WO2021131256A1 - 非水電解質二次電池用セパレータ及び非水電解質二次電池 - Google Patents

非水電解質二次電池用セパレータ及び非水電解質二次電池 Download PDF

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Publication number
WO2021131256A1
WO2021131256A1 PCT/JP2020/038924 JP2020038924W WO2021131256A1 WO 2021131256 A1 WO2021131256 A1 WO 2021131256A1 JP 2020038924 W JP2020038924 W JP 2020038924W WO 2021131256 A1 WO2021131256 A1 WO 2021131256A1
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Prior art keywords
separator
electrolyte secondary
secondary battery
aqueous electrolyte
base material
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PCT/JP2020/038924
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English (en)
French (fr)
Japanese (ja)
Inventor
聡 澁谷
貴仁 中山
修平 内田
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202080089417.3A priority Critical patent/CN114846692A/zh
Priority to US17/788,092 priority patent/US12603390B2/en
Priority to EP20905933.6A priority patent/EP4084204A4/en
Priority to JP2021566842A priority patent/JP7584105B2/ja
Publication of WO2021131256A1 publication Critical patent/WO2021131256A1/ja
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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
    • 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
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to a separator for a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery.
  • the nail piercing test is, for example, a test in which a nail is pierced into a battery to generate an internal short circuit in a simulated manner, and the degree of heat generation is examined to confirm the safety of the battery. It is important to suppress the heat generation of the battery at the time of such nail sticking in order to ensure the safety of the battery.
  • a separator having excellent safety can be provided by providing a porous layer containing inorganic particles and a basic phosphate in a separator arranged between a positive electrode and a negative electrode. Is disclosed.
  • the separator for a non-aqueous electrolyte secondary battery includes a separator base material and an aggregate of filler particles existing in dots on the surface of the separator base material, and the filler particles are Compound particles containing at least one of phosphorus, silicon, boron, nitrogen, potassium, sodium, and bromine having a transformation point of 180 ° C. to 1000 ° C. for transformation from a solid phase to a liquid phase or thermal decomposition. The range.
  • the non-aqueous electrolyte secondary battery according to one aspect of the present disclosure has a positive electrode, a negative electrode, and a separator arranged between the positive electrode and the negative electrode, and the separator is for the non-aqueous electrolyte secondary battery. It is a separator.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the separator according to the present embodiment.
  • FIG. 2 is a schematic cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of the embodiment.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the separator according to the present embodiment.
  • the separator 60 shown in FIG. 1 is a separator for a non-aqueous electrolyte secondary battery.
  • the separator 60 shown in FIG. 1 includes a separator base material 63 having a porous base material 62 and a heat-resistant layer 64 formed on the porous base material 62.
  • the separator 60 shown in FIG. 1 includes an aggregate 66 of filler particles existing in a dot shape on the surface of the heat-resistant layer 64.
  • the heat-resistant layer 64 is not essential, and the separator base material 63 may be a porous base material 62.
  • the aggregate 66 exists in a dot shape on the surface of the porous base material 62 which is the separator base material 63. Further, the aggregate 66 may be arranged on one surface of the separator base material 63, or may be arranged on both sides.
  • the surface structure of the separator 60 according to the present embodiment is a sea-island structure having a sea region on the surface of the separator base material and an island region of the aggregate 66.
  • the aggregate 66 is a collection of a plurality of filler particles.
  • the filler particles constituting the aggregate 66 are compound particles containing at least one of phosphorus, silicon, boron, nitrogen, potassium, sodium, and bromine, and are transformed from a solid phase to a liquid phase or thermally decomposed.
  • the transformation point is in the range of 180 ° C to 1000 ° C.
  • the rise in battery temperature in the nail piercing test is suppressed. This mechanism is not clear enough, but the following can be inferred. Due to the heat generated by the battery during the nail piercing test, that is, the heat generated by the battery when a nail is pierced into the battery to generate an internal short circuit in a simulated manner, the filler particles constituting the aggregate 66 are transformed from a solid phase to a liquid phase. The film flows on the surface of the separator base material 63 or extends on the surface of the separator base material 63 by thermal decomposition to form a film covering the surface of the separator base material 63.
