CN108701858A - Battery with nonaqueous electrolyte - Google Patents

Battery with nonaqueous electrolyte Download PDF

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Publication number
CN108701858A
CN108701858A CN201780015233.0A CN201780015233A CN108701858A CN 108701858 A CN108701858 A CN 108701858A CN 201780015233 A CN201780015233 A CN 201780015233A CN 108701858 A CN108701858 A CN 108701858A
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China
Prior art keywords
battery
nonaqueous electrolyte
aforementioned
cathode
electrolytic solution
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Inventor
关谷智仁
山田将之
政冈妥则
畠山敦
守上英寿
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Mike Seir Holdings Co Ltd
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Mike Seir Holdings Co Ltd
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Publication of CN108701858A publication Critical patent/CN108701858A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Electrode Carriers And Collectors (AREA)

Abstract

The present invention provides battery with nonaqueous electrolyte also good even across the part throttle characteristics under low temperature after high-temperature storage, excellent in reliability.The battery with nonaqueous electrolyte of the present invention is characterized in that anode contains the compound with olivine-type structure as a positive electrode active material;(1) cathode has containing the not laminated body with Li alloyed metal (AM)s substrate layer and the Al metal layers for being engaged in aforementioned metal substrate layer, and at least surface side of aforementioned Al metal layers is formed with Li-Al alloys, or (2) cathode has that negative electrode active material can be used as with the alloy of the elements of Li alloyings and Li, and nonaqueous electrolytic solution contains the phosphate cpd or boronic acid compounds that intramolecular has the group of specific structure.

Description

Battery with nonaqueous electrolyte
Technical field
The present invention relates to the good battery with nonaqueous electrolyte of storing property.
Background technology
Nonaqueous electrolytic solution secondary battery is used for various uses using characteristics such as high power capacity, high voltages.Moreover, with its application The expansion in field requires nonaqueous electrolytic solution secondary battery the raising of various characteristics.
Especially in recent years, with functionization of electric vehicle etc., the demand of vehicle-mounted nonaqueous electrolyte battery constantly increases, main To be applied in the driving power of electric car engine, on the other hand, application in addition to this is also promoting.For example, at present It is carrying out for, by the exploitation of its emergency annunciation system for being notified to each related fields, being ground in vehicle experience accident etc. Study carefully application of the nonaqueous electrolytic solution secondary battery as its power supply.
The limited opportunities of such system real work, but must certainly work in Emergency time.Therefore, for as power supply Battery, it is desirable that the reliability of its characteristic can be well maintained long-term storage.
In addition, the case blown out in vehicle traveling in view of tire and lead to major accident happens occasionally, in order to ensure vehicle row Safety in sailing is equipped with the vehicle of tire pressure monitoring system (TirePressure Monitoring System (TPMS)) It is gradually universal.As the power supply of aforementioned system, what is utilized is battery with nonaqueous electrolyte (one-shot battery), but since system is arranged In in the tire as hot and humid environment, thus for the battery as its power supply, also it is required to maintain long-time quality Reliability.
One of the technology that characteristic as battery with nonaqueous electrolyte as realization improves, has studied the improvement of nonaqueous electrolytic solution, It is proposed in order to enable electrolyte flame-retardant improve the safety of battery, the durability in order to improve battery, proof voltage and It is added in nonaqueous electrolytic solution (patent documents 1,2) such as the phosphate compounds of specific structure.
On the other hand, the negative electrode active material of nonaqueous electrolytic solution one-shot battery uses lithium metal, Li-Al (lithium-aluminium) alloy etc. Lithium alloy, and lithium alloy can also be used as negative electrode active material in nonaqueous electrolytic solution secondary battery, therefore, it is also proposed that pass through Cathode is constituted using the cladding material of the metal that can absorb, release lithium and the not same metal of the ability without absorbing, releasing lithium, To realize the stabilisation (patent document 3~5) of battery behavior.
In turn, also, it has been proposed that by with Li in patent document 62Mn2O4,LiFePO4Or LiWO3Make for positive active material, cathode Non-aqueous electrolyte secondary battery is constituted with aluminum or aluminum alloy, and the battery with excellent preservation characteristics is made.
Existing technical literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2001-319685 bulletins
Patent document 2:Japanese Unexamined Patent Publication 2015-72864 bulletins
Patent document 3:Japanese Unexamined Patent Publication 8-293302 bulletins
Patent document 4:Japanese Unexamined Patent Publication 10-106628 bulletins
Patent document 5:International Publication No. 2016/39323
Patent document 6:Japanese Unexamined Patent Publication 2004-363016 bulletins
Invention content
Problems to be solved by the invention
Generally, in the case of foregoing system being equipped on vehicle, battery is exposed to the height of the possibility under hot environment, right In the heat resistance that battery request is excellent, on the other hand, vehicle can also be used in cold zone sometimes, need to set even if for a long time After under hot environment, deterioration in characteristics is also few, can play the battery of good part throttle characteristics at low ambient temperatures.
However, only for the technology described in aforementioned patent literature 1~6, use lithium alloy as negative electrode active material In the battery with nonaqueous electrolyte such as secondary cell, it is difficult to take into account excellent high-temperature storage characteristic and low-temperature characteristics.
The present invention makes in view of the foregoing, it is intended that providing even across the load under low temperature after high-temperature storage Also good, the excellent in reliability battery with nonaqueous electrolyte of characteristic.
The method used for solving the problem
It can realize that the battery with nonaqueous electrolyte of the present invention of foregoing purpose is characterized in that thering is electrode body and non-aqueous solution electrolysis Liquid, the electrode body are overlapped by anode and cathode across diaphragm, and aforementioned positive electrode is made with the compound with olivine structural For positive active material, aforementioned cathode has a laminated body, the laminated body contain not with Li alloyed metal (AM)s substrate layer and connect Together in the Al metal layers of aforementioned metal substrate layer, at least surface side of aforementioned Al metal layers is formed with Li-Al alloys.
In addition, the another way of the battery with nonaqueous electrolyte of the present invention is characterized in that, there is cathode, anode and non-aqueous solution electrolysis Liquid, aforementioned cathode has can be with the element of Li alloyings and the alloy of Li as negative electrode active material, and aforementioned positive electrode contains tool There is the compound of olivine structural as a positive electrode active material, aforementioned nonaqueous electrolytic solution, which contains intramolecular, to be had by the following general formula (1) phosphate cpd or boronic acid compounds of the group represented by.
[Change 1]
In aforementioned formula (1), X Si, Ge or Sn, R1,R2And R3Each independently represent the alkyl of carbon number 1~10, carbon number 2~ 10 alkenyl or the aryl of carbon number 6~10, part or all of hydrogen atom can be replaced by fluorine.
The effect of invention
In accordance with the invention it is possible to provide also good, excellent in reliability even across the part throttle characteristics under low temperature after high-temperature storage Battery with nonaqueous electrolyte.
Description of the drawings
Fig. 1 is an example for schematically showing the cathode (cathode precursor) that can be used in the battery with nonaqueous electrolyte of the present invention The sectional view of son.
Fig. 2 is the plan view for an example for schematically showing the battery with nonaqueous electrolyte of the present invention.
Fig. 3 is the I-I line sectional views of Fig. 2.
Fig. 4 is the partial longitudinal section figure for the other examples for schematically showing the battery with nonaqueous electrolyte of the present invention.
Fig. 5 is the stereogram of Fig. 4.
Specific implementation mode
The one or both sides in collector, which can be used for example, in anode that battery with nonaqueous electrolyte is related to has positive electrode material mixture layer The electrode of structure, the positive electrode material mixture layer is such as containing positive active material, conductive auxiliary agent and adhesive.
Positive active material uses the compound with olivine structural.
In general, positive active material is reacted with nonaqueous electrolytic solution under high temperature environment, reaction product is deposited on anode, simultaneously Generate gas.If using commonly used cobalt acid lithium, at high temperature, cobalt acid lithium in nonaqueous electrolytic solution secondary battery Surface is reacted with nonaqueous electrolytic solution, and the reaction product containing Co is accumulated on surface, while generating gas, but the reaction containing Co Product further decomposes, and Co is dissolved out in nonaqueous electrolytic solution.Moreover, the surface of cobalt acid lithium and nonaqueous electrolytic solution secondary response again, Generate reaction product and gas containing Co.That is, if containing a large amount of cobalt acid lithiums in positive active material, whenever battery is sudden and violent When being exposed to high temperature, Co can continue to dissolve out, and also will continue to generate gas.
On the other hand, the compound script structure with olivine structural is just stablized, therefore even if battery can if being exposed to high temperature Enough inhibit the generation of the dissolution and gas of metal.Therefore, if positive active material uses the compound with olivine structural, The generation that can inhibit gas then even if as 1 month when long-term storage, can inhibit the volume change of battery.
