[go: up one dir, main page]

WO2017110842A1 - Batterie rechargeable à électrolyte non aqueux et procédé permettant de fabriquer cette dernière - Google Patents

Batterie rechargeable à électrolyte non aqueux et procédé permettant de fabriquer cette dernière Download PDF

Info

Publication number
WO2017110842A1
WO2017110842A1 PCT/JP2016/088038 JP2016088038W WO2017110842A1 WO 2017110842 A1 WO2017110842 A1 WO 2017110842A1 JP 2016088038 W JP2016088038 W JP 2016088038W WO 2017110842 A1 WO2017110842 A1 WO 2017110842A1
Authority
WO
WIPO (PCT)
Prior art keywords
separator
secondary battery
positive electrode
negative electrode
aqueous secondary
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2016/088038
Other languages
English (en)
Japanese (ja)
Inventor
丈主 加味根
岸見　光浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Maxell Ltd
Original Assignee
Hitachi Maxell Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Maxell Ltd filed Critical Hitachi Maxell Ltd
Publication of WO2017110842A1 publication Critical patent/WO2017110842A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H01M50/466—U-shaped, bag-shaped or folded
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a non-aqueous secondary battery excellent in productivity and reliability and a manufacturing method thereof.
  • Non-aqueous secondary batteries such as lithium ion secondary batteries have high voltage and high capacity, and thus are highly expected for their development.
  • a device using an electrode body (laminated electrode body) having a structure in which a plate-like positive electrode, a negative electrode, and a separator are stacked is also known.
  • the positive electrode, the negative electrode, and the separator are likely to be displaced from each other during the production of the laminated electrode body or the assembly of the battery.
  • the separator is displaced and the positive electrode and the negative electrode come into contact with each other, a short circuit occurs, and when the positive electrode and the negative electrode are displaced and the area of the opposing portion through the separator between the positive electrode and the negative electrode is reduced, the capacity is reduced. There is a risk of doing. For this reason, in a battery using a laminated electrode body, it is required to suppress misalignment of the positive electrode, the negative electrode, and the separator in the laminated electrode body.
  • Patent Document 1 a technology to avoid such problems is being studied.
  • two separators arranged above and below a positive electrode are joined to each other by thermal welding at their peripheral portions, whereby a positive electrode is formed into a bag-shaped separator formed by two separators.
  • a technique for suppressing the occurrence of problems due to misalignment between the positive electrode and the negative electrode and the separator has been proposed.
  • non-aqueous secondary batteries are also applied to applications that are exposed to relatively high temperatures such as in-vehicle applications. Therefore, in a non-aqueous secondary battery, for example, a laminated layer provided with a layer having high heat resistance instead of a polyolefin separator that has been conventionally used so that sufficient functions can be exhibited even when applied to such applications.
  • a heat-resistant separator such as a mold separator or a separator made of a resin having high heat resistance may be used.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a non-aqueous secondary battery excellent in productivity and reliability, and a method for manufacturing the same.
  • the nonaqueous secondary battery of the present invention that has achieved the above object has a laminated electrode body in which a positive electrode and a negative electrode are laminated via a separator, and at least one of the positive electrode and the negative electrode
  • the separators arranged on both sides of the electrode each have a crimping part at least at a part of the peripheral edge, and are joined to each other at the crimping part.
  • the method for producing a non-aqueous secondary battery of the present invention is a method for producing a non-aqueous secondary battery having a laminated electrode body in which a positive electrode and a negative electrode are laminated via a separator, the positive electrode and the negative electrode A step of disposing a separator on both sides of at least one of the electrodes, and a step of crimping and joining at least a part of the peripheral edge of the separator disposed on both sides of the electrode.
  • the nonaqueous secondary battery of the present invention has a laminated electrode body in which a positive electrode and a negative electrode are laminated via a separator.
  • the separators disposed on both sides of at least one of the positive electrode and the negative electrode in the laminated electrode body each have a crimp portion on at least a part of the peripheral portion, and are joined to each other at the crimp portion. Yes.
  • Alignment between the separator and the electrode (positive electrode or negative electrode) disposed therebetween is prevented by disposing the positive electrode or the negative electrode between the separators in which at least a part of the peripheral edge is pressure-bonded and joined to each other. Therefore, in the non-aqueous secondary battery of the present invention, it is possible to suppress the occurrence of a short circuit due to the direct contact between the positive electrode and the negative electrode due to the displacement of the separator in the laminated electrode body. Moreover, in the battery after completion, the deterioration of characteristics due to the short circuit can be suppressed.
  • the laminated electrode body only the portion where the positive electrode and the negative electrode face each other via the separator functions during the battery reaction, and the region not facing the counter electrode cannot participate in the battery reaction.
  • capacitance of a battery falling also arises.
