WO2017154592A1 - Batterie à électrolyte non aqueux - Google Patents

Batterie à électrolyte non aqueux Download PDF

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WO2017154592A1
WO2017154592A1 PCT/JP2017/006813 JP2017006813W WO2017154592A1 WO 2017154592 A1 WO2017154592 A1 WO 2017154592A1 JP 2017006813 W JP2017006813 W JP 2017006813W WO 2017154592 A1 WO2017154592 A1 WO 2017154592A1
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positive electrode
battery
aqueous electrolyte
negative electrode
electrolyte battery
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PCT/JP2017/006813
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English (en)
Japanese (ja)
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智仁 関谷
山田　將之
妥則 政岡
敦 畠山
英寿 守上
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日立マクセル株式会社
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Priority to JP2017516978A priority Critical patent/JPWO2017154592A1/ja
Priority to CN201780015233.0A priority patent/CN108701858A/zh
Priority to KR1020187025239A priority patent/KR20180118657A/ko
Publication of WO2017154592A1 publication Critical patent/WO2017154592A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte battery having good storage characteristics.
  • Non-aqueous electrolyte secondary batteries are used in various applications by taking advantage of characteristics such as high capacity and high voltage. And with the spread of the application field, various characteristics improvement is calculated
  • Such a system is required to operate reliably in an emergency, although the opportunity to actually operate is limited. For this reason, a battery serving as a power source is required to have a reliability capable of maintaining its characteristics well even when stored for a long period of time.
  • tire pressure monitoring systems [TirePressure Monitoring System ( Vehicles equipped with TPMS)] are becoming widespread.
  • a non-aqueous electrolyte battery (primary battery) is used as a power source for the system.
  • the battery serving as the power source can be used for a long time. Reliability that can maintain the characteristics is required.
  • Patent Documents 1 and 2 propose proposals have been made to add a phosphoric acid ester compound having a specific structure to the non-aqueous electrolyte (Patent Documents 1 and 2).
  • lithium alloys such as metallic lithium and Li—Al (lithium-aluminum) alloys are used as the negative electrode active material of the non-aqueous electrolyte primary battery. Since a lithium alloy can be used as an active material, battery characteristics can be stabilized by forming a negative electrode using a clad material of a metal that can occlude and release lithium and a metal that does not occlude and release lithium. Has also been proposed (Patent Documents 3 to 5).
  • Patent Document 6 describes excellent storage by forming a nonaqueous electrolyte secondary battery using Li 2 Mn 2 O 4 , LiFePO 4 or LiWO 3 as a positive electrode active material and aluminum or an aluminum alloy as a negative electrode. It has been proposed to obtain a battery having characteristics.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a non-aqueous electrolyte battery that has good load characteristics at low temperatures even after high-temperature storage and has excellent reliability. is there.
  • the nonaqueous electrolyte battery of the present invention that has achieved the above object has an electrode body in which a positive electrode and a negative electrode are stacked with a separator interposed therebetween, and a nonaqueous electrolyte, and the positive electrode has an olivine structure.
  • the negative electrode has a laminate containing a metal base layer that is not alloyed with Li, and an Al metal layer bonded to the metal base layer, and the Al metal layer At least on the surface side, a Li—Al alloy is formed.
  • nonaqueous electrolyte battery of the present invention includes a negative electrode, a positive electrode, and a nonaqueous electrolyte
  • the negative electrode includes an alloy of Li and an element that can be alloyed with Li, and a negative electrode active material.
  • the positive electrode has a compound having an olivine structure as a positive electrode active material
  • the non-aqueous electrolyte has a phosphoric acid compound or boric acid having a group represented by the following general formula (1) in the molecule It is characterized by containing a compound.
  • X is Si, Ge or Sn
  • R 1 , R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or Represents an aryl group having 6 to 10 carbon atoms, and part or all of the hydrogen atoms may be substituted with fluorine.
  • FIG. 5 is a perspective view of FIG. 4.
  • the positive electrode related to the nonaqueous electrolyte battery for example, one having a structure in which a positive electrode mixture layer containing a positive electrode active material, a conductive additive, a binder, and the like is provided on one side or both sides of the current collector can be used.
  • a compound having an olivine structure is used as the positive electrode active material.
  • the positive electrode active material reacts with a non-aqueous electrolyte in a high temperature environment, a reaction product is deposited on the positive electrode, and gas is generated at the same time.
  • a reaction product is deposited on the positive electrode, and gas is generated at the same time.
  • the surface of lithium cobaltate reacts with the non-aqueous electrolyte at high temperatures to deposit reaction products containing Co on the surface.
  • gas is generated, but the reaction product containing Co is further decomposed and Co is eluted into the non-aqueous electrolyte.
  • the surface of the lithium cobalt oxide again reacts with the nonaqueous electrolytic solution to generate a reaction product containing Co and a gas. That is, if the positive electrode active material contains a large amount of lithium cobalt oxide, Co will continue to elute and gas will continue to be generated each time the battery is exposed to high temperatures.
  • the compound having an olivine structure is stable in the first place, even if the battery is exposed to a high temperature, metal elution and gas generation are suppressed. Therefore, when a compound having an olivine structure is used as the positive electrode active material, gas generation can be suppressed even during long-term storage such as one month, and a change in volume of the battery can be suppressed.
  • the compound having an olivine structure used as the positive electrode active material is a compound represented by a general formula such as LiM 1 PO 4 (M 1 : Co, Ni, Mn, Fe, etc.).
  • the compound having an olivine structure may contain one or more elements other than M 1 such as Al and Y as additive elements.
  • the compound having an olivine structure contained in the positive electrode mixture layer may be one that does not contain the additive element as described above or one that contains the additive element, or two or more kinds. It may be.
  • M 1 in the compound having an olivine structure is Fe
  • the compound having an olivine structure lithium iron phosphate it is preferable to use those represented by the following general formula (2).
  • M 2 is Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, It is at least one element selected from the group consisting of Mg, Al, Ca, Nb, Mo, Zr and Hf.
  • the average particle diameter of the compound particles having an olivine structure is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
  • the average particle size of the particles of the compound having an olivine structure becomes too large, the conductivity of the positive electrode mixture layer decreases and the charge / discharge characteristics decrease, so the average particle size is 20 ⁇ m or less. Is more preferable, it is more preferable that it is 17 micrometers or less, and it is especially preferable that it is 15 micrometers or less.
  • the particles of the compound having an olivine structure may be composed of primary particles, but are secondary particles in which primary particles having a particle diameter of about 10 to 100 nm are aggregated, or a granulated body obtained by granulating the primary particles.
  • the charge / discharge characteristics can be further improved as compared with primary particles having the same particle diameter, which is preferable.
  • the average particle size in this case may be calculated based on the particle size of the secondary particles or the granulated body.
  • the average particle diameter is a number average particle diameter measured using a laser scattering particle size distribution analyzer (for example, “LA-920” manufactured by Horiba, Ltd.).