The compound with olivine structural used as a positive electrode active material is by LiM1PO4(M1:Co, Ni, Mn, Fe etc.) Compound represented by equal general formulas.Compound with olivine structural can contain the aforementioned M such as Al, Y1In addition a kind or more Element as addition element.In addition, the compound with olivine structural that positive electrode material mixture layer contains can be only it is aforementioned that The compound without addition element of sample, a kind in the aforementioned compound containing addition element, or two or more.
It should be noted that the aforementioned M in the compound with olivine structural1In the case of for Fe, that is, there is olivine structural Compound be LiFePO4 in the case of, it is preferable to use substance represented by general formula below (2).
LixFe1-yM2 yPO4 (2)
In aforementioned formula (2), 0.8≤x≤1.2,0≤y≤0.5, M2For be selected from by Ti, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, At least one kind of element in the group of Mg, Al, Ca, Nb, Mo, Zr and Hf composition.
The average grain diameter of compound particles with olivine structural is preferably 5 μm or more, more preferably 8 μm or more, especially excellent It is selected as 10 μm or more.It is able to maintain that by being set as aforementioned particle size, if even if reducing the content of adhesive in positive electrode material mixture layer excellent Adhesiveness, charge-discharge characteristic can be further increased.
On the other hand, if the average grain diameter of the particle of the compound with olivine structural is excessive, positive electrode material mixture layer is led Electrically reduce, charge-discharge characteristic reduce, therefore, average grain diameter be preferably 20 μm hereinafter, more preferably 17 μm hereinafter, particularly preferably It is 15 μm or less.
The particle of compound with olivine structural can be made of primary particle, but be the one of 10~100nm of grain size or so Offspring made of secondary particles aggregate, aforementioned primary particle is granulated obtained by the case of granule, with same particle size Primary particle is compared, and charge-discharge characteristic can be further increased, so it is preferred that.In this case average grain diameter is based on secondary grain The grain size calculating of son, granule.
Aforementioned average grain diameter in this specification is that (such as hole field makes made " LA- using laser diffraction particle size distribution meter 920 ") number average bead diameter measured.
It should be noted that in order to improve the electric conductivity of the low compound particles with olivine structural of electric conductivity, in particle table Face setting carbon coating is preferred, and the electric conductivity in positive electrode material mixture layer becomes better as a result,.
About the method that there will be the compound carbon material of olivine structural coating, previously known method may be used.Tool Body, it can be mentioned, for example be burnt into the organic material and the mixture of the compound with olivine structural that are used as carbon precursor Method, make carbon with olivine structural while the gas for making to be used as carbon precursor decomposes by vapor phase growth (CVD) method The common coating method such as method that is precipitated of compound surface.
From the viewpoint of make the electric conductivity of anode is good, can realize more effective discharge and recharge reaction, will have olivine knot The amount of carbon in the case that the compound carbon material of structure is coating has the compound of olivine structural relative to 100 mass parts, It is more than preferably 1 mass parts.But if the amount of the carbon of the compound surface with olivine structural is excessive, exist in lithium Ion, which is inserted into carbon when being detached from reaction, becomes obstacle, becomes the major reason of the part throttle characteristics reduction of such as battery with nonaqueous electrolyte It may.Accordingly, the amount of the carbon by the compound carbon material with olivine structural in the case of coating, relative to 100 mass Part has the compound of olivine structural, and preferably 5 is below mass part.
It should be noted that put it more simply, the case where carbon coating is arranged in the particle surface of the compound with olivine structural Under grain size the grain size of the entire particle including aforementioned coating can be considered as the compound particles with olivine structural Grain size.
In addition, in order to make the charge-discharge characteristic of battery further increase, the content of the adhesive in positive electrode material mixture layer is preferably reduced, And in order to also maintain excellent adhesiveness in such a state, prevent the problems such as stripping of positive electrode material mixture layer, there is olive The BET specific surface area of the compound of olive stone structure is preferably set to 25m2/ g is hereinafter, be more preferably set as 15m2/ g is hereinafter, particularly preferably It is set as 13m2/ g is hereinafter, be most preferably set as 10m2/ g or less.On the other hand, in the compound with olivine structural, by ensuring More than a certain amount of response area, so as to make the charge-discharge characteristic of battery under high current improve, thus with olivine structural The BET specific surface area of compound is preferably set to 5m2/ g or more is more preferably set as 8m2/ g or more.
Aforementioned BET specific surface area in this specification is measured to the gas adsorption method by using nitrogen using BET method Gas absorption amount is parsed and the value that acquires.
In addition, in the aforementioned compound with olivine structural, can also be used in mixed way by Li1+zM3O2(- 0.1 < z < 0.1, M3:Co, Ni, Mn, Al, Mg etc.) represented by layer structure lithium-contained composite oxide, LiMn2O4Or a part of quilt of its element Other active materials such as the lithium manganese oxide of spinel structure of other elements substitution.
As the lithium-contained composite oxide of aforementioned layered structure, in addition to LiCoO2Etc. cobalt acid lithiums, LiNi1-aCoa-bAlbO2(0.1≦ A≤0.3,0.01≤b≤0.2) etc. other than, at least oxide (LiMn containing Co, Ni and Mn can also be illustrated1/3Ni1/3Co1/ 3O2,LiMn5/12Ni5/12Co1/6O2,LiNi3/5Mn1/5Co1/5O2Deng) etc..
In addition, as other than lithium-contained composite oxide can positive active material, may be exemplified manganese dioxide, five oxygen Change the metal sulfides such as metal oxides, titanium disulfide, the molybdenum disulfide such as vanadium, chromium oxide.
The conductive auxiliary agent that positive electrode material mixture layer is related to can use for example:Acetylene black, Ketjen black, channel black, furnace black, lamp method The carbon blacks class such as carbon black, thermal crack black, the carbon materials such as carbon fiber;And the conducting fibres class such as metallic fiber;Fluorocarbons, copper, The metal powders class such as nickel, organic conductive materials such as polyphenylene derivatives etc..
As the adhesive that positive electrode material mixture layer is related to, it can be mentioned, for example polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), Styrene butadiene ribber (SBR), carboxymethyl cellulose (CMC), polyvinylpyrrolidone (PVP), acrylic resin (poly- third Olefin(e) acid ester) etc..
Anode can for example be manufactured through following processes:Anode containing positive active material, conductive auxiliary agent and adhesive etc. is closed Agent is dispersed in solvent (organic solvents such as NMP, water), modulation composition containing anode mixture (paste, slurry etc.), this is closed containing anode Agent composition is coated on one or both sides of collector etc. and drying, implements pressurized treatments as needed.
Further, it is also possible to form formed body using aforementioned positive electrode mixture, make part or all and anode of the formed body one side Collector is bonded, and anode is made.Anode mixture formed body can be carried out with being bonded for positive electrode collector by pressurized treatments etc..
As the collector of anode, foil, punch metal, net, the steel expanded meshes of metals such as Al, Al alloy etc. can be used, is led to Often it is preferable to use Al foils.The thickness of positive electrode collector is preferably 10~30 μm.
As the composition of positive electrode material mixture layer, such as positive active material is preferably set as 80.0~99.8 mass %, helps conduction Agent is set as 0.1~10 mass %, adhesive is set as to 0.1~10 mass %.In addition, the thickness of positive electrode material mixture layer is preferably current collection 30~300 μm of every face of body.
Positive wire body can be conventionally set on the collector of anode.
The cathode that battery with nonaqueous electrolyte is related to, which uses, to be made with the element (Al, Si, Sn etc.) of Li alloyings and the alloy of Li For negative electrode active material.
Aforementioned various alloys, which are used as negative electrode active material, can enumerate following methods:By the powder of aforementioned alloy and adhesive etc. one Mixture is played, is coated on the surface of the metal foil as collector, the method for constituting cathode;To include can be with Li alloys The mixture together such as the powder of the element of change and adhesive is coated on the surface of the metal foil as collector, is made and is used In the electrode for constituting cathode, so that it is contacted with nonaqueous electrolytic solution after assembled battery, further charged and (implemented at chemical conversion Reason), to make the aforementioned powder of former electrodes and the method etc. of Li alloyings.
Al, Si, Sn, Pb, In etc. can be illustrated with the element of Li alloyings as aforementioned, structure is for example easy from flexibility height It is set out at rolled electrode bodies, high power capacity etc., it is preferable to use Al.
In addition, for example, using Li-Al alloys as negative electrode active material in the case of, can also use:Li foils are bonded with Al foils, It imports in battery, so that Li is reacted with Al under the coexisting of nonaqueous electrolytic solution, form the method etc. of Li-Al alloys.Assembled battery Afterwards, by making the process of Al and Li alloyings by charging, the Li-Al alloys of target cathode are formed, thus also can be further Improve the part throttle characteristics after high-temperature storage.
