JP5462016B2 - Binder for heat-resistant protective layer of secondary battery and composition for heat-resistant protective layer - Google Patents
Binder for heat-resistant protective layer of secondary battery and composition for heat-resistant protective layer Download PDFInfo
- Publication number
- JP5462016B2 JP5462016B2 JP2010025442A JP2010025442A JP5462016B2 JP 5462016 B2 JP5462016 B2 JP 5462016B2 JP 2010025442 A JP2010025442 A JP 2010025442A JP 2010025442 A JP2010025442 A JP 2010025442A JP 5462016 B2 JP5462016 B2 JP 5462016B2
- Authority
- JP
- Japan
- Prior art keywords
- protective layer
- heat
- resistant protective
- secondary battery
- binder
- 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.)
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- 239000011241 protective layer Substances 0.000 title claims description 72
- 239000011230 binding agent Substances 0.000 title claims description 39
- 239000000203 mixture Substances 0.000 title claims description 38
- 239000000178 monomer Substances 0.000 claims description 78
- 229920000642 polymer Polymers 0.000 claims description 46
- 239000004816 latex Substances 0.000 claims description 45
- 229920000126 latex Polymers 0.000 claims description 45
- 150000001993 dienes Chemical class 0.000 claims description 38
- 239000000945 filler Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 17
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 11
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 3
- 150000002500 ions Chemical class 0.000 claims 3
- 229910052744 lithium Inorganic materials 0.000 claims 3
- 238000006116 polymerization reaction Methods 0.000 description 42
- -1 etc. Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
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- 239000011149 active material Substances 0.000 description 8
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 8
- 229920003169 water-soluble polymer Polymers 0.000 description 8
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
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- 239000008151 electrolyte solution Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000001256 steam distillation Methods 0.000 description 6
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 229960005070 ascorbic acid Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
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- 238000010828 elution Methods 0.000 description 4
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
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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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、二次電池耐熱保護層用バインダーおよび耐熱保護層用組成物に関するものである。更に詳しくは、耐熱保護層フィラーとの結着能力に優れた二次電池耐熱保護層用バインダーおよび強固な結着能力を有した二次電池耐熱保護層用組成物に関するものである。 The present invention relates to a binder for a heat resistant protective layer for a secondary battery and a composition for a heat resistant protective layer. More specifically, the present invention relates to a secondary battery heat-resistant protective layer binder excellent in binding ability with a heat-resistant protective layer filler, and a secondary battery heat-resistant protective layer composition having strong binding ability.
リチウムイオン二次電池は、軽量でエネルギー密度が大きいことから、小型電子機器を初めとして、自動車あるいは住宅の電源としての活用が検討されており、安全性の更なる向上が要望されている。従来から、正負極間の短絡防止を目的に、無機フィラーを主剤とした保護層を電池内部に設けることが提案されている。
例えば、特開平９−１４７９１６号公報（特許文献１）では、無機フィラーと水溶性ポリマーから構成される保護層を電極上に設けることで、安全性に優れた非水二次電池が得られることが提案されている。また、ＷＯ２００９−０９６５２８号公報（特許文献２）では、無機フィラーおよびポリマーバインダーとして特定重合度の水溶性高分子および粒子状の非水溶性高分子を用いた耐熱保護層を電池内部に設けることによる短絡防止が提案されている。
Lithium ion secondary batteries are lightweight and have a high energy density. Therefore, their use as a power source for automobiles or houses, including small electronic devices, has been studied, and further improvements in safety are desired. Conventionally, for the purpose of preventing a short circuit between positive and negative electrodes, it has been proposed to provide a protective layer containing an inorganic filler as a main component inside the battery.
For example, in JP-A-9-147916 (Patent Document 1), a non-aqueous secondary battery excellent in safety can be obtained by providing a protective layer composed of an inorganic filler and a water-soluble polymer on an electrode. Has been proposed. In WO2009-096528 (Patent Document 2), a heat-resistant protective layer using a water-soluble polymer having a specific polymerization degree and a particulate water-insoluble polymer as an inorganic filler and a polymer binder is provided inside the battery. Short circuit prevention has been proposed.
しかしながら、上記特許文献１に記載の水溶性ポリマーや、特許文献２に記載のポリマーバインダーは、フィラー同士、およびフィラーと活物質層との結着力が不十分であり、耐熱保護層としての機能が不十分である。
そこで、本発明の目的は、フィラーや活物質層などとの結着力に優れた二次電池耐熱保護層用バインダーおよび耐熱保護層用組成物を提供することにある。
However, the water-soluble polymer described in Patent Document 1 and the polymer binder described in Patent Document 2 have insufficient bonding power between fillers and between the filler and the active material layer, and function as a heat-resistant protective layer. It is insufficient.
Then, the objective of this invention is providing the binder for secondary battery heat-resistant protective layers excellent in the binding power with a filler, an active material layer, etc., and the composition for heat-resistant protective layers.
上記した課題を解決するため、フィラーとバインダーを含有するリチウムイオン二次電池耐熱保護層において、該バインダーが、脂肪族共役ジエン系単量体とエチレン系不飽和カルボン酸単量体を含む単量体混合物を乳化重合して得られるカルボキシ変性ジエン系重合体ラテックスであり、ラテックス中の重合体粒子の数平均粒子径が５０〜２５０ｎｍであることを特徴としている。 In order to solve the above problems, a lithium ion secondary battery heat-resistant protective layer containing a filler and a binder, wherein the binder comprises an aliphatic conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer Ri carboxy-modified diene polymer latex der obtained a body mixture by emulsion polymerization, the number-average particle size of the polymer particles in the latex is characterized by a 50 to 250 nm.
本発明の二次電池耐熱保護層用バインダーは、カルボキシ変性ジエン系重合体ラテックスであることを特徴としているため、フィラーや活物質層などとの結着力、および耐電解液性に優れており、その結果として短絡防止効果に優れた耐熱保護層を形成することができる。 Since the binder for the heat-resistant protective layer of the secondary battery of the present invention is characterized by being a carboxy-modified diene polymer latex, it has excellent binding power to the filler and active material layer, etc., and electrolyte resistance, As a result, it is possible to form a heat-resistant protective layer having an excellent short circuit prevention effect.