  • the film functions as a resistance component, the amount of short-circuit current flowing between the positive and negative electrodes via the nail is suppressed, and as a result, the rise in battery temperature in the nail piercing test is also suppressed.
  • the formation of the film after the transformation of the filler particles into the liquid phase depends on the type of the filler particles, but for example, the temperature rise above the melting point of the filler material, the heat fusion reaction, the dehydration condensation reaction, the thermal polymerization reaction, etc. It is due to.
  • the separator for a non-aqueous electrolyte secondary battery according to the present embodiment, an increase in battery resistance is suppressed.
  • the aggregate 66 of the filler particles is a material having low lithium ion conductivity, so if it exists in layers, it inhibits the movement of lithium ions and reduces the battery resistance. Causes a rise.
  • it since it is dot-shaped in the present embodiment, there is a gap between the aggregates 66, and ions such as lithium ions can easily pass through the gap.
  • the lithium ions move smoothly between the positive and negative electrodes as compared with the case where the entire surface of the separator base material 63 is covered with the coating layer of the filler particles without gaps, so that the battery resistance increases. Is thought to be suppressed.
  • the filler particles are compound particles containing at least one of phosphorus, silicon, boron, nitrogen, potassium, sodium, and bromine, and have a transformation point of 180 ° C. for transformation from a solid phase to a liquid phase or thermal decomposition. It is not particularly limited as long as it is in the range of about 1000 ° C.
  • the filler particles have a transformation point of 180 ° C., for example, among phosphoric acid compounds, silicic acid compounds, boric acid compounds, melamine salt compounds, potassium salt compounds, sodium salt compounds and the like, which transforms from a solid phase to a liquid phase or thermally decomposes. Examples include compounds in the range of ⁇ 1000 ° C.
  • Examples of the phosphoric acid compound include phosphoric acid-lithium salt, phosphoric acid-sodium salt, phosphoric acid-potassium salt, phosphoric acid-calcium salt, phosphoric acid-magnesium salt, metal phosphate such as aluminum phosphate, and ammonium polyphosphate. , Condensed phosphates such as sodium tripolyphosphate and melamine polyphosphate, and phosphate esters such as trimethylphosphate and triphenylphosphate.
  • the borate compound includes, for example, boric acid-sodium salt, boric acid-potassium salt, boric acid-calcium salt, borate-magnesium salt, aluminum borate, metal borate salt such as melamine borate, trimethyl borate and the like.
  • Examples thereof include boric acid ester, boron oxide and condensed borate.
  • Examples of the silicic acid compound include silicic acid-sodium salt, silicic acid-potassium salt, silicic acid-calcium salt, silicic acid-magnesium salt, silicic acid-barium salt, silicic acid-metal salt such as manganese salt and the like.
  • Examples of the melamine salt compound include melamine cyanurate, melamine pyrophosphate, ethylene dimelamine, trimethylene dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene melanmin.
  • potassium salt compound examples include potassium pyrosulfate (K 2 S 2 O 7 ), potassium citrate monohydrate (C 6 H 5 K 3 O 7 ⁇ H 2 O), potassium carbonate and the like.
  • sodium salt compound examples include sodium carbonate and the like.
  • Boron oxide, ethylene-1,2-bis (pentabromophenyl), ethylenebistetrabromophthalimide, potassium carbonate, sodium carbonate are preferable.
  • the transformation point of the filler particles may be in the range of 180 ° C. to 1000 ° C., preferably 180 ° C. to 1000 ° C. so as to appropriately transform or thermally decompose from the solid phase to the liquid phase by the heat generated by the battery in the nail piercing test. It is in the range of 900 ° C, more preferably 180 ° C to 600 ° C.
  • the coverage of the aggregate 66 on the surface of the separator base material 63 is preferably 90% or less, more preferably 65% or less, in terms of suppressing an increase in battery resistance. Further, 20% or more is preferable, and 30% or more is more preferable, in terms of suppressing an increase in the battery temperature in the nail piercing test.