After assembled battery, in the case of making Al and Li alloyings by charging, the powder of Al can be used to make as described above Cathode makes cathode using Al foils etc., after assembled battery, charges the battery, makes Al and Li that electrochemical reaction occur.
It should be noted that when using Al foils, in the case of using collector, if only making the metal foil (Cu as collector (copper) foil, Cu Alloy Foils etc.) it simply overlaps onto on the laminated body of Li foils and Al foils and is inserted into battery, then after there is storage The case where internal resistance of (after especially storing in a high temperauture environment) battery increases, can not obtain sufficient characteristic.
This is because in battery, volume change can occur when being formed with Li-Al alloys on the laminated body of Li foils and Al foils, Or micronizing occurs to which cathode becomes easy absorption nonaqueous electrolytic solution and generates volume and becomes due to forming Li-Al alloys Change, is unable to ensure the adaptation of layer (the Al foils) and collector of Li-Al alloys.
Therefore, in the present invention, in order to inhibit deformation of cathode etc. caused by volume change when alloying, with its battery Volume change preferably plays a role by the Al metal layers for being used to form Li-Al alloys (Al foils etc.), with as collector in advance Do not engaged with Li alloyed metal (AM)s substrate layer (Cu foils etc.) form laminated body (laminated metal foil), by the laminated body for electricity The assembling in pond.In turn, preferably by following manner:By making at least surface side of aforementioned Al metal layers be closed with Li Aurification and form Li-Al alloys, the cathode being made of the laminated body of aforementioned metal substrate layer and Li-Al alloy-layers is made.
When constituting aforementioned cathode, the Li-Al alloys of at least surface side of Al metal layers are using aforementioned laminated body (stacking gold Belong to foil) assembled battery when formed by aforementioned laminated body and nonaqueous electrolytic solution contact, especially make in battery with nonaqueous electrolyte In the case of for secondary cell use, preferably Li-Al is formed in the process that the aforementioned battery to being assembled carries out chemical conversion treatment Alloy.
First, by carrying out the laminated metal foil for being bonded to Al metal layers on the surface of metal substrate layer across diaphragm with anode Stacking etc. and constitute electrode body.Next, former electrodes body is loaded in external packing body, further injected in external packing body After nonaqueous electrolytic solution, the opening portion of external packing body is sealed, to which assembling has the electrode before becoming aforementioned cathode (before cathode Body) battery.
Then, in the battery assembled, cathode precursor forms Li-Al by being contacted with nonaqueous electrolytic solution, becomes cathode, Especially in the case where battery with nonaqueous electrolyte is secondary cell, the battery assembled passes through by having the process to charge (charging process) preferably further also has the process of the chemical conversion treatment for the process (electric discharge process) discharged, to make to bear Pole precursor becomes cathode, as battery with nonaqueous electrolyte, can generate more good function.That is, in aforementioned charging process, it is aforementioned Electrochemical reaction occurs for Li ions in the Al and nonaqueous electrolytic solution of Al metal layers, the Al metal layer opposite with anode at least Surface side forms Li-Al alloys, constitutes the cathode with aforementioned metal substrate layer and the laminated body of Li-Al alloy-layers.
Aforementioned metal substrate layer (hereinafter referred to as " the base material recorded previously as the preferred embodiment for being used to form cathode Layer ") can by the metals such as Cu, Ni, Ti, Fe or these elements and other elements alloy (still, be stainless steel etc. not with Li The alloy of reaction) constitute, but in order to keeping the thickness of substrate layer thinning it is abundant inhibit charging when cathode expansion, can be with By constituting substrate layer selected from the high material of the metal of Ni, Ti and Fe or the such tensile strength of its alloy, preferably with drawing at room temperature It is 400N/mm to stretch intensity2Above material is constituted.
That is, for smaller button-type batteries of the area of electrode etc., even if by Cu (tensile strengths:220N/mm2) draw like that It stretches the low material of intensity and constitutes substrate layer, the influence brought by the expansion of cathode is also small, it may be thus possible, for example, to by by substrate layer Resistance welding constitutes the battery of predetermined properties in hush panel, but more in the case where the area of electrode becomes larger or being laminated with The case where a cathode, is inferior, and characteristic reduction caused by the expansion by cathode can become larger.On the other hand, by with Ni (490N/ mm2),Ti(410N/mm2),SUS304(600N/mm2) etc. selected from Ni, Ti and Fe metal or its alloy constitute substrate layer, to Even if thickness can obtain excellent expansion suppression if thin, especially (there is a situation where multiple in the area of Al active layers Under, it is the gross area) it is 10cm2It is more notable by being set as effect caused by previous materials in the case of above.
In addition, by have have by foregoing tensile strength be 400N/mm2The substrate layer that above material is constituted is born Pole, to which the battery volume change with cathode deformation can also be inhibited better.
On the other hand, in order to reduce the impedance of cathode, substrate layer is constituted preferably by the low material of volume intrinsic resistance at room temperature, Preferably volume intrinsic resistance is 80 × 10-6Ω cm materials below, more preferably volume intrinsic resistance are 30 × 10-6 Ω cm materials below, particularly preferably volume intrinsic resistance are 15 × 10-6Ω cm materials below.
The volume intrinsic resistance of previous materials is Ni respectively:6.8×10-6Ω·cm,Ti:55×10-6Ω·cm,SUS304:72 ×10-6Ω cm particularly preferably constitute substrate layer from volume intrinsic resistance aspect by Ni or its alloy.
Specifically, aforementioned substrates layer is made of the foil of aforementioned metal or alloy, evaporation film, plated film etc..
In addition, aforementioned Al metal layers are made of the foil of Al or Al alloys, evaporation film, plated film etc., as by substrate layer and Al metals Layer engagement and the laminated metal foil that is formed, it is preferable to use constitute the cladding material of the foil of metal foil and Al the or Al alloys of substrate layer, The stacked film etc. of Al metal layers is formed in the surface evaporating Al or Al alloys that constitute the metal foil of substrate layer.
It should be noted that Al metal layers can be set to the one side of substrate layer, it can also be set to two sides, but connect on the two sides of substrate layer The situation that Al metal layers simultaneously form Li-Al alloys in at least surface side of each Al metal layers is closed, and only in the one side of substrate layer The engagement for carrying out Al metal layers is compared with the situation of the formation of Li-Al alloys, can further suppress the deformation (bending of cathode Deng), with its battery volume change and deterioration in characteristics, thus the two sides for being preferably used in substrate layer is bonded to Al metals respectively The laminated metal foil of layer carrys out assembled battery.
It is illustrated hereinafter, illustrating the case where the case where substrate layer is Cu (Cu foil) and substrate layer are Ni (Ni foils), substrate layer is It is also same in the case of material other than Cu, Ni.
As Cu layers are engaged with Al metal layers and the Cu layers that are related to of the laminated metal foil that is formed, can enumerate:It (and can not be kept away by Cu The impurity exempted from) formed layer;By contain Zr, Cr, Zn, Ni, Si, P etc. be used as alloying component, surplus be Cu and inevitably it is miscellaneous What the Cu alloys (content of aforementioned alloying component for example adds up to 10 mass % hereinafter, preferably 1 mass % or less) of matter were formed Layer etc..
As Ni layers are engaged with Al metal layers and the Ni layers that are related to of the laminated metal foil that is formed, can enumerate:It (and can not be kept away by Ni The impurity exempted from) formed layer;It is used as alloying component by containing Zr, Cr, Zn, Cu, Fe, Si, P etc., surplus is for Ni and unavoidably Impurity the layer that is formed of Ni alloys (content of aforementioned alloying component such as add up to 20 mass % or less).
In turn, as Cu layers are engaged with Al metal layers and formed laminated metal foil, Ni layers are engaged and shape with Al metal layers At the Al metal layers that are related to of laminated metal foil, can enumerate:The layer formed by Al (and inevitable impurity);By contain Fe, Ni, Co, Mn, Cr, V, Ti, Zr, Nb, Mo etc. are used as alloying component, and surplus is Al and the Al alloys of inevitable impurity are (aforementioned The content of alloying component is such as adding up to 50 mass % or less) the layer that is formed.