以下に本発明について詳しく説明する。
本発明におけるカルボキシ変性ジエン系重合体ラテックスは、脂肪族共役ジエン系単量体とエチレン系不飽和カルボン酸単量体を必須成分とし、任意成分として、これらと共重合可能な他の単量体を共重合して得られるものである。
The present invention is described in detail below.
The carboxy-modified diene polymer latex in the present invention comprises an aliphatic conjugated diene monomer and an ethylenically unsaturated carboxylic acid monomer as essential components, and other monomers copolymerizable with these as optional components. Is obtained by copolymerization.
脂肪族共役ジエン系単量体としては、１，３−ブタジエン、２−メチル−１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエン、２−クロル−１，３−ブタジエン、置換直鎖共役ペンタジエン類、置換および側鎖共役ヘキサジエン類などが挙げられ、１種または２種以上用いることができる。特に１，３−ブタジエンが好ましい。
脂肪族共役ジエン系単量体は、５〜８５重量％（全単量体の合計は１００重量％）であることが好ましく、さらに好ましくは、１０〜７０重量％である。５重量％未満であると、バインダーとして機能せず結着力に劣る傾向にあり、８５重量％を超えると、共重合体ラテックスの重合安定性が劣り凝集物が増えるなど生産性が劣る傾向があり、好ましくない。
Aliphatic conjugated diene monomers include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted Examples thereof include linear conjugated pentadienes, substituted and side chain conjugated hexadienes, and one or more kinds can be used. 1,3-butadiene is particularly preferable.
The aliphatic conjugated diene monomer is preferably 5 to 85% by weight (total of all monomers is 100% by weight), more preferably 10 to 70% by weight. If it is less than 5% by weight, it does not function as a binder and tends to be inferior in binding power. If it exceeds 85% by weight, the copolymer latex tends to be inferior in polymerization stability and productivity tends to be inferior. Is not preferable.
エチレン系不飽和カルボン酸単量体としては、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマール酸、イタコン酸などのモノまたはジカルボン酸（無水物）等が挙げられ、これらを１種または２種以上使用することができる。 Examples of the ethylenically unsaturated carboxylic acid monomer include mono- or dicarboxylic acids (anhydrides) such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. More than seeds can be used.
エチレン系不飽和カルボン酸単量体は０．１〜２０重量％（全単量体の合計は１００重量％）であることが好ましい。エチレン系不飽和カルボン酸単量体が０．１重量％未満ではフィラーの結着性が劣る傾向にあり、耐熱保護層の剥離が起こり、短絡防止機能を示さなくなるため、安全上問題である。また、２０重量％を超えるとラテックスの粘度が高くなり、共重合体ラテックス自身の取り扱い上の問題を生じる傾向にあるため好ましくない。さらに好ましくは０．５〜１０重量％である。 The ethylenically unsaturated carboxylic acid monomer is preferably 0.1 to 20% by weight (the total of all monomers is 100% by weight). If the amount of the ethylenically unsaturated carboxylic acid monomer is less than 0.1% by weight, the binding property of the filler tends to be inferior, the heat-resistant protective layer is peeled off, and the short-circuit preventing function is not exhibited, which is a safety problem. On the other hand, if it exceeds 20% by weight, the viscosity of the latex tends to be high, which tends to cause problems in handling the copolymer latex itself, which is not preferable. More preferably, it is 0.5 to 10% by weight.
これらと共重合可能な他の単量体としては、芳香族ビニル系単量体、シアン化ビニル系単量体、不飽和カルボン酸アルキルエステル系単量体、ヒドロキシアルキル基を含有する不飽和単量体、不飽和カルボン酸アミド系単量体等が挙げられ、これらは、１種または２種以上用いることができる。中でも、芳香族ビニル系単量体、シアン化ビニル系単量体および／または不飽和カルボン酸アルキルエステル系単量体を用いることで、フィラーや活物質層などとの結着力と、耐電解液性のバランスが良好となるため、これらを組み合わせることが好ましい。 Other monomers copolymerizable with these include aromatic vinyl monomers, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, and unsaturated monomers containing a hydroxyalkyl group. Examples thereof include monomers and unsaturated carboxylic acid amide monomers, and these can be used alone or in combination of two or more. Among them, by using an aromatic vinyl monomer, a vinyl cyanide monomer and / or an unsaturated carboxylic acid alkyl ester monomer, the binding force with a filler or an active material layer, etc. Since the balance of properties becomes good, it is preferable to combine them.
芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、メチルα−メチルスチレン、ビニルトルエンおよびジビニルベンゼン等が挙げられ、１種または２種以上用いることができる。特にスチレンが好ましい。 Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, methyl α-methylstyrene, vinyltoluene, divinylbenzene, and the like, and one or more can be used. Styrene is particularly preferable.
シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、α−クロルアクリロニトリル、α−エチルアクリロニトリルなどが挙げられ、１種または２種以上用いることができる。特にアクリロニトリル、メタクリロニトリルが好ましい。 Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile and the like, and one or more can be used. In particular, acrylonitrile and methacrylonitrile are preferable.
不飽和カルボン酸アルキルエステル系単量体としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、グリシジルメタクリレート、ジメチルフマレート、ジエチルフマレート、ジメチルマレエート、ジエチルマレエート、ジメチルイタコネート、モノメチルフマレート、モノエチルフマレート、２−エチルヘキシルアクリレート等が挙げられ、１種または２種以上用いることができる。特にメチルメタクリレート、ブチルアクリレートが好ましい。 Unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate , Monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate and the like, and one kind or two or more kinds can be used. In particular, methyl methacrylate and butyl acrylate are preferable.
