JP6693689B2 - リチウムイオン(lithiumion)二次電池用セパレータ(separator)及びリチウムイオン二次電池 - Google Patents
リチウムイオン(lithiumion)二次電池用セパレータ(separator)及びリチウムイオン二次電池 Download PDFInfo
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- JP6693689B2 JP6693689B2 JP2013265970A JP2013265970A JP6693689B2 JP 6693689 B2 JP6693689 B2 JP 6693689B2 JP 2013265970 A JP2013265970 A JP 2013265970A JP 2013265970 A JP2013265970 A JP 2013265970A JP 6693689 B2 JP6693689 B2 JP 6693689B2
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- Prior art keywords
- layer
- ion secondary
- separator
- secondary battery
- inorganic particle
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 48
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- 150000004706 metal oxides Chemical class 0.000 claims description 4
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- 229920000573 polyethylene Polymers 0.000 description 18
- 239000002002 slurry Substances 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 239000007773 negative electrode material Substances 0.000 description 16
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
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- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000002391 graphite-based active material Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
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- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- MHWAJHABMBTNHS-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C.FC(F)=C(F)F MHWAJHABMBTNHS-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
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- GDJDGYJGJLGDMZ-UHFFFAOYSA-M C(CCCCCCC)S(=O)(=O)O.[Li+].C(CCCCCCC)S(=O)(=O)[O-] Chemical compound C(CCCCCCC)S(=O)(=O)O.[Li+].C(CCCCCCC)S(=O)(=O)[O-] GDJDGYJGJLGDMZ-UHFFFAOYSA-M 0.000 description 1
- XDJQVCIRFIRWKY-UHFFFAOYSA-N C=C.C(=C)(F)F Chemical group C=C.C(=C)(F)F XDJQVCIRFIRWKY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002642 lithium compounds Chemical class 0.000 description 1
- IRDCEJVOXCGYAV-UHFFFAOYSA-M lithium;2-dodecylbenzenesulfonate Chemical compound [Li+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O IRDCEJVOXCGYAV-UHFFFAOYSA-M 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- NTWKDFWKALPPII-UHFFFAOYSA-M lithium;octadecane-1-sulfonate Chemical compound [Li+].CCCCCCCCCCCCCCCCCCS([O-])(=O)=O NTWKDFWKALPPII-UHFFFAOYSA-M 0.000 description 1
- OVFPMHMGYFIJQX-UHFFFAOYSA-N lithium;octadecane-1-sulfonic acid Chemical compound [Li].CCCCCCCCCCCCCCCCCCS(O)(=O)=O OVFPMHMGYFIJQX-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
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- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
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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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
- 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
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Description