Cu layers are being engaged with Al metal layers and the laminated metal foil formed, the stacking that Ni layers are engaged with Al metal layers and formed In metal foil, in order to which the ratio of the Li-Al alloys of negative electrode active material will be used as to be set as more than centainly, substrate layer will be used as Cu layers, Ni layers of thickness is when being set as 100, the thickness of Al metal layers is (wherein, on the Cu layers as substrate layer, Ni layers of two sides In the case of being bonded to Al metal layers, for the thickness per face.It is same as below.) it is preferably 10 or more, more preferably 20 or more, into One step is preferably 50 or more, and particularly preferably 70 or more.In addition, in order to improve current collection effect, Li-Al alloys are fully kept, Cu layers are engaged with Al metal layers and formed laminated metal foil, make the Ni layers of laminated metal foil for engaging and being formed with Al metal layers In, when Cu layers, Ni layers of the thickness of substrate layer will be used as to be set as 100, the thickness of Al metal layers is preferably 180 hereinafter, more excellent 150 are selected as hereinafter, particularly preferably 120 hereinafter, most preferably 100 or less.
It should be noted that Cu layers, Ni layers of the thickness as substrate layer are preferably 10~50 μm, more preferably 40 μm hereinafter, special It You Xuanwei not be 30 μm or less.In addition, the thickness of Al metal layers (wherein, is bonded to Al on the Cu layers as substrate layer, Ni layers of two sides In the case of metal layer, for per face thickness) be preferably 5 μm or more, more preferably 10 μm or more, particularly preferably 15 μm with On, furthermore it is preferred that for 100 μm hereinafter, more preferably 70 μm hereinafter, particularly preferably 50 μm hereinafter, most preferably 30 μm or less.
More than the capacity of cathode is set as certain, Cu layers are engaged with Al metal layers and formed laminated metal foil, by Ni The thickness of laminated metal foil that layer is engaged with Al metal layers and formed is preferably 50 μm or more, more preferably 60 μm or more, in addition, In order to which proper range, preferably 200 μm will be set as with the capacity of positive active material ratio hereinafter, more preferably 150 μm hereinafter, special It You Xuanwei not be 120 μm or less.
It should be noted that for the purpose of according to the type of positive active material or the irreversible capacity to adjust Li-Al alloys, It can also use and be fitted with Li foils in advance on the surface of Al metal layers and be further laminated with the laminated metal foil of Li foils to assemble Battery charges to the battery after assembling, forms the Li-Al alloy-layers of target composition.
Fig. 1, which is shown, schematically shows that the laminated body for being used to form the cathode that can be used in battery with nonaqueous electrolyte is (negative Pole precursor) an example sectional view.The cathode precursor 100 of Fig. 1 is that Al metal layers 101b, 101b are being engaged in base material The two sides of layer 101a and the laminated metal foil 101 that constitutes, Al metal layers 101b, 101b surface fitting Li foils 102,102 and The laminated body of formation.
As described above, in the case where being used without the cathode precursor of Li foils, Al will be engaged in the one or both sides of substrate layer Metal layer and the laminated body (such as laminated metal foil shown in Fig. 1 101) that constitutes is used as cathode precursor.
In addition, before assembled battery, it can be conventionally in the aforementioned layers used as the cathode precursor for being used to form cathode Negative wire body is set on the Cu layers, the substrate layers such as Ni layers in stack.
In battery with nonaqueous electrolyte, anode and cathode (including cathode precursor) use for example in the form of following:It is overlapped across diaphragm And constitute electrode body, by former electrodes body further wind it is spiral and formed rolled electrode bodies or be alternately laminated with The multilayer electrode body of multiple anodes and multiple cathode.
Diaphragm preferably has in the occlusion of 170 DEG C of 80 DEG C or more (more preferable 100 DEG C or more) or less (more preferable 150 DEG C or less) its hole Property (i.e. failure of current (shut down) function), can use and to be used in common nonaqueous electrolytic solution secondary battery etc. The microporous membrane of the polyolefin such as diaphragm, such as polyethylene (PE), polypropylene (PP).The microporous membrane for constituting diaphragm for example can be with It is using only PE, the microporous membrane using only PP, in addition it is also possible to be the layer of the microporous membrane and the microporous membrane of PP of PE Stack.
Further, it is also possible to by by adhesive in the microporous membrane surface bonding aluminium oxide of aforementioned polyolefins, boehmite, kaolinite Soil, Mg (OH)2Equal inorganic particulates and the laminated body of multiple aperture plasma membrane, the multiple aperture plasma membrane for being formed with aramid fiber that constitutes is used for diaphragm.
The thickness of diaphragm is for example preferably 10~30 μm.
The nonaqueous electrolytic solution of battery with nonaqueous electrolyte is dissolved in solution obtained by organic solvent using by lithium salts.
The organic solvent that nonaqueous electrolytic solution is related to it can be mentioned, for example:Ethylene carbonate, propylene carbonate (PC), butylene carbonate, The cyclic carbonates such as vinylene carbonate;The linear carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate;Propionic acid first The chains ester such as ester;The cyclic esters such as the compound with lactonic ring;Dimethoxy-ethane, ether, 1,3- dioxolanes, diethylene glycol The chains ether such as dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether;Dioxane, tetrahydrofuran, 2- methyltetrahydrofurans etc. Cyclic ether;The nitriles such as acetonitrile, propionitrile, methoxypropionitrile;Sulfurous esters such as glycol sulfite ester etc.;They can also be mixed Two or more and use.In order to which the more good battery of characteristic is made, with the mixed of the linear carbonate of cyclic carbonate and aforementioned illustration Bonding solvent etc. can obtain the combination of high conductivity to use be preferred.
In addition, the organic solvent of nonaqueous electrolytic solution more preferably uses PC.PC is particularly useful to ensure battery with nonaqueous electrolyte low Flash-over characteristic under temperature.For example, the organic solvent for the nonaqueous electrolytic solution that battery with nonaqueous electrolyte is related to uses ethylene carbonate more, But since the solidification point of PC is lower than ethylene carbonate, the output of battery can be improved in the environment of lower temperature Characteristic.
In turn, from the viewpoint of further increasing the flash-over characteristic of battery with nonaqueous electrolyte at low temperature, as non-aqueous solution electrolysis The organic solvent of liquid is preferably used together the compound with lactonic ring with PC.
As the compound with lactonic ring, gamma-butyrolacton, the α lactones etc. with substituent group can be enumerated.
In addition, the α lactones with substituent group are preferably the lactone of such as 5 membered rings (carbon number for constituting ring is 4).It is aforementioned The substituent group of the positions α of lactone can be 1, or 2.
As foregoing substituents, alkyl, halogen (fluorine-based, chloro, bromo, iodo) etc. can be enumerated.As alkyl, optimizing alkyl, Aryl etc., preferably its carbon number are 1 or more 15 or less (6 or less more preferably).In the case that foregoing substituents are alkyl, further Preferably methyl, ethyl, propyl, butyl, phenyl etc..
As the specific example of the α lactones with substituent group, Alpha-Methyl-gamma-butyrolacton, α-ethyl-can be enumerated Gamma-butyrolacton, α-propyl-gamma-butyrolacton, α-butyl-gamma-butyrolacton, α-phenyl-gamma-butyrolacton, α- The chloro- gamma-butyrolacton of fluoro- gamma-butyrolacton, α-, the bromo- gamma-butyrolactons of α-, alpha-iodine-gamma-butyrolacton, α, α-two Methyl-gamma-butyrolactone, α, α-diethyl-gamma-butyrolacton, α, α-diphenyl-gamma-butyrolacton, α-ethyl-α- Methyl-gamma-butyrolactone, Alpha-Methyl-α-phenyl-gamma-butyrolacton, α, the fluoro- gamma-butyrolactons of α-two, α, α-two Chloro- gamma-butyrolacton, α, the bromo- gamma-butyrolactons of α-two, α, iodo- gamma-butyrolactons of α-two etc. can be used only in them 1 kind, can also be used in combination of two or more.Wherein, more preferable Alpha-Methyl-gamma-butyrolacton.
For the content of the PC in whole organic solvents for being used in nonaqueous electrolytic solution, from being ensured well by using it to be brought Foregoing advantages from the perspective of, preferably 10 volume % or more, more preferably 30 volume % or more.It should be noted that as above Described, the organic solvent of nonaqueous electrolytic solution can be only PC, thus, PC in the whole organic solvents used in nonaqueous electrolytic solution The upper limit value of preferred content is 100 volume %.
It should be noted that in the case of using the compound with lactonic ring, from the effect ensured well by using it to bring From the perspective of, the content of the compound with lactonic ring is preferably 0.1 in the whole organic solvents used in nonaqueous electrolytic solution Quality % or more, preferably in the range of the content of PC in meeting the preferred value and whole organic solvents meets aforementioned preferred value It uses.
It is preferable to use LiBF for the lithium salts that nonaqueous electrolytic solution is related to4, this is because in addition to heat resistance height, nonaqueous electrolytic solution can be improved Battery other than storing property, also has the function of the corrosion for the aluminium for inhibiting to use in battery in a high temperauture environment.
