WO2015122164A1 - Séparateur pour batteries secondaires à électrolyte non aqueux - Google Patents

Séparateur pour batteries secondaires à électrolyte non aqueux Download PDF

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Publication number
WO2015122164A1
WO2015122164A1 PCT/JP2015/000539 JP2015000539W WO2015122164A1 WO 2015122164 A1 WO2015122164 A1 WO 2015122164A1 JP 2015000539 W JP2015000539 W JP 2015000539W WO 2015122164 A1 WO2015122164 A1 WO 2015122164A1
Authority
WO
WIPO (PCT)
Prior art keywords
separator
inorganic particles
electrolyte secondary
inorganic particle
aqueous electrolyte
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/JP2015/000539
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English (en)
Japanese (ja)
Inventor
伸宏 鉾谷
泰三 砂野
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.)
Sanyo Electric Co Ltd
Original Assignee
Sanyo Electric Co 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 Sanyo Electric Co Ltd filed Critical Sanyo Electric Co Ltd
Publication of WO2015122164A1 publication Critical patent/WO2015122164A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • H01M50/431—Inorganic 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
    • H01M50/44—Fibrous 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
    • H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator for a non-aqueous electrolyte secondary battery.
  • a separator having a heat-resistant layer containing inorganic particles has been proposed as a separator.
  • Patent Document 1 it is proposed to use plate-like inorganic particles for the heat-resistant layer to suppress the thermal contraction of the separator.
  • a separator for a non-aqueous electrolyte secondary battery includes a microporous film and an inorganic particle film formed on the microporous film, and the inorganic particle film has a needle shape.
  • the needle-like inorganic particles have a major axis / minor axis ratio of 12 or more and 20 or less.
  • the non-aqueous electrolyte secondary battery using the non-aqueous electrolyte secondary battery separator of the present invention can suppress the thermal contraction of the separator at a high temperature because the strength of the inorganic particle film is increased.
  • a nonaqueous electrolyte secondary battery which is an example of an embodiment of the present invention includes a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a nonaqueous electrolyte including a nonaqueous solvent, and a separator.
  • a positive electrode including a positive electrode active material a positive electrode active material
  • a negative electrode including a negative electrode active material a nonaqueous electrolyte including a nonaqueous solvent
  • separator As an example of the non-aqueous electrolyte secondary battery, there is a structure in which an electrode body in which a positive electrode and a negative electrode are wound via a separator and a non-aqueous electrolyte are accommodated in an exterior body.
  • the average pore diameter of the microporous membrane is 0.03 to 3 ⁇ m, more preferably 0.03 to 0.3 ⁇ m. If the average pore size of the microporous membrane is too large, the shutdown function due to melting of the microporous membrane at a high temperature tends to be insufficient. If the average pore size of the microporous membrane is too small, there is a possibility that the electrolyte decomposition products accompanying charge / discharge may clog the pores and inhibit the movement of lithium ions.
  • the average thickness of the microporous membrane is 5 to 30 ⁇ m, more preferably 5 to 20 ⁇ m.
  • the inorganic particle film formed on the microporous film preferably includes acicular inorganic particles having a major axis / minor axis ratio of 10 or more and 20 or less.
  • acicular inorganic particles having a major axis / minor axis ratio of 10 or more and 20 or less are provided, the strength of the inorganic particle layer increases due to the entanglement of the inorganic particles, and the microporous membrane is thermally contracted to cause the microporous membrane and the inorganic particles to shrink.
  • the major axis / minor axis ratio is preferably 10 to 20, more preferably 12 to 15.
  • the short diameter of the needle-like inorganic particles is preferably 0.05 to 1 ⁇ m, more preferably 0.1 to 0.5 ⁇ m. If the minor axis is too large, the inorganic particle layer becomes thick and the energy density of the battery tends to decrease. If the minor axis is too small, inorganic particles may enter the pores of the microporous membrane and clog the pores.
  • the mass of the binder with respect to the mass of the acicular inorganic particles is preferably 3 to 25% by mass, and more preferably 3 to 20% by mass.
  • the content is less than 3% by mass, the adhesion between the inorganic particle layer and the microporous film is lowered, and the above-described effect of suppressing the thermal shrinkage of the separator tends to be reduced. It tends to close the hole.
  • the average pore diameter of the microporous membrane is preferably smaller than the minor diameter of the acicular inorganic particles in the inorganic particle membrane.
  • the short diameter of the inorganic particles is smaller than the pore diameter of the microporous membrane, the inorganic particles tend to enter the pores of the microporous membrane and easily close the pores.
  • the thickness of the inorganic particle film is preferably 1 to 5 ⁇ m, more preferably 1 to 2 ⁇ m. If the thickness is too large, the energy density of the battery tends to decrease. If the thickness is too small, the strength of the inorganic particle layer becomes insufficient, and the above-described effect of suppressing the heat shrinkage of the microporous film decreases. Tend.
  • the air permeability of the separator represented by the Gurley value is preferably 10 to 500 s / 100 mL.
  • the Gurley value is more preferably 100 to 200 s / 100 mL.