ヒドロキシアルキル基を含有する不飽和単量体としては、β−ヒドロキシエチルアクリレート、β−ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート、ジ−（エチレングリコール）マレエート、ジ−（エチレングリコール）イタコネート、２−ヒドロキシエチルマレエート、ビス（２−ヒドロキシエチル）マレエート、２−ヒドロキシエチルメチルフマレートなどが挙げられ、１種または２種以上用いることができる。特にβ−ヒドロキシエチルアクリレート、β−ヒドロキシエチルメタクリレートが好ましい。 Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, and 3-chloro-2-hydroxypropyl. Methacrylate, di- (ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. More than one species can be used. In particular, β-hydroxyethyl acrylate and β-hydroxyethyl methacrylate are preferable.
不飽和カルボン酸アミド系単量体としては、アクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド等が挙げられ、１種または２種以上用いることができる。特にアクリルアミド、メタクリルアミドが好ましい。 Examples of unsaturated carboxylic acid amide monomers include acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylacrylamide, and the like, and one or more of them can be used. Particularly preferred are acrylamide and methacrylamide.
さらに、上記単量体の他に、エチレン、プロピレン、酢酸ビニル、プロピオン酸ビニル、塩化ビニル、塩化ビニリデン等、通常の乳化重合において使用される単量体は何れも使用可能である。 Further, in addition to the above monomers, any of the monomers used in ordinary emulsion polymerization such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride can be used.
脂肪族共役ジエン系単量体とエチレン性不飽和カルボン酸単量体の必須成分と共重合可能な他の単量体は、０〜９４．９重量％が好ましいが、さらに好ましくは５〜８９．５重量％（全単量体の合計は１００重量％）である。特に、芳香族ビニル系単量体、シアン化ビニル系単量体および／または不飽和カルボン酸アルキルエステル系単量体の合計は、５〜８５重量％、さらに好ましくは１０〜７５重量％（全単量体の合計は１００重量％）の範囲であることが好ましい。この範囲内にすることで、フィラーや活物質層などとの結着力と耐電解液性のバランスがより良好となる。 The other monomer copolymerizable with the essential component of the aliphatic conjugated diene monomer and the ethylenically unsaturated carboxylic acid monomer is preferably 0 to 94.9% by weight, more preferably 5 to 89%. 0.5% by weight (total of all monomers is 100% by weight). In particular, the total of the aromatic vinyl monomer, vinyl cyanide monomer and / or unsaturated carboxylic acid alkyl ester monomer is 5 to 85% by weight, more preferably 10 to 75% by weight (total The total of the monomers is preferably in the range of 100% by weight. By making it within this range, the balance between the binding force with the filler, the active material layer, and the like and the resistance to the electrolytic solution become better.
上述の単量体を乳化重合してカルボキシ変性ジエン系重合体ラテックスを製造するに際しては、常用の乳化剤、重合開始剤、還元剤、連鎖移動剤、酸化還元触媒、炭化水素系溶剤、電解質、重合促進剤、キレート剤等を使用することができる。 In producing a carboxy-modified diene polymer latex by emulsion polymerization of the above-mentioned monomers, conventional emulsifiers, polymerization initiators, reducing agents, chain transfer agents, redox catalysts, hydrocarbon solvents, electrolytes, polymerization Accelerators, chelating agents and the like can be used.
乳化剤としては、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤あるいはポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型等のノニオン性界面活性剤が挙げられ、これらを１種又は２種以上使用することができる。特に、アルキルベンゼンスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩が好ましい。 As an emulsifier, anionic surfactants such as sulfate esters of higher alcohols, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, sulfate esters of nonionic surfactants, etc. Examples thereof include nonionic surfactants such as an alkyl ester type, an alkyl phenyl ether type, and an alkyl ether type of polyethylene glycol, and one or more of these can be used. In particular, alkylbenzene sulfonate and alkyl diphenyl ether disulfonate are preferable.
重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の水溶性重合開始剤、クメンハイドロパーオキサイド、過酸化ベンゾイル、t−ブチルハイドロパーオキサイド、アセチルパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、１，１，３，３−テトラメチルブチルハイドロパーオキサイド等の油溶性重合開始剤を適宜用いることができる。特に過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウムの水溶性重合開始剤、クメンハイドロパーオキサイドの油溶性重合開始剤の使用が好ましい。 As the polymerization initiator, water-soluble polymerization initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, An oil-soluble polymerization initiator such as 1,1,3,3-tetramethylbutyl hydroperoxide can be appropriately used. In particular, water-soluble polymerization initiators such as potassium persulfate, sodium persulfate and ammonium persulfate and oil-soluble polymerization initiators of cumene hydroperoxide are preferred.
還元剤としては、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、亜ニチオン酸塩、ニチオン酸塩、チオ硫酸塩、ホルムアルデヒドスルホン酸塩、ベンズアルデヒドスルホン酸塩、また、Ｌ−アスコルビン酸、エリソルビン酸、酒石酸、クエン酸などのカルボン酸類及びその塩、更にはデキストロース、サッカロースなどの還元糖類、更にはジメチルアニリン、トリエタノールアミンなどのアミン類が挙げられる。特にＬ−アスコルビン酸、エリソルビン酸、が好ましい。 As a reducing agent, sulfite, bisulfite, pyrosulfite, nitrite, nithionate, thiosulfate, formaldehyde sulfonate, benzaldehyde sulfonate, L-ascorbic acid, erythorbic acid, tartaric acid And carboxylic acids such as citric acid and salts thereof, further reducing sugars such as dextrose and saccharose, and amines such as dimethylaniline and triethanolamine. In particular, L-ascorbic acid and erythorbic acid are preferable.