As other lithium salts that nonaqueous electrolytic solution is related to, it can be mentioned, for example LiClO4,LiPF6,LiAsF6,LiSbF6,LiCF3SO3, LiCF3CO2,Li2C2F4(SO3)2,LiN(CF3SO2)2,LiC(CF3SO2)3,LiCnF2n+1SO3(n≧2),LiN(RfOSO2)2(this In, Rf is fluoroalkyl) etc..
The concentration of lithium salts is preferably 0.6mol/l or more in nonaqueous electrolytic solution, more preferably 0.9mol/l or more.
It should be noted that the concentration of whole lithium salts is preferably 1.8mol/l hereinafter, more preferably 1.6mol/l in nonaqueous electrolytic solution Below.Therefore, LiBF is used only in lithium salts4In the case of, preferably make in the range of its concentration meets aforementioned preferred upper limit value With.On the other hand, by other lithium salts and LiBF4In the case of being used together, preferably in LiBF4Concentration meet it is aforementioned preferably The concentration of whole lithium salts uses in the range of meeting aforementioned preferred upper limit value while lower limiting value.
Nonaqueous electrolytic solution preferably comprises the phosphate cpd or boration for the group that intramolecular has represented by aforementioned formula (1) Close object.Cathode is added to aforementioned phosphate compound or boronic acid compounds using in the battery with nonaqueous electrolyte of Li alloys in use Nonaqueous electrolytic solution in the case of, be able to maintain that the part throttle characteristics after high-temperature storage height.That is, using aforementioned additive, it can The reacting of electrolyte and negative terminal surface, thin and high-quality protection envelope can be inhibited by being formed in negative terminal surface.The protection quilt Film can prevent and assemble cathode and electricity due to effectively playing a role under 110 DEG C or more of hot environment Brought into when pond gas caused by the reaction of moisture in battery etc. generate, the deterioration in characteristics etc. of cathode.
In addition, in the battery with nonaqueous electrolyte of aforementioned composition, the effect of aforementioned phosphate compound or boronic acid compounds substantially relies on In combined positive active material, by using containing the compound with olivine structural as a positive electrode active material just Pole, it is more excellent to the effect of aforementioned additive.
There is LiFePO4 etc. the compound of olivine structural to contain alkaline impurities due to the relationship of its manufacturing method, contain Water is also easy to increase.Especially in order to improve the electric conductivity of material and its surface carbon material is coating in the case of, become It is easy adsorption moisture, water content can further increase.Anode is made using such positive active material and is directly used in In the case of the making of battery, large quantity of moisture is brought into battery.
Aforementioned moisture contained in anode is for example easy the LiPF with the electrolyte for being widely used as nonaqueous electrolytic solution6It is inorganic etc. fluorine-containing Lithium salts reacts, and becomes the reason of hydrogen fluoride is generated in battery.Therefore, such feelings in the case where battery is positioned over hot environment for a long time Under condition, it may occur that the deterioration of constituent material of electrode etc. makes the characteristic of battery reduce.
And in contrast, nonaqueous electrolytic solution contains the phosphate cpd for the group that intramolecular has represented by aforementioned formula (1) Or in the case of boronic acid compounds, aforementioned additive is promoted due to generated hydrogen fluoride and forms protection quilt in negative terminal surface The reaction of film, therefore by using the compound with olivine structural, the effect of aforementioned additive is easy tod produce instead.Especially Using the coating compound with olivine structural of surface carbon material, adsorption moisture becomes more, therefore more holds The easily effect of performance aforementioned additive.
Aforementioned phosphate compound has at least one in hydrogen atom possessed by phosphoric acid by the base represented by aforementioned formula (1) The structure of group's substitution.
In addition, aforementioned boronic acid compounds have at least one in hydrogen atom possessed by boric acid by represented by aforementioned formula (1) Group substitution structure.
In aforementioned formula (1), X Si, Ge or Sn, as aforementioned phosphate compound, it is preferable to use X is the phosphoric acid silicyl of Si Ester, as aforementioned boronic acid compounds, it is preferable to use X is the boric acid silyl ester of Si.
In addition, in aforementioned formula (1), R1,R2And R3Be each independently the alkyl of carbon number 1~10, the alkenyl of carbon number 2~10 or The aryl of carbon number 6~10, more preferable methyl or ethyl.In addition, R1,R2And R3In, part or all of hydrogen atom can be by fluorine Substitution.Moreover, as the group represented by aforementioned formula (1), particularly preferred trimethyl silyl.
It, can be with only 1 in hydrogen atom possessed by phosphoric acid by the base represented by aforementioned formula (1) in aforementioned phosphate compound Group's substitution, can also be in hydrogen atom possessed by phosphoric acid 2 are replaced by the group represented by aforementioned formula (1), can be with Whole 3 in hydrogen atom possessed by phosphoric acid are replaced by the group represented by aforementioned formula (1), and more preferable phosphoric acid is had Hydrogen atom in all 3 replaced by the group represented by aforementioned formula (1).
As such aforementioned phosphate compound, such as mono phosphoric acid ester (trimethyl silyl) ester, di(2-ethylhexyl)phosphate (trimethyl can be enumerated Monosilane) ester, tricresyl phosphate (trimethyl silyl) ester, di(2-ethylhexyl)phosphate methyl trimethoxy base monosilane ester, bis- (the trimethyl first of phosphoric acid methyl Silane) ester, di(2-ethylhexyl)phosphate ethyl trimethyl silicane ester, diphenyl phosphate (trimethyl silyl) ester, tricresyl phosphate (silicohetane Alkane) ester, tricresyl phosphate (vinyl-dimethyl base monosilane) ester, tricresyl phosphate (triisopropyl monosilane) ester, tricresyl phosphate (dimethyl ethyl Monosilane) ester, tricresyl phosphate (dimethyl ethyl monosilane) ester, tricresyl phosphate (butyldimethylsilyl) ester, tricresyl phosphate (vinyl Dimethyl silane) ester, tricresyl phosphate (triphenylsilyl) ester etc., preferably mono phosphoric acid ester (trimethyl silyl) ester, di(2-ethylhexyl)phosphate (three Methyl silicane) ester, tricresyl phosphate (trimethyl silyl) ester, di(2-ethylhexyl)phosphate methyl trimethoxy base monosilane ester, the bis- (front threes of phosphoric acid methyl Base monosilane) ester, particularly preferred tricresyl phosphate (trimethyl silyl) ester.
In addition, in aforementioned boronic acid compounds, it can be with only 1 in hydrogen atom possessed by boric acid by by aforementioned formula (1) institute table The group substitution shown, can also be in hydrogen atom possessed by boric acid 2 are replaced by the group represented by aforementioned formula (1), It can be replaced by the group represented by aforementioned formula (1) with whole 3 in hydrogen atom possessed by boric acid, more preferable boric acid Whole 3 in possessed hydrogen atom are replaced by the group represented by aforementioned formula (1).
As such aforementioned boronic acid compounds, such as boric acid list (trimethyl silyl) ester, two (trimethyl of boric acid can be enumerated Monosilane) ester, boric acid three (trimethyl silyl) ester, boric acid dimethyl trimethyl silyl ester, bis- (the trimethyl first of boric acid methyl Silane) ester, boric acid diethyl trimethyl silyl ester, boric acid diphenyl (trimethyl silyl) ester, three (silicohetane of boric acid Alkane) ester, boric acid three (vinyl-dimethyl base monosilane) ester, boric acid three (triisopropyl monosilane) ester, three (dimethyl ethyl of boric acid Monosilane) ester, boric acid three (dimethyl ethyl monosilane) ester, boric acid three (butyldimethylsilyl) ester, three (vinyl of boric acid Dimethyl silane) ester, boric acid three (triphenylsilyl) ester etc., preferred boric acid list (trimethyl silyl) ester, boric acid two (three Methyl silicane) ester, boric acid three (trimethyl silyl) ester, boric acid dimethyl trimethyl silyl ester, the bis- (front threes of boric acid methyl Base monosilane) ester, particularly preferred boric acid three (trimethyl silyl) ester.
There is the phosphate cpd or boric acid of the group represented by aforementioned formula (1) in nonaqueous electrolytic solution, intramolecular The additive amount of compound, from the viewpoint of better assuring that by using its caused foregoing advantages, preferably 0.1 mass % More than, more preferably 0.3 mass % or more, further preferably 0.5 mass % or more, particularly preferably 0.7 mass % or more, Most preferably 1 mass % or more.In addition, if its content is excessive, then can increase in the thickness for the envelope that negative terminal surface is formed, by There are resistance to become larger for this, part throttle characteristics reduce possibility, thus in nonaqueous electrolytic solution, intramolecular have by aforementioned formula (1) The phosphate cpd of represented group or the additive amount of boronic acid compounds are preferably 10 mass % hereinafter, more preferably 8 matter Measure % hereinafter, further preferably 7 mass % hereinafter, particularly preferably 5 mass % hereinafter, most preferably 3 mass % or less.