  • the Gurley value is a value of the number of seconds that 100 mL of air permeates through the membrane under a pressure of 0.879 g / mm 2 measured by a method according to JIS P 8117. If the Gurley value is too large, the ion permeability decreases, whereas if it is too small, the strength of the separator may decrease.
  • the inorganic particle film may be formed on one side of the microporous film or on both sides.
  • the positive electrode is preferably composed of a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • a positive electrode current collector for example, a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the positive electrode such as aluminum, or a film having a metal surface layer such as aluminum is used.
  • the positive electrode active material layer preferably contains a conductive material and a binder in addition to the positive electrode active material.
  • the positive electrode active material includes an oxide including lithium and a metal element M, and the metal element M includes at least one selected from the group including cobalt and nickel.
  • Preferred is a lithium-containing transition metal oxide.
  • the lithium-containing transition metal oxide may contain non-transition metal elements such as Mg and Al. Specific examples include lithium-containing transition metal oxides such as lithium cobaltate, Ni—Co—Mn, Ni—Mn—Al, and Ni—Co—Al. These positive electrode active materials may be used alone or in combination of two or more.
  • the negative electrode preferably includes a negative electrode current collector and a negative electrode mixture layer formed on the negative electrode current collector.
  • a negative electrode current collector for example, a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the negative electrode such as copper, or a film having a metal surface layer such as copper is used.
  • the negative electrode mixture layer preferably contains a binder in addition to the negative electrode active material and carboxymethylcellulose ammonium salt (CMC ammonium salt).
  • CMC ammonium salt carboxymethylcellulose ammonium salt
  • SBR styrene-butadiene rubber
  • polyimide polyimide
  • Non-aqueous electrolyte examples include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , and lower aliphatic carboxylic acid.
  • Lithium, LiCl, LiBr, LiI, chloroborane lithium, borates, imide salts, and the like can be used.
  • LiPF 6 is preferably used from the viewpoint of ion conductivity and electrochemical stability.
  • One electrolyte salt may be used alone, or two or more electrolyte salts may be used in combination. These electrolyte salts are preferably contained at a ratio of 0.8 to 1.5 mol with respect to 1 L of the nonaqueous electrolyte.
  • non-aqueous electrolyte solvent for example, a cyclic carbonate, a chain carbonate, a cyclic carboxylic acid ester or the like is used.
  • cyclic carbonate examples include propylene carbonate (PC), ethylene carbonate (EC), and fluoroethylene carbonate (FEC).
  • chain carbonate examples include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
  • examples of the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • examples of the chain carboxylic acid ester examples include methyl propionate (MP) fluoromethyl propionate (FMP).
  • a non-aqueous solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
  • acicular titanium oxide major axis: 1.68 ⁇ m, minor axis: 0.13 ⁇ m, aspect ratio 12.9
  • carboxymethyl cellulose carboxymethyl cellulose
  • styrene-butadiene rubber have a mass ratio of 100: 1.
  • water as a dispersion medium was added so that titanium oxide was 15% by mass to prepare a slurry.
  • the prepared slurry was coated on the surface of a polyethylene microporous film (film thickness: 16 ⁇ m, Gurley value: 156 s / 100 mL, pore size: 0.06 ⁇ m) by a gravure method, and water was dried and removed.
  • Separator A1 was produced in which an inorganic particle film containing acicular titanium oxide was formed on one side of the microporous film. The thickness of the inorganic particle film was set to 2 ⁇ m.
  • Separator heat shrinkage inhibition rate (melting area of separator R1 ⁇ melting area of each separator) / melting area of separator R1 ⁇ 100 (%) (1)
  • the Gurley values of the separators A1 to A3 are smaller than those of the separators B1 to B2, and it can be seen that the separators A1 to A3 are separators with high ion permeability. This is because a porous inorganic particle film with more voids was formed by entanglement of the needle-like inorganic particles, and therefore the increase in the Gurley value due to the formation of the inorganic particle film was suppressed more than B1 and B2. It is guessed.
  • the inorganic particle film provided with acicular particles needs to be formed on the microporous film so as to be adhered.
  • the effect of suppressing the thermal shrinkage of the separator described above is exhibited only when the base material on which the inorganic particle film including needle-like particles is formed is a microporous film.
  • the nonwoven fabric does not thermally shrink even at a high temperature of 300 ° C. or higher.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne un séparateur pour batteries secondaires à électrolyte non aqueux présentant une excellente résistance au retrait thermique. L'invention concerne un séparateur pour batteries secondaires à électrolyte non aqueux comprenant un film poreux et un film poreux résistant à la chaleur formé sur ledit film poreux. Un film de particules inorganiques comprend des particules inorganiques en forme d'aiguilles et un liant. Le rapport grand diamètre/petit diamètre des particules inorganiques en forme d'aiguilles est de 10-20. De manière idéale, le petit diamètre des particules inorganiques en forme d'aiguilles est de 0,05-1 µm. De manière idéale, le diamètre moyen des pores du film finement poreux est de 0,03-0,3 µm.
PCT/JP2015/000539 2014-02-17 2015-02-06 Séparateur pour batteries secondaires à électrolyte non aqueux Ceased WO2015122164A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-027176 2014-02-17
JP2014027176 2014-02-17