連鎖移動剤としては、ｎ−ヘキシルメルカプタン、ｎ−オクチルメルカプタン、ｔ−オクチルメルカプタン、ｎ−ドデシルメルカプタン、ｔ−ドデシルメルカプタン、ｎ−ステアリルメルカプタン等のアルキルメルカプタン、ジメチルキサントゲンジサルファイド、ジイソプロピルキサントゲンジサルファイド等のキサントゲン化合物、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラメチルチウラムモノスルフィド等のチウラム系化合物、２，６−ジ−ｔ−ブチル−４−メチルフェノール、スチレン化フェノール等のフェノール系化合物、アリルアルコール等のアリル化合物、ジクロルメタン、ジブロモメタン、四臭化炭素等のハロゲン化炭化水素化合物、α−ベンジルオキシスチレン、α−ベンジルオキシアクリロニトリル、α−ベンジルオキシアクリルアミド等のビニルエーテルなどの他、ターピノレン、トリフェニルエタン、ペンタフェニルエタン、アクロレイン、メタアクロレイン、チオグリコール酸、チオリンゴ酸、２−エチルヘキシルチオグリコレート、α−メチルスチレンダイマー等が挙げられ、これらを１種または２種以上使用することができる。特に、ｎ−オクチルメルカプタン、ｔ−ドデシルメルカプタン、α−メチルスチレンダイマーが好ましい。これらの連鎖移動剤の量は特に限定されないが、通常、単量体１００重量部に対して０〜５重量部にて使用される。 Examples of chain transfer agents include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-stearyl mercaptan, dimethylxanthogen disulfide, diisopropylxanthogen disulfide, etc. Xanthogen compounds, tetramethylthiuram disulfide, tetraethylthiuram disulfide, thiuram compounds such as tetramethylthiuram monosulfide, phenol compounds such as 2,6-di-t-butyl-4-methylphenol, styrenated phenol, allyl alcohol Allyl compounds such as dichloromethane, dibromomethane, halogenated hydrocarbon compounds such as carbon tetrabromide, α-benzyloxystyrene, α-benzyloxy In addition to vinyl ethers such as acrylonitrile and α-benzyloxyacrylamide, terpinolene, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexylthioglycolate, α-methylstyrene dimer, etc. 1 type, or 2 or more types can be used. In particular, n-octyl mercaptan, t-dodecyl mercaptan, and α-methylstyrene dimer are preferable. The amount of these chain transfer agents is not particularly limited, but is usually 0 to 5 parts by weight with respect to 100 parts by weight of the monomer.
また、重合に際してペンテン、ヘキセン、ヘプテン、シクロペンテン、シクロヘキセン、シクロヘプテン、４−メチルシクロヘキセン、１−メチルシクロヘキセン等の不飽和炭化水素を使用しても良い。特に、沸点が適度に低く、重合終了後に水蒸気蒸留などによって回収、再利用しやすいシクロヘキセンが、本発明の目的とは異なるものの、環境問題の観点から好適である。 In the polymerization, unsaturated hydrocarbons such as pentene, hexene, heptene, cyclopentene, cyclohexene, cycloheptene, 4-methylcyclohexene, and 1-methylcyclohexene may be used. In particular, cyclohexene, which has a moderately low boiling point and can be easily recovered and reused after the completion of polymerization by steam distillation or the like, is preferable from the viewpoint of environmental problems although it differs from the object of the present invention.
さらに、カルボキシ変性ジエン系重合体ラテックスには、必要に応じて、老化防止剤、防腐剤、分散剤、増粘剤などを適宜添加することができる。 Furthermore, an anti-aging agent, a preservative, a dispersant, a thickener, and the like can be appropriately added to the carboxy-modified diene polymer latex as necessary.
カルボキシ変性ジエン系重合体ラテックス重合方法としては、一段重合、二段重合、多段階重合、シード重合法等何れを採用してもよい。また、重合における各種成分の添加方法についても特に制限されるものではなく、一括添加方法、分割添加方法、連続添加方法、パワーフィード法の何れも採用することができる。 As the carboxy-modified diene polymer latex polymerization method, any one of single-stage polymerization, two-stage polymerization, multi-stage polymerization, seed polymerization method and the like may be adopted. Further, the addition method of various components in the polymerization is not particularly limited, and any of a batch addition method, a divided addition method, a continuous addition method, and a power feed method can be adopted.
カルボキシ変性ジエン系重合体ラテックスのガラス転移温度（Ｔｇ）には特に制限はないが、−６０〜７０℃であることが好ましい。ガラス転移温度が−６０℃未満では、耐電解液性に劣る傾向があり、好ましくない。ガラス転移温度が７０℃を超えると、フィラーとの結着性が劣ることで耐熱保護層の剥離が発生し、短絡防止機能を示さなくなる傾向があるため好ましくない。 The glass transition temperature (Tg) of the carboxy-modified diene polymer latex is not particularly limited, but is preferably −60 to 70 ° C. If the glass transition temperature is less than −60 ° C., the resistance to electrolytic solution tends to be inferior, which is not preferable. When the glass transition temperature exceeds 70 ° C., the heat-resistant protective layer is peeled off due to poor binding properties with the filler, and this is not preferable because it does not exhibit a short-circuit preventing function.
カルボキシ変性ジエン系重合体ラテックスにおける重合体粒子の数平均粒子径には特に制限はないが、５０〜２５０ｎｍであることが好ましい。数平均粒子径が５０ｎｍ未満では、ラテックスの粘度が高くなり、共重合体ラテックス自身の取り扱い上の問題を生じるため好ましくない。数平均粒子径が２５０ｎｍを超えると、フィラーとの結着性が劣ることで耐熱保護層の剥離が発生し、短絡防止機能を示さなくなる傾向があるため好ましくない。 The number average particle diameter of the polymer particles in the carboxy-modified diene polymer latex is not particularly limited, but is preferably 50 to 250 nm. If the number average particle diameter is less than 50 nm, the viscosity of the latex is increased, which causes a problem in handling the copolymer latex itself, which is not preferable. When the number average particle diameter exceeds 250 nm, the heat-resistant protective layer is peeled off due to poor binding properties with the filler, and the short-circuit preventing function tends not to be exhibited.
カルボキシ変性ジエン系重合体ラテックスにおける重合体のトルエン不溶分（ゲル含有量）には特に制限はないが、２０重量％以上、さらに４０〜９９重量％、特に６０〜９８重量％であることが好ましい。トルエン不溶分が２０重量％未満では、耐電解液性に劣る傾向があり、好ましくない。 The toluene-insoluble content (gel content) of the polymer in the carboxy-modified diene polymer latex is not particularly limited, but is preferably 20% by weight or more, more preferably 40 to 99% by weight, and particularly preferably 60 to 98% by weight. . When the toluene insoluble content is less than 20% by weight, the electrolytic solution resistance tends to be inferior, which is not preferable.