In the case of containing aforementioned phosphate compound and aforementioned boronic acid compounds simultaneously, in such a way that its total amount is in aforementioned range It is adjusted.
In addition, nonaqueous electrolytic solution preferably comprises nitrile compound as additive.By using the non-water power for being added to nitrile compound Liquid is solved, to which nitrile compound is adsorbed in the surface of positive active material and forms envelope, since the envelope inhibits by non-aqueous solution electrolysis Gas caused by the oxygenolysis of liquid generates, thus when more particularly to inhibit to store under high temperature environment battery expansion.As Nitrile compound can enumerate dintrile such as succinonitrile, glutaronitrile, adiponitrile etc..
In turn, can also contain as needed in nonaqueous electrolytic solution:The saturated rings such as 1,3- propane sultones, 1,4- butane sultones Shape sultone compound;The unsaturated cyclics sultone compound such as 1,3- propene sultones;Maleic anhydride, phthalic anhydride etc. Acid anhydrides;LiB(C2O4)2Equal additives.
In addition, nonaqueous electrolytic solution can also use well known polymer isogel agent, gel (gel-like electrolyte) is made.
Battery with nonaqueous electrolyte is for example manufactured by following methods:Electrode body is loaded in external packing body, further in outsourcing Dress injects nonaqueous electrolytic solution in vivo, and electrode body is made to be impregnated in nonaqueous electrolytic solution, and then, the opening portion of external packing body is sealed.
The external packing body of battery with nonaqueous electrolyte can use steel, aluminum, outer package jar made of aluminum alloy, by vapor deposition have metal The external packing body etc. that constitutes of laminated film.
It, can be with Li in order to be formed using aforementioned cathode precursor when constituting the battery with nonaqueous electrolyte of the present invention The element of alloying and the alloy of Li can implement the battery after assembling at least have 1 charging process or in addition to battery charger Also there is the chemical conversion treatment of electric discharge process other than sequence.
In aforementioned charging process, what cathode precursor contained can send out with the Li ions in the element and nonaqueous electrolytic solution of Li alloyings Raw electrochemical reaction, being formed can be with the element of Li alloyings and the alloy of Li, to which cathode precursor becomes cathode.
It should be noted that in aforementioned chemical conversion treatment, when forming Li-Al alloys, big volume expansion occurs for Al metal layers, therefore, A large amount of cracks are generated in Li-Al alloy-layers, compared with the case where not carrying out chemical conversion treatment, can further increase high-temperature storage Part throttle characteristics afterwards.The condition of the chemical conversion treatments such as charge condition can be suitably set according to necessary characteristic.
The battery with nonaqueous electrolyte of the present invention can charge repeatedly, can be used as secondary cell, but according in cathode The formation degree of Li-Al alloys can be used as the one-shot battery only to discharge use.
Embodiment
Hereinafter, being based on embodiment, present invention is described in detail.But following embodiments are not intended to limit the present invention.
(embodiment 1)
The packet of 25mm × 40mm sizes obtained by the Al foils of 30 μm of thickness will be laminated with respectively on the two sides of the Ni foils of 30 μm of thickness It covers material (laminated metal foil) and is used as cathode precursor.In the Cu foils of the end ultrasonic welding current collection of aforementioned cladding material, further exist The Ni lugs that the end ultrasonic welding of the Cu foils is used to be conductively connected with outside batteries, use it for the assembling of battery.
On the other hand, anode is following operates to make.It modulates 97 mass parts LiFePO4s (surface carbon is coating), 1.5 mass Slurry obtained by part is dispersed in as the PVDF of adhesive in NMP as the acetylene black of conductive auxiliary agent and 1.5 mass parts, will It is coated on the one side of the Al foils of 12 μm of thickness, dry, carries out pressurized treatments, to be formed about in the one side of Al foil collectors 17mg/cm2The positive electrode material mixture layer of quality.It should be noted that the part in slurry coats face be equipped with do not form positive electrode material mixture layer and Expose the position of Al foils.Next, aforementioned Al foils collector to be cut into the size of 20mm × 45mm, in the aforementioned position for exposing Al foils Al lug of the ultrasonic welding for being conductively connected with outside batteries is set, the one side to be produced on collector has 20mm × 30mm The anode of the positive electrode material mixture layer of size.
In the both sides for the cathode precursor for being welded with aforementioned Ni lugs, across the diaphragm formed by the PE microporous films of 16 μm of thickness Aforementioned positive electrode is laminated respectively, makes one group of electrode body.In addition, in the volume of propylene carbonate (PC) and methyl ethyl carbonate (EMC) Than being 1:2 in the mixed solvent, by LiBF4It is dissolved by the concentration of 1mol/l, modulates nonaqueous electrolytic solution.By former electrodes body true In the air, it after 15 hours dry at 60 DEG C, is enclosed in laminated film external packing body together with aforementioned nonaqueous electrolytic solution, it is specified to make Capacity 30mAh, the battery with nonaqueous electrolyte with appearance shown in Fig. 2, cross section structure shown in Fig. 3.
Here, Fig. 2 and Fig. 3 are illustrated, Fig. 2 is the plan view for schematically showing battery with nonaqueous electrolyte, and Fig. 3 is Fig. 2's I-I line sectional views.Battery with nonaqueous electrolyte 1 is, in the laminated film external packing body 2 being made of 2 laminated films, accommodate by Anode 5 and cathode 6 are laminated across diaphragm 7 and the multilayer electrode body and nonaqueous electrolytic solution (not shown) of composition, for laminated film External packing body 2 seals upper and lower laminated film thermal welding by its peripheral part.It should be noted that in order to avoid attached drawing becomes Must be complicated, each layer and each layer of anode 5 and cathode 6 that constitute laminated film external packing body 2 are not differently shown in Fig. 3.
Anode 5 is connect via lead body with positive external terminal 3 in the battery 1, in addition, although it is not shown, but cathode 6 and It is connect with negative outer terminal 4 via lead body in battery 1.Moreover, positive external terminal 3 and negative outer terminal 4 be with One end, is led to the outside of laminated film external packing body 2 by the mode that can be connect with external equipment etc..
(embodiment 2)
Positive active material is changed to LiFePO4 and LiNi used in embodiment 10.80Co0.15Al0.05O2In mass ratio 50:The substance that 50 ratio is obtained by mixing operates similarly with example 1 in addition to this, makes anode, removes and uses the anode In addition, it operates similarly with example 1, makes battery with nonaqueous electrolyte.
(embodiment 3)
Positive active material is changed to LiFePO4 used in embodiment 1 and is incited somebody to action LiCo0.9795Mg0.011Zr0.0005Al0.009O2Surface Al2O3Positive electrode obtained by coating in mass ratio 50:50 ratio The substance being obtained by mixing operates similarly with example 1 in addition to this, anode is made, other than using the anode, with reality It applies example 1 similarly to operate, makes battery with nonaqueous electrolyte.
(embodiment 4)
Positive active material is changed to LiFePO4 and LiNi used in embodiment 10.33Co0.33Mn0.33O2In mass ratio 50:The substance that 50 ratio is obtained by mixing operates similarly with example 1 in addition to this, anode is made, in addition to using this just It other than pole, operates similarly with example 1, makes battery with nonaqueous electrolyte.
(embodiment 5)
It is laminated with the cladding of 25mm × 40mm sizes obtained by the Al foils of 30 μm of thickness respectively on the two sides of 30 μm of Cu foils of thickness The Cu foils of the end ultrasonic welding current collection of material (laminated metal foil) are further used for and electricity in the end ultrasonic welding of the Cu foils The Ni lugs of pond external conductive connection, are used as cathode precursor, in addition to this, operate similarly with example 1, make non-aqueous Electrolyte battery.
(embodiment 6)
In the cladding material (layer for being laminated with 25mm × 40mm sizes obtained by the Al foils of 30 μm of thickness on one side of 30 μm of Ni foils of thickness Folded metal foil) end ultrasonic welding current collection Cu foils, further the end ultrasonic welding of the Cu foils be used for outside battery The Ni lugs that portion is conductively connected, are used as cathode precursor, in addition to this, operate similarly with example 1, and make non-aqueous solution electrolysis Solution battery.
(embodiment 7)
Use LiPF6Instead of LiBF4, in addition to this, operate similarly with example 1, nonaqueous electrolytic solution modulated, in addition to using this It other than nonaqueous electrolytic solution, operates similarly with example 1, makes battery with nonaqueous electrolyte.
