WO2017033316A1 - Batterie à électrolyte non aqueux et bloc-batterie - Google Patents

Batterie à électrolyte non aqueux et bloc-batterie Download PDF

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WO2017033316A1
WO2017033316A1 PCT/JP2015/074065 JP2015074065W WO2017033316A1 WO 2017033316 A1 WO2017033316 A1 WO 2017033316A1 JP 2015074065 W JP2015074065 W JP 2015074065W WO 2017033316 A1 WO2017033316 A1 WO 2017033316A1
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negative electrode
battery
active material
positive electrode
electrode active
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PCT/JP2015/074065
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English (en)
Japanese (ja)
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高見　則雄
康宏 原田
一浩 安田
圭吾 保科
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株式会社 東芝
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Priority to PCT/JP2015/074065 priority Critical patent/WO2017033316A1/fr
Priority to JP2016510840A priority patent/JP6054575B1/ja
Publication of WO2017033316A1 publication Critical patent/WO2017033316A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • 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

  • Embodiments of the present invention relate to a nonaqueous electrolyte battery and a battery pack.
  • Non-aqueous electrolyte batteries using lithium metal, lithium alloys, lithium compounds, or carbonaceous materials as negative electrodes are expected as high energy density batteries and are actively researched and developed. So far, lithium ion batteries including a positive electrode containing LiCoO 2 or LiMn 2 O 4 as an active material and a negative electrode containing a carbonaceous material that occludes and releases lithium have been widely put into practical use for portable devices.
  • the positive electrode because of the storage performance, cycle performance, high output long-term reliability of the non-aqueous electrolyte battery in a high temperature environment (for example, 45 ° C or higher),
  • a high temperature environment for example, 45 ° C or higher
  • a material excellent in chemical and electrochemical stability, strength, and corrosion resistance is required.
  • high performance is required even in a cold region, and high output performance and long life performance in a low temperature environment (for example, ⁇ 40 ° C.) are desired.
  • non-aqueous electrolytes non-volatile and non-flammable electrolytes are being developed from the viewpoint of improving safety performance, but they have not yet been put into practical use due to a decrease in output characteristics, low temperature performance, and long life performance. . Therefore, it is desired that the lithium ion battery mounted on the vehicle is excellent in high temperature durability and low temperature output performance.
  • Li 4/3 + x Ti 5/3 O 4 (0 ⁇ x ⁇ 1), monoclinic structure titanium dioxide (for example, the use of TiO 2 (B)) as a negative electrode active material has been studied.
  • a non-aqueous electrolyte battery including a negative electrode containing monoclinic titanium dioxide as a negative electrode active material has a problem that the battery swells under a high temperature environment of about 45 ° C. or higher, resulting in poor cycle performance.
  • a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte is provided.
  • the negative electrode includes a negative electrode active material containing a titanium-containing oxide having a monoclinic structure and releasing 0.01 to 0.5% by weight of H 2 O in a temperature range of 300 to 600 ° C.
  • a battery pack including a non-aqueous electrolyte battery is provided.
  • FIG. 1 is a partially cutaway perspective view showing a nonaqueous electrolyte battery according to an embodiment.
  • FIG. 2 is an enlarged cross-sectional view of a part A in FIG.
  • FIG. 3 is a partially cutaway cross-sectional view of the nonaqueous electrolyte battery of the embodiment.
  • FIG. 4 is a side view of the battery of FIG.
  • FIG. 5 is a partially cutaway perspective view schematically showing the nonaqueous electrolyte battery of the embodiment.
  • FIG. 6 is a perspective view illustrating an example of an assembled battery used in the battery pack according to the embodiment.
  • FIG. 7 is a perspective view schematically showing an example of the battery pack according to the embodiment.
  • FIG. 8 is an exploded perspective view of another example of the battery pack according to the embodiment.
  • FIG. 9 is a block diagram showing an electric circuit of the battery pack of FIG. It is a figure which shows the thermogravimetric analysis result about the negative electrode active material of an Example and a comparative example.
  • a nonaqueous electrolyte battery including a positive electrode, a negative electrode, and a nonaqueous electrolyte is provided.
  • the negative electrode includes a negative electrode active material containing a titanium-containing oxide having a monoclinic structure that releases 0.01 to 0.5% by weight of H 2 O in a temperature range of 300 to 600 ° C.
  • the nonaqueous electrolyte battery contains moisture as an inevitable impurity.
  • water hydrolyzes LiPF 6 which is a lithium salt to generate protons (H + ).
  • a negative electrode active material containing a titanium-containing oxide having a monoclinic structure that releases 0.01 to 0.5% by weight of H 2 O in a temperature range of 300 to 600 ° C. is used in a high temperature environment of a nonaqueous electrolyte battery.
  • the cycle life performance can be greatly improved.
  • H 2 O released from a titanium-containing oxide having a monoclinic structure in a temperature range of 300 to 600 ° C. is not chemically or physically adsorbed on the particle surface of the titanium-containing oxide but contains titanium. Although it exists in the crystal
  • H 2 O is present in the crystal of the titanium-containing oxide.
  • Oxonium ions (H 3 + O) or protons (H + ) are taken into the particles, and as a result, hydrolysis reaction and gas generation caused by these cations are suppressed.
  • a more preferable range of the release amount of H 2 O is 0.02 to 0.3% by weight.
  • TG Thermogravimetry
  • MS Mass spectrometry
  • the specific measurement method is as follows.
  • a nonaqueous electrolyte battery having a battery voltage of 1.5 V or less is disassembled, and titanium-containing oxide particles having a monoclinic structure are taken out from the negative electrode.
  • the titanium-containing oxide particles taken out are sufficiently washed with water or the like to remove deposits (for example, non-aqueous electrolyte, lithium salt, conductive agent, binder) on the particle surface, and then the titanium-containing oxide particles are added to 100
  • deposits for example, non-aqueous electrolyte, lithium salt, conductive agent, binder
  • a titanium-containing oxide having a monoclinic structure can occlude and release lithium ions or sodium ions.
  • titanium dioxide can be obtained.
  • lithium titanium oxide can be obtained.
  • sodium titanium oxide can be taken. Therefore, the general formula of the titanium-containing oxide having a monoclinic structure is represented by Li x TiO 2 (0 ⁇ x ⁇ 1) or Na y TiO 2 (0 ⁇ y ⁇ 1).
  • the titanium-containing oxide having a monoclinic structure preferably has an intensity ratio (Ib / Ia) of 0 or more and 0.7 or less.