  • the coverage of the aggregate 66 is calculated as follows.
  • the coverage can be determined by elemental mapping of the separator surface with SEM-EDX (Energy Dispersive X-ray spectroscopy) or the like. For example, it is obtained by distinguishing the island region of the aggregate 66 from the sea region on the surface of the separator base material by element mapping and calculating the ratio of the area of the island region to the total area of the island region and the sea region.
  • SEM-EDX Electromagnetic X-ray spectroscopy
  • the average particle size of the filler particles is preferably in the range of 0.1 ⁇ m to 5 ⁇ m, more preferably in the range of 0.2 ⁇ m to 1 ⁇ m.
  • the filler particles are rapidly transformed from the solid phase to the liquid phase due to the heat generated by the battery during the nail piercing test, as compared with the case where the above range is not satisfied.
  • the rise in battery temperature in the nail piercing test can be effectively suppressed.
  • the aggregate 66 may contain a binder in addition to the filler particles described above. By including the binder, it is possible to improve the binding property between the filler particles and the binding property between the filler particles and the separator base material 63.
  • the binder include polyvinylidene fluoride (PVdF), ethylene dimethacrylate, allyl methacrylate, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, and methacrylic acid.
  • Polyvinylidene fluoride (PVdF), ethylene dimethacrylate, allyl methacrylate, t-dodecyl mercaptan, ⁇ -methylstyrene dimer, and methacrylic acid are electrodes of the aggregate 66 when pressure and / or heat is applied. And the separator can be adhered. Further, the aggregate 66 may contain compound particles other than the above-mentioned filler particles. Examples of compound particles other than the above-mentioned filler particles include inorganic particles such as alumina, boehmite, and titania.
  • the porous base material 62 is, for example, a porous sheet such as a microporous thin film, a woven fabric, or a non-woven fabric, which has ion permeability and insulating properties.
  • the material constituting the porous base material 62 include polyethylene, polypropylene, polyolefins such as a copolymer of polyethylene and ⁇ -olefin, acrylic resin, polystyrene, polyester, and cellulose.
  • the porous base material 62 may have a single-layer structure or a laminated structure.
  • the thickness of the porous base material 62 is not particularly limited, but is, for example, in the range of 3 ⁇ m to 20 ⁇ m.
  • the porosity of the porous base material 62 is preferably, for example, 30% or more and 70% or less in terms of ensuring ion permeability and the like.
  • the porosity of the porous base material 62 is measured by the following method. (1) Ten points of the base material are punched into a circle having a diameter of 2 cm, and the thickness h and the mass w of the central portion of the punched small pieces of the base material are measured. (2) From the thickness h and mass w, the volume V and mass W of 10 small pieces are obtained, and the porosity ⁇ is calculated from the following formula.
  • Porosity ⁇ (%) (( ⁇ V ⁇ W) / ( ⁇ V)) ⁇ 100 ⁇ : Density of the material constituting the base material
  • the average pore size of the porous base material 62 is, for example, 0.02 ⁇ m or more and 0.5 ⁇ m or less, preferably 0.03 ⁇ m or more and 0.3 ⁇ m or less.
  • the average pore size of the porous base material 62 is measured using a palm poromometer (manufactured by Seika Sangyo Co., Ltd.) capable of measuring the pore size by the bubble point method (JIS K3832, ASTM F316-86).
  • the maximum pore size of the base material 24 is, for example, 0.05 ⁇ m or more and 1 ⁇ m or less, preferably 0.05 ⁇ m or more and 0.5 ⁇ m or less.
  • the heat-resistant layer 64 is composed of inorganic particles such as alumina, boehmite, and titania. By providing the heat-resistant layer 64, it is possible to improve the heat resistance of the separator 60.
  • the heat-resistant layer 64 may include, for example, a binder. By including the binder, the adhesiveness between the porous base material 62 and the heat-resistant layer 64 can be ensured.
  • the binder is not particularly limited, and examples thereof include polyvinylidene fluoride (PVdF) and methacrylic acid.