  • Conventionally known methods can be adopted as a method of coating a compound having an olivine structure with a carbon material. Specifically, for example, a method of firing a mixture of an organic material that becomes a carbon precursor and a compound having an olivine structure; an olivine structure is decomposed while decomposing a gas that becomes a carbon precursor by a vapor deposition (CVD) method. And a general coating method such as a method of depositing carbon on the surface of a compound having the same.
  • CVD vapor deposition
  • the amount of carbon when the compound having the olivine structure is coated with the carbon material is 100 parts by mass of the compound having the olivine structure from the viewpoint of improving the conductivity of the positive electrode and enabling a more efficient charge / discharge reaction. On the other hand, it is preferably 1 part by mass or more. However, if the amount of carbon on the surface of the compound having an olivine structure is too large, carbon may become a barrier during the lithium ion insertion / release reaction, which may cause a reduction in load characteristics of the nonaqueous electrolyte battery, for example. Therefore, when the compound having an olivine structure is coated with a carbon material, the amount of carbon is preferably 5 parts by mass or less with respect to 100 parts by mass of the compound having an olivine structure.
  • the particle diameter when a carbon coating layer is provided on the particle surface of the compound having an olivine structure is the same as the particle diameter of the compound particle having the olivine structure. May be considered.
  • the BET specific surface area of the compound having an olivine structure is preferably 25 m 2 / g or less, more preferably 15 m 2 / g or less, and 13 m 2. / G or less is particularly preferable, and 10 m 2 / g or less is most preferable.
  • the BET specific surface area of the compound having an olivine structure is 5 m 2 / It is preferable to set it as g or more, and it is more preferable to set it as 8 m ⁇ 2 > / g or more.
  • the BET specific surface area is a value obtained by analyzing a gas adsorption amount measured by a gas adsorption method using nitrogen gas using the BET method.
  • the compound having the olivine structure includes lithium having a layered structure represented by Li 1 + z M 3 O 2 ( ⁇ 0.1 ⁇ z ⁇ 0.1, M 3 : Co, Ni, Mn, Al, Mg, etc.).
  • Other active materials such as a composite oxide containing oxide, LiMn 2 O 4 and lithium manganese oxide having a spinel structure in which a part of the element is substituted with another element can also be used.
  • lithium-containing composite oxide having a layered structure examples include lithium cobalt oxide such as LiCoO 2 and LiNi 1-a Co ab Al b O 2 (0.1 ⁇ a ⁇ 0.3, 0.01 ⁇ b ⁇ 0). .2) and other oxides containing at least Co, Ni and Mn (LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiNi 3 / 5 Mn 1/5 Co 1/5 O 2 etc.).
  • lithium cobalt oxide such as LiCoO 2 and LiNi 1-a Co ab Al b O 2 (0.1 ⁇ a ⁇ 0.3, 0.01 ⁇ b ⁇ 0).
  • other oxides containing at least Co, Ni and Mn LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiNi 3 / 5 Mn 1/5 Co 1/5 O 2 etc.
  • Examples of the conductive auxiliary agent related to the positive electrode mixture layer include acetylene black; ketjen black; carbon blacks such as channel black, furnace black, lamp black, and thermal black; carbon materials such as carbon fibers; and metal fibers.
  • Conductive fibers such as carbon fluoride, metal powders such as copper and nickel, organic conductive materials such as polyphenylene derivatives, and the like can be used.
  • binder relating to the positive electrode mixture layer examples include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyvinyl pyrrolidone (PVP), and acrylic resin (polyethylene). Acrylic ester) and the like.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • PVP polyvinyl pyrrolidone
  • acrylic resin polyethylene
  • a positive electrode mixture containing a positive electrode active material, a conductive additive and a binder is dispersed in a solvent (an organic solvent such as NMP or water) to form a positive electrode mixture-containing composition (paste, slurry, etc.).
  • a solvent an organic solvent such as NMP or water
  • the positive electrode mixture-containing composition can be prepared, applied to one side or both sides of the current collector, dried, and subjected to a press treatment as necessary.
  • a molded body may be formed using the positive electrode mixture, and a part or all of one side of the molded body may be bonded to a positive electrode current collector to form a positive electrode. Bonding of the positive electrode mixture molded body and the positive electrode current collector can be performed by press treatment or the like.
  • metal foil such as Al or Al alloy, punching metal, net, expanded metal, or the like can be used, but Al foil is usually preferably used.
  • the thickness of the positive electrode current collector is preferably 10 to 30 ⁇ m.
  • the composition of the positive electrode mixture layer is, for example, 80.0 to 99.8% by mass of the positive electrode active material, 0.1 to 10% by mass of the conductive auxiliary agent, and 0.1 to 10% by mass of the binder. It is preferable.
  • the thickness of the positive electrode mixture layer is preferably 30 to 300 ⁇ m per side of the current collector.
  • the positive electrode current collector can be provided with a positive electrode lead body according to a conventional method.
  • An alloy of Li and an alloyable element (Al, Si, Sn, etc.) and Li is used as the negative electrode active material for the negative electrode of the nonaqueous electrolyte battery.
  • a method of forming a negative electrode by combining the alloy powder with a binder or the like and applying this to the surface of a metal foil as a current collector Li and an alloy Non-aqueous electrolysis after assembling the battery by preparing an electrode to form a negative electrode by combining a powder composed of an element that can be converted with a binder, etc., and applying this to the surface of a metal foil as a current collector.
  • Examples include a method of alloying the powder of the electrode with Li by bringing it into contact with a liquid or further charging (subjecting a chemical conversion treatment).
  • Examples of the elements that can be alloyed with Li include Al, Si, Sn, Pb, and In, but they are highly flexible, for example, from the viewpoint of easy configuration of a wound electrode body and high capacity.
  • Al is preferably used.
  • a Li—Al alloy as a negative electrode active material
  • a Li foil and an Al foil are bonded together and introduced into a battery, and Li and Al are reacted in the presence of a non-aqueous electrolyte.
  • the negative electrode is made using Al powder as described above, or the negative electrode is made using Al foil, etc. What is necessary is just to charge a battery and to make Al react with Li electrochemically.
  • a metal foil (Cu (copper) foil, Cu alloy foil, etc.) to be a current collector is simply stacked on a laminate of Li foil and Al foil. If the battery is simply inserted into the battery, the internal resistance of the battery may increase after storage (particularly after storage in a high temperature environment), and sufficient characteristics may not be obtained.
  • the volume change occurs when the Li—Al alloy is formed by the laminated body of the Li foil and the Al foil, or the Li—Al alloy is formed and pulverization occurs. This is because the water electrolyte solution is easily absorbed and a volume change occurs, and the adhesion between the Li—Al alloy layer (Al foil) and the current collector cannot be secured.
  • an Al metal layer (Al foil or the like) for forming the Li—Al alloy is used. It is preferable to use a laminate (laminated metal foil) in which Li acting as a current collector and a metal base layer (such as Cu foil) that is not alloyed are joined in advance for assembling the battery. Further, it is preferable to form a Li—Al alloy by alloying at least the surface side of the Al metal layer with Li, and to form a negative electrode composed of a laminate of the metal base layer and the Li—Al alloy layer. Let it be an aspect.