次に、リチウムイオン二次電池10の製造方法について説明する。正極20は、以下のように作製される。まず、正極活物質、導電剤、及び結着剤を混合したものを、溶媒(例えばN−メチル−2−ピロリドン(NMP))に分散させることでスラリーを形成する。次いで、スラリーを集電体21上に形成(例えば塗工)し、乾燥させることで、正極活物質層22を形成する。なお、塗工の方法は、特に限定されない。塗工の方法としては、例えば、ナイフコーター(knife coater)法、グラビアコータ(gravure coater)法等が考えられる。以下の各塗工工程も同様の方法により行われる。次いで、プレス(press)機により正極活物質層22をプレスする。これにより、正極20が作製される。
(無機粒子層の作製)
無機粒子としてアルミナ(スミコランダムAA03<住友化学>)94質量部と、バインダとしてポリエチレン水分散体(ケミパールS100<三井化学>)5質量部、及びCMC(2200<ダイセル化学>)1質量%とを混合し、当該混合物にイオン交換水を加え超音波分散機で分散し塗工液とした。塗工液中の固形分の質量%は、塗工液の総質量に対して20質量%となった。
樹脂としてPVdF(KF9300<クレハ>)をNMPに加え撹拌して完全に溶解させることで、塗工液を作製した。樹脂の塗工液中の濃度は塗工液の総質量に対して5質量%であった。次に、ディップコータ(Dip coater)を用い無機粒子層が形成されたポリエチレン多孔質膜上の両面に塗布し、水浴で凝固させた後乾燥させた。これにより、樹脂層をポリエチレン多孔質膜の両面に形成した。樹脂層の乾燥後の膜厚(すなわち、セパレータの総厚)は12μmであった。したがって、実施例1では、ポリエチレン多孔質膜の一方の表面に表面処理層を形成し、他方の表面に樹脂層を形成した。
セパレータをTD×MD=60mm×80mmとなるように切り出し、TD/MD方向にノギスを用いて50mmの間隔で印を入れた。ついで、セパレータを二つ折りにしたアルミ箔の間にはさみ、130℃の恒温槽中に15分静置した。セパレータを取り出した後、TD/MDそれぞれの印の間隔をノギスで読み取り、次式にしたがって熱収縮率を算出した。
収縮率(%)=(1−(50−加熱後の間隔)/50)×100)
(正極の作製)
固溶体酸化物Li1.20Mn0.55Co0.10Ni0.15O296質量部、ケッチェンブラック2質量部、PVDF2質量部をNMPに分散させることで正極合剤スラリーを形成した。ついで、この正極合剤スラリーをアルミニウム箔上に均一に塗工することで塗工層を形成し、塗工層を80℃に設定した送風型乾燥機で15分乾燥し、アルミニウム箔とともに圧延した。ついで、塗工層を100℃で6時間真空乾燥した。これにより、アルミニウム箔上に正極活物質層を形成した。すなわち、正極を形成した。正極活物質層の充填密度は3.0g/cm3であった。
炭素材(人造黒鉛)、CMC(カルボキシメチルセルロースナトリウム)、及びSBR(スチレンブタジエンゴム)を97.5:1:1.5の質量比で混合することで負極合剤を作製した。ついで、負極合剤を溶媒である水に分散させることで、負極合剤スラリーを得た。
出来上がったラミネートセルを、0.2Cで4.2VまでCC充電し、その後0.05CまでCV充電した。
負荷特性=C2/C1×100
このラミネートセルを解体し、手でセパレータと電極を引き剥がした。セパレータと電極の接着性があると、電極合材がセパレータに転写する。それぞれの負極版をデジタルカメラで撮影し、負極合材が銅箔上に残存している割合を算出し接着性の指標とした。
セパレータの最表面をSEMで観察し、樹脂と無機粒子の存在を目視判断した。
無機粒子層のアルミナの占有率を80体積%に変更した以外は、実施例1と同様の処理を行った。
無機粒子の種類をベーマイトにした以外は、実施例1と同様の処理を行った。
樹脂層を以下の処理により形成した他は、実施例1と同様の処理を行った。
(樹脂層の形成:水ミスト噴霧)
樹脂としてPVdF(KF9300<クレハ>)をNMPに加え撹拌して完全に溶解させることで、塗工液を作製した。樹脂の塗工液中の濃度は塗工液の総質量に対して5質量%であった。
無機粒子層を厚さ7μmのポリエチレン多孔質膜の両面に塗布しセパレータの総厚を10μmとした以外は実施例1と同様の処理を行った。したがって、実施例5では、ポリエチレン多孔質膜の両面に表面処理層を形成した。
無機粒子の比率を70体積%にした以外は、実施例1と同様の処理を行った。
無機粒子としてアルミナ(スミコランダムAA03<住友化学>)と、バインダとしてPVdF(KF9300<クレハ>)とを混合し、当該混合物にNMPを加え超音波分散機で分散し塗工液とした。ついで、塗工液をディップコータを用いポリエチレン多孔質膜上の両面に塗布し、水浴で凝固させた後乾燥させた。これにより、ポリエチレン多孔質膜の両面に無機粒子分散樹脂層を形成した。無機粒子分散樹脂層は、本実施形態の樹脂層に無機粒子を分散させた層である。なお、アルミナの無機粒子分散樹脂層全体に対する占有率は80体積%とした。
樹脂層の形成処理を以下の方法に変更した以外は実施例1と同様の処理を行った。
(樹脂層の形成:そのまま乾燥)
樹脂としてPVdF(KF9300<クレハ>)をNMPに加え撹拌して完全に溶解させることで、塗工液を作製した。樹脂の塗工液中の濃度は塗工液の総質量に対して5質量%であった。
20 正極
21 集電体
22 正極活物質層
30 負極
31 集電体
32 負極活物質層
40 セパレータ
40a 多孔質膜
40b、40c 表面処理層
40b−1 無機粒子層
40b−2 樹脂層
Claims (6)
- 多孔質膜と、
前記多孔質膜の少なくとも一方の表面に形成され、無機粒子が層全体の80体積%以上を占める無機粒子層と、
前記無機粒子層の表面に形成され、前記無機粒子層と一体化された多孔質の樹脂層と、
を備え、
前記樹脂層が前記無機粒子層の表面の無機粒子間の隙間に入り込んでいる、リチウムイオン二次電池用セパレータ。 - 前記無機粒子層は、前記多孔質膜の両面に形成されていることを特徴とする、請求項1記載のリチウムイオン二次電池用セパレータ。
- 前記樹脂層は、フッ素樹脂を含むことを特徴とする、請求項1または2記載のリチウムイオン二次電池用セパレータ。
- 前記無機粒子は、金属酸化物粒子を含むことを特徴とする、請求項1〜3のいずれか1項に記載のリチウムイオン二次電池用セパレータ。
- TD、MDの熱収縮率がいずれも10%以下であることを特徴とする、請求項1〜4のいずれか1項に記載のリチウムイオン二次電池用セパレータ。
- 請求項1〜5のいずれか1項に記載のリチウムイオン二次電池用セパレータを備えることを特徴とする、リチウムイオン二次電池。
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