  • the intensity Ia is the intensity of the peak top (Pa) of the (002) plane where the diffraction angle (2 ⁇ ) appears at 27 deg to 29 deg in the powder X-ray diffraction method using a Cu—K ⁇ ray source, and the intensity Ib is Cu—K ⁇ .
  • it is 0 or more and 0.5 or less.
  • the intensity Ib is set to zero.
  • the titanium-containing oxide having a monoclinic structure preferably has a crystallite size in the range of 5 to 100 nm by X-ray diffraction. By being in this range, since the diffusion distance of lithium ions in the solid is shortened, the diffusibility of lithium ions in the solid is improved.
  • the crystallite size is preferably in the range of 10 to 30 nm. Thereby, it becomes possible to keep the content of H 2 O molecules in the crystal in an appropriate range.
  • a titanium-containing oxide having a monoclinic structure releasing 0.01 to 0.5% by weight of H 2 O in a temperature range of 300 to 600 ° C. can be produced by the following synthesis method.
  • This manufacturing method includes a step of obtaining an alkali titanate compound, a step of reacting an acid with the alkali titanate compound to proton exchange an alkali cation to obtain a titanate proton compound as a proton exchanger, and a proton exchanger (titanium Heat treating the acid proton compound) in a temperature range of 250 to 500 ° C. in a pressurized atmosphere.
  • a proton exchanger (a titanate proton compound) is added at 1.1 to 3 atm. It is preferable to perform heat treatment for a long time (for example, 5 hours or more) in a low temperature range of 200 to 350 ° C. in a pressurized atmosphere in the range. Alternatively, it is preferable to perform the heat treatment for a short time (for example, 1 hour or less) at a high temperature of 400 to 500 ° C. in a pressurized atmosphere in the range of 1.2 atmospheres to 5 atmospheres in a range in which anatase TiO 2 is not generated. . By setting the firing temperature to 500 ° C. or lower, it is possible to suppress the production of anatase TiO 2 .
  • alkali titanate compounds include K 2 Ti 2 O 5 , Na 2 T 3 O 7 , K 2 Ti 4 O 9 and Cs 2 Ti 5 O 12 .
  • the acid include hydrochloric acid, nitric acid, and sulfuric acid.
  • the concentration of the aqueous acid solution is preferably in the range of 0.5 to 2M.
  • Negative electrode This negative electrode has a negative electrode current collector and a negative electrode active material-containing layer (negative electrode material layer) supported on one or both sides of the current collector and containing an active material, a conductive agent, and a binder.
  • the negative electrode active material only a monoclinic structure titanium-containing oxide may be used, but other negative electrode active materials may be included.
  • other negative electrode active materials include spinel-type lithium titanium oxide (for example, general formula Li 4/3 + x Ti 5/3 O 4 (0 ⁇ x ⁇ 1.1)), ramsdellite-type lithium titanium oxide Product (for example, Li 2 + x Ti 3 O 7 ( ⁇ 1 ⁇ x ⁇ 3)), Li 1 + x Ti 2 O 4 (0 ⁇ x ⁇ 1), Li 1.1 + x Ti 1.8 O 4 (0 ⁇ x ⁇ 1) ), Li 1.07 + x Ti 1.86 O 4 (0 ⁇ x ⁇ 1), niobium titanium oxide, and the like.
  • the ratio of the other negative electrode active material to the whole negative electrode active material is desirably 50% by weight or less.
  • niobium titanium oxide examples include Li a TiM b Nb 2 ⁇ ⁇ O 7 ⁇ ⁇ (0 ⁇ a ⁇ 5, 0 ⁇ b ⁇ 0.3, 0 ⁇ ⁇ ⁇ 0.3, 0 ⁇ ⁇ ⁇ 0.3).
  • M includes one represented by one or more elements selected from the group consisting of Fe, V, Mo, and Ta.
  • Examples of the conductive agent include acetylene black, carbon black, coke, carbon fiber, graphite, Li 4 Ti 5 O 12 , metal compound powder, and metal powder.
  • the type of the conductive agent can be one type or two or more types.
  • Examples of preferable conductive agents include coke having a heat treatment temperature of 800 ° C. to 2000 ° C. and an average particle size of 10 ⁇ m or less, graphite, acetylene black, metal compound powder (eg, TiO, TiC, TiN powder), metal powder (eg, Al, Ni, Cu, Fe powder).
  • Further preferable examples include graphite, carbon fiber having a fiber diameter of 1 ⁇ m or less, acetylene black, coke, and Li 4 Ti 5 O 12 .
  • electrode resistance can be reduced and cycle life performance can be improved. Further, by using carbon fibers having a fiber diameter of 1 ⁇ m or less and / or Li 4 Ti 5 O 12 as a conductive agent, it is possible to reduce electrode resistance and improve cycle life performance.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine rubber, acrylic rubber, styrene butadiene rubber, core shell binder, and polyimide.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • fluorine rubber acrylic rubber
  • styrene butadiene rubber core shell binder
  • core shell binder examples include polyimide.
  • the kind of binder can be made into 1 type, or 2 or more types.
  • the compounding ratio of the negative electrode active material, the conductive agent and the binder is preferably in the range of 80 to 95% by weight of the negative electrode active material, 1 to 18% by weight of the conductive agent, and 2 to 7% by weight of the binder.
  • the porosity of the negative electrode (excluding the current collector) is preferably in the range of 20 to 50%. Thereby, it is possible to obtain a negative electrode having excellent affinity between the negative electrode and the non-aqueous electrolyte and a high density. A more preferable range of the porosity is 25 to 40%.
  • the negative electrode current collector is preferably an aluminum foil or an aluminum alloy foil.
  • the thickness of the aluminum foil and the aluminum alloy foil is 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the purity of the aluminum foil is preferably 99.99% by weight or more.
  • As the aluminum alloy an aluminum alloy containing at least one element selected from the group consisting of magnesium, zinc and silicon is preferable.
  • transition metals such as iron, copper, nickel, and chromium are preferably 100 ppm by weight or less.
  • the negative electrode active material particles, the conductive agent and the binder are suspended in an appropriate solvent, and the suspension is applied to a current collector, dried, and subjected to a press (for example, a warming press). It is produced by this.
  • a press for example, a warming press
  • This positive electrode comprises a positive electrode current collector and a positive electrode active material-containing layer (positive electrode material layer) that is carried on one or both surfaces of the current collector and contains a positive electrode active material, a conductive agent, and a binder.
  • LiMn 1.5 Ni 0 .5 O 4 is preferred.
  • the potential of the positive electrode containing LiMn 1.5 Ni 0.5 O 4 can be as high as 4.7 (V vs. Li / Li + ).