(embodiment 8)
It is 1 in the volume ratio of ethylene carbonate (EC) and EMC:2 in the mixed solvent dissolves LiBF by the concentration of 1mol/l4, adjust Nonaqueous electrolytic solution processed operates similarly with example 1 other than using the nonaqueous electrolytic solution, makes battery with nonaqueous electrolyte.
(comparative example 1)
Positive active material is changed to LiNi0.80Co0.15Al0.05O2, in addition to this, operate similarly with example 1, make Anode operates similarly with example 1 other than using the anode, makes battery with nonaqueous electrolyte.
(comparative example 2)
Positive active material is changed to LiCo0.9795Mg0.011Zr0.0005Al0.009O2Surface Al2O3Coating positive material Material, in addition to this, operates similarly with example 1, and makes anode, other than using the anode, grasps similarly to Example 1 Make, makes battery with nonaqueous electrolyte.
(comparative example 3)
Positive active material is changed to LiNi0.33Co0.33Mn0.33O2, in addition to this, operate similarly with example 1, make Anode operates similarly with example 1 other than using the anode, makes battery with nonaqueous electrolyte.
For the battery with nonaqueous electrolyte of Examples 1 to 8 and comparative example 1~3, following storing properties 1 and storing property 2 are carried out Low temperature discharge evaluation after evaluation and high-temperature storage.
1 > of < storing properties
For each battery of Examples 1 to 8 and comparative example 1~3, constant current (6mA)-constant pressure (4.0V) charging is carried out, in charging electricity Stream stops charging at the time of being reduced to 0.3mA.In turn, it is charged with aforementioned charge condition, so that battery is become and be full of electricity condition. Each battery full of electricity condition is hung with thin silk thread, is immersed in pure water until battery measures completely not in underwater Weight in water.After being stored 10 days at 85 DEG C in each battery full of electricity condition, be cooled to room temperature, then with previously in the same manner as Operation, measures weight in water, according to and storage before the difference of weight calculate the volume differences of the front and back battery of storage, by the volume Volume change of the difference as battery.
2 > of < storing properties
For each battery (batteries different from the battery for having stored 10 days) of Examples 1 to 8 and comparative example 1~3, with aforementioned side Method similarly operates, and it is full of electricity condition to make battery.Each battery full of electricity condition is hung with thin silk thread, is immersed in pure water In until battery completely not in underwater, measure weight in water.30 will be stored at 85 DEG C in each battery full of electricity condition After it, be cooled to room temperature, then with previously in the same manner as operate, measure weight in water, according to and storage before weight difference The volume differences for calculating the front and back battery of storage, using the volume differences as the volume change of battery.
Cryogenic discharging characteristic > after < high-temperature storages
For each battery (battery for storing 30 days after assembling) of Examples 1 to 8 and comparative example 1~3, in the same manner as preceding method Operation, it is full of electricity condition to make battery.After each battery full of electricity condition is stored 10 days at 85 DEG C, in -20 DEG C of environment Under, it carries out being discharged to 2.0V with 45mA constant currents, measures the length of discharge time at this time.
The composition of each battery is shown in table 1, will be aforementioned evaluation result is shown in table 2.
&#91;Table 1&#93;
&#91;Table 2&#93;
As shown in Table 1 and Table 2, for comprising with the anode as a positive electrode active material of the compound with olivine structural, with And by substrate layer cathode precursor of the surface with Al metal layers or the cathode precursor with the big substrate layer of tensile strength and For the battery with nonaqueous electrolyte of the Examples 1 to 8 of the cathode of formation, in the evaluation of storing property 1 and storing property 2, electricity The deformations such as gas generation, the bending of cathode in pond are inhibited, and volume change is small, have excellent high-temperature storage characteristic. In addition, discharge time when cryogenic discharging characteristic evaluation of the battery of Examples 1 to 8 after high-temperature storage is long, through high-temperature storage Part throttle characteristics afterwards at low temperature is also good.
And in contrast, for using the comparative example 1~3 of the positive active material other than the compound with olivine structural For battery, the volume change in the evaluation of storing property 2 is big, and high-temperature storage characteristic is poor, or after high-temperature storage Discharge time when cryogenic discharging characteristic is evaluated is short, and the part throttle characteristics after high-temperature storage at low temperature is poor.
(use the non-of the nonaqueous electrolytic solution containing phosphate cpd of the intramolecular with the group represented by aforementioned formula (1) The example of water electrolysis solution battery)
(embodiment 9)
The making > of < anodes
Modulation make 97 mass parts as a positive electrode active material, olivine-type LiFePO4 that surface carbon material is coating (LiFePO4, average grain diameter:13 μm, BET specific surface area:9m2/ g), 1.5 mass parts as conductive auxiliary agent acetylene black and Slurry obtained by 1.5 mass parts are dispersed in as the acrylic resin of adhesive in NMP is coated on the Al foils of 12 μm of thickness Two sides, it is dry simultaneously to carry out pressurized treatments, to form about 12.7mg/cm in the one side of Al foil collectors2The anode of quality Mixture layer.In turn, the pressurized treatments of positive electrode material mixture layer are carried out, and the lead body of aluminum is installed, to make length 974mm, The band-like anode of width 43mm.
The making > of < cathode
The two sides of Cu foils in 35 μm of thickness is laminated with 988mm × 44.5mm sizes obtained by the Al foils of 20 μm of thickness respectively Coat the making that material (laminated metal foil) is used for cathode.Nickel of the installation for being conductively connected with outside batteries on aforementioned cladding material Lead body processed, as cathode (cathode precursor).
Aforementioned positive electrode and aforementioned cathode are laminated across following diaphragms, after winding is spiral, flattens and forms flat electricity Polar body, the diaphragm useful acrylic resin formed by boehmite bonding by the surface of the PE microporous films in 12 μm of thickness and Laminated body is formed obtained by the multiple aperture plasma membrane of 4 μm of the thickness of composition.When making former electrodes body, be set as diaphragm is bonded with Bo Mu The surface side of stone is opposite with anode.
In addition, in the volume ratio 17 of propylene carbonate (PC), methyl ethyl carbonate (EMC) and dimethyl carbonate (DEC):63:20 In the mixed solvent dissolves LiBF by the concentration of 1.2mol/l4, further press 5 mass % of adiponitrile, tricresyl phosphate (trimethyl first silicon Alkane) 3 mass % of ester (TMSP), 1,3- propene sultones (PRS), 0.5 mass % amount be added, to modulate non-aqueous solution electrolysis Liquid.
It, will after injecting aforementioned nonaqueous electrolytic solution by the rectangular cell container made of aluminum alloy of former electrodes body inserting thickness 0.8mm Battery case seals, to be assembled into the rectangular battery with nonaqueous electrolyte of 103450 sizes by Fig. 4 and structure shown in fig. 5.
Here Fig. 4 and battery shown in fig. 5 are illustrated, Fig. 4 is its partial section view, and anode 11 and cathode 12 are across diaphragm After 13 windings are spiral, pressurizeing, it is flat to become, and flat rolled electrode bodies 16 is made, together with nonaqueous electrolytic solution It is contained in rectangular (prismatic) battery case 14.It is not shown positive 11, cathode 12 in Fig. 4 but in order to avoid complicating Each layer, nonaqueous electrolytic solution etc..
Battery case 14 is aluminium alloy system, constitutes the external packing body of battery, and the simultaneous battery case 14 is positive terminal.Moreover, electric The bottom of pool capacity device 14 is configured with the insulator 15 formed by PE pieces, flat from being formed by anode 11, cathode 12 and diaphragm 13 Shape rolled electrode bodies 16 lead to the positive wire body 17 and negative wire body 18 for being connected to anode 11 and 12 one end of cathode. In addition, on the sealing cover board 19 made of aluminum alloy for sealing the opening portion of battery case 14, via the insulation of polypropylene Packaging 20 is equipped with the terminal 21 of stainless steel, and on the terminal 21, the lead plate of stainless steel is equipped with via insulator 22 23。
Moreover, the cover board 19 is inserted into the opening portion of battery case 14, the joint portion of the two is welded, to opening for battery case 14 Oral area is enclosed, and inside battery is closed.In addition, in the battery of Fig. 4, cover board 19 is equipped with nonaqueous electrolytic solution inlet 24, at this In the state of inserting seal member in nonaqueous electrolytic solution inlet 24, for example, by welded seals such as laser weldings, it is ensured that electricity The seal in pond.In turn, cover board 19 is equipped with explosion-proof valve 25 and internal gas is expelled to outside as when battery temperature rises Mechanism.
In the battery of the embodiment 9, by the way that positive wire body 17 is directly welded in cover board 19, to battery case 14 and cover board 19 function as positive terminal, by the way that negative wire body 18 is welded in lead plate 23, and make to bear via the lead plate 23 Pole lead body 18 is connected with terminal 21, to which terminal 21 is functioned as negative terminal, according to the material etc. of battery case 14 Difference, its positive and negative anodes can be opposite sometimes.