Publications (1)

Publication Number Publication Date
WO2015122164A1 true WO2015122164A1 (fr) 2015-08-20

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PCT/JP2015/000539 Ceased WO2015122164A1 (fr) 2014-02-17 2015-02-06 Séparateur pour batteries secondaires à électrolyte non aqueux

Country Status (1)

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WO (1) WO2015122164A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4210160A3 (fr) * 2022-01-06 2023-07-26 SK Innovation Co., Ltd. Séparateur pour une batterie secondaire et son procédé de fabrication

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001019906A1 (fr) * 1999-09-13 2001-03-22 Teijin Limited Film poreux polymere a base de polymethaphenylene isophtalamide, son procede de fabrication et separateur de cellules
JP2008234853A (ja) * 2007-03-16 2008-10-02 Matsushita Electric Ind Co Ltd 非水系二次電池用セパレータおよびこれを備えた非水系二次電池
WO2008149986A1 (fr) * 2007-06-06 2008-12-11 Asahi Kasei E-Materials Corporation Film poreux multicouches
JP2009129668A (ja) * 2007-11-22 2009-06-11 Asahi Kasei Chemicals Corp 多層多孔膜
JP2010202987A (ja) * 2009-02-27 2010-09-16 Asahi Kasei Corp 複合シート材料及びその製法
JP2011023162A (ja) * 2009-07-14 2011-02-03 Teijin Ltd 非水系二次電池用セパレータ
JP2011154937A (ja) * 2010-01-28 2011-08-11 Mitsubishi Paper Mills Ltd 多孔性セパレータ膜
JP2012003938A (ja) * 2010-06-17 2012-01-05 Hitachi Maxell Ltd 電池用セパレータおよびリチウム二次電池
WO2014148036A1 (fr) * 2013-03-19 2014-09-25 ソニー株式会社 Séparateur, batterie, bloc de batteries, appareil électronique, véhicule électrique, dispositif de stockage d'énergie, et système d'énergie

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001019906A1 (fr) * 1999-09-13 2001-03-22 Teijin Limited Film poreux polymere a base de polymethaphenylene isophtalamide, son procede de fabrication et separateur de cellules
JP2008234853A (ja) * 2007-03-16 2008-10-02 Matsushita Electric Ind Co Ltd 非水系二次電池用セパレータおよびこれを備えた非水系二次電池
WO2008149986A1 (fr) * 2007-06-06 2008-12-11 Asahi Kasei E-Materials Corporation Film poreux multicouches
JP2009129668A (ja) * 2007-11-22 2009-06-11 Asahi Kasei Chemicals Corp 多層多孔膜
JP2010202987A (ja) * 2009-02-27 2010-09-16 Asahi Kasei Corp 複合シート材料及びその製法
JP2011023162A (ja) * 2009-07-14 2011-02-03 Teijin Ltd 非水系二次電池用セパレータ
JP2011154937A (ja) * 2010-01-28 2011-08-11 Mitsubishi Paper Mills Ltd 多孔性セパレータ膜
JP2012003938A (ja) * 2010-06-17 2012-01-05 Hitachi Maxell Ltd 電池用セパレータおよびリチウム二次電池
WO2014148036A1 (fr) * 2013-03-19 2014-09-25 ソニー株式会社 Séparateur, batterie, bloc de batteries, appareil électronique, véhicule électrique, dispositif de stockage d'énergie, et système d'énergie

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4210160A3 (fr) * 2022-01-06 2023-07-26 SK Innovation Co., Ltd. Séparateur pour une batterie secondaire et son procédé de fabrication

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