-04 퀀텀스케이프 배터리, 인코포레이티드 혼합 입자 크기를 가진 전극 물질
KR102689418B1 (ko) 2014-06-04 2024-07-30 퀀텀스케이프 배터리, 인코포레이티드 혼합 입자 크기를 가진 전극 물질
WO2018145565A1 (fr) * 2017-02-09 2018-08-16 上海蔚来汽车有限公司 Matériau d'électrode positive composite destiné à être utilisé dans une batterie au lithium-ion à semi-conducteur et son procédé de préparation
JP2020015661A (ja) * 2018-07-24 2020-01-30 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド チオリン酸リチウム複合体材料のマイクロ波合成
JP7362332B2 (ja) 2018-07-24 2023-10-17 トヨタ モーター エンジニアリング アンド マニュファクチャリング ノース アメリカ，インコーポレイティド チオリン酸リチウム複合体材料のマイクロ波合成
CN114864885A (zh) * 2021-02-04 2022-08-05 丰田自动车株式会社 全固体电池
CN114864885B (zh) * 2021-02-04 2024-02-09 丰田自动车株式会社 全固体电池

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