  • the Li—Al alloy on at least the surface side of the Al metal layer is in contact with the non-aqueous electrolyte when the battery is assembled using the laminate (laminated metal foil).
  • the non-aqueous electrolyte battery is used as a secondary battery, it is preferable to form a Li—Al alloy in the chemical conversion treatment of the assembled battery.
  • an electrode body is formed by laminating a laminated metal foil in which an Al metal layer is bonded to the surface of a metal base layer and a positive electrode through a separator.
  • an electrode body is formed by laminating a laminated metal foil in which an Al metal layer is bonded to the surface of a metal base layer and a positive electrode through a separator.
  • the non-aqueous electrolyte battery when the negative electrode precursor comes into contact with the non-aqueous electrolyte, Li—Al is formed and changes to the negative electrode.
  • the non-aqueous electrolyte battery is a secondary battery, it is assembled.
  • the battery has a step of charging (charging step), preferably through a chemical conversion treatment step that further includes a step of discharging (discharging step), thereby changing the negative electrode precursor to a negative electrode, and non-aqueous electrolysis. A better function as a liquid battery can be produced.
  • Al in the Al metal layer electrochemically reacts with Li ions in the non-aqueous electrolyte, and a Li—Al alloy is formed on at least the surface side of the Al metal layer facing the positive electrode.
  • a negative electrode having a laminate of the metal substrate layer and the Li—Al alloy layer is formed.
  • the metal base layer described above as a preferred embodiment for forming the negative electrode is a metal such as Cu, Ni, Ti, Fe, or other elements and other elements.
  • the substrate layer may be made of a material having a high tensile strength such as a metal selected from Ni, Ti and Fe or an alloy thereof, and a material having a tensile strength at room temperature of 400 N / mm 2 or more. It is preferable to do.
  • a battery having a predetermined characteristic can be formed by resistance welding the base material layer to the sealing plate.
  • the characteristic deterioration due to the expansion of the negative electrode is increased.
  • the base material layer is made of a metal selected from Ni, Ti and Fe, such as Ni (490 N / mm 2 ), Ti (410 N / mm 2 ), SUS304 (600 N / mm 2 ), or an alloy thereof.
  • Ni 490 N / mm 2
  • Ti 410 N / mm 2
  • SUS304 600 N / mm 2
  • an alloy thereof an alloy thereof.
  • the negative electrode having a base material layer made of a material having a tensile strength of 400 N / mm 2 or more as described above, a change in the volume of the battery accompanying the deformation of the negative electrode can be further suppressed.
  • the base material layer should be composed of a material having a low volume resistivity at room temperature, and the volume resistivity should be 80 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less. More preferably, the material has a volume resistivity of 30 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less, and particularly preferably a material having a volume resistivity of 15 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or less.
  • the volume resistivity of the material is Ni: 6.8 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, Ti: 55 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, and SUS304: 72 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, respectively. From the point of view, it is particularly preferable that the base material layer is made of Ni or its alloy.
  • the base material layer is composed of the metal or alloy foil, a vapor deposition film, a plating film, or the like.
  • the Al metal layer is made of an Al or Al alloy foil, a vapor-deposited film, a plating film, etc., and the laminated metal foil formed by joining the base material layer and the Al metal layer constitutes the base material layer.
  • a clad material of a metal foil and an Al or Al alloy foil, or a laminated film in which an Al metal layer is formed by vapor-depositing Al or an Al alloy on the surface of the metal foil constituting the base layer is preferably used. .
  • the Al metal layer can be provided on one side or both sides of the base material layer, but the Al metal layer is bonded to both sides of the base material layer, and at least on the surface side of each Al metal layer.
  • the deformation (curvature, etc.) of the negative electrode and the accompanying battery are compared with the case where the Al metal layer is bonded to only one surface of the base material layer and the Li—Al alloy is formed. Therefore, it is desirable to assemble a battery using a laminated metal foil in which an Al metal layer is bonded to both surfaces of a base material layer.
  • the base material layer is Cu (Cu foil) and the case where the base material layer is Ni (Ni foil) will be described as an example, but the base material layer is a material other than Cu or Ni. Is the same.
  • the Cu layer related to the laminated metal foil formed by joining the Cu layer and the Al metal layer a layer made of Cu (and inevitable impurities), Zr, Cr, Zn, Ni, Si, P, etc. as alloy components are used. And a layer composed of Cu alloy with the balance being Cu and inevitable impurities (the content of the alloy components is, for example, 10% by mass or less, preferably 1% by mass or less in total).
  • the Ni layer related to the laminated metal foil formed by joining the Ni layer and the Al metal layer includes a layer made of Ni (and inevitable impurities), and Zr, Cr, Zn, Cu, Fe, Si, P as alloy components. And the like, and the balance is Ni and an inevitable impurity Ni alloy (the content of the alloy components is, for example, 20% by mass or less in total).
  • Al As an Al metal layer related to a laminated metal foil formed by joining a Cu layer and an Al metal layer or a laminated metal foil formed by joining an Ni layer and an Al metal layer, Al (and inevitable impurities) is used.
  • the ratio of the Li—Al alloy serving as the negative electrode active material is a certain level or more. Therefore, when the thickness of the Cu layer or Ni layer as the base material layer is 100, the thickness of the Al metal layer (however, the Al metal layer is bonded to both sides of the Cu layer or Ni layer as the base material layer). In this case, the thickness per side.
  • the thickness of the Al metal layer is preferably 180 or less, more preferably 150 or less, when the thickness of the Cu layer or Ni layer as the base material layer is 100. It is particularly preferred that it be less than 100, and most preferred is 100 or less.
  • the thickness of the Cu layer or Ni layer as the base material layer is preferably 10 to 50 ⁇ m, more preferably 40 ⁇ m or less, and particularly preferably 30 ⁇ m or less.
  • the thickness of the Al metal layer (however, when the Al metal layer is bonded to both surfaces of the Cu layer and Ni layer as the base material layer), the thickness per side is preferably 5 ⁇ m or more. More preferably, it is 15 ⁇ m or more, more preferably 100 ⁇ m or less, more preferably 70 ⁇ m or less, particularly preferably 50 ⁇ m or less, and 30 ⁇ m or less. Is most preferred.
  • the thickness of the laminated metal foil formed by joining the Cu layer and the Al metal layer and the thickness of the laminated metal foil formed by joining the Ni layer and the Al metal layer are 50 ⁇ m or more in order to make the capacity of the negative electrode constant or more.
  • it is preferably 200 ⁇ m or less, and more preferably 150 ⁇ m or less. It is especially preferable that it is 120 micrometers or less.
  • a Li foil is laminated on the surface of the Al metal layer in advance, and the Li foil is further laminated. It is also possible to assemble a battery using a metal foil and charge the assembled battery to form a Li—Al alloy layer having a desired composition.