  • the thickness of the heat-resistant layer 64 is not particularly limited, but is, for example, in the range of 1 ⁇ m to 10 ⁇ m.
  • the heat-resistant layer 64 may be provided on one surface of the porous base material 62, or may be provided on both sides.
  • An example of a method for manufacturing the separator 60 will be described.
  • the solvent contained in the slurry include water, N-methyl-2-pyrrolidone (NMP) and the like.
  • the dot-shaped aggregate can be produced, for example, by using a gravure coater method using a dot-shaped plate or a spray coating method using a mask forming a dot-shaped penetrating pattern.
  • FIG. 2 is a schematic cross-sectional view of a non-aqueous electrolyte secondary battery which is an example of the embodiment.
  • the non-aqueous electrolyte secondary battery 10 shown in FIG. 2 has a wound electrode body 14 in which a positive electrode 11 and a negative electrode 12 are wound via a separator 13, a non-aqueous electrolyte, and above and below the electrode body 14, respectively.
  • An arranged insulating plates 18 and 19 and a battery case 15 for accommodating the above members are provided.
  • the battery case 15 is composed of a bottomed cylindrical case body 16 and a sealing body 17 that closes an opening of the case body 16.
  • the winding type electrode body 14 instead of the winding type electrode body 14, another form of an electrode body such as a laminated type electrode body in which positive electrodes and negative electrodes are alternately laminated via a separator may be applied.
  • the battery case 15 include a metal case such as a cylinder, a square, a coin, and a button, and a resin case (so-called laminated type) formed by laminating a resin sheet.
  • the case body 16 is, for example, a bottomed cylindrical metal container.
  • a gasket 28 is provided between the case body 16 and the sealing body 17 to ensure the airtightness inside the battery.
  • the case body 16 has, for example, an overhanging portion 22 that supports the sealing body 17 with a part of the side surface overhanging inward.
  • the overhanging portion 22 is preferably formed in an annular shape along the circumferential direction of the case body 16, and the sealing body 17 is supported on the upper surface thereof.
  • the sealing body 17 has a structure in which a filter 23, a lower valve body 24, an insulating member 25, an upper valve body 26, and a cap 27 are laminated in this order from the electrode body 14 side.
  • Each member constituting the sealing body 17 has, for example, a disk shape or a ring shape, and each member except the insulating member 25 is electrically connected to each other.
  • the lower valve body 24 and the upper valve body 26 are connected to each other at the central portion thereof, and an insulating member 25 is interposed between the peripheral portions thereof.
  • the lower valve body 24 deforms and breaks so as to push the upper valve body 26 toward the cap 27 side, and the lower valve body 24 and the upper valve body 26 The current path between them is cut off.
  • the upper valve body 26 breaks and gas is discharged from the opening of the cap 27.
  • the positive electrode lead 20 attached to the positive electrode 11 extends to the sealing body 17 side through the through hole of the insulating plate 18, and the negative electrode lead 21 attached to the negative electrode 12 insulates. It extends to the bottom side of the case body 16 through the outside of the plate 19.
  • the positive electrode lead 20 is connected to the lower surface of the filter 23, which is the bottom plate of the sealing body 17, by welding or the like, and the cap 27, which is the top plate of the sealing body 17 electrically connected to the filter 23, serves as the positive electrode terminal.
  • the negative electrode lead 21 is connected to the inner surface of the bottom of the case body 16 by welding or the like, and the case body 16 serves as a negative electrode terminal.
  • the positive electrode 11 has, for example, a positive electrode current collector and a positive electrode active material layer provided on the positive electrode current collector.
  • a positive electrode current collector for example, a metal foil stable in the potential range of the positive electrode such as aluminum, a film in which the metal is arranged on the surface layer, or the like can be used.
  • the positive electrode active material layer contains a positive electrode active material, and preferably contains a conductive material or a binder.
  • Examples of the positive electrode active material include lithium transition metal composite oxides, and specifically, lithium cobaltate, lithium manganate, lithium nickelate, lithium nickel-manganese composite oxide, lithium nickel-cobalt composite oxide and the like are used. Al, Ti, Zr, Nb, B, W, Mg, Mo and the like may be added to these lithium transition metal composite oxides.