Fig. 5 is the stereogram for the appearance for schematically showing aforementioned battery shown in Fig. 4, which is to show that aforementioned battery is side It is illustrated for the purpose of shape battery, battery is diagrammatically illustrated in the Fig. 4, illustrated only special in the component parts of battery Fixed part.In addition, in Fig. 4, the part of electrode body inner circumferential side does not carry out section.
(embodiment 10)
It is used in mixed way the coating olivine-type LiFePO4 of 48.5 mass of surface carbon materials and 48.5 mass parts LiNi0.8Co0.15Al0.05O2As a positive electrode active material, in addition to this, it operates similarly to Example 9, assembles nonaqueous electrolytic solution Battery.
(embodiment 11)
It is used in mixed way the coating olivine-type LiFePO4 of 48.5 mass of surface carbon materials and 48.5 mass parts LiNi0.33Co0.33Mn0.33O2As a positive electrode active material, in addition to this, it operates similarly to Example 9, assembles non-aqueous solution electrolysis Solution battery.
(embodiment 12)
The additive amount of tricresyl phosphate (trimethyl silyl) ester in nonaqueous electrolytic solution is set as 0.5 mass %, in addition to this, with reality It applies example 9 similarly to operate, assembles battery with nonaqueous electrolyte.
(embodiment 13)
The additive amount of tricresyl phosphate (trimethyl silyl) ester in nonaqueous electrolytic solution is set as 8 mass %, in addition to this, with implementation Example 9 similarly operates, and assembles battery with nonaqueous electrolyte.
(comparative example 4)
It is not added with tricresyl phosphate (trimethyl silyl) ester in nonaqueous electrolytic solution to operate similarly to Example 9 in addition to this, group Fill battery with nonaqueous electrolyte.
(comparative example 5)
Use 97 mass parts LiNi0.8Co0.15Al0.05O2As a positive electrode active material, in addition to this, it grasps similarly to Example 9 Make, assembles battery with nonaqueous electrolyte.
(comparative example 6)
There is the LiCoO of Al oxide coatings using 97 mass of surface2As a positive electrode active material, in addition to this, with reality It applies example 9 similarly to operate, assembles battery with nonaqueous electrolyte.
(comparative example 7)
Use 97 mass parts LiNi0.33Co0.33Mn0.33O2As a positive electrode active material, in addition to this, it grasps similarly to Example 9 Make, assembles battery with nonaqueous electrolyte.
(comparative example 8)
Using natural graphite as negative electrode active material, by 96 mass parts negative electrode active materials, 2 mass parts SBR, 2 mass parts CMC And water mixing, composition containing cathode agent is modulated, the two sides of the copper foil of 12 μm of thickness is coated on, makes it dry, to make Cathode.Then, it other than using aforementioned cathode, operates similarly to Example 9, assembles nonaqueous electrolyte battery.
For each battery of embodiment 9~13 and comparative example 4~8, carries out constant current-constant-voltage charge and held to 3.8V and then with constant current The continuous charge and discharge for being discharged to 2.0V 3 times, to carry out chemical conversion treatment.
For each battery after chemical conversion treatment, persistently fill with the constant-current charge of 0.2C to 3.8V and then with the constant pressure of 3.8V Electricity is reduced up to current value to constant current-constant-voltage charge of 0.01C, will be put into 85 DEG C of thermostats in each battery of charged state, is protected It holds 30 days.
Next, each battery after holding is taken out from thermostat, after battery is cooled to room temperature, decomposed in atoleine, The gas released out of battery case is collected using graduated cylinder, the value of scale is read, so as to find out the gas generated of each battery.
In addition, for the battery different from the battery of aforementioned decomposition, placement is cooled to room temperature, after being cooled further to -20 DEG C, The constant-current discharge that 1.5C is carried out in the environment of -20 DEG C measures discharge time when cell voltage is reduced to 2.0V.
It will be aforementioned each evaluation result is shown in table 3.
&#91;Table 3&#93;
As shown in table 3, for having, contain can be with the alloy of the elements of Li alloyings and Li as the negative of negative electrode active material Pole and containing the compound with olivine structural as a positive electrode active material anode embodiment 9~13 non-water power For solving solution battery, by using the non-of the phosphate cpd containing intramolecular with the group represented by aforementioned formula (1) Water electrolysis liquid, to which the gas in high-temperature storage generates less, and the cryogenic discharging characteristic after high-temperature storage is excellent.
On the other hand, for the battery for the comparative example 4 that aforementioned additive (aforementioned phosphate compound) is not added in nonaqueous electrolytic solution, And it is not used in positive active material for the battery of comparative example 5~7 of the compound with olivine structural, high-temperature storage Cryogenic discharging characteristic afterwards reduces.The especially battery of comparative example 6 and 7, the moisture that positive active material contains is few, in addition with olive Olive stone-type LiFePO4 is compared, and the metal dissolved out from positive active material becomes more, therefore gas generated big when high-temperature storage Width increases.
In addition, compared with using natural graphite as the battery of the comparative example 8 of negative electrode active material, with can be with the element of Li alloyings Alloy with Li, which is the battery of the embodiment 9 of negative electrode active material, can improve the cryogenic discharging characteristic after high-temperature storage.
Without departing from the spirit and scope of the present invention, the present invention can other than aforementioned in a manner of implement.It is disclosed in the present application Embodiment is an example, and the present invention is not limited to these embodiments.It is preferential to use compared with the record of aforementioned specification The scope of the present invention is explained in the record of the attached claims, is included in whole changes in claim equivalents In claim.
Industry utilizability
The battery with nonaqueous electrolyte of the present invention can also play excellent load even across the storage under hot environment under low temperature Characteristic can be preferably applied to such as vehicle emergency annunciation system in addition, reliability is also excellent, thus utilizes such characteristic Power supply purposes as, it is desirable that even if the use that can be discharged well if after being placed under hot environment at low temperature is on the way.
Symbol description
1:Battery with nonaqueous electrolyte
2:Laminated film external packing body
5,11:Anode
6,12:Cathode
7,13:Diaphragm
100:Cathode precursor
101:Laminated metal foil
101a:Metal substrate layer
101b:Al metal layers
102:Li foils.

Claims (10)

1. a kind of battery with nonaqueous electrolyte, which is characterized in that
With electrode body and nonaqueous electrolytic solution, the electrode body is overlapped by anode and cathode across diaphragm,
It is described anode with the compound with olivine structural as a positive electrode active material,
The cathode has a laminated body, the laminated body include not with Li alloyed metal (AM)s substrate layer and be engaged in the metal The Al metal layers of substrate layer,
At least surface side of the Al metal layers is formed with Li-Al alloys.
2. battery with nonaqueous electrolyte according to claim 1, in the laminated body, the Al metal layers are engaged in the gold Belong to the two sides of substrate layer.
3. battery with nonaqueous electrolyte according to claim 1 or 2, the anode contains LiFePO4 has olive as described The compound of olive stone structure.
4. battery with nonaqueous electrolyte according to claim 3, in the positive active material total amount that the anode contains, phosphoric acid The content of iron lithium is 50 mass % or more.
5. battery with nonaqueous electrolyte according to any one of claims 1 to 4, the thickness of the metal substrate layer is 10~ 50μm。
6. a kind of battery with nonaqueous electrolyte, which is characterized in that
It is the battery with nonaqueous electrolyte with cathode, anode and nonaqueous electrolytic solution,
The cathode have can with the alloy of the elements of Li alloyings and Li as negative electrode active material,
The anode contains the compound with olivine structural as a positive electrode active material,
The nonaqueous electrolytic solution contains the phosphate cpd or boration for the group that intramolecular has represented by the following general formula (1) Object is closed,
&#91;Change 1&#93;
In the general formula (1), X Si, Ge or Sn, R1,R2And R3Each independently represent the alkyl of carbon number 1~10, carbon number 2~ 10 alkenyl or the aryl of carbon number 6~10, part or all of hydrogen atom can be replaced by fluorine.
7. battery with nonaqueous electrolyte according to claim 6, the alloy with Li and Al is as the negative electrode active material.
8. the battery with nonaqueous electrolyte described according to claim 6 or 7, in the nonaqueous electrolytic solution, the phosphate cpd or The additive amount of the boronic acid compounds is 8 mass % or less.
9. the battery with nonaqueous electrolyte according to any one of claim 6~8, the compound with olivine structural Surface it is coating by carbon material.
10. the battery with nonaqueous electrolyte according to any one of claim 6~9, the chemical combination with olivine structural The BET specific surface area of object is 5m2/ g or more.
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