  • FIG. 1 is a cross-sectional view schematically showing an example of a laminate (negative electrode precursor) for forming a negative electrode usable for a nonaqueous electrolyte battery.
  • the negative electrode precursor 100 of FIG. 1 includes a laminated metal foil 101 formed by bonding Al metal layers 101b and 101b on both surfaces of a base material layer 101a, and Li foils 102 and 102 are formed on the surfaces of the Al metal layers 101b and 101b. It is a laminated body formed by bonding.
  • a laminate for example, the laminated metal foil 101 shown in FIG. 1 configured by bonding an Al metal layer to one or both sides of the base material layer, What is necessary is just to use as a negative electrode precursor.
  • a negative electrode lead body can be provided on a base material layer such as a Cu layer or a Ni layer in the laminate used as a negative electrode precursor for forming a negative electrode according to a conventional method before assembling the battery.
  • the positive electrode and the negative electrode are, for example, an electrode body formed by stacking via a separator, and a wound electrode formed by further winding the electrode body in a spiral shape Or a laminated electrode body in which a plurality of positive electrodes and a plurality of negative electrodes are alternately stacked.
  • the separator preferably has a property of blocking its pores (that is, a shutdown function) at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower).
  • a separator used in a water electrolyte secondary battery for example, a microporous membrane made of polyolefin such as polyethylene (PE) or polypropylene (PP) can be used.
  • the microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be.
  • a porous membrane formed by binding inorganic particles such as alumina, boehmite, kaolin, Mg (OH) 2 with a binder, or an aramid porous membrane is formed on the surface of the microporous membrane made of polyolefin. You may use the laminated body for a separator.
  • the thickness of the separator is preferably 10 to 30 ⁇ m, for example.
  • nonaqueous electrolyte solution of the nonaqueous electrolyte battery a solution in which a lithium salt is dissolved in an organic solvent is used.
  • organic solvent related to the non-aqueous electrolyte examples include cyclic carbonates such as ethylene carbonate, propylene carbonate (PC), butylene carbonate, and vinylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; methyl propionate Chain esters such as compounds having a lactone ring; chain ethers such as dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme, tetraglyme; dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, etc.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate (PC), butylene carbonate, and vinylene carbonate
  • chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate
  • methyl propionate Chain esters such as compounds having a lactone ring
  • Cyclic ethers such as acetonitrile, propionitrile, methoxypropionitrile; sulfites such as ethylene glycol sulfite; etc.
  • nitriles such as acetonitrile, propionitrile, methoxypropionitrile
  • sulfites such as ethylene glycol sulfite; etc.
  • the recited, it can also be used as a mixture of two or more.
  • PC contributes particularly to securing discharge characteristics at low temperatures of non-aqueous electrolyte batteries.
  • ethylene carbonate is often used as the organic solvent of the non-aqueous electrolyte solution related to the non-aqueous electrolyte battery, but since PC has a lower freezing point than ethylene carbonate, the output of the battery even in a lower temperature environment It becomes possible to improve the characteristics.
  • Examples of the compound having a lactone ring include ⁇ -butyrolactone and lactones having a substituent at the ⁇ -position.
  • the lactone having a substituent at the ⁇ -position is preferably, for example, a 5-membered ring (having 4 carbon atoms constituting the ring).
  • the ⁇ -position substituent of the lactone may be one or two.
  • the substituent examples include a hydrocarbon group and a halogen group (fluoro group, chloro group, bromo group, iodo group) and the like.
  • a hydrocarbon group an alkyl group, an aryl group, etc. are preferable, and it is preferable that the carbon number is 1 or more and 15 or less (more preferably 6 or less).
  • the substituent is a hydrocarbon group, a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and the like are more preferable.
  • lactones having a substituent at the ⁇ -position include ⁇ -methyl- ⁇ -butyrolactone, ⁇ -ethyl- ⁇ -butyrolactone, ⁇ -propyl- ⁇ -butyrolactone, ⁇ -butyl- ⁇ -butyrolactone, ⁇ -phenyl - ⁇ -butyrolactone, ⁇ -fluoro- ⁇ -butyrolactone, ⁇ -chloro- ⁇ -butyrolactone, ⁇ -bromo- ⁇ -butyrolactone, ⁇ -iodo- ⁇ -butyrolactone, ⁇ , ⁇ -dimethyl- ⁇ -butyrolactone, ⁇ , ⁇ -Diethyl- ⁇ -butyrolactone, ⁇ , ⁇ -diphenyl- ⁇ -butyrolactone, ⁇ -ethyl- ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -phenyl- ⁇ -butyrolactone, ⁇ , ⁇ ,
  • the content of PC in the total organic solvent used for the non-aqueous electrolyte is preferably 10% by volume or more, and preferably 30% by volume or more, from the viewpoint of ensuring the above-described effects due to its use. More preferred.
  • the organic solvent of the nonaqueous electrolytic solution may be only PC, the upper limit value of the preferred content of PC in the total organic solvent used in the nonaqueous electrolytic solution is 100% by volume. is there.
  • the content of the compound having a lactone ring in the total organic solvent used in the non-aqueous electrolyte is from the viewpoint of ensuring the effect of the use satisfactorily.
  • the content is preferably 1% by mass or more, and it is desirable to use it within a range that satisfies this preferable value and the content of PC in the total organic solvent satisfies the above preferable value.
  • Lithium salts related to non-aqueous electrolytes have high heat resistance and can improve the storage characteristics of non-aqueous electrolyte batteries in high-temperature environments, and also have a function to suppress corrosion of aluminum used in the batteries. since you are, it is preferable to use LiBF 4.
  • lithium salts according to the non-aqueous electrolyte solution for example, LiClO 4, LiPF 6, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3) 2, LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO 2 ) 2 [where Rf is a fluoroalkyl group] and the like.
  • LiClO 4 LiPF 6, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li 2 C 2 F 4 (SO 3) 2, LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (RfOSO 2 ) 2 [where Rf is a fluoroalkyl group] and the like.
  • the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.6 mol / l or more, and more preferably 0.9 mol / l or more.
  • the concentration of the total lithium salt in the nonaqueous electrolytic solution is preferably 1.8 mol / l or less, and more preferably 1.6 mol / l or less. Therefore, when only LiBF 4 is used for the lithium salt, it is preferable to use it in a range where the concentration satisfies the above-described preferred upper limit value. On the other hand, when using other lithium salt with LiBF 4, while the concentration of LiBF 4 satisfies preferable lower limit of the, it is preferably used in a range where the concentration of total lithium salt satisfies the preferred upper limit of the .
  • the non-aqueous electrolyte contains a phosphoric acid compound or a boric acid compound having a group represented by the general formula (1) in the molecule.
  • the load characteristics after high-temperature storage can be maintained high. . That is, by the additive, a thin and high-quality protective film that can suppress the reaction between the electrolyte solution and the negative electrode surface is formed on the negative electrode surface. Since this protective film works effectively even in a high temperature environment of 110 ° C. or higher, it can prevent gas generation due to reaction between moisture and the like brought into the battery when the negative electrode and the battery are assembled, and deterioration of the characteristics of the negative electrode. .