  • the laminated electrode body is formed in a state in which the positive electrode or the negative electrode is disposed between the separators bonded to each other at least at a part of the peripheral edge, misalignment between the positive electrode and the negative electrode is difficult to occur. It is possible to reduce the incidence of defective products with insufficient capacity at the time of manufacture, and to suppress capacity reduction due to misalignment between the positive electrode and the negative electrode in a completed battery.
  • the separator joined to at least a part of the peripheral portion according to the non-aqueous secondary battery of the present invention is composed of two or more separators present on both sides of the positive electrode or the negative electrode, and at least one of the peripheral portions.
  • the part has a crimping part for joining these separators.
  • both are pressure-bonded.
  • the separators are made of materials that are difficult to heat-seal as described above or cannot be heat-sealable, they are strong enough to accommodate the electrodes and prevent displacement. Both can be joined.
  • the separators can be joined by a simpler operation than the thermal welding even in a case using a separator made of a material capable of thermal welding (polyolefin or the like).
  • the productivity and reliability of the non-aqueous secondary battery can be improved.
  • the embodiment to which the present invention is applicable is not limited to the case where one separator is disposed on each side of the electrode, and there are two or more separators disposed on one or both sides of the electrode.
  • the present invention can also be applied to a case where one separator is folded and disposed on both sides of the electrode.
  • the separators to be disposed on both surfaces of the electrodes are joined together in advance at least at a part of the peripheral edge by pressure bonding, and then the electrodes are inserted between the opposing separators, whereby the non-aqueous secondary battery of the present invention May be configured.
  • a polyolefin microporous film or nonwoven fabric generally used as a separator for non-aqueous secondary batteries can be used.
  • Examples of the polyolefin constituting the separator include polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer.
  • the polyolefin microporous film or non-woven fabric may have a single-layer structure containing one or more kinds of polyolefins, or a multilayer structure having a plurality of layers containing different types of polyolefins (for example, It may be a two-layer structure in which a PE layer and a PP layer are laminated, or a three-layer structure in which a PP layer is provided on both sides of the PE layer.
  • the separator does not have a melting point, that is, a material having a melting temperature of 250 ° C. or higher measured using a differential scanning calorimeter (DSC) in accordance with the provisions of JIS K 7121, It is also possible to use a material containing a heat resistant material such as a material that is thermally decomposed before melting.
  • a separator containing such a heat-resistant material even if the battery is used in an environment where it is exposed to high temperatures, it is possible to suppress the deterioration of battery characteristics and the occurrence of short circuits due to melting of the separator.
  • a non-aqueous secondary battery having higher heat resistance and suitable for use in a high temperature environment can be obtained.
  • the separator containing the heat resistant material for example, at least one resin (heat resistant resin) selected from the group consisting of polyamide, polyimide, polyamideimide, polyphenylene sulfide, polyester, polyacrylonitrile, aramid, and cellulose is used. What is contained is mentioned, For example, the nonwoven fabric etc. which were comprised with at least 1 sort (s) of these can be illustrated.
  • resin heat resistant resin
  • a laminated separator in which a heat-resistant porous layer is provided on the above-mentioned polyolefin microporous film or non-woven fabric can be used.
  • the separator shrinkage can be suppressed even when the temperature in the battery rises, and a short circuit due to contact between the positive electrode and the negative electrode can be suppressed.
  • the temperature becomes high a non-aqueous secondary battery with higher safety can be obtained, which can ensure a shutdown function that closes the pores of the separator by melting the polyolefin.
  • the heat-resistant porous layer related to the laminated separator can be formed of, for example, a nonwoven fabric composed of the heat-resistant resin exemplified above.
  • a laminated separator is made by heat-welding a non-woven fabric made of a heat-resistant resin on one side or both sides of a microporous film made of polyolefin or a non-woven fabric, or by melting a part of the polyolefin, Can be formed.
  • the laminated separator has a heat-resistant porous layer mainly comprising inorganic particles having a heat-resistant temperature of 250 ° C. or more on one side or both sides of a substrate layer made of a polyolefin microporous film or nonwoven fabric. The formed one is also included.
  • the “heat-resistant temperature is 250 ° C. or higher” in the inorganic particles in the present specification means that deformation such as softening is not observed at least at 250 ° C.
  • boehmite As the inorganic particles to be contained in the heat-resistant porous layer, boehmite, alumina, silica, titanium oxide and the like are preferable, and one or more of these can be used.
  • the heat-resistant porous layer includes a binder for binding the inorganic particles to each other or bonding the heat-resistant porous layer and the base material layer (polyolefin microporous film or nonwoven fabric). It is preferable to contain.
  • the binder includes an ethylene-vinyl acetate copolymer (EVA, having a structural unit derived from vinyl acetate of 20 to 35 mol%), an ethylene-acrylic acid copolymer such as an ethylene-ethyl acrylate copolymer, and a fluorine-based rubber.
  • Styrene butadiene rubber SBR
  • CMC carboxymethyl cellulose
  • HEC hydroxyethyl cellulose
