JP2014116186A - リチウムイオン電池セパレータおよびリチウムイオン電池セパレータ用塗工液 - Google Patents
リチウムイオン電池セパレータおよびリチウムイオン電池セパレータ用塗工液 Download PDFInfo
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- JP2014116186A JP2014116186A JP2012269220A JP2012269220A JP2014116186A JP 2014116186 A JP2014116186 A JP 2014116186A JP 2012269220 A JP2012269220 A JP 2012269220A JP 2012269220 A JP2012269220 A JP 2012269220A JP 2014116186 A JP2014116186 A JP 2014116186A
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- Prior art keywords
- lithium ion
- ion battery
- battery separator
- salt
- separator
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- 239000011248 coating agent Substances 0.000 title claims abstract description 44
- 239000007788 liquid Substances 0.000 title claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 37
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 37
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 37
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 37
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 28
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- JSYPRLVDJYQMAI-ODZAUARKSA-N (z)-but-2-enedioic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)\C=C/C(O)=O JSYPRLVDJYQMAI-ODZAUARKSA-N 0.000 claims abstract description 17
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- -1 alkali metal salt Chemical class 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 239000004745 nonwoven fabric Substances 0.000 abstract description 25
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- 239000000178 monomer Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000011247 coating layer Substances 0.000 description 12
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 229910001593 boehmite Inorganic materials 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
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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 3
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- 159000000000 sodium salts Chemical class 0.000 description 3
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
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- 241000282320 Panthera leo Species 0.000 description 2
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- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
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- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
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- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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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- Cell Separators (AREA)
Abstract
【解決手段】少なくとも無機顔料とバインダーポリマーとマレイン酸−アクリル酸共重合物の塩とカルボキシメチルセルロースの塩とを含有してなるリチウムイオン電池セパレータ及びリチウムイオン電池セパレータ用塗工液、並びに、該塗工液を不織布に塗工、乾燥してなるリチウムイオン電池セパレータ。
【選択図】なし
Description
(1)少なくとも無機顔料とバインダーポリマーとマレイン酸−アクリル酸共重合物の塩とカルボキシメチルセルロースの塩とを含有することを特徴とするリチウムイオン電池セパレータ、
(2)上記カルボキシメチルセルロースの塩がカルボキシメチルセルロースのアルカリ金属塩である上記(1)のリチウムイオン電池セパレータ、
(3)少なくとも無機顔料とバインダーポリマーとマレイン酸−アクリル酸共重合物の塩とカルボキシメチルセルロースの塩とを含有することを特徴とするリチウムイオン電池セパレータ用塗工液、
(4)上記カルボキシメチルセルロースの塩がカルボキシメチルセルロースのアルカリ金属塩である上記(3)のリチウムイオン電池セパレータ用塗工液、
(5)上記(3)又は(4)のリチウムイオン電池セパレータ用塗工液を多孔質基材に塗工、乾燥してなるリチウムイオン電池セパレータ、