  • a positive electrode containing LiMn 1.5 Ni 0.5 O 4 with a negative electrode it is preferable because a high voltage of 3.1 V can be obtained as the intermediate voltage of the battery (cell intermediate voltage). Further, gas generation can be suppressed even at high temperatures, and the cycle life can be greatly improved.
  • LiFeSO 4 F having a tabolite structure or a triplite structure LiFe 0.9 Mn 0.1 SO 4 F having a tabolite structure or a triplite structure is preferable.
  • the BET specific surface area of an active material particle can be 5 m ⁇ 2 > / g or more.
  • the intermediate voltage (cell intermediate voltage) of the battery can be set to 1.95V.
  • the intermediate voltage of the battery (cell intermediate voltage) can be set to 2.3V.
  • the specific surface area of the LiboSO 4 F of the tabolite structure or LiFe 0.9 Mn 0.1 SO 4 F of the triplite structure is set to 5 m 2 / g or more.
  • gas generation can be suppressed even at high temperatures, and the cycle life can be greatly improved.
  • the phosphate compound having an olivine structure represented by Li x Fe 1-yz Mn y M z PO 4 LiMn 0.85 Fe 0.1 Mg 0.05 PO 4 and LiFePO 4 are preferable.
  • the BET specific surface area of an active material particle can be 8 m ⁇ 2 > / g or more.
  • the positive electrode containing LiMn 0.85 Fe 0.1 Mg 0.05 PO 4 in the negative electrode containing a negative electrode active material according to the embodiment is an intermediate voltage of the battery (cell intermediate voltage) to 2.5V it can.
  • the battery intermediate voltage (cell intermediate voltage) can be 1.8V.
  • the specific surface area of the phosphate compound having an olivine structure represented by Li x Fe 1-yz Mn y M z PO 4 is set to 8 m 2 / g or more.
  • gas generation can be suppressed even at high temperatures, and the cycle life can be greatly improved.
  • the positive electrode containing a phosphate compound and / or a fluorinated sulfuric acid compound having an olivine structure may contain an oxide of at least one metal selected from the group consisting of cobalt, nickel and manganese. More preferable examples of the metal oxide include Li x CoO 2 (0 ⁇ x ⁇ 1), LiNi 1-e Co e Mn f O 2 (0 ⁇ e ⁇ 1, 0 ⁇ f ⁇ 1), Li x Mn 2 O 4 (0 ⁇ x ⁇ 1) and the like are included.
  • the addition amount of the metal oxide to the positive electrode active material-containing layer 30% by weight or less, the electrode density is increased and the volume specific capacity of the electrode is improved.
  • the average particle diameter (diameter) of the primary particles of the positive electrode active material is 1 ⁇ m or less, more preferably 0.05 to 0.5 ⁇ m. It is preferable that at least a part of the particle surface of the positive electrode active material is coated with a carbon material.
  • the carbon material may take the form of a layer structure, a particle structure, or an aggregate of particles.
  • Examples of the conductive agent include acetylene black, carbon black, graphite, carbon fiber and the like. Carbon fibers having a fiber diameter of 1 ⁇ m or less, particularly vapor-grown carbon fibers having a fiber diameter of 1 ⁇ m or less are preferred. By including a carbon fiber having a fiber diameter of 1 ⁇ m or less, the problem of large electron conduction resistance of the positive electrode can be improved by a network of carbon fibers having a small fiber diameter, and the positive electrode resistance can be effectively reduced. For this reason, the output performance of a positive electrode can be improved significantly.
  • the positive electrode may contain an oxide of at least one metal selected from the group consisting of cobalt, nickel and manganese. More preferable examples of the metal oxide include Li x CoO 2 (0 ⁇ x ⁇ 1), LiNi 1-e Co e Mn f O 2 (0 ⁇ e ⁇ 1, 0 ⁇ f ⁇ 1), Li x Mn 2 O 4 (0 ⁇ x ⁇ 1) and the like are included.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, acrylic acid, and the like.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • fluorine-based rubber acrylic acid, and the like.
  • the kind of binder can be made into 1 type, or 2 or more types.
  • the compounding ratio of the positive electrode active material, the conductive agent and the binder is preferably in the range of 80 to 95% by weight of the positive electrode active material, 3 to 19% by weight of the conductive agent, and 1 to 7% by weight of the binder.
  • the current collector is preferably an aluminum foil or an aluminum alloy foil, and the thickness is desirably 20 ⁇ m or less, more preferably 15 ⁇ m or less.
  • the positive electrode is produced, for example, by suspending a positive electrode active material, a conductive agent, and a binder in a suitable solvent, applying the suspension to a current collector, drying, and pressing.
  • the specific surface area by the BET method of the positive electrode active material-containing layer is preferably in the range of 0.1 to 10 m 2 / g.
  • Non-aqueous electrolyte is a liquid, gel-like, solid electrolyte having lithium ion conductivity, and may contain an organic electrolyte containing a lithium salt, an ionic liquid, a polymer solid electrolyte, and an inorganic solid electrolyte. preferable. Further, it is a liquid, gel, or solid electrolyte having sodium ion conductivity, and may contain an organic electrolyte containing sodium salt, an ionic liquid, a polymer solid electrolyte, or an inorganic solid electrolyte.
  • non-aqueous electrolytes examples include a liquid organic electrolyte prepared by dissolving an electrolyte in an organic solvent, a gel organic electrolyte obtained by combining a liquid organic solvent and a polymer material, lithium metal oxide, lithium metal Examples thereof include solid nonaqueous electrolytes in which a sulfide or lithium salt electrolyte and a polymer material are combined. Moreover, you may use the normal temperature molten salt (ionic melt) containing lithium ion as a non-aqueous electrolyte.
  • the polymer material examples include polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyethylene oxide (PEO), and the like.
  • a liquid non-aqueous electrolyte is prepared by dissolving a lithium salt electrolyte in an organic solvent at a concentration of 0.5 to 2.5 mol / L.
  • lithium salt electrolytes examples include LiBF 4 , LiPF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ). 2 , Li (CF 3 SO 2 ) 3 C, LiB [(OCO) 2 ] 2 and the like.
  • the type of electrolyte used can be one type or two or more types. Among them, LiPF 6, LiBF 4, LiN (FSO 2) preferably comprises one or more selected from the group consisting of 2. Thereby, the chemical stability of the organic solvent is increased, the film resistance on the negative electrode can be reduced, and the low temperature performance and cycle life performance can be greatly improved.
  • a sodium salt electrolyte in which lithium ions are replaced with sodium ions can be used.