  • carbon powders such as carbon black, acetylene black, ketjen black, and graphite may be used alone or in combination of two or more.
  • binder examples include fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. These may be used alone or in combination of two or more.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide resins, acrylic resins, and polyolefin resins. These may be used alone or in combination of two or more.
  • the negative electrode 12 has, for example, a negative electrode current collector and a negative electrode active material layer provided on the negative electrode current collector.
  • a negative electrode current collector for example, a metal foil stable in the potential range of the negative electrode such as copper, a film in which the metal is arranged on the surface layer, or the like can be used.
  • the negative electrode active material layer contains a negative electrode active material, and preferably contains a binder or the like.
  • a carbon material capable of storing and releasing lithium ions can be used, and in addition to graphite, non-graphite carbon, easily graphitable carbon, fibrous carbon, coke, carbon black and the like should be used. Can be done. Further, as the non-carbon material, silicon, tin, and alloys and oxides mainly containing these can be used.
  • binder examples include fluororesin, PAN, polyimide resin, acrylic resin, polyolefin resin, styrene-butadiene rubber (SBR), nitrile-butadiene rubber (NBR), carboxymethyl cellulose (CMC) or a salt thereof.
  • SBR styrene-butadiene rubber
  • NBR nitrile-butadiene rubber
  • CMC carboxymethyl cellulose
  • PAA Polyacrylic acid
  • PAA-Na, PAA-K, etc., or a partially neutralized salt polyvinyl alcohol (PVA), and the like. These may be used alone or in combination of two or more.
  • the above-mentioned separator 60 is applied to the separator 13.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous solvent for example, esters, ethers, nitriles, amides, and a mixed solvent of two or more of these are used.
  • the non-aqueous solvent may contain a halogen substituent in which at least a part of hydrogen in these solvents is substituted with a halogen atom such as fluorine.
  • the electrolyte salt for example, a lithium salt such as LiPF 6 is used.
  • Example> [Preparation of positive electrode] 100 parts by weight of the positive electrode active material represented by LiNi 0.82 Co 0.15 Al 0.03 O 2 , 1 part by weight of acetylene black (AB), and 1 part by weight of polyvinylidene fluoride (PVdF). After mixing, an appropriate amount of N-methyl-2-pyrrolidone (NMP) was added to prepare a positive electrode mixture slurry. Next, the positive electrode mixture slurry was applied to both sides of the positive electrode current collector made of aluminum foil and dried. This was cut into a predetermined electrode size and rolled using a roller to form positive electrode active material layers on both sides of the positive electrode current collector.
  • NMP N-methyl-2-pyrrolidone
  • a negative electrode mixture slurry was prepared by mixing 100 parts by weight of graphite powder, 1 part by weight of carboxymethyl cellulose (CMC), and 1 part by weight of styrene-butadiene rubber (SBR), and further adding an appropriate amount of water. Next, the negative electrode mixture slurry was applied to both sides of the negative electrode current collector made of copper foil and dried. This was cut into a predetermined electrode size and rolled using a roller to form negative electrode active material layers on both sides of the negative electrode current collector.
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • LiPF 6 Lithium hexafluorophosphate
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • Example 2 In the production of the separator, this was used as the separator of Example 2 in the same manner as in Example 1 except that the gravure mesh roll pattern of the gravure coater device was changed. When the surface of the separator of Example 2 was observed by SEM-EDX, it was confirmed that the aggregates of the melamine polyphosphate particles were dot-shaped, and the coverage of the aggregates of the melamine polyphosphate particles was 90%. ..
  • Example 3 In the preparation of the filler slurry, this was used as the separator of Example 3 in the same manner as in Example 1 except that polyvinylidene fluoride was replaced with butyl acrylate. When the surface of the separator of Example 3 was observed by SEM-EDX, it was confirmed that the aggregates of the melamine polyphosphate particles were dot-shaped, and the coverage of the aggregates of the melamine polyphosphate particles was 30%. ..