  • PVA polyvinyl alcohol
  • PVB polyvinyl butyral
  • PVP polyvinyl pyrrolidone
  • cross-linked acrylic resin polyurethane, epoxy resin, etc.
  • the inorganic particles are included as the main component, and the content of the inorganic particles in the heat-resistant porous layer is the heat-resistant porous layer.
  • the total volume of the components constituting the stratified layer in the total volume excluding the void portion, it is preferably 50% by volume or more, more preferably 70% by volume or more, and 99% by volume or less. It is more preferable (the remainder may be the above binder).
  • the thickness of the separator is preferably 500 ⁇ m or less, and more preferably 450 ⁇ m or less from the viewpoint of suppressing a decrease in the energy density of the battery.
  • the thickness is preferably 10 ⁇ m or more, and particularly a separator made of a nonwoven fabric or a heat resistant porous layer made of a nonwoven fabric. In the case of a laminated separator having a thickness of 100 ⁇ m or more, more preferably 150 ⁇ m or more.
  • the porosity of the separator is preferably 30% or more and 80% or less, and more preferably 50% or more in the case of a separator made of a nonwoven fabric.
  • the separator as described above is disposed on both sides of the electrode, and a crimping part for joining the separators is formed on at least a part of the peripheral part. And either one of a positive electrode and a negative electrode is accommodated between the separators which oppose.
  • FIG. 1 is a plan view of the separator
  • FIG. 2 is a cross-sectional view taken along the line II of FIG.
  • the separator 30 is formed into a bag-like shape by providing a pressure-bonding portion 31 (indicated by a lattice pattern in the drawing) that joins the separators 30a and 30b to each other at least at a part of the peripheral edge. It has become.
  • the positive electrode is housed in the bag-shaped separator 30, that is, the positive electrode is inserted between the separator 30a and the separator 30b.
  • the mode that the tab part 13 of the positive electrode utilized for electrical connection with another member protrudes is illustrated.
  • the crimping part 31 that joins the two separators 30a and 30b can be configured to bend in the thickness direction (vertical direction in the figure) of the separators 30a and 30b, for example, as shown in FIG.
  • the above-mentioned separators made of heat-resistant resin and heat-resistant porous layers can be used. Even if it is difficult or impossible to heat-separate the separators, such as a laminated separator having a separator, the separators are joined to each other with such a strength that the displacement of the electrodes accommodated therein can be suppressed. be able to.
  • 2 can be formed by corrugating, for example.
  • the separators on both sides of the electrodes are Can be bonded by pressure bonding.
  • it is possible to bond the separators by pressing the roll sheet with the positive electrode or negative electrode sandwiched between two separators between the rolls with grooves on the surface. is there.
  • the depth of the groove is not particularly limited as long as the separator does not break.
  • the shape and area of the crimping can also be appropriately changed according to the battery shape by changing the shape of the mold used for processing.
  • the crimping part in the separator may be provided on the whole peripheral part except the part from which the tab part of the electrode accommodated in the separator is pulled out, or may be provided only in a part. Specifically, it is preferable that a portion having a length of 5% or more in the entire length of the outer periphery of the separator is a crimping portion.
  • the peripheral portion of the separator may be formed with only one continuous long crimping portion, or a plurality of crimping portions may be formed discontinuously as shown in FIG.
  • compression-bonding part is formed in each of three sides other than the edge
  • compression-bonding part 31 is provided also in the edge
  • compression-bonding part provided in two adjacent sides may be continued including the corner
  • the positive electrode according to the nonaqueous secondary battery of the present invention for example, one having a structure having a positive electrode mixture layer containing a positive electrode active material, a binder, a conductive additive and the like on one side or both sides of a current collector is used.
  • the active material generally used as a positive electrode for nonaqueous secondary batteries such as a lithium containing transition metal oxide.
  • the lithium-containing transition metal oxide include, for example, Li x CoO 2 , Li x NiO 2 , Li x MnO 2 , Li x Co y Ni 1-y O 2 , Li x Mny y Ni z Co 1-y. -Z O 2 , Li x Mn 2 O 4 and the like are exemplified (in the above structural formulas, 0 ⁇ x ⁇ 1.1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1). .
  • the binder related to the positive electrode mixture layer the same binder as that used in the positive electrode mixture layer related to the positive electrode for a known non-aqueous secondary battery can be used.
  • the binder related to the positive electrode mixture layer the same binder as that used in the positive electrode mixture layer related to the positive electrode for a known non-aqueous secondary battery can be used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PAI polyamideimide
  • PI polyimide
  • acrylic styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • Examples of the conductive aid for the positive electrode mixture layer include graphite such as natural graphite (eg, scaly graphite) and artificial graphite; carbon such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. -Bon black; carbon fiber;
  • a positive electrode active material, a binder and a conductive additive are dispersed in a solvent such as an organic solvent such as N-methyl-2-pyrrolidone (NMP) to prepare a positive electrode mixture-containing composition (however, the binder May be dissolved in a solvent), and may be produced by a method of forming a positive electrode mixture layer by applying this to one or both sides of a current collector and drying it. Moreover, you may perform a calendar process as needed after formation of a positive mix layer.