  • organic solvent examples include cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC), chain carbonates such as diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC), dimethoxyethane ( DME) and chain ethers such as diethoxyethane (DEE), cyclic ethers such as tetrahydrofuran (THF) and dioxolane (DOX), ⁇ -butyrolactone (GBL), 2-methyl- ⁇ -butyrolactone (MBL), acetonitrile (AN) ), 3-methoxypropiononitrile (MOPN), sulfolane (SL), and the like.
  • cyclic carbonates such as propylene carbonate (PC) and ethylene carbonate (EC)
  • chain carbonates such as diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC)
  • DME dim
  • organic solvents can be used alone or in the form of a mixture of two or more.
  • the main component is one or more selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), and ⁇ -butyrolactone (GBL), and the boiling point becomes 200 ° C. or higher, resulting in high thermal stability. .
  • ⁇ -butyrolactone GBL
  • 2-methyl- ⁇ -butyrolactone MBL
  • 3-methoxypropiononitrile MOPN
  • GBL ⁇ -butyrolactone
  • MBL 2-methyl- ⁇ -butyrolactone
  • MOPN 3-methoxypropiononitrile
  • the lithium ion concentration at the interface between the positive electrode and the non-aqueous electrolyte is rapidly reduced during discharge with a large current, and the output may be significantly reduced.
  • the concentration exceeds 3 mol / L the viscosity of the non-aqueous electrolyte increases, and the migration rate of lithium ions may decrease, resulting in a significant decrease in output.
  • the room temperature molten salt (ionic melt) is preferably composed of lithium ions or sodium ions, an organic cation, and an organic anion.
  • the room temperature molten salt is preferably liquid at room temperature or lower.
  • an electrolyte containing a room temperature molten salt will be described.
  • Room temperature molten salt refers to a salt that is at least partially liquid at room temperature
  • room temperature refers to a temperature range in which the power supply is assumed to normally operate.
  • the temperature range in which the power supply is assumed to operate normally has an upper limit of about 120 ° C., in some cases about 60 ° C., and a lower limit of about ⁇ 40 ° C., in some cases about ⁇ 20 ° C. In particular, a range of ⁇ 20 ° C. or more and 60 ° C. or less is suitable.
  • ionic melt composed of lithium ions, organic cations and anions.
  • the ionic melt is preferably in a liquid state even at room temperature or lower.
  • organic cation examples include alkyl imidazolium ions and quaternary ammonium ions having a skeleton shown in Chemical Formula 1 below.
  • alkyl imidazolium ion a dialkyl imidazolium ion, a trialkyl imidazolium ion, a tetraalkyl imidazolium ion and the like are preferable.
  • dialkylimidazolium 1-methyl-3-ethylimidazolium ion (MEI + ) and the like are preferable.
  • trialkylimidazolium ion 1,2-diethyl-3-propylimidazolium ion (DMPI + ) and the like are preferable.
  • tetraalkylimidazolium ion 1,2-diethyl-3,4 (5) -dimethylimidazolium ion and the like are preferable.
  • quaternary ammonium ions tetraalkylammonium ions, cyclic ammonium ions and the like are preferable.
  • tetraalkylammonium ion dimethylethylmethoxyethylammonium ion, dimethylethylmethoxymethylammonium ion, dimethylethylethoxyethylammonium ion, and trimethylpropylammonium ion are preferable.
  • the melting point can be made 100 ° C. or lower, more preferably 20 ° C. or lower. Furthermore, the reactivity with the negative electrode can be lowered.
  • the concentration of lithium ions is preferably 20 mol% or less. A more preferred range is from 1 to 10 mol%. By setting it within the above range, a liquid room temperature molten salt can be easily formed even at a low temperature of 20 ° C. or lower. Further, the viscosity can be lowered even at room temperature or lower, and the ionic conductivity can be increased.
  • at least one anion selected from (CF 3 SO 2 ) 2 ⁇ , N (C 2 F 5 SO 2 ) 2 ⁇ , (CF 3 SO 2 ) 3 C ⁇ and the like coexists.
  • More preferred anions include BF 4 ⁇ , (FSO 2 ) 2 N ⁇ , CF 3 SO 3 ⁇ , CF 3 COO ⁇ , CH 3 COO ⁇ , CO 3 2 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , N (C 2 F 5 SO 2 ) 2 ⁇ and (CF 3 SO 2 ) 3 C ⁇ .
  • These anions make it easier to form a room temperature molten salt at 0 ° C. or lower.
  • the nonaqueous electrolyte battery may include a separator and an exterior member in addition to the positive electrode, the negative electrode, and the nonaqueous electrolyte.
  • a separator and an exterior member in addition to the positive electrode, the negative electrode, and the nonaqueous electrolyte.
  • a separator can be disposed between the positive electrode and the negative electrode.
  • the separator include a synthetic resin nonwoven fabric, a porous film, and a cellulose nonwoven fabric.
  • a porous film can be formed from polyolefin, such as polyethylene and a polypropylene, for example.
  • the separator is preferably a non-woven fabric or a porous membrane containing cellulose and / or polyolefin having a thickness of 30 ⁇ m or less and a porosity of 50% or more. It is preferable to use a cellulose fiber separator having a porosity of 60% or more. The fiber diameter is preferably 10 ⁇ m or less. Examples of the separator include non-woven fabric, film, and paper. Cellulose fiber separators with a porosity of 60% or more have good nonaqueous electrolyte impregnation properties, and can provide high output performance from low to high temperatures. A more preferable range of the porosity is 62% to 80%.
  • the negative electrode containing the negative electrode active material of the embodiment does not react with a separator made of cellulose fiber having a porosity of 60% or more even during long-term charge storage, float charge or overcharge, and the negative electrode formed by lithium metal dendride precipitation No short circuit with the positive electrode occurs. Furthermore, by making the fiber diameter 10 ⁇ m or less, the affinity between the separator and the non-aqueous electrolyte is improved, and the battery resistance can be reduced. A more preferable fiber diameter range is 3 ⁇ m or less.
  • the separator preferably has a thickness of 20 to 100 ⁇ m and a density of 0.2 to 0.9 g / cm 3 . Within this range, it is possible to balance the mechanical strength and the battery resistance reduction, and it is possible to provide a battery that is high in output and hardly shorts internally. Moreover, there is little heat shrinkage in a high temperature environment, and good high temperature storage performance can be obtained.
  • Exterior member examples include a laminate film container and a metal container.
  • the shape of the container depends on the form of the nonaqueous electrolyte battery.
  • the nonaqueous electrolyte battery examples include a flat battery, a square battery, a cylindrical battery, a coin battery, a button battery, a sheet battery, a stacked battery, a large battery mounted on an electric vehicle, and the like.