を見出した。
繊度0.06dtex(平均繊維径2.4μm)、繊維長3mmの配向結晶化ポリエチレンテレフタレート(PET)系短繊維45質量部と繊度0.1dtex(平均繊維径3.0μm)、繊維長3mmの配向結晶化PET系短繊維15質量部と繊度0.2dtex(平均繊維径4.3μm)、繊維長3mmの単一成分型バインダー用PET系短繊維(軟化点120℃、融点230℃)40質量部とを一緒に混合し、パルパーにより水中で離解させ、アジテーターによる撹拌のもと、濃度1質量%の均一な抄造用スラリーを調製した。円網抄紙機を用い、この抄造用スラリーを湿式方式で抄き上げ、120℃のシリンダードライヤーによって、バインダー用PET系短繊維を接着させて不織布強度を発現させ、目付15.2g/m2の不織布とした。更に、この不織布を金属ロール−金属ロールからなる1ニップの熱カレンダーを使用して、ロール温度185℃、線圧740N/cm、搬送速度20m/分で加熱処理を実施し、厚み27μmの不織布を作製した。
アルミナ水和物A(ベーマイト、ナバルテック社製、商品名:APYRAL(登録商標)−AOH100XP)を固形分換算で100質量部、花王社製ポイズ(登録商標)520を固形分換算で0.3質量部をホモジナイザーにて混合、撹拌し、次いでカルボキシメチルセルロースナトリウム塩(1質量%水溶液B粘度7000mPa・s、エーテル化度0.7)を固形分換算で0.7質量部を混合、撹拌し、次にスチレンブタジエンラテックスを固形分換算で3.5質量部を混合、撹拌し、更にイオン交換水を加えて、固形分濃度25質量%の塗工液Aを作製した。上記熱カレンダー処理後の不織布に、グラビアコーターにて、乾燥固形分10.2g/m2となるように、不織布片面にこの塗工液を均一に塗工して、厚み30.2μmのリチウムイオン電池セパレータを得た。
実施例1において花王社製ポイズ(登録商標)520の代わりに花王社製ポイズ(登録商標)532Aを用いた以外は、実施例1と同様にして塗工液Bを調製、塗工し、塗工層の乾燥固形分10.5g/m2、厚み31.0μmのリチウムイオン電池セパレータを得た。
実施例1において花王社製ポイズ(登録商標)520の代わりに東亜合成社製アロン(登録商標)A−6310を用いた以外は、実施例1と同様にして塗工液Cを調製、塗工し、塗工層の乾燥固形分10.5g/m2、厚み31.0μmのリチウムイオン電池セパレータを得た。
実施例1において花王社製ポイズ(登録商標)520の代わりにライオン社製ポリティ(登録商標)A−550を用いた以外は、実施例1と同様にして塗工液Dを調製、塗工し、塗工層の乾燥固形分10.5g/m2、厚み31.0μmのリチウムイオン電池セパレータを得た。
実施例1においてアルミナ水和物Aの代わりにアルミナ水和物B(ベーマイト、大明化学社製、商品名:C20)を用いた以外は、実施例1と同様にして塗工液Eを調製、塗工し、塗工層の乾燥固形分10.2g/m2、厚み28.9μmのリチウムイオン電池セパレータを得た。
実施例1においてカルボキシメチルセルロースナトリウム塩の代わりにカルボキシメチルセルロースアンモニウム塩を用いた以外は、実施例1と同様にして塗工液Fを調製、塗工し、塗工層の乾燥固形分10.2g/m2、厚み28.9μmのリチウムイオン電池セパレータを得た。
実施例1において花王社製ポイズ(登録商標)520を使用しなかった以外は、実施例1と同様にして塗工液Gを調製、塗工し、塗工層の乾燥固形分10.1g/m2、厚み29.7μmのリチウムイオン電池セパレータを得た。
実施例1において花王社製ポイズ(登録商標)520の代わりにアロン(登録商標)T−50(東亜合成社製、ポリアクリル酸ナトリウム塩)を使用した以外は、実施例1と同様にして塗工液Hを調製、塗工し、塗工層の乾燥固形分10.1g/m2、厚み30.8μmのリチウムイオン電池セパレータを得た。
実施例1においてカルボキシメチルセルロースナトリウム塩を使用しなかった以外は、実施例1と同様にして塗工液Iを調製、塗工し、塗工層の乾燥固形分10.4g/m2、厚み31.6μmのリチウムイオン電池セパレータを得た。
実施例及び比較例で得られたリチウムイオン電池セパレータについて、下記の評価を行い、結果を表1に示した。
作製したセパレータについて、10cm×10cmの大きさでセパレータのピンホールの発生状況を透過光を用いて目視で確認し、次の度合いで評価した。
◎:全く透過光が観察されず、ピンホールの発生は見られない。
○:ピンホールの発生は見られないが、若干のムラが見られる。
×:ピンホールが見られる。
Claims (5)
- 少なくとも無機顔料とバインダーポリマーとマレイン酸−アクリル酸共重合物の塩とカルボキシメチルセルロースの塩とを含有することを特徴とするリチウムイオン電池セパレータ。
- 該カルボキシメチルセルロースの塩がカルボキシメチルセルロースのアルカリ金属塩である請求項1記載のリチウムイオン電池セパレータ。
- 少なくとも無機顔料とバインダーポリマーとマレイン酸−アクリル酸共重合物の塩とカルボキシメチルセルロースの塩とを含有することを特徴とするリチウムイオン電池セパレータ用塗工液。
- 該カルボキシメチルセルロースの塩がカルボキシメチルセルロースのアルカリ金属塩である請求項3記載のリチウムイオン電池セパレータ用塗工液。
- 請求項3又は4記載のリチウムイオン電池セパレータ用塗工液を多孔質基材に塗工、乾燥してなるリチウムイオン電池セパレータ。
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CN107078299A (zh) * | 2014-10-31 | 2017-08-18 | 日本瑞翁株式会社 | 锂离子二次电池负极用糊组合物、锂离子二次电池负极用复合颗粒、锂离子二次电池负极用浆料组合物、锂离子二次电池用负极、以及锂离子二次电池 |
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CN107078299A (zh) * | 2014-10-31 | 2017-08-18 | 日本瑞翁株式会社 | 锂离子二次电池负极用糊组合物、锂离子二次电池负极用复合颗粒、锂离子二次电池负极用浆料组合物、锂离子二次电池用负极、以及锂离子二次电池 |
CN107078298A (zh) * | 2014-10-31 | 2017-08-18 | 日本瑞翁株式会社 | 锂离子二次电池正极用粘合剂组合物、锂离子二次电池正极用浆料组合物、锂离子二次电池用正极、及锂离子二次电池 |
CN107078299B (zh) * | 2014-10-31 | 2020-11-13 | 日本瑞翁株式会社 | 锂离子二次电池及其所用负极、负极用糊组合物、负极用复合颗粒、以及负极用浆料组合物 |
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CN115224436A (zh) * | 2022-07-20 | 2022-10-21 | 惠州锂威新能源科技有限公司 | 一种锂离子电池隔膜的制备方法 |
CN115224436B (zh) * | 2022-07-20 | 2023-08-01 | 惠州锂威新能源科技有限公司 | 一种锂离子电池隔膜的制备方法 |
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