  • Examples 4 to 8 In the preparation of the filler slurry, the melamine polyphosphate particles were replaced with ammonium polyphosphate particles in Example 4, sodium tripolyphosphate particles in Example 5, and sodium silicate (Na 2 SiO 3 ) particles in Example 6. Instead, in Example 7, it was replaced with sodium borate (Na 2 B 4 O 7 ) particles, and in Example 8, it was replaced with potassium citrate monohydrate (C 6 H 5 K 3 O 7 ⁇ H 2 O) particles. Except for this, a separator was prepared in the same manner as in Example 1. When the surface of the separators of Examples 4 to 8 was observed by SEM-EDX, it was confirmed that the aggregates of the filler particles were dot-shaped, and the coverage of the aggregates of the filler particles was 30%. It was.
  • Example 1 A non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 except that the filler slurry was not used.
  • the battery resistance of the non-aqueous electrolyte secondary batteries of Examples 1 to 8 and Comparative Examples 1 and 2 was measured as follows. In a temperature environment of 25 ° C., the non-aqueous electrolyte secondary battery is charged with a constant current of 0.3 C until the battery voltage reaches 4.2 V, and then charged with a constant voltage until the current value reaches 0.05 C. Then, it was discharged with a constant current of 0.3C to set the SOC to 50%. Next, the voltage values when the discharge currents of 0A, 0.1A, 0.5A, and 1.0A were applied for 10 seconds were acquired. DC-IR was calculated from the absolute value of the slope when the voltage value after 10 seconds for each discharge current value was linearly approximated by the least squares method, and this value is summarized in Table 1 as the battery resistance.
  • Example 9 In the preparation of the filler slurry, the melamine polyphosphate particles were replaced with lithium metaphosphate ((LiPO 3 ) n ) particles in Example 9 and potassium dihydrogen phosphate (KH 2 PO 4 ) particles in Example 10.
  • LiPO 3 lithium metaphosphate
  • KH 2 PO 4 potassium dihydrogen phosphate
  • Example 11 instead of melamine cyanurate, in Example 12, instead of potassium pyrosulfate (K 2 S 2 O 7 ) particles, in Example 13, instead of boron oxide (B 2 O 3 ) particles, and in Example 14, ethylene.
  • Example 15 instead of -1,2-bis (pentabromophenyl) particles, in Example 15, instead of ethylene bistetrabromophthalimide particles, in Example 16, instead of potassium carbonate (K 2 CO 3 ) particles, in Example 17, sodium carbonate.
  • a separator was prepared in the same manner as in Example 1 except that 80 parts by weight of polyphosphate melamine particles / 20 parts by weight of alumina particles were replaced with particles in place of (Na 2 CO 3) particles. When the surface of the separators of Examples 9 to 18 was observed by SEM-EDX, it was confirmed that the aggregates of the filler particles were dot-shaped, and the coverage of the aggregates of the filler particles was 30%. It was.
  • Table 2 summarizes the coverage of the aggregate of filler particles in Examples 9 to 18. Further, in the non-aqueous electrolyte secondary batteries of Examples 9 to 18, the above-mentioned nail piercing test and battery resistance measurement were performed, and the results are summarized in Table 2.
  • Example 9 the battery temperature after the nail piercing test was lower than that in Comparative Example 1 in which there were no filler particles on the surface of the polyethylene porous base material. Further, although the battery resistance was higher than that of Comparative Example 1, it was about the same as that of Example 2. That is, it can be said that Examples 9 to 18 were also able to suppress the heat generation of the battery in the nail piercing test while suppressing the increase in battery resistance.
  • Non-aqueous electrolyte secondary battery 11 Positive electrode 12 Negative electrode 13 Separator 14 Electrode body 15 Battery case 16 Case body 17 Sealing body 18, 19 Insulating plate 20 Positive electrode lead 21 Negative electrode lead 22 Overhanging part 23 Filter 24 Lower valve body 25 Insulating member 26 Upper valve body 27 Cap 28 Gasket 60 Separator 62 Porous base material 64 Heat resistant layer 66 Aggregate

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