  • NMP N-methyl-2-pyrrolidone
  • the same one used for the positive electrode of a conventionally known non-aqueous secondary battery can be used, and for example, an aluminum foil having a thickness of 10 to 30 ⁇ m is preferable.
  • the thickness of the positive electrode mixture layer (the thickness per side when the positive electrode mixture layer is formed on both sides of the current collector) is preferably 30 to 95 ⁇ m.
  • the content of the positive electrode active material is preferably 85 to 98% by mass
  • the content of the binder is preferably 1 to 10% by mass
  • the content of the conductive auxiliary agent is It is preferably 1 to 10% by mass.
  • a negative electrode mixture layer containing a negative electrode active material, a binder or the like is used on one side or both sides of a current collector.
  • the negative electrode active material a conventionally known negative electrode active material used for a negative electrode of a non-aqueous secondary battery, that is, an active material capable of occluding and releasing Li ions can be used.
  • a negative electrode active material include, for example, graphite (natural graphite; artificial graphite obtained by graphitizing graphitized carbon such as pyrolytic carbons, mesophase carbon microbeads, and carbon fibers at 2800 ° C.
  • the same binders as those exemplified above as those that can be used for the positive electrode mixture layer can be used.
  • the same thing as the various conductive support agents illustrated previously as what can be used for a positive mix layer can be used for the conductive support agent.
  • the negative electrode having the negative electrode mixture layer includes, for example, a negative electrode active material and a binder, and a paste-like or slurry-like negative electrode mixture in which a conductive auxiliary agent is dispersed in an organic solvent such as NMP or a solvent such as water as necessary. It can be produced by preparing a containing composition (however, the binder may be dissolved in a solvent), applying this to one or both sides of the current collector and drying to form a negative electrode mixture layer. . Moreover, you may perform a calendar process as needed after formation of a negative mix layer.
  • the thickness of the negative electrode mixture layer is preferably, for example, 10 to 100 ⁇ m per one side of the current collector.
  • the amount of the negative electrode active material is preferably 85 to 99% by mass, and the amount of the binder is preferably 1.0 to 10% by mass.
  • the amount of the conductive auxiliary in the negative electrode mixture layer is preferably 0.5 to 10% by mass.
  • the negative electrode current collector may be made of copper, copper alloy, nickel, nickel alloy foil, punching metal, net, expanded metal, or the like, but copper foil is usually used.
  • the thickness of the negative electrode current collector is preferably 5 to 30 ⁇ m, for example.
  • a laminated electrode body configured using a positive electrode, a negative electrode, and at least a part of the peripheral edge are bonded to each other and bonded, for example, a bag-shaped separator is used.
  • a positive electrode or a negative electrode may be arranged between separators bonded to each other by pressure bonding depending on the laminated configuration.
  • planar shape of the electrodes positive electrode and negative electrode
  • the planar shape of the electrodes according to the non-aqueous secondary battery of the present invention, depending on the shape of the exterior body to be employed, such as a circle or a polygon (such as a square, a pentagon, or a hexagon).
  • a circle or a polygon such as a square, a pentagon, or a hexagon
  • the planar shape of the bag-shaped separator that accommodates this electrode is also the planar shape of the electrode that accommodates it, such as a circle or a polygon (such as a square, pentagon, or hexagon shown in FIG. 1).
  • any shape may be adopted.
  • the above-mentioned laminated electrode body is enclosed in an exterior body together with a non-aqueous electrolyte solution to obtain the non-aqueous secondary battery of the present invention.
  • a non-aqueous electrolyte solution to obtain the non-aqueous secondary battery of the present invention.
  • the exterior body one having a form suitable for accommodating the laminated electrode body can be used.
  • a flat exterior can including coin shape and button shape
  • a square exterior can a metal laminate film exterior body Etc.
  • non-aqueous electrolyte solution a solution containing a lithium salt and an organic solvent and in which the lithium salt is dissolved in the organic solvent is used.
  • lithium salt examples include inorganic lithium salts such as LiClO 4 , LiBF 4 , LiAsF 6 , and LiSbF 6 ; LiCF 3 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (FSO 2 ) 2 [LiFSI], LiN (CF 3 SO 2 ) 2 [LiTFSI], LiN (C 2 F 5 SO 2 ) 2 ,
  • organic lithium salts such as lithium bisoxalate borate (LiBOB) can be used.
  • organic solvents include cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate; chain esters such as methyl propionate; ⁇ -butyrolactone, substituted at the ⁇ -position Cyclic esters such as lactones having a group; chain ethers such as dimethoxyethane, diethyl ether, 1,3-dioxolane, diglyme, triglyme and tetraglyme; cyclic ethers such as dioxane, tetrahydrofuran and 2-methyltetrahydrofuran; acetonitrile, pro Nitriles such as pionitrile and methoxypropionitrile; sulfites such as ethylene glycol sulfite; and the like.
  • cyclic carbonates such as ethylene carbonate, propylene carbonate, and butylene carbonate
  • lactones having a substituent at the ⁇ -position are also preferable to use as the organic solvent. Since the lactone having a substituent at the ⁇ -position has a high boiling point of 150 ° C. or higher, it is difficult to volatilize even when the battery is placed in a high temperature environment, and the composition of the non-aqueous electrolyte changes and the outer body swells. Therefore, a battery having higher heat resistance and excellent storage characteristics at high temperatures can be configured.