  • the preferable range of the thickness of the laminate film is 0.5 mm or less. A more preferable range is 0.2 mm or less. Moreover, it is desirable that the lower limit value of the thickness of the laminate film be 0.01 mm.
  • the more preferable range of the plate thickness of the metal container is 0.5 mm or less. Further, the lower limit value of the plate thickness of the metal container is desirably 0.05 mm.
  • the laminate film examples include a multilayer film including a metal layer and a resin layer covering the metal layer.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil.
  • the resin layer is for reinforcing the metal layer, and can be formed of a polymer such as polypropylene (PP), polyethylene (PE), nylon, polyethylene terephthalate (PET).
  • a laminate film container can be obtained, for example, by laminating a laminate film by heat fusion.
  • the metal container is preferably formed from aluminum or an aluminum alloy.
  • the strength is increased by a metal container made of an aluminum alloy, and sufficient mechanical strength can be ensured even if the thickness of the container is reduced. Thereby, since the heat dissipation of a container can be improved, the raise of battery temperature can be suppressed. Further, the energy density can be improved to reduce the weight and size of the battery.
  • the aluminum alloy an alloy containing at least one element selected from the group consisting of magnesium, zinc and silicon is preferable.
  • the content of transition metals such as iron, copper, nickel, and chromium in aluminum and aluminum alloy is 100 ppm or less.
  • the metal container can be sealed with a laser. For this reason, the volume of a sealing part can be decreased compared with the container made from a laminate film, and an energy density can be improved.
  • the non-aqueous electrolyte battery of the embodiment can be applied to various forms of non-aqueous electrolyte batteries such as a square, cylindrical, flat, thin, coin type, etc. Examples include a rectangular battery or a cylindrical battery using a manufactured exterior member, and a thin battery using a laminated film exterior member. An example of the nonaqueous electrolyte battery will be described with reference to FIGS.
  • FIG. 1 and FIG. 2 show an example of a nonaqueous electrolyte battery using a laminate film exterior member.
  • the laminated electrode group 1 is housed in a bag-like container 2 made of a laminate film in which a metal layer is interposed between two resin films.
  • the stacked electrode group 1 has a structure in which positive electrodes 3 and negative electrodes 4 are alternately stacked with separators 5 interposed therebetween.
  • a plurality of negative electrodes 4 are present, each including a current collector 4a and a negative electrode active material-containing layer 4b formed on both surfaces of the current collector 4a.
  • One side of the current collector 4 a of each negative electrode 4 protrudes from the positive electrode 3.
  • the protruding current collector 4 a is electrically connected to the strip-shaped negative electrode terminal 6.
  • the tip of the strip-like negative electrode terminal 6 is drawn out from the container 2 to the outside.
  • the current collector 3a of the positive electrode 3 has a side protruding from the negative electrode 4 on the side opposite to the protruding side of the current collector 4a.
  • the current collector 3 a protruding from the negative electrode 4 is electrically connected to the belt-like positive electrode terminal 7.
  • the tip of the strip-like positive electrode terminal 7 is located on the opposite side to the negative electrode terminal 6 and is drawn out from the side of the container 2 to the outside.
  • 3 and 4 show an example of a nonaqueous electrolyte battery using a metal container.
  • the electrode group 11 is housed in a rectangular cylindrical metal container 12.
  • the electrode group 11 has a structure in which a positive electrode 13 and a negative electrode 14 are wound in a spiral shape so that a flat shape is formed with a separator 15 interposed therebetween.
  • a nonaqueous electrolyte (not shown) is held by the electrode group 11.
  • a strip-like positive electrode lead 16 is electrically connected to each of a plurality of locations at the end of the positive electrode 13 located on the end face of the electrode group 1.
  • a strip-like negative electrode lead 17 is electrically connected to each of a plurality of locations at the end of the negative electrode 14 located on this end face.
  • the plurality of positive electrode leads 16 are electrically connected to the positive electrode conductive tab 18 in a bundled state.
  • a positive electrode terminal is constituted by the positive electrode lead 16 and the positive electrode conductive tab 18.
  • the negative electrode lead 17 is connected to the negative electrode conductive tab 19 in a bundled state.
  • the negative electrode lead 17 and the negative electrode conductive tab 19 constitute a negative electrode terminal.
  • the metal sealing plate 20 is fixed to the opening of the metal container 12 by welding or the like.
  • the positive electrode conductive tab 18 and the negative electrode conductive tab 19 are each drawn out from an extraction hole provided in the sealing plate 20.
  • the inner peripheral surface of each extraction hole of the sealing plate 20 is covered with an insulating member 21 in order to avoid a short circuit due to contact with the positive electrode conductive tab 18 and the negative electrode conductive tab 19.
  • FIG. 5 shows another example of a nonaqueous electrolyte battery using a metal container.
  • the flat or thin nonaqueous electrolyte battery shown in FIG. 5 is a rectangular parallelepiped aluminum alloy container 22, an electrode group 23 housed in the container 22, and housed in the container 22 and held by the electrode group 23.
  • Non-aqueous electrolyte (not shown).
  • the electrode group 23 has a structure in which a positive electrode 24 and a negative electrode 25 are wound in a spiral shape so that a flat shape is formed with a separator 26 interposed therebetween.
  • the electrode group 23 is produced, for example, by winding a positive electrode 24 and a negative electrode 25 in a spiral shape with a separator 26 interposed therebetween, and then applying a heat press.
  • the strip-like positive electrode lead 27 is electrically connected to the positive electrode 24.
  • the strip-shaped negative electrode lead 28 is electrically connected to the negative electrode 25.
  • the positive electrode lead 27 is electrically connected to the container 22, and the negative electrode lead 28 is electrically connected to a negative electrode terminal 29 that is insulated from the container 22.
  • the assembled battery which uses a nonaqueous electrolyte battery as a unit cell, and the battery pack containing this assembled battery can be provided.
  • the nonaqueous electrolyte of the first embodiment can be used for the nonaqueous electrolyte battery.
  • Examples of the assembled battery include a plurality of unit cells electrically connected in series or in parallel as a constituent unit, a unit composed of a plurality of unit cells electrically connected in series, or electrically connected in parallel Examples include a unit including a unit composed of a plurality of unit cells.
  • Examples of a form in which a plurality of non-aqueous electrolyte batteries are electrically connected in series or in parallel include those in which a plurality of batteries each having an exterior member are electrically connected in series or in parallel, and are accommodated in a common housing.
  • a plurality of electrode groups electrically connected in series or in parallel are included.