  • the action of the phosphoric acid compound or boric acid compound greatly depends on the positive electrode active material to be combined, and a positive electrode containing a compound having an olivine structure as the positive electrode active material is used. As a result, the effect of the additive becomes more excellent.
  • a compound having an olivine structure such as lithium iron phosphate contains an alkaline impurity because of its production method, and therefore, the water content tends to increase.
  • the surface of the material is coated with a carbon material in order to improve the conductivity of the material, moisture is easily adsorbed, and the moisture content is further increased.
  • a positive electrode is produced using such a positive electrode active material and used as it is for producing a battery, a large amount of moisture is brought into the battery.
  • the moisture contained in the positive electrode easily reacts with a fluorine-containing inorganic lithium salt such as LiPF 6 that is widely used as an electrolyte of a nonaqueous electrolytic solution, and causes hydrogen fluoride to be generated in the battery. For this reason, in a situation where the battery is left in a high temperature environment for a long time, the constituent materials of the electrode are deteriorated and the characteristics of the battery are deteriorated.
  • a fluorine-containing inorganic lithium salt such as LiPF 6 that is widely used as an electrolyte of a nonaqueous electrolytic solution
  • the additive when the nonaqueous electrolytic solution contains a phosphoric acid compound or a boric acid compound having a group represented by the general formula (1) in the molecule, the additive is added by the generated hydrogen fluoride.
  • the reaction for forming a protective film on the negative electrode surface is promoted, the use of a compound having an olivine structure tends to produce the effect of the additive.
  • the amount of adsorbed moisture increases, so that the effect of the additive is more likely to appear.
  • the phosphoric acid compound has a structure in which at least one of hydrogen atoms of phosphoric acid is substituted with a group represented by the general formula (1).
  • the boric acid compound has a structure in which at least one of hydrogen atoms of boric acid is substituted with a group represented by the general formula (1).
  • X is Si, Ge, or Sn.
  • a phosphoric acid silyl ester in which X is Si is preferably used.
  • X is Si.
  • the boric acid silyl ester is preferably used.
  • R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. However, a methyl group or an ethyl group is more preferable.
  • R 1 , R 2 and R 3 may have part or all of the hydrogen atoms substituted with fluorine.
  • the group represented by the general formula (1) is particularly preferably a trimethylsilyl group.
  • the phosphoric acid compound only one of the hydrogen atoms of phosphoric acid may be substituted with the group represented by the general formula (1), and two of the hydrogen atoms of phosphoric acid may be substituted.
  • the group represented by the general formula (1) may be substituted, and all three hydrogen atoms of phosphoric acid may be substituted with the group represented by the general formula (1). It is more preferable that all three hydrogen atoms of phosphoric acid are substituted with the group represented by the general formula (1).
  • Examples of the phosphoric acid compound include mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphate, dimethyltrimethylsilyl phosphate, methylbis (trimethylsilyl) phosphate, diethyltrimethylsilyl phosphate, Diphenyl phosphate (trimethylsilyl), Tris phosphate (triethylsilyl), Tris phosphate (vinyldimethylsilyl), Tris phosphate (triisopropylsilyl), Tris phosphate (dimethylethylsilyl), Tris phosphate (dimethylethylsilyl) , Tris (butyldimethylsilyl) phosphate, tris (vinyldimethylsilyl) phosphate, tris (triphenylsilyl) phosphate, mono (trimethylsilyl) phosphate, di (trimethylsilyl) phosphate,
  • boric acid compound only one of the hydrogen atoms possessed by boric acid may be substituted with the group represented by the general formula (1). Two of them may be substituted with the group represented by the general formula (1), and all three hydrogen atoms of boric acid may be substituted with the group represented by the general formula (1). However, it is more preferable that all three hydrogen atoms of boric acid are substituted with the group represented by the general formula (1).
  • boric acid compounds include mono (trimethylsilyl) borate, di (trimethylsilyl) borate, tris (trimethylsilyl) borate, dimethyltrimethylsilylborate, methylbis (trimethylsilyl) borate, diethyltrimethylsilylborate, Diphenyl borate (trimethylsilyl), tris (triethylsilyl) borate, tris (vinyldimethylsilyl) borate, tris (triisopropylsilyl) borate, tris (dimethylethylsilyl) borate, tris (dimethylethylsilyl) borate, Examples thereof include tris (butyldimethylsilyl) borate, tris (vinyldimethylsilyl) borate, tris (triphenylsilyl) borate, mono (trimethylsilyl) borate, di (trimethylsilyl) borate, Tris (trimethylsilyl) borate dimethyl
  • the addition amount of the phosphoric acid compound or boric acid compound having in the molecule thereof the group represented by the general formula (1) in the non-aqueous electrolyte is from the viewpoint of ensuring better the above-mentioned effects due to its use. It is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 0.7% by mass or more. Most preferably, it is 1 mass% or more. In addition, if the content is too large, the thickness of the coating that can be formed on the negative electrode surface increases, which may increase resistance and decrease load characteristics.
  • the addition amount of the phosphoric acid compound or boric acid compound having a group represented by the formula (1) in the molecule is preferably 10% by mass or less, more preferably 8% by mass or less, and 7% by mass. More preferably, it is more preferably 5% by mass or less, and most preferably 3% by mass or less.
  • the total amount may be adjusted to be within the above range.
  • the non-aqueous electrolyte contains a nitrile compound as an additive.
  • the nitrile compound is adsorbed on the surface of the positive electrode active material to form a film, which suppresses gas generation due to oxidative decomposition of the non-aqueous electrolyte.
  • the battery can be prevented from swelling when stored in a high temperature environment.
  • the nitrile compound include dinitriles such as succinonitrile, glutaronitrile, and adiponitrile.
  • the non-aqueous electrolyte may be a saturated cyclic sultone compound such as 1,3-propane sultone or 1,4-butane sultone; an unsaturated cyclic sultone compound such as 1,3-propene sultone; maleic anhydride Additives such as acid anhydrides such as phthalic anhydride; LiB (C 2 O 4 ) 2 ;
  • non-aqueous electrolyte may be made into a gel (gel electrolyte) using a known gelling agent such as a polymer.
  • a nonaqueous electrolyte battery is, for example, loaded with an electrode body in an exterior body, injecting a nonaqueous electrolyte into the exterior body and immersing the electrode body in the nonaqueous electrolyte solution, and then opening the opening of the exterior body. Manufactured by sealing.
  • an exterior body made of steel, aluminum, aluminum alloy, an exterior body composed of a metal-deposited laminate film, or the like can be used.
  • the assembled battery is formed at least once in order to form an alloy of Li and an alloyable element with Li. Or a chemical conversion treatment having a discharging step in addition to the charging step.
  • an element that can be alloyed with Li contained in the negative electrode precursor electrochemically reacts with Li ions in the nonaqueous electrolytic solution to form an alloy of Li and an element that can be alloyed with Li.