  • high-boiling solvents having a boiling point of 150 ° C. or higher are known, but generally high-boiling solvents have low permeability to polyolefin separators, In order to increase the permeability of the non-aqueous electrolyte to the separator, it is necessary to use another solvent (generally having a low boiling point).
  • lactones having a substituent at the ⁇ -position have good permeability to polyolefin separators, by using a non-aqueous electrolyte using this, for example, without impairing the load characteristics of the battery, Heat resistance can be improved.
  • 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, ⁇ , ⁇ ,
  • lactones having a substituent at the ⁇ -position are used in the organic solvent, only lactones having a substituent at the ⁇ -position may be used, but when other organic solvents are used together, 150 ° C or higher It is preferable to use a high-boiling solvent having a boiling point (ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane, trimethyl phosphate, triethyl phosphate, etc.).
  • a high-boiling solvent having a boiling point ethylene carbonate, propylene carbonate, ⁇ -butyrolactone, sulfolane, trimethyl phosphate, triethyl phosphate, etc.
  • the ratio in the total organic solvent in the non-aqueous electrolyte is preferably 70 to 100% by volume.
  • the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.6 to 1.8 mol / L, and more preferably 0.9 to 1.6 mol / L.
  • vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, biphenyl, fluorobenzene are added to the non-aqueous electrolyte.
  • Additives such as t-butylbenzene and halogen-substituted cyclic carbonates (4-fluoro-1,3-dioxolan-2-one etc.) can also be added as appropriate.
  • a gel (gel electrolyte) obtained by adding a gelling agent such as a known polymer to the non-aqueous electrolyte may be used.
  • Example 1 Preparation of positive electrode> LiNi 0.5 Co 0.2 Mn 0.3 O 2 as a positive electrode active material: 96.5 parts by mass, NMP solution containing PVDF as a binder at a concentration of 10% by mass: 20 parts by mass, and a conductive additive Acetylene black: 1.5 parts by mass was kneaded using a biaxial kneader, and NMP was added to adjust the viscosity to prepare a positive electrode mixture-containing paste. This paste is applied to both sides of an aluminum foil having a thickness of 15 ⁇ m, vacuum-dried at 120 ° C. for 12 hours, a positive electrode mixture layer is formed on both sides of the aluminum foil, and press treatment is performed. By cutting, a belt-like positive electrode was obtained.
  • the thickness of the positive electrode mixture layer of the obtained positive electrode was 41 ⁇ m.
  • FIG. 3 is a plan view schematically showing the battery positive electrode (however, in order to facilitate understanding of the structure of the positive electrode, the size of the positive electrode shown in FIG. 3 does not necessarily match the actual one).
  • the positive electrode 10 has a tab portion 13 punched out so that a part of the exposed portion of the positive electrode current collector 12 protrudes, and the shape of the forming portion of the positive electrode mixture layer 11 is a substantially rectangular shape with four corners curved.
  • the lengths a, b and c were 61 mm, 137 mm and 10 mm, respectively.
  • the negative electrode active material 96 parts by mass of soft carbon, acrylic resin: 2 parts by mass, CMC: 2 parts by mass, and water were mixed to prepare a negative electrode mixture-containing paste.
  • the negative electrode mixture-containing paste is applied to both sides of a copper foil having a thickness of 10 ⁇ m and dried to form a negative electrode mixture layer on both sides of the copper foil, and press treatment is performed to set the density of the negative electrode mixture layer to 1. After adjusting to 00 g / cm 3 , it was cut to a predetermined size to obtain a strip-shaped negative electrode.
  • the thickness of the negative electrode mixture layer of the obtained negative electrode was 61.5 ⁇ m.
  • FIG. 4 is a plan view schematically showing the battery negative electrode (however, in order to facilitate understanding of the structure of the negative electrode, the size of the negative electrode shown in FIG. 4 does not necessarily match the actual one).
  • the negative electrode 20 has a shape having a tab portion 23 punched out so that a part of the exposed portion of the negative electrode current collector 22 protrudes, and the shape of the forming portion of the negative electrode mixture layer 21 is a substantially rectangular shape with four corners curved.
  • the lengths d, e, and f were 64 mm, 142.5 mm, and 10 mm, respectively.
  • a laminated electrode body was formed using 18 positive electrodes for a battery in which a positive electrode mixture layer was formed on both sides of the positive electrode current collector and 19 negative electrodes for a battery in which a negative electrode mixture layer was formed on both sides of the negative electrode current collector.
  • all the battery positive electrodes were housed in the bag-shaped separator. Then, the upper and lower ends are set as battery negative electrodes, the battery positive electrodes and the battery negative electrodes are alternately arranged between them, and the tab portions between the positive electrodes and the tab portions between the negative electrodes are welded respectively to form a laminated electrode body. Produced.
  • the laminated electrode body is inserted into the depression of an aluminum laminate film having a thickness of 5.7 mm, a width of 78 mm, and a height of 161 mm in which a depression is formed so that the laminated electrode body can be accommodated.