  • the positive terminals and the negative terminals of a plurality of nonaqueous electrolyte batteries are connected by a metal bus bar (for example, aluminum, nickel, copper).
  • a plurality of electrode groups are accommodated in a single casing in an electrochemically insulated state by partition walls, and these electrode groups are electrically connected in series.
  • a metal can made of aluminum alloy, iron, stainless steel, a plastic container, or the like can be used. Further, the plate thickness of the container is desirably 0.5 mm or more.
  • Assembled battery 31 shown in FIG. 6 includes a plurality non-aqueous electrolyte battery of the square according to the first embodiment (e.g. FIG. 3, FIG. 4) 32 1 to 32 5 as a unit cell.
  • a battery 32 1 of the positive electrode conductive tab 18, a negative electrode conductive tab 19 of the battery 32 2 located next to it, are electrically connected by a lead 33.
  • a negative electrode conductive tab 19 of the battery 32 3 positioned positive electrode conductive tab 18 of the battery 32 2 next to it are electrically connected by a lead 33. In this way, the batteries 32 1 to 32 5 are connected in series.
  • the battery pack 40 includes an assembled battery composed of the nonaqueous electrolyte battery shown in FIGS.
  • the battery pack 40 includes a housing 41 and an assembled battery 42 accommodated in the housing 41.
  • Battery pack 42 is to nonaqueous electrolyte battery 43 1-43 5 a plurality (e.g. five) are electrically connected in series.
  • a nonaqueous electrolyte battery 43 1-43 5 are stacked in the thickness direction.
  • the housing 41 has an opening 44 on each of the upper part and the four side surfaces. Side nonaqueous electrolyte battery 43 1-43 5 of the positive and negative electrode terminals 6 and 7 are protruded is exposed to the opening 44 of the housing 41.
  • Output positive terminal of the assembled battery 42 45 form a strip, one end is electrically connected to the 6 one of the positive terminal of the nonaqueous electrolyte battery 43 1-43 5, and the other end of the housing 41 opening 44 protrudes from the upper portion of the housing 41.
  • the output negative terminal 46 of the assembled battery 42 without a band, one end of which is connected one of the negative electrode terminal 7 and electrically non-aqueous electrolyte battery 43 1-43 5, and the other end of the housing 41 It protrudes from the opening 44 and protrudes from the upper part of the housing 41.
  • a plurality of unit cells 51 composed of a flat type non-aqueous electrolyte battery are stacked so that the negative electrode terminal 52 and the positive electrode terminal 53 extending to the outside are aligned in the same direction, and are assembled by fastening with an adhesive tape 54.
  • a battery 55 is configured.
  • the printed wiring board 56 is disposed to face the side surface of the unit cell 51 from which the negative electrode terminal 52 and the positive electrode terminal 53 extend. As shown in FIG. 9, a thermistor 57, a protection circuit 58, and a terminal 59 for energizing an external device are mounted on the printed wiring board 56. An insulating plate (not shown) is attached to the surface of the printed wiring board 56 facing the assembled battery 55 in order to avoid unnecessary connection with the wiring of the assembled battery 55.
  • the positive electrode lead 60 is connected to the positive electrode terminal 53 located at the lowermost layer of the assembled battery 55, and the tip thereof is inserted into the positive electrode connector 61 of the printed wiring board 56 and electrically connected thereto.
  • the negative electrode lead 62 is connected to the negative electrode terminal 52 located on the uppermost layer of the assembled battery 55, and the tip thereof is inserted into and electrically connected to the negative electrode side connector 63 of the printed wiring board 56.
  • These connectors 61 and 63 are connected to the protection circuit 58 through wirings 64 and 65 formed on the printed wiring board 56.
  • the thermistor 57 detects the temperature of the unit cell 51, and the detection signal is transmitted to the protection circuit 58.
  • the protection circuit 58 can cut off the plus wiring 66a and the minus wiring 66b between the protection circuit 58 and the energization terminal 59 to the external device under a predetermined condition.
  • the predetermined condition is, for example, when the temperature detected by the thermistor 57 is equal to or higher than a predetermined temperature.
  • the predetermined condition is when an overcharge, overdischarge, overcurrent, or the like of the unit cell 51 is detected. This detection of overcharge or the like is performed for each unit cell 51 or the assembled battery 55.
  • the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected. In the latter case, a lithium electrode used as a reference electrode is inserted into each unit cell 51. 8 and 9, a voltage detection wiring 67 is connected to each unit cell 51, and a detection signal is transmitted to the protection circuit 58 through the wiring 67.
  • Protective sheets 68 made of rubber or resin are arranged on the three side surfaces of the assembled battery 55 excluding the side surfaces from which the positive electrode terminal 53 and the negative electrode terminal 52 protrude.
  • the assembled battery 55 is stored in a storage container 69 together with each protective sheet 68 and the printed wiring board 56. That is, the protective sheet 68 is disposed on each of the inner side surface in the long side direction and the inner side surface in the short side direction of the storage container 69, and the printed wiring board 56 is disposed on the inner side surface on the opposite side in the short side direction.
  • the assembled battery 55 is located in a space surrounded by the protective sheet 68 and the printed wiring board 56.
  • the lid 70 is attached to the upper surface of the storage container 69.
  • a heat shrink tape may be used in place of the adhesive tape 54 for fixing the assembled battery 55.
  • protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tape is circulated, and then the heat shrinkable tape is heat shrunk to bind the assembled battery.
  • the mode of the battery pack is appropriately changed depending on the application.
  • a use of the battery pack one in which charging / discharging with a large current is desired is preferable.
  • Specific examples include a power source for a digital camera, a vehicle for a two- to four-wheel hybrid electric vehicle, a two- to four-wheel electric vehicle, an assist bicycle, and the like.
  • the vehicle-mounted one is suitable.
  • Example 1 LiMn 0.85 Fe 0.1 Mg 0.05 PO 4 particles having an olivine structure were prepared.
  • These particles contain secondary particles, and the average particle size of the primary particles was 50 nm.
  • the BET specific surface area was 25 m 2 / g.
  • Carbon fine particles having an average particle diameter of 5 nm were attached to the surface of LiMn 0.85 Fe 0.1 Mg 0.05 PO 4 particles.
  • the amount of carbon fine particles attached to the LiMn 0.85 Fe 0.1 Mg 0.05 PO 4 particles was 0.1% by weight.