  • the negative electrode precursor changes to a negative electrode.
  • the Al metal layer undergoes a large volume expansion, so that a large number of cracks are generated in the Li—Al alloy layer, compared with the case where the chemical conversion treatment is not performed.
  • the load characteristics after high temperature storage can be further improved.
  • Conditions for chemical conversion treatment such as charging conditions can be appropriately set according to required characteristics.
  • the non-aqueous electrolyte battery of the present invention can be repeatedly charged and can be used as a secondary battery.
  • the non-aqueous electrolyte battery can be used as a primary battery that performs only discharge. Use is also possible.
  • Example 1 A clad material (laminated metal foil) having a size of 25 mm ⁇ 40 mm obtained by laminating an Al foil having a thickness of 30 ⁇ m on both surfaces of a Ni foil having a thickness of 30 ⁇ m was used as a negative electrode precursor. Assembling the battery, the Cu foil for current collection is ultrasonically welded to the end of the clad material, and the Ni tab for conductive connection with the outside of the battery is ultrasonically welded to the end of the Cu foil. Used for.
  • the positive electrode was produced as follows. Lithium iron phosphate (surface coated with carbon): 97 parts by mass, acetylene black as a conductive auxiliary agent: 1.5 parts by mass, PVDF as a binder: 1.5 parts by mass, NMP
  • the slurry dispersed in the above is prepared, applied to one side of a 12 ⁇ m thick Al foil, dried, and subjected to press treatment, whereby a positive electrode having a mass of about 17 mg / cm 2 is applied to one side of the Al foil current collector. A mixture layer was formed.
  • the positive electrode mixture layer was not formed on a part of the application surface of the slurry, and a portion where the Al foil was exposed was provided.
  • the Al foil current collector is cut into a size of 20 mm ⁇ 45 mm, and an Al tab for conductive connection with the outside of the battery is ultrasonically welded to a place where the Al foil is exposed, thereby collecting the current collector.
  • a positive electrode having a positive electrode mixture layer with a size of 20 mm ⁇ 30 mm on one side was prepared.
  • the positive electrodes were laminated on both sides of the negative electrode precursor to which the Ni tab was welded via a separator made of a microporous film made of PE having a thickness of 16 ⁇ m, thereby producing a set of electrode bodies. Further, LiBF 4 was dissolved at a concentration of 1 mol / l in a mixed solvent of propylene carbonate (PC) and ethyl methyl carbonate (EMC) in a volume ratio of 1: 2 to prepare a nonaqueous electrolytic solution. The electrode body is dried at 60 ° C. in a vacuum for 15 hours, and then encapsulated in a laminate film outer package together with the non-aqueous electrolyte, whereby the rated capacity is 30 mAh and the appearance shown in FIG. A non-aqueous electrolyte battery having a cross-sectional structure shown in FIG.
  • FIG. 2 is a plan view schematically showing the nonaqueous electrolyte battery
  • FIG. 3 is a cross-sectional view taken along the line II of FIG.
  • the nonaqueous electrolyte battery 1 includes a laminated electrode body formed by laminating a positive electrode 5 and a negative electrode 6 via a separator 7 in a laminate film outer package 2 constituted by two laminated films, and a nonaqueous electrolyte solution. (Not shown) is accommodated, and the laminate film outer package 2 is sealed by heat-sealing the upper and lower laminate films at the outer peripheral portion thereof.
  • the layers constituting the laminate film outer package 2 and the layers of the positive electrode 5 and the negative electrode 6 are not shown separately in order to avoid the drawing from becoming complicated.
  • the positive electrode 5 is connected to the positive electrode external terminal 3 in the battery 1 through a lead body.
  • the negative electrode 6 is also connected to the negative electrode external terminal 4 in the battery 1 through a lead body. is doing.
  • the positive electrode external terminal 3 and the negative electrode external terminal 4 are drawn out to the outside of the laminate film exterior body 2 so that they can be connected to an external device or the like.
  • Example 2 (Example 2) Implementation was carried out except that the positive electrode active material was changed to a mixture of lithium iron phosphate used in Example 1 and LiNi 0.80 Co 0.15 Al 0.05 O 2 in a mass ratio of 50:50.
  • a positive electrode was produced in the same manner as in Example 1, and a nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that this positive electrode was used.
  • Example 3 The mass ratio of the positive electrode active material to the lithium iron phosphate used in Example 1 and the positive electrode material in which the surface of LiCo 0.9795 Mg 0.011 Zr 0.0005 Al 0.009 O 2 was coated with Al 2 O 3 A non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that this positive electrode was used except that the mixture was changed to a mixture of 50:50.
  • Example 4 (Example 4) Implementation was carried out except that the positive electrode active material was changed to a mixture of lithium iron phosphate used in Example 1 and LiNi 0.33 Co 0.33 Mn 0.33 O 2 in a mass ratio of 50:50.
  • a positive electrode was produced in the same manner as in Example 1, and a nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that this positive electrode was used.
  • Example 5 A Cu foil for current collection is ultrasonically welded to the end of a 25 mm ⁇ 40 mm clad material (laminated metal foil) in which a 30 ⁇ m thick Al foil is laminated on both sides of a 30 ⁇ m thick Cu foil, A non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that an ultrasonic welded Ni tab for conductive connection with the outside of the battery was used as the negative electrode precursor at the end of the Cu foil. .
  • Example 6 A Cu foil for current collection was ultrasonically welded to the end of a 25 mm ⁇ 40 mm clad material (laminated metal foil) in which a 30 ⁇ m thick Al foil was laminated on one side of a 30 ⁇ m thick Ni foil, A non-aqueous electrolyte battery was produced in the same manner as in Example 1, except that an ultrasonic welded Ni tab for conductive connection with the outside of the battery was used as the negative electrode precursor at the end of the Cu foil.
  • Example 7 A non-aqueous electrolyte was prepared in the same manner as in Example 1 except that LiPF 6 was used instead of LiBF 4 , and a non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that this non-aqueous electrolyte was used. Produced.
  • Example 8 Except that LiBF 4 was dissolved at a concentration of 1 mol / l in a mixed solvent of ethylene carbonate (EC) and EMC in a volume ratio of 1: 2 to prepare a non-aqueous electrolyte, and this non-aqueous electrolyte was used. In the same manner as in Example 1, a nonaqueous electrolyte battery was produced.
  • EC ethylene carbonate
  • Example 1 A positive electrode was produced in the same manner as in Example 1 except that the positive electrode active material was changed to LiNi 0.80 Co 0.15 Al 0.05 O 2 , and the same as in Example 1 except that this positive electrode was used. A water electrolyte battery was produced.
  • Example 2 A positive electrode was produced in the same manner as in Example 1 except that the positive electrode active material was changed to a positive electrode material in which the surface of LiCo 0.9795 Mg 0.011 Zr 0.0005 Al 0.009 O 2 was coated with Al 2 O 3.