  • An aluminum laminate film of the same size was placed and three sides of both aluminum laminate films were heat-welded. Then, from the remaining one side of both aluminum laminate films, LiPF 6 was dissolved at a concentration of 1 mol / l in a non-aqueous electrolyte (a mixed solvent of ethylene carbonate and diethyl carbonate in a volume ratio of 3: 7), and vinylene carbonate was further added. The solution added in an amount of 2% by mass) was injected. Thereafter, the remaining one side of both aluminum laminate films was vacuum heat sealed to produce a non-aqueous secondary battery having the cross-sectional structure shown in FIG. 6 with the appearance shown in FIG.
  • FIG. 5 is a plan view schematically showing a non-aqueous secondary battery
  • FIG. 6 is a cross-sectional view taken along the line II-II in FIG.
  • the nonaqueous secondary battery 100 includes a laminated electrode body 102 constituted by laminating a positive electrode and a negative electrode with a separator in an aluminum laminated film outer package 101 constituted by two aluminum laminated films, and a nonaqueous electrolytic solution. (Not shown) is housed, and the aluminum laminate film outer package 101 is sealed by heat-sealing the upper and lower aluminum laminate films at the outer peripheral portion thereof.
  • the layers constituting the aluminum laminate film outer package 101 and the positive electrode, the negative electrode, and the separator constituting the laminated electrode body are not shown separately. .
  • Each positive electrode of the laminated electrode body 102 is integrated by welding the tab portions together, and the integrated product of the welded tab portions is connected to the positive electrode external terminal 103 in the battery 100, although not shown.
  • the negative electrodes of the laminated electrode body 102 are also integrated by welding the tab portions together, and the integrated product of the welded tab portions is connected to the negative electrode external terminal 104 in the battery 100.
  • the positive electrode external terminal 103 and the negative electrode external terminal 104 are drawn out to the outside of the aluminum laminate film exterior body 101 so that they can be connected to an external device or the like.
  • Example 2 A bag-like separator was produced in the same manner as in Example 1 except that paper (that is, a cellulose nonwoven fabric, no melting point of cellulose, and a thickness of 20 ⁇ m) was used instead of the polyimide nonwoven fabric. And the non-aqueous secondary battery was produced like Example 1 except having used this bag-shaped separator.
  • paper that is, a cellulose nonwoven fabric, no melting point of cellulose, and a thickness of 20 ⁇ m
  • Example 3 instead of polyimide non-woven fabric, a laminate with a three-layer structure having layers made of an aramid non-woven fabric on both sides of a PE microporous film [PE melting point: 130 ° C., PE microporous film thickness: 16 ⁇ m, aramid melting point None, the thickness of the layer made of an aramid nonwoven fabric (one side): 3 ⁇ m, the total thickness of the laminate: 22 ⁇ m, the porosity of the laminate: 50%], and the bag-like separator as in Example 1. Was made. And the non-aqueous secondary battery was produced like Example 1 except having used this bag-shaped separator.
  • Example 4 instead of polyimide non-woven fabric, a laminate (PE melting point: 130 ° C., PE) having a heat-resistant porous layer containing 97% by volume of boehmite on one side of the PE microporous film (the remainder being an acrylic resin as a binder)
  • the bag was made in the same manner as in Example 1 except that the thickness of the microporous film made was 16 ⁇ m, the thickness of the heat-resistant porous layer was 5 ⁇ m, the total thickness of the laminate: 21 ⁇ m, and the porosity of the laminate: 45%.
  • a shaped separator was prepared.
  • the non-aqueous secondary battery was produced like Example 1 except having used this bag-shaped separator.
  • Example 5 The non-aqueous electrolyte was mixed with propylene carbonate and ⁇ -methyl- ⁇ -butyrolactone in a 3: 7 volume ratio, LiBF 4 at a concentration of 1 mol / L, and LiBOB at a concentration of 0.03 mol / L.
  • a non-aqueous secondary battery was produced in the same manner as in Example 2 except that each was dissolved and further changed to a solution in which vinylene carbonate was added in an amount of 5% by mass.
  • Example 6 Olivine type lithium iron phosphate as a positive electrode active material (average particle size 13 ⁇ m): 89 parts by mass, acetylene black as a conductive auxiliary agent: 3.5 parts by mass and 1.5 parts by mass of graphite, acrylic resin: 3. 3 parts by mass, polyvinylpyrrolidone (dispersing agent): 0.3 parts by mass, CMC (thickening agent): 2.4 parts by mass, and using a positive electrode mixture-containing paste prepared by mixing water Produced a positive electrode for a battery in the same manner as in Example 1. The thickness of the positive electrode mixture layer (thickness per one surface) of the obtained positive electrode was 65 ⁇ m.
  • LiBF 4 was dissolved at a concentration of 1 mol / L and LiBOB at a concentration of 0.03 mol / L in a mixed solvent of propylene carbonate and ⁇ -methyl- ⁇ -butyrolactone at a volume ratio of 3: 7, Further, vinylene carbonate was added in an amount of 2.5% by mass to prepare a nonaqueous electrolytic solution.
  • a nonaqueous secondary battery was produced in the same manner as in Example 2 except that the battery positive electrode and the nonaqueous electrolyte were used.
  • Example 7 A non-aqueous secondary battery was produced in the same manner as in Example 2 except that the same positive electrode as that produced in Example 6 was used.
  • Example 8 A bag-like separator was prepared in the same manner as in Example 1 except that a PE microporous film (PE melting point: 130 ° C., thickness: 18 ⁇ m) was used instead of the polyimide nonwoven fabric. And the non-aqueous secondary battery was produced like Example 1 except having used this bag-shaped separator.
  • PE microporous film PE melting point: 130 ° C., thickness: 18 ⁇ m
  • Comparative Example 1 A laminated electrode body was produced in the same manner as in Example 2 except that the cellulose nonwoven fabric was not formed into a bag shape and was interposed between the positive electrode and the negative electrode as a separator. And the non-aqueous secondary battery was produced like Example 6 except having used this laminated electrode body.