また、本発明の二次電池耐熱保護層用バインダーは、耐熱保護層中において、フィラー粒子同士、フィラー粒子と正極活物質塗工層表面、フィラー粒子と負極活物質塗工層表面、または、フィラー粒子とセパレータ表面とを結着させるバインダーとして機能する。
具体的には、カルボキシ変性ジエン系重合体ラテックスを、フィラーに配合することにより、二次電池耐熱保護層用組成物が調製される。
Further, the binder for the heat-resistant protective layer of the secondary battery according to the present invention includes the filler particles, the filler particles and the positive electrode active material coating layer surface, the filler particles and the negative electrode active material coating layer surface, or filler in the heat-resistant protective layer. It functions as a binder that binds the particles to the separator surface.
Specifically, a composition for a secondary battery heat-resistant protective layer is prepared by blending a carboxy-modified diene polymer latex with a filler.
耐熱保護層の主剤となるフィラーとしては、酸化アルミニウム（アルミナ）、酸化マグネシウム、二酸化チタン、タルクなどの無機物やアラミドなどの有機物が挙げられ、特に無機フィラーである酸化アルミニウム（アルミナ）が好ましい。酸化アルミニウム（アルミナ）の粒子径（体積基準Ｄ５０）には、特に制限はないが、０．１〜１０μｍであることが、好ましい。 Examples of the filler used as the main component of the heat-resistant protective layer include inorganic substances such as aluminum oxide (alumina), magnesium oxide, titanium dioxide, and talc, and organic substances such as aramid, and aluminum oxide (alumina) that is an inorganic filler is particularly preferable. The particle size of the aluminum oxide (alumina) (volume basis D 50), is not particularly limited, it is, preferably 0.1 to 10 [mu] m.
本発明の二次電池耐熱保護層用組成物（第二発明）とは、フィラー、バインダーを含有する二次電池耐熱保護層において、該フィラーが無機フィラーであり、かつバインダーがカルボキシ変性ジエン系重合体ラテックスであることを特徴とする二次電池耐熱保護層用組成物である。二次電池耐熱保護層用組成物を構成するフィラーおよびバインダーの配合比率には特に制限はないが、フィラー１００重量部に対して二次電池耐熱保護層用バインダーを、固形分換算で０．１〜１０重量部、好ましくは０．５〜５重量部となるように配合する。
フィラー１００重量部に対するバインダー（固形分）が、０．１重量部未満では、良好な結着力が得られず、耐熱保護層の剥離が起こり、短絡防止機能を示さなくなる可能性が高く、１０重量部を超えると、二次電池として組み立てたときの体積エネルギー密度に不利となるため、好ましくない。
The composition for a secondary battery heat-resistant protective layer according to the present invention (second invention) is a secondary battery heat-resistant protective layer containing a filler and a binder, wherein the filler is an inorganic filler and the binder is a carboxy-modified diene-based heavy. It is a composition for a secondary battery heat-resistant protective layer, which is a combined latex. Although there is no restriction | limiting in particular in the mixture ratio of the filler and binder which comprise the composition for secondary battery heat-resistant protective layers, the binder for secondary battery heat-resistant protective layers is 0.1 in conversion of solid content with respect to 100 weight part of fillers. -10 parts by weight, preferably 0.5 to 5 parts by weight.
When the binder (solid content) with respect to 100 parts by weight of the filler is less than 0.1 parts by weight, it is highly possible that a good binding force cannot be obtained, the heat-resistant protective layer is peeled off, and the short-circuit preventing function is not exhibited. Exceeding the portion is not preferable because it is disadvantageous for volume energy density when assembled as a secondary battery.
二次電池耐熱保護層用組成物には、フィラーならびにバインダー以外に、必要により、水溶性高分子、分散剤、安定化剤などの各種添加剤を添加することができる。水溶性高分子としては、例えば、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、ポリアクリル酸（塩）、酸化スターチ、リン酸化スターチ、カゼインなどが挙げられ、分散剤としては、例えば、ヘキサメタリン酸ソーダ、トリポリリン酸ソーダ、ピロリン酸ソーダ、ポリアクリル酸ソーダなどが挙げられ、安定化剤としては、例えば、ノニオン性、アニオン性界面活性剤などが挙げられる。 In addition to the filler and the binder, various additives such as a water-soluble polymer, a dispersant, and a stabilizer can be added to the composition for a secondary battery heat-resistant protective layer, if necessary. Examples of the water-soluble polymer include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (salt), oxidized starch, phosphorylated starch, and casein. Examples of the dispersant include hexametalin. Examples include acid soda, sodium tripolyphosphate, sodium pyrophosphate, and sodium polyacrylate, and examples of the stabilizer include nonionic and anionic surfactants.
二次電池耐熱保護層用組成物に水溶性高分子を添加する場合には、例えば、フィラー１００重量部に対して固形分換算で、０．０５〜１０重量部、好ましくは、０．１〜５重量部の割合で配合する。 In the case of adding a water-soluble polymer to the composition for a secondary battery heat-resistant protective layer, for example, 0.05 to 10 parts by weight, preferably 0.1 to 0.1 parts by weight in terms of solid content with respect to 100 parts by weight of the filler. It mix | blends in the ratio of 5 weight part.
本発明の二次電池耐熱保護層用組成物は、正極活物質層表面上、負極活物質層表面上、セパレータ表面上の、少なくともいずれかに塗布、乾燥することにより、二次電池耐熱保護層として設けられる。 The composition for a secondary battery heat-resistant protective layer of the present invention is applied to at least one of the surface of the positive electrode active material layer, the surface of the negative electrode active material layer, and the surface of the separator. It is provided as.
また、本発明の二次電池耐熱保護層用組成物を電極またはセパレータに塗布する方法としては、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法など任意のコーターヘッドを用いることができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できる。乾燥温度は、５０℃以上で行うことが好ましい。 In addition, as a method of applying the composition for heat-resistant protective layer of the secondary battery of the present invention to an electrode or a separator, any coater head such as a reverse roll method, a comma bar method, a gravure method, an air knife method can be used, As the method, standing drying, blower dryer, hot air dryer, infrared heater, far-infrared heater and the like can be used. The drying temperature is preferably 50 ° C. or higher.