  • the positive electrode active material thus obtained, 3% by weight of vapor-grown carbon fiber having a fiber diameter of 0.1 ⁇ m as a conductive agent, 5% by weight of graphite powder, and 5% by weight of graphite powder as a conductive agent. 5% by weight of PVdF was mixed and dispersed in an n-methylpyrrolidone (NMP) solvent to prepare a slurry. The obtained slurry was applied to both sides of a 15 ⁇ m thick aluminum alloy foil (purity 99% by weight), dried, and subjected to a pressing process. The thickness of the positive electrode active material-containing layer on one side was 43 ⁇ m, and the electrode density was 2.2 g. A positive electrode of / cm 3 was produced. The specific surface area of the positive electrode active material-containing layer was 8 m 2 / g. After producing the positive electrode, vacuum drying at 90 ° C. was performed for 24 hours.
  • NMP n-methylpyrrolidone
  • a negative electrode active material was produced by the following method. Spherical secondary particles of potassium titanate (K 2 Ti 2 O 5 ) having an average particle size of 10 ⁇ m were obtained by spray drying. Proton exchange was performed by adding potassium titanate particles in 1 M sulfuric acid solution and stirring at 25 ° C. for 2 weeks. The resulting proton exchanger is H 2 Ti 4 O 9 . The proton exchanger powder was washed with pure water and then washed until the pH of the washing solution was in the range of 6-7.
  • K 2 Ti 2 O 5 potassium titanate having an average particle size of 10 ⁇ m
  • the proton exchanger (H 2 Ti 4 O 9 ) was baked in an electric furnace at a temperature of 320 ° C. for 6 hours.
  • the atmosphere in the electric furnace was changed to a pressurized atmosphere by increasing the water vapor pressure.
  • Table 1 shows the atmospheric pressure. After heating, it was quickly removed from the electric furnace and rapidly cooled in the atmosphere.
  • the fired product was stored in a vacuum at 100 ° C. to remove adsorbed water and dried to obtain a sample of a titanium dioxide compound.
  • This sample was subjected to powder X-ray diffraction measurement using Cu—K ⁇ rays as a radiation source, and it was confirmed from the obtained diffraction rays that the titanium dioxide had a monoclinic structure belonging to the space group C2 / m.
  • the intensity ratio (Ib / Ia) was 0.43.
  • the intensity Ia is the intensity of the peak top (Pa) of the (002) plane where the diffraction angle (2 ⁇ ) in the powder X-ray diffraction method using a Cu—K ⁇ ray source appears as 27 deg to 29 deg
  • the intensity Ib is the diffraction angle ( 2 ⁇ ) is the intensity of the peak top (Pb) appearing at 29 deg to 32 deg.
  • the crystallite size by X-ray diffraction was 100 nm.
  • the obtained titanium dioxide particles have a 0.15 wt% H 2 O generated in the temperature range of 300 ° C. to 600 ° C. and a specific surface area of 20 m 2 / g by the BET method by N 2 adsorption. Met.
  • the average particle diameter of the primary particles was 0.3 ⁇ m, and the average particle diameter of the secondary particles was 10 ⁇ m.
  • a method for measuring the weight percentage of H 2 O will be described. With respect to 20 mg of titanium dioxide particles, TG measurement and MS measurement were performed under the condition of increasing the temperature from room temperature to 600 ° C. (temperature increase rate: 5 ° C./min). In MS measurement, He was used as a carrier gas. MS measurement revealed that the gas generated in the temperature range of 300 ° C.
  • Particles of titanium dioxide compound, acetylene black powder as a conductive agent, graphite powder having an average particle diameter of 6 ⁇ m, and PVdF as a binder are blended in a weight ratio of 85: 6: 5: 4, and n ⁇
  • a slurry was prepared by dispersing in a methylpyrrolidone (NMP) solvent and using a ball mill with stirring at a rotational speed of 1000 rpm and a stirring time of 2 hours.
  • NMP methylpyrrolidone
  • the obtained slurry was applied to an aluminum alloy foil (purity: 99.3% by weight) having a thickness of 15 ⁇ m, dried, and subjected to a heat press process, whereby the thickness of the negative electrode active material-containing layer on one side was 59 ⁇ m, and the electrode density Produced a negative electrode of 2.8 g / cm 3 .
  • vacuum drying at 90 ° C. was performed for 24 hours.
  • the BET specific surface area of the negative electrode active material-containing layer (surface area per 1 g of the negative electrode active material-containing layer) was 8 m 2 / g.
  • the porosity of the negative electrode excluding the current collector was 40%.
  • a plurality of positive electrodes and a plurality of negative electrodes were laminated with a separator made of a polyethylene porous film having a thickness of 12 ⁇ m interposed therebetween, to produce an electrode group.
  • a strip-shaped positive electrode terminal was electrically connected to the aluminum foil current collector of each of the plurality of positive electrodes, and a strip-shaped negative electrode terminal was electrically connected to the aluminum foil current collector of each of the plurality of negative electrodes.
  • This electrode group was accommodated in a laminate film container (exterior member) having a thickness of 6 mm, a width of 70 mm, and a height of 110 mm.
  • a liquid nonaqueous electrolyte was prepared by dissolving 1.5 mol / L of a lithium salt made of LiPF 6 in an organic solvent made of propylene carbonate (PC).
  • the obtained nonaqueous electrolyte was poured into a container to produce a thin nonaqueous electrolyte secondary battery having the structure shown in FIG.
  • the method for measuring the particles of the negative electrode active material is shown below.
  • a laser diffraction distribution measuring device Shiadzu SALD-300.
  • Electrode active material, and a BET specific surface area by N 2 adsorption of the negative electrode was measured under the following conditions.
  • Two pieces of 1 g of powdered negative electrode active material or 2 ⁇ 2 cm 2 negative electrodes were cut out and used as samples.
  • a BET specific surface area measuring apparatus manufactured by Yuasa Ionics was used, and nitrogen gas was used as an adsorption gas.
  • the specific surface area of the positive electrode active material-containing layer was measured by the same method as the BET specific surface area by N 2 adsorption of the negative electrode.
  • the porosity of the negative electrode is determined by comparing the volume of the negative electrode active material-containing layer with the volume of the negative electrode active material-containing layer when the porosity is 0%, and the volume of the negative electrode active material-containing layer when the porosity is 0%. This is calculated by regarding the increase in the volume as the pore volume.
  • the volume of the negative electrode active material-containing layer is the sum of the volumes of the negative electrode active material-containing layers on both sides when the negative electrode active material-containing layer is formed on both sides of the current collector.
  • Examples 2 to 15 and Comparative Examples 1 to 2 and 5 The type of positive electrode active material, the specific surface area of the positive electrode active material-containing layer (m 2 / g), the type of negative electrode active material, the pressure of the heat treatment atmosphere in the production of the negative electrode active material, released from the negative electrode active material at 300 to 600 ° C.
  • a nonaqueous electrolyte secondary battery was fabricated in the same manner as described in Example 1 except that the H 2 O amount (% by weight) was set as shown in Table 1 below.
  • Comparative Example 3 A nonaqueous electrolyte secondary battery was produced in the same manner as described in Example 1 except that the negative electrode active material produced by the following method was used.
  • the particles of the obtained lithium titanate (Li 4/3 Ti 5/3 O 4) is, 300 °C ⁇ H 2 O wt% of which occurred in the temperature range of 600 ° C. is 0 wt%, BET by N 2 adsorption
  • the specific surface area determined by the method was 8 m 2 / g.
  • the average particle diameter of the primary particles was 0.3 ⁇ m, and the average particle diameter of the secondary particles was 5 ⁇ m.
  • a nonaqueous electrolyte secondary battery was produced in the same manner as described in Example 1 except that the negative electrode active material described below was used.
  • anatase titanium dioxide (TiO 2 ) were used as the negative electrode active material.
  • the particles of anatase titanium dioxide (TiO 2 ) had 0% by weight of H 2 O generated in the temperature range of 300 ° C. to 600 ° C., and the specific surface area by the BET method by N 2 adsorption was 5 m 2 / g. It was.
  • the average particle diameter of the primary particles was 0.3 ⁇ m, and the average particle diameter of the secondary particles was 5 ⁇ m.
  • the nonaqueous electrolyte secondary battery is the same as described in Comparative Example 3 except that the type of the positive electrode active material and the specific surface area (m 2 / g) of the positive electrode active material-containing layer are set as shown in Table 1 below. Was made.
  • the nonaqueous electrolyte secondary battery is the same as described in Comparative Example 4 except that the type of the positive electrode active material and the specific surface area (m 2 / g) of the positive electrode active material-containing layer are set as shown in Table 1 below. Was made.
  • Examples 1 to 15 and Comparative Examples 1 to 7 were at a constant current of 1 C (1 hour rate) at 25 ° C. After charging to 3 V in 90 minutes, the discharge capacity (Ah) when discharged at 1 C to 1.5 V and the open circuit voltage (V) with a discharge rate of 50% were measured.
  • the 50 ° C high-temperature cycle test repeats the cycle of charging to 3V at a constant current of 3C in a 50 ° C environment, and then discharging at 3C to 1.5V, and the number of cycles and battery when the capacity reaches 80% of the initial capacity. The thickness change was measured.
  • Example 6 to 11 and Comparative Example 5 discharge capacity (Ah) when charging at a constant current of 1 C (1 hour rate) at 25 ° C. to 2.8 V in 90 minutes and then discharging to 1.2 V at 1 C Then, an open circuit voltage (V) with a discharge rate of 50% was measured.
  • the 50 ° C high-temperature cycle test repeats a cycle of charging to 2.8V at a constant current of 3C in a 50 ° C environment and then discharging at 3C to 1.2V, and the number of cycles when the capacity reaches 80% of the initial capacity. The battery thickness change was measured.
  • Example 12 to 15 and Comparative Examples 6 to 7 the discharge capacity when charging at a constant current of 1 C (1 hour rate) at 25 ° C. to 3.7 V in 90 minutes and then discharging to 2.5 V at 1 C ( Ah) and an open circuit voltage (V) with a discharge rate of 50%.
  • the 50 ° C high-temperature cycle test repeats a cycle of charging to 3.7V at a constant current of 3C in a 50 ° C environment and then discharging at 3C to 2.5V, and the number of cycles when the capacity reaches 80% of the initial capacity.
  • the battery thickness change was measured.
  • the nonaqueous electrolyte secondary batteries of Examples 1 to 15 are superior to Comparative Examples 1 to 7 in the balance of battery capacity, 50 ° C. high-temperature cycle life performance, and battery swelling.
  • Examples 8 and 9 having a H 2 O release amount of 0.02 to 0.3% by weight are compared with Example 10, Compared to 11, the battery capacity, 50 ° C high-temperature cycle life performance, and battery swelling are excellent.
  • Examples 12 and 13 having a H 2 O release amount of 0.02 to 0.3% by weight are compared with Examples 14 and 13, respectively.
  • the battery capacity, 50 ° C. high-temperature cycle life performance and battery swelling are excellent.
  • Example 6 using LiFePO 4 as the positive electrode active material has a battery capacity, 50 ° C. high-temperature cycle life performance, and battery swelling. The balance is excellent.
  • FIG. 10 shows the temperature change of the weight reduction rate of the negative electrode active material in the TG measurement of the negative electrode active material of Example 3 and Comparative Example 1.
  • the weight reduction rate up to 300 ° C. is smaller than that in Comparative Example 1, and the weight reduction rate increases when the temperature range is 300 to 600 ° C. If the temperature exceeds °C, there is almost no change in the weight loss rate.
  • the weight reduction rate up to 300 ° C. is larger than that in Example 3, and a slight weight reduction is observed in the temperature range exceeding 600 ° C.
  • the weight loss up to 300 ° C. is considered to be adsorbed water or crystal water of TiO 2 particles.
  • FIG. 11 shows the results of MS measurement of the negative electrode active materials of Example 3 and Comparative Example 1.
  • a negative electrode containing a monoclinic structure titanium-containing oxide that releases 0.01 to 0.5 wt% of H 2 O in a temperature range of 300 to 600 ° C. Since it contains an active material, it is possible to provide a nonaqueous electrolyte battery in which swelling under a high temperature environment is suppressed and cycle life performance is improved.
  • Nonaqueous electrolyte battery 33 ... Lead, 40 ... Battery pack , 41 ... housing, 42 ... assembled battery, 44 ... opening, 45 ... output positive terminal, 46 ... output negative terminal, 51 ... unit cell, 55 ... assembled battery, 56 ... printed wiring board, 57 ... thermistor, 58 .. protection circuit, 59... Terminal for energizing external equipment.

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Abstract

La présente invention porte, selon un mode de réalisation, sur une batterie à électrolyte non aqueux qui comprend une électrode positive 3, une électrode négative 4 et un électrolyte non aqueux. L'électrode négative contient une matière active d'électrode négative contenant un oxyde contenant du titane qui a une structure cristalline monoclinique et décharge de 0,01 à 0,5 % en poids de H2O dans la plage de température allant de 300 à 600 °C.
PCT/JP2015/074065 2015-08-26 2015-08-26 Batterie à électrolyte non aqueux et bloc-batterie WO2017033316A1 (fr)

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