  • Comparative Example 2 A laminated electrode body was produced in the same manner as in Example 2 except that the cellulose nonwoven fabric was not formed into a bag shape and was interposed between the positive electrode and the negative electrode as a separator. And the non-aqueous secondary battery was produced like Example 2 except having used this laminated electrode body.
  • Example A bag-like separator was produced in the same manner as in Example 8 except that two PE microporous films were joined by heat welding. And the non-aqueous secondary battery was produced like Example 8 except having used this bag-shaped separator.
  • each of 100 non-aqueous secondary batteries was charged at a constant current until the voltage reached 3.85 V at a current value of 300 mA in an environment of 25 ° C., and then the current value was reduced to 60 mA. After being charged at a constant voltage of 3.85 V until the voltage reached, a constant current discharge was performed until the voltage became 2.0 V at a current value of 3000 mA, and the discharge capacity (initial discharge capacity) was measured.
  • the non-aqueous secondary batteries of Examples 1 to 8 using a bag-shaped separator having a crimping part for joining two separators are the batteries of reference examples (two sheets) corresponding to conventional products.
  • Comparative Example 1 using a non-bag-like separator whereas the generation of defective products was not observed, as in the case of a battery using a bag-like separator formed by thermally welding a PE microporous film, In the battery of 2, a defective product with insufficient discharge capacity was generated. Therefore, it was found that the batteries of Examples 1 to 8 were superior in productivity and reliability to the batteries of Comparative Examples 1 and 2.
  • the bag-shaped separator used in the batteries of Examples 1 to 8 can be produced by a simpler operation than the separator according to the battery of the reference example in which two PE microporous films are formed into a bag shape by heat welding. Therefore, it can be said that the batteries of Examples 1 to 8 are more productive than the battery of the reference example.
  • non-aqueous secondary batteries of Examples 1 to 8 and Reference Example were subjected to the following high-temperature storage tests 1 and 2 and high-temperature charge / discharge cycle characteristics evaluation.
  • ⁇ High temperature storage test 1> About each battery, after performing constant current charge and constant voltage charge on the same conditions as the time of first time discharge capacity measurement, it stored for 48 hours in a 100 degreeC thermostat. After each battery is taken out of the thermostat and cooled to room temperature, constant current discharge is performed under the same conditions as the initial discharge capacity measurement, and constant current charge and constant voltage charge are performed under the same conditions as the initial discharge capacity measurement. Then, a constant current discharge was performed, and a discharge capacity (recovery capacity) was measured. And about each battery, the value which remove
  • a series of operations for performing constant-current discharge (however, the discharge end voltage is 2.0 V) was set as one cycle, and this was performed for 1000 cycles.
  • the capacity maintenance rate was calculated
  • Table 2 shows the results of the high-temperature storage tests 1 and 2 and the high-temperature charge / discharge cycle characteristics evaluation.
  • heat fusion such as a nonwoven fabric made of polyimide or a nonwoven fabric made of cellulose is made by crimping and joining at least a part of the peripheral portion of the separator disposed on both sides of the electrode. Since it is possible to easily join separators that cannot be joined by adhesion, productivity and reliability are the same as when joining a microporous film made of PE by thermal welding, even when using a separator with high heat resistance. It is possible to provide a non-aqueous secondary battery excellent in the above.
  • the nonaqueous secondary battery of the present invention can ensure high reliability in addition to good productivity even when it has a particularly excellent heat resistance structure (a structure using a heat resistant separator). Therefore, it can be preferably used for applications that are highly likely to be placed in a high temperature environment such as in-vehicle use, and also applied to applications where conventionally known non-aqueous secondary batteries are used. Can do.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention porte sur une batterie rechargeable à électrolyte non aqueux qui présente une productivité et une fiabilité excellentes ; ainsi que sur un procédé permettant de fabriquer cette batterie rechargeable à électrolyte non aqueux. Une batterie rechargeable à électrolyte non aqueux selon la présente invention est caractérisée en ce qu'elle comprend un corps d'électrode multicouche qui est obtenu par stratification d'une électrode positive et d'une électrode négative, un séparateur étant interposé entre ces dernières, et est également caractérisée en ce que des séparateurs disposés sur les deux côtés de l'électrode positive et/ou de l'électrode négative comportent respectivement une partie liée par compression dans au moins une partie de la partie périphérique et sont liés les uns aux autres au niveau des parties liées par compression. Cette batterie rechargeable à électrolyte non aqueux peut être fabriquée par un procédé de fabrication selon la présente invention, qui comprend une étape consistant à disposer des séparateurs sur les deux côtés d'une électrode positive et/ou d'une électrode négative et une étape consistant à lier par compression les unes aux autres au moins des parties des parties périphériques des séparateurs disposés sur les deux côtés de l'électrode.
PCT/JP2016/088038 2015-12-25 2016-12-21 Batterie rechargeable à électrolyte non aqueux et procédé permettant de fabriquer cette dernière Ceased WO2017110842A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-253898 2015-12-25
JP2015253898 2015-12-25