本発明の二次電池耐熱保護層用バインダーおよび組成物を用いた電池を製造する際に使用される集電体、セパレータ、電解液、端子、絶縁体、電池容器等については、既存のものが特に制限無く使用可能である。 Regarding current collectors, separators, electrolytes, terminals, insulators, battery containers, and the like used in manufacturing a battery using the binder and composition for a heat-resistant secondary battery layer of the present invention, existing ones It can be used without any particular restrictions.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明はその要旨を変更しない限り、これらの実施例に限定されるものではない。なお実施例中、割合を示す部および％は重量基準によるものである。また実施例における諸物性の評価は次の方法に拠った。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these Examples, unless the summary is changed. In the examples, parts and percentages indicating percentages are based on weight. In addition, various physical properties in the examples were evaluated by the following methods.
カルボキシ変性ジエン系重合体ラテックス中の重合体のガラス転移温度（Ｔｇ）の測定
重合体ラテックスをガラス板上に流延し７０℃で４時間乾燥してフィルムを作製し、示差走査熱量計（セイコーインスツルメンツ社製 ＤＳＣ６２００）を用いて昇温速度１０℃／ｍｉｎにて測定した。
Measurement of glass transition temperature (Tg) of polymer in carboxy-modified diene polymer latex Casting polymer latex on a glass plate and drying at 70C for 4 hours to produce a film, differential scanning The measurement was performed at a heating rate of 10 ° C./min using a calorimeter (DSC6200 manufactured by Seiko Instruments Inc.).
カルボキシ変性ジエン系重合体ラテックス中の重合体粒子の数平均粒子径（μｍ）の測定
数平均粒子径を動的光散乱法により測定した。測定に際しては、大塚電子株式会社製ＦＰＡＲ−１０００を使用した。
Measurement of number average particle diameter (μm) of polymer particles in carboxy-modified diene polymer latex The number average particle diameter was measured by a dynamic light scattering method. In the measurement, FPAR-1000 manufactured by Otsuka Electronics Co., Ltd. was used.
カルボキシ変性ジエン系重合体ラテックス中の重合体のトルエン不溶分（ゲル含有量）の測定
温度８０℃の雰囲気にてラテックスフィルムを作成した。その後ラテックスフィルムを約１ｇ秤量し、これを４００ｍｌのトルエンに入れ４８時間膨潤溶解させた。その後、これを３００メッシュの金網で濾過し、金網に捕捉されたトルエン不溶部を乾燥後、秤量し、下記式より重量％で算出した。
ゲル含有量（％）＝１００×（トルエン不溶部重量）／（溶解前のフィルム重量）
Measurement of toluene insoluble content (gel content) of polymer in carboxy-modified diene polymer latex A latex film was prepared in an atmosphere at a temperature of 80C. Thereafter, about 1 g of the latex film was weighed and placed in 400 ml of toluene to swell and dissolve for 48 hours. Thereafter, this was filtered through a 300-mesh wire mesh, and the toluene-insoluble portion captured by the wire mesh was dried and weighed, and the weight percent was calculated from the following formula.
Gel content (%) = 100 × (toluene insoluble part weight) / (film weight before dissolution)
カルボキシ変性ジエン系重合体ラテックスＡ，Ｅ，Ｆ，Ｇ，Ｈ，Ｋ，Ｍの作製
耐圧性の重合反応器に、窒素雰囲気下で、表１および２の「添加１」に示す各単量体、ｔ−ドデシルメルカプタン、シクロヘキセン、ドデシルベンゼンスルホン酸ナトリウム、純水を加えて７０℃に昇温した後に、過硫酸カリウムを加えて重合を開始した。重合開始から２時間後に表１および２の「添加２」に示す各単量体、ｔ−ドデシルメルカプタン、ドデシルベンゼンスルホン酸ナトリウム、純水を添加し、重合を継続した。重合開始から８時間以降に、重合転化率が９７％を超えたことを確認して、重合停止剤を添加し、内温を３５℃以下に冷却後、水酸化ナトリウム水溶液でｐＨを７.５に調整した。その後に、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去して、表１および２に示すガラス転移温度、数平均粒子径、トルエン不溶分の重合体ラテックスＡ，Ｅ，Ｆ，Ｇ，Ｈ，Ｋ，Ｍを得た。
Preparation of Carboxy-modified Diene Polymer Latex A, E, F, G, H, K, M Each monomer shown in “Addition 1” in Tables 1 and 2 in a pressure resistant polymerization reactor in a nitrogen atmosphere , T-dodecyl mercaptan, cyclohexene, sodium dodecylbenzenesulfonate and pure water were added and the temperature was raised to 70 ° C., and then potassium persulfate was added to initiate polymerization. Two hours after the start of polymerization, each monomer, t-dodecyl mercaptan, sodium dodecylbenzenesulfonate, and pure water shown in “Addition 2” in Tables 1 and 2 were added, and polymerization was continued. After 8 hours from the start of polymerization, it was confirmed that the polymerization conversion rate exceeded 97%, a polymerization terminator was added, the internal temperature was cooled to 35 ° C. or lower, and the pH was adjusted to 7.5 with an aqueous sodium hydroxide solution. Adjusted. Thereafter, unreacted monomers and other low-boiling compounds are removed by steam distillation, and the glass transition temperatures, number average particle sizes, and toluene-insoluble polymer latexes A, E, F, and Tables shown in Tables 1 and 2 are used. G, H, K, M were obtained.
カルボキシ変性ジエン系重合体ラテックスＢ，Ｉ，Ｊの作製
耐圧性の重合反応器に、窒素雰囲気下で、表１および２の「添加1」に示す各単量体、α-メチルスチレンダイマー、アルキルジフェニルエーテルジスルホン酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、硫酸第一鉄、純水を加えて３５℃に昇温した後に、クメンハイドロパーオキサイド、Ｌ−アスコルビン酸を加えて重合を開始した。重合開始から２０時間以降に、重合転化率が９７％を超えたことを確認して、重合停止剤を添加し、内温を３５℃以下に冷却後、アンモニア水溶液でｐＨを７.５に調整した。その後に、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去して、表１および２に示すガラス転移温度、数平均粒子径、トルエン不溶分の重合体ラテックスＢ，Ｉ，Ｊを得た。
Preparation of Carboxy-modified Diene Polymer Latex B, I, J In a pressure-resistant polymerization reactor, each monomer, α-methylstyrene dimer and alkyl listed in “Addition 1” in Tables 1 and 2 are placed under a nitrogen atmosphere. Sodium diphenyl ether disulfonate, sodium dodecylbenzenesulfonate, ferrous sulfate, and pure water were added and the temperature was raised to 35 ° C., and then cumene hydroperoxide and L-ascorbic acid were added to initiate polymerization. After 20 hours from the start of polymerization, after confirming that the polymerization conversion rate exceeded 97%, a polymerization terminator was added, the internal temperature was cooled to 35 ° C or lower, and the pH was adjusted to 7.5 with an aqueous ammonia solution. did. Thereafter, unreacted monomers and other low-boiling compounds are removed by steam distillation, and the glass transition temperatures, number average particle diameters, and toluene-insoluble polymer latexes B, I, and J shown in Tables 1 and 2 are obtained. Obtained.
カルボキシ変性ジエン系重合体ラテックスＣの作製
耐圧性の重合反応器に、窒素雰囲気下で、表１の「添加１」に示す各単量体、ｔ−ドデシルメルカプタン、ドデシルベンゼンスルホン酸ナトリウム、純水を加えて６０℃に昇温した後に、過硫酸カリウムを加えて重合を開始した。重合開始から３時間後に温度を８０℃に昇温し、表１の「添加２」に示す各単量体、ｔ−ドデシルメルカプタン、ドデシルベンゼンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、純水を添加し、重合を継続した。重合開始から７時間以降に、重合転化率が９７％を超えたことを確認して、重合停止剤を添加し、内温を３５℃以下に冷却後、水酸化カリウム水溶液でｐＨを７.５に調整した。その後に、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去して、表１に示すガラス転移温度、数平均粒子径、トルエン不溶分の重合体ラテックスＣを得た。
Preparation of Carboxy-modified Diene Polymer Latex C In a pressure resistant polymerization reactor, each monomer, t-dodecyl mercaptan, sodium dodecylbenzenesulfonate, pure water shown in “Addition 1” in Table 1 in a nitrogen atmosphere. And the temperature was raised to 60 ° C., and then potassium persulfate was added to initiate polymerization. 3 hours after the start of polymerization, the temperature was raised to 80 ° C., and each monomer, t-dodecyl mercaptan, sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, and pure water shown in Table 1 “Addition 2” were added. The polymerization was continued. After 7 hours from the start of polymerization, it was confirmed that the polymerization conversion rate exceeded 97%, a polymerization terminator was added, the internal temperature was cooled to 35 ° C. or lower, and the pH was adjusted to 7.5 with an aqueous potassium hydroxide solution. Adjusted. Thereafter, unreacted monomers and other low-boiling compounds were removed by steam distillation to obtain a polymer latex C having a glass transition temperature, a number average particle diameter, and a toluene-insoluble content shown in Table 1.
カルボキシ変性ジエン系重合体ラテックスＤの作製
耐圧性の重合反応器に、窒素雰囲気下で、表１の「添加1」に示す各単量体、ｔ−ドデシルメルカプタン、ドデシルベンゼンスルホン酸ナトリウム、硫酸第一鉄、純水を加えて４０℃に昇温した後に、クメンハイドロパーオキサイド、Ｌ−アスコルビン酸を加えて重合を開始した。重合開始から１５時間以降に、重合転化率が９７％を超えたことを確認して、重合停止剤を添加し、内温を３５℃以下に冷却後、水酸化カリウム水溶液及びアンモニア水溶液でｐＨを７.５に調整した。その後に、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去して、表１に示すガラス転移温度、数平均粒子径、トルエン不溶分の重合体ラテックスＤを得た。
Preparation of Carboxy-modified Diene Polymer Latex D In a pressure resistant polymerization reactor, each monomer, t-dodecyl mercaptan, sodium dodecylbenzenesulfonate, sulfuric acid After adding ferrous iron and pure water and raising the temperature to 40 ° C., cumene hydroperoxide and L-ascorbic acid were added to initiate polymerization. After 15 hours from the start of the polymerization, after confirming that the polymerization conversion rate exceeded 97%, a polymerization terminator was added, the internal temperature was cooled to 35 ° C. or lower, and the pH was adjusted with an aqueous potassium hydroxide solution and an aqueous ammonia solution. Adjusted to 7.5. Thereafter, unreacted monomers and other low-boiling compounds were removed by steam distillation to obtain a polymer latex D having a glass transition temperature, a number average particle diameter, and a toluene-insoluble content shown in Table 1.
カルボキシ変性ジエン系重合体ラテックスＬの作製
耐圧性の重合反応器に、窒素雰囲気下で、表２の「添加１」に示す各単量体、ドデシルベンゼンスルホン酸ナトリウム、純水を加えて６０℃に昇温した後に、過硫酸カリウムを加えて重合を開始した。重合開始から２時間後に表２の「添加２」に示す各単量体、ドデシルベンゼンスルホン酸ナトリウム、純水を添加し、重合を継続した。重合開始から８時間以降に、重合転化率が９７％を超えたことを確認して、重合停止剤を添加し、内温を３５℃以下に冷却後、アンモニア水溶液でｐＨを７.５に調整した。その後に、水蒸気蒸留により未反応単量体および他の低沸点化合物を除去して、表２に示すガラス転移温度、数平均粒子径、トルエン不溶分の重合体ラテックスＬを得た。
Preparation of Carboxy-modified Diene Polymer Latex L In a nitrogen atmosphere, each monomer, sodium dodecylbenzenesulfonate and pure water shown in “Addition 1” in Table 2 were added to a pressure resistant polymerization reactor at 60 ° C. After the temperature was raised to 1, potassium persulfate was added to initiate polymerization. Two hours after the start of polymerization, each monomer shown in “Addition 2” in Table 2, sodium dodecylbenzenesulfonate, and pure water were added, and polymerization was continued. After 8 hours from the start of polymerization, confirm that the polymerization conversion rate exceeded 97%, add a polymerization terminator, cool the internal temperature to 35 ° C or lower, and adjust the pH to 7.5 with aqueous ammonia solution did. Thereafter, unreacted monomers and other low-boiling compounds were removed by steam distillation to obtain a polymer latex L having a glass transition temperature, a number average particle diameter, and a toluene-insoluble content shown in Table 2.
耐熱保護層用組成物の作成
フィラーとしてα−アルミナ「ＡＫＰ−３０００（住友化学株式会社製、平均粒子径（体積基準Ｄ５０）０．４〜０．６μｍ）」を１００部、表３に示す水溶性高分子を固形分で１部、バインダーとして重合体ラテックスＡ〜Ｍを固形分で３部とを全固形分が６０％となるように適量の水を加えて、混合分散し、耐熱保護層用組成物１〜１６を調整した。なお、耐熱保護層用組成物１７は、水溶性高分子を３部配合したこと、バインダーとして重合体ラテックスＡを含まないこと以外は、組成物２と同様にして調整した。
Table 3 shows 100 parts of α-alumina “AKP-3000 (manufactured by Sumitomo Chemical Co., Ltd., average particle diameter (volume basis D 50 ) 0.4 to 0.6 μm)” as a filler for preparing the heat-resistant protective layer composition. Add 1 part of water-soluble polymer in solid content, 3 parts of polymer latex A to M as binder and 3 parts in solid content, add appropriate amount of water so that the total solid content is 60%, mix and disperse, heat protection Layer compositions 1-16 were prepared. The composition 17 for heat-resistant protective layer was prepared in the same manner as the composition 2 except that 3 parts of a water-soluble polymer was blended and the polymer latex A was not included as a binder.
耐熱保護層を有した負極の作成
負極活物質として天然黒鉛を１００部、増粘剤としてカルボキシメチルセルロース水溶液を固形分で１部、結着剤として共重合体ラテックス「ＡＬ−１００１（日本エイアンドエル株式会社製）」を固形分で２部とを全固形分が４０％となるように適量の水を加えて混練し、負極用組成物を調製した。得られたスラリーを集電体として厚さ２０μｍの銅箔の両面に塗布乾燥後、室温でプレスして、塗工層の厚みが８０μｍの負極を得た。
こうして得られた両面の活物質塗工層表面上に、上記の耐熱保護層用組成物１〜１７を塗布乾燥し、耐熱保護層の厚みが１０μｍの負極を得た。
Preparation of negative electrode having heat-resistant protective layer 100 parts of natural graphite as a negative electrode active material, 1 part of carboxymethyl cellulose aqueous solution as a thickener, and copolymer latex “AL-1001 (Nippon A & L Co., Ltd.) as a binder. 2) in a solid content and kneaded with an appropriate amount of water so that the total solid content is 40%, to prepare a negative electrode composition. The obtained slurry was applied to both sides of a 20 μm thick copper foil as a current collector and then dried at room temperature to obtain a negative electrode having a coating layer thickness of 80 μm.
On the surfaces of the active material coating layers thus obtained, the compositions 1 to 17 for the heat-resistant protective layer were applied and dried to obtain a negative electrode having a heat-resistant protective layer having a thickness of 10 μm.
耐熱保護層を有した正極の作成
正極活物質としてＬｉＣｏＯ２を１００部、導電剤としてアセチレンブラックを５部、結着剤として共重合体ラテックス「ＡＬ−１００１（日本エイアンドエル株式会社製）」を固形分で２部とを全固形分が４０％となるように適量の水を加えて混練し、正極用組成物を調製した。得られたスラリーを集電体として厚さ２０μｍのアルニミウム箔の両面に塗布乾燥後、室温でプレスして、塗工層の厚みが８０μｍの正極を得た。
こうして得られた両面の活物質塗工層表面上に、上記の耐熱保護層用組成物１〜１７を塗布乾燥し、耐熱保護層の厚みが１０μｍの正極を得た。
Preparation of positive electrode having heat-resistant protective layer 100 parts of LiCoO 2 as a positive electrode active material, 5 parts of acetylene black as a conductive agent, and solid copolymer latex “AL-1001 (manufactured by Nippon A & L Co., Ltd.)” as a binder An appropriate amount of water was added and kneaded so that the total solid content would be 40%, and a composition for positive electrode was prepared. The obtained slurry was applied to both sides of an aluminum foil having a thickness of 20 μm as a current collector, dried and then pressed at room temperature to obtain a positive electrode having a coating layer thickness of 80 μm.
On the surfaces of the active material coating layers on both sides thus obtained, the compositions 1 to 17 for the heat-resistant protective layer were applied and dried to obtain a positive electrode having a heat-resistant protective layer having a thickness of 10 μm.
耐熱保護層を有したセパレータの作成
厚みが２０μｍのポリエチレン製多孔膜である市販のセパレータ両面の表面上に、上記の耐熱保護層用組成物１〜１７を塗布乾燥し、耐熱保護層の厚みが１０μｍの耐熱保護層を有するセパレータを得た。
Preparation of a separator having a heat-resistant protective layer On the surfaces of both surfaces of a commercially available separator, which is a polyethylene porous film having a thickness of 20 μm, the compositions 1 to 17 for the heat-resistant protective layer are applied and dried. A separator having a 10 μm heat-resistant protective layer was obtained.
耐熱保護層の結着力の測定
各実施例および各比較例の正負極電極シートの表面、および耐熱保護層を有したセパレータ表面上に、ナイフを用いて、耐熱保護層から活物質塗工層表面、またはセパレータ表面に達する深さまでの切り込みを、２ｍｍ間隔で縦横それぞれ６本入れ、２