  • a nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that this positive electrode was used.
  • Example 3 A positive electrode was produced in the same manner as in Example 1 except that the positive electrode active material was changed to LiNi 0.33 Co 0.33 Mn 0.33 O 2 , and the same as in Example 1 except that this positive electrode was used. A water electrolyte battery was produced.
  • a positive electrode having a compound having an olivine structure as a positive electrode active material, and a negative electrode precursor having an Al metal layer on the surface of the base material layer, or a base material layer having a high tensile strength In the non-aqueous electrolyte batteries of Examples 1 to 8 having the negative electrode formed through the negative electrode precursor having the negative electrode precursor, when the storage characteristics 1 and 2 were evaluated, deformation such as gas generation in the battery and bending of the negative electrode occurred. It was suppressed, had a small volume change, and had excellent high-temperature storage characteristics. In addition, the batteries of Examples 1 to 8 had a long discharge time when the low-temperature discharge characteristics were evaluated after high-temperature storage, and good load characteristics at low temperatures after high-temperature storage.
  • the batteries of Comparative Examples 1 to 3 using a positive electrode active material other than the compound having an olivine structure have a large volume change amount at the time of evaluation of the storage characteristics 2 and are inferior in high-temperature storage characteristics, or high temperature
  • the discharge time at the time of low temperature discharge characteristic evaluation after storage was short, and the load characteristic at low temperature after high temperature storage was inferior.
  • Example 9 Preparation of positive electrode> It is a positive electrode active material, olivine type lithium iron phosphate whose surface is coated with a carbon material (LiFePO 4 , average particle size: 13 ⁇ m, BET specific surface area: 9 m 2 / g): 97 parts by mass, and a conductive additive A slurry in which 1.5 parts by mass of acetylene black and 1.5 parts by mass of an acrylic resin as a binder are dispersed in NMP is prepared, and this is applied to both sides of an Al foil having a thickness of 12 ⁇ m and dried.
  • a positive electrode active material olivine type lithium iron phosphate whose surface is coated with a carbon material (LiFePO 4 , average particle size: 13 ⁇ m, BET specific surface area: 9 m 2 / g): 97 parts by mass, and a conductive additive
  • the positive electrode mixture layer having a mass of approximately 12.7 mg / cm 2 was formed on one surface of the Al foil current collector by performing a press treatment. Furthermore, the positive electrode mixture layer was pressed and an aluminum lead body was attached to produce a strip-like positive electrode having a length of 974 mm and a width of 43 mm.
  • a clad material (laminated metal foil) having a size of 988 mm ⁇ 44.5 mm, in which an Al foil having a thickness of 20 ⁇ m was laminated on both surfaces of a 35 ⁇ m-thick Cu foil, was used for the production of the negative electrode.
  • a nickel lead body for conductive connection with the outside of the battery was attached to the clad material to form a negative electrode (negative electrode precursor).
  • LiBF 4 was dissolved at a concentration of 1.2 mol / l in a mixed solvent of propylene carbonate (PC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DEC) at a volume ratio of 17:63:20, and adiponitrile was further added.
  • a nonaqueous electrolytic solution was prepared by adding 5% by mass, tris (trimethylsilyl) phosphate (TMSP): 3% by mass, and 1,3-propene sultone (PRS): 0.5% by mass. .
  • the electrode body is inserted into a rectangular battery container made of aluminum alloy having a thickness of 0.8 mm, and after the nonaqueous electrolyte is injected, the battery container is sealed to obtain the structure shown in FIGS. 4 and 5. , 103450 size square non-aqueous electrolyte battery was assembled.
  • FIG. 4 is a partial sectional view of the battery, in which the positive electrode 11 and the negative electrode 12 are spirally wound via the separator 13 and then flattened. Pressurized and accommodated in a rectangular (square tube) battery container 14 as a flat wound electrode body 16 together with a non-aqueous electrolyte.
  • a rectangular (square tube) battery container 14 as a flat wound electrode body 16 together with a non-aqueous electrolyte.
  • the layers of the positive electrode 11 and the negative electrode 12, the nonaqueous electrolyte, and the like are not shown in order to avoid complication.
  • the battery container 14 is made of an aluminum alloy and constitutes an outer package of the battery.
  • the battery container 14 also serves as a positive electrode terminal.
  • the insulator 15 which consists of PE sheets is arrange
  • the positive electrode lead body 17 and the negative electrode lead body 18 are drawn out.
  • a stainless steel terminal 21 is attached to a sealing lid plate 19 made of aluminum alloy for sealing the opening of the battery container 14 via a polypropylene insulating packing 20, and an insulator 22 is attached to the terminal 21.
  • a stainless steel lead plate 23 is attached.
  • this cover plate 19 is inserted into the opening of the battery case 14, and the opening of the battery case 14 is sealed and the inside of the battery is sealed by welding the joint of both.
  • a non-aqueous electrolyte inlet 24 is provided in the lid plate 19, and a sealing member is inserted into the non-aqueous electrolyte inlet 24, for example, laser welding or the like. As a result, the battery is sealed by welding.
  • the lid plate 19 is provided with a cleavage vent 25 as a mechanism for discharging the internal gas to the outside when the battery temperature rises.
  • the positive electrode lead body 17 is directly welded to the lid plate 19 so that the battery container 14 and the lid plate 19 function as a positive electrode terminal, and the negative electrode lead body 18 is welded to the lead plate 23.
  • the terminal 21 functions as a negative electrode terminal by conducting the negative electrode lead body 18 and the terminal 21 through the lead plate 23.
  • the sign may be reversed. There is also.
  • FIG. 5 is a perspective view schematically showing the external appearance of the battery shown in FIG. 4.
  • FIG. 5 is shown for the purpose of showing that the battery is a square battery.
  • FIG. 1 schematically shows a battery, and only specific members of the battery are shown. Also in FIG. 4, the inner peripheral portion of the electrode body is not cross-sectional.
  • Example 10 As a positive electrode active material, olivine type lithium iron phosphate whose surface is coated with a carbon material: 48.5 parts by mass and LiNi 0.8 Co 0.15 Al 0.05 O 2 : 48.5 parts by mass are mixed. A nonaqueous electrolyte battery was assembled in the same manner as in Example 9 except that it was used.
  • Example 11 As a positive electrode active material, olivine type lithium iron phosphate whose surface is coated with a carbon material: 48.5 parts by mass and LiNi 0.33 Co 0.33 Mn 0.33 O 2 : 48.5 parts by mass are mixed. A nonaqueous electrolyte battery was assembled in the same manner as in Example 9 except that it was used.
  • Example 12 A nonaqueous electrolyte battery was assembled in the same manner as in Example 9 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was 0.5 mass%.
  • Example 13 A nonaqueous electrolyte battery was assembled in the same manner as in Example 9 except that the amount of tris (trimethylsilyl) phosphate added to the nonaqueous electrolyte was 8% by mass.
  • Example 4 A non-aqueous electrolyte battery was assembled in the same manner as in Example 9 except that tris (trimethylsilyl) phosphate was not added to the non-aqueous electrolyte.
  • Example 5 A nonaqueous electrolyte battery was assembled in the same manner as in Example 9 except that LiNi 0.8 Co 0.15 Al 0.05 O 2 : 97 parts by mass was used as the positive electrode active material.
  • Example 6 A nonaqueous electrolyte battery was assembled in the same manner as Example 9 except that 97 parts by mass of LiCoO 2 having an Al oxide coating layer on the surface was used as the positive electrode active material.
  • Example 7 A nonaqueous electrolyte battery was assembled in the same manner as in Example 9 except that LiNi 0.33 Co 0.33 Mn 0.33 O 2 : 97 parts by mass was used as the positive electrode active material.
  • Natural graphite is used as the negative electrode active material, and the negative electrode active material: 96 parts by mass, SBR: 2 parts by mass, and CMC: 2 parts by mass and water are mixed to prepare a negative electrode mixture-containing composition having a thickness of 12 ⁇ m.
  • the negative electrode was produced by applying on both sides of the copper foil and drying. And the nonaqueous electrolyte battery was assembled like Example 9 except having used the said negative electrode.
  • Each battery after chemical conversion treatment is charged to 3.8V at a constant current of 0.2C, and then charged until the current value decreases to 0.01C at a constant voltage of 3.8V.
  • Each battery that was charged and charged was placed in a thermostatic bath at 85 ° C. and held for 30 days.
  • each battery after being held is taken out of the thermostatic chamber, cooled to room temperature, then decomposed in liquid paraffin, and the gas coming out of the battery container is collected using a graduated cylinder. The amount of gas generated from each battery was determined by reading the value.
  • the battery other than the disassembled battery was allowed to cool to room temperature, further cooled to ⁇ 20 ° C., and then subjected to a constant current discharge of 1.5 C in an environment of ⁇ 20 ° C., and the battery voltage was 2 The discharge time until the voltage dropped to 0.0 V was measured.
  • Examples 9 to 13 each including a negative electrode containing an alloy of Li and an alloy capable of alloying with Li as a negative electrode active material, and a positive electrode containing a compound having an olivine structure as a positive electrode active material.
  • This non-aqueous electrolyte battery uses a non-aqueous electrolyte solution containing a phosphoric acid compound having a group represented by the general formula (1) in the molecule, thereby generating less gas during high-temperature storage, and The low-temperature discharge characteristics after high-temperature storage were excellent.
  • the battery of Comparative Example 4 in which the additive (the phosphoric acid compound) was not added to the non-aqueous electrolyte and the batteries of Comparative Examples 5 to 7 in which the compound having an olivine structure was not used as the positive electrode active material The low-temperature discharge characteristics after high-temperature storage were deteriorated.
  • the batteries of Comparative Examples 6 and 7 in addition to the low water content of the positive electrode active material metal elution from the positive electrode active material increased compared to the olivine-type lithium iron phosphate, so that gas generation during high-temperature storage occurred. The amount has increased significantly.
  • the battery of Example 9 using an alloy of Li and an alloyable element and Li as a negative electrode active material had a low temperature discharge characteristic after high temperature storage as compared with the battery of Comparative Example 8 using natural graphite as a negative electrode active material. was able to improve.
  • the non-aqueous electrolyte battery of the present invention can exhibit excellent load characteristics even at low temperatures even after being stored in a high temperature environment, and also has excellent reliability. Thus, for example, it can be preferably applied to an application that is required to discharge well even at a low temperature after being placed in a high temperature environment, such as a power supply application for a vehicle emergency notification system.

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Abstract

L'invention concerne une batterie à électrolyte non aqueux qui présente de bonnes caractéristiques de charge à basses températures même après un stockage à températures élevées, et qui présente une excellente fiabilité. Une batterie à électrolyte non aqueux selon la présente invention est caractérisée en ce que : l'électrode positive contient, en tant que matériau actif d'électrode positive, un composé ayant une structure à olivine ; et (1) l'électrode négative comprend un stratifié contenant une couche de base métallique, qui n'est pas alliée avec du Li, et une couche métallique d'Al liée à la couche de base métallique, un alliage de Li-Al étant formé au moins sur la surface avant de la couche métallique d'Al, ou (2) l'électrode négative contient, en tant que matériau actif d'électrode négative, un alliage de Li et un élément qui est apte à être allié avec du Li, et la solution d'électrolyte contient un composé d'acide phosphorique ou un composé d'acide borique qui a un groupe ayant une structure spécifique dans chaque molécule.
PCT/JP2017/006813 2016-03-07 2017-02-23 Batterie à électrolyte non aqueux WO2017154592A1 (fr)

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JP2020004596A (ja) * 2018-06-27 2020-01-09 マクセルホールディングス株式会社 非水電解液二次電池およびその製造方法
CN111108642A (zh) * 2017-09-22 2020-05-05 三菱化学株式会社 非水系电解液、非水系电解液二次电池及能源装置
JP2020149763A (ja) * 2019-03-11 2020-09-17 マクセルホールディングス株式会社 非水電解液電池
JP7193671B1 (ja) 2022-06-21 2022-12-20 積水化学工業株式会社 非水電解質二次電池用正極、並びにこれを用いた非水電解質二次電池、電池モジュール、及び電池システム、非水電解質二次電池用正極の製造方法
WO2023190198A1 (fr) * 2022-03-31 2023-10-05 住友化学株式会社 Électrode négative en aluminium et batterie secondaire à électrolyte non aqueux

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CN113346095A (zh) * 2021-05-17 2021-09-03 上海超碳石墨烯产业技术有限公司 一种具有耐高温系统的扣式电池

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JP7112265B2 (ja) 2018-06-27 2022-08-03 マクセル株式会社 非水電解液二次電池およびその製造方法
JP2020149763A (ja) * 2019-03-11 2020-09-17 マクセルホールディングス株式会社 非水電解液電池
JP7337515B2 (ja) 2019-03-11 2023-09-04 マクセル株式会社 非水電解液電池
WO2023190198A1 (fr) * 2022-03-31 2023-10-05 住友化学株式会社 Électrode négative en aluminium et batterie secondaire à électrolyte non aqueux
JP2024000649A (ja) * 2022-06-21 2024-01-09 積水化学工業株式会社 非水電解質二次電池用正極、並びにこれを用いた非水電解質二次電池、電池モジュール、及び電池システム、非水電解質二次電池用正極の製造方法
WO2023249066A1 (fr) * 2022-06-21 2023-12-28 積水化学工業株式会社 Électrode positive pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux mettant en œuvre celle-ci, module de batterie, système de batterie, et procédé de fabrication d'électrode positive pour batterie secondaire à électrolyte non aqueux
JP7193671B1 (ja) 2022-06-21 2022-12-20 積水化学工業株式会社 非水電解質二次電池用正極、並びにこれを用いた非水電解質二次電池、電池モジュール、及び電池システム、非水電解質二次電池用正極の製造方法

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