Publications (1)

Publication Number Publication Date
WO2017110842A1 true WO2017110842A1 (fr) 2017-06-29

Family

ID=59089420

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/088038 Ceased WO2017110842A1 (fr) 2015-12-25 2016-12-21 Batterie rechargeable à électrolyte non aqueux et procédé permettant de fabriquer cette dernière

Country Status (1)

Country Link
WO (1) WO2017110842A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019106314A (ja) * 2017-12-13 2019-06-27 ハイメカ株式会社 二次電池のセパレータ接合装置、二次電池および二次電池のセパレータ接合方法
CN113228400A (zh) * 2018-12-26 2021-08-06 松下知识产权经营株式会社 非水电解质二次电池
CN115989605A (zh) * 2020-08-24 2023-04-18 株式会社村田制作所 二次电池及二次电池的制造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008269819A (ja) * 2007-04-17 2008-11-06 Sony Corp 非水電解液二次電池
JP2013143337A (ja) * 2012-01-12 2013-07-22 Nissan Motor Co Ltd 二次電池の製造方法、二次電池、溶着装置
JP2014003002A (ja) * 2012-05-23 2014-01-09 Toyota Industries Corp 電極収納セパレータ、蓄電装置、及び電極収納セパレータの製造方法
WO2014199979A1 (fr) * 2013-06-14 2014-12-18 日本電気株式会社 Accumulateur lithium-ion et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008269819A (ja) * 2007-04-17 2008-11-06 Sony Corp 非水電解液二次電池
JP2013143337A (ja) * 2012-01-12 2013-07-22 Nissan Motor Co Ltd 二次電池の製造方法、二次電池、溶着装置
JP2014003002A (ja) * 2012-05-23 2014-01-09 Toyota Industries Corp 電極収納セパレータ、蓄電装置、及び電極収納セパレータの製造方法
WO2014199979A1 (fr) * 2013-06-14 2014-12-18 日本電気株式会社 Accumulateur lithium-ion et son procédé de production

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019106314A (ja) * 2017-12-13 2019-06-27 ハイメカ株式会社 二次電池のセパレータ接合装置、二次電池および二次電池のセパレータ接合方法
CN113228400A (zh) * 2018-12-26 2021-08-06 松下知识产权经营株式会社 非水电解质二次电池
CN113228400B (zh) * 2018-12-26 2023-03-21 松下知识产权经营株式会社 非水电解质二次电池
CN115989605A (zh) * 2020-08-24 2023-04-18 株式会社村田制作所 二次电池及二次电池的制造方法

Similar Documents

Publication Publication Date Title
CN110400922B (zh) 非水电解质二次电池用正极和非水电解质二次电池
JP4927064B2 (ja) 二次電池
JP2011081931A (ja) リチウムイオン二次電池
JP6359454B2 (ja) 非水電解質二次電池
JP6184810B2 (ja) 非水二次電池
JP2015072805A (ja) 非水二次電池
JP5552398B2 (ja) リチウムイオン電池
JP2015125948A (ja) リチウムイオン二次電池
JP2008262788A (ja) 非水電解質電池
JP6243666B2 (ja) リチウムイオン二次電池用セパレータおよびその製造方法、並びにリチウムイオン二次電池およびその製造方法
JP7686477B2 (ja) リチウムイオン二次電池用正極およびリチウムイオン二次電池
JP5614431B2 (ja) リチウムイオン二次電池用非水電解液及びリチウムイオン二次電池
JP2008097879A (ja) リチウムイオン二次電池
WO2017110842A1 (fr) Batterie rechargeable à électrolyte non aqueux et procédé permettant de fabriquer cette dernière
JP5721802B2 (ja) リチウム二次電池用セパレータ、並びにリチウム二次電池およびその製造方法
JP6875820B2 (ja) リチウムイオン二次電池
JP2019169307A (ja) 電気化学素子
JP2017021986A (ja) 非水二次電池
JP7177210B2 (ja) リチウムイオン二次電池用電極、及びリチウムイオン二次電池
JP2016181457A (ja) 平板状ラミネート電池およびその組電池
JP2014112478A (ja) 非水電解質二次電池パック
JP5614432B2 (ja) リチウムイオン二次電池用非水電解液及びリチウムイオン二次電池
JP5639903B2 (ja) リチウムイオン二次電池
JP2000348705A (ja) 非水電解質二次電池
WO2015037522A1 (fr) Batterie secondaire non aqueuse

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16878729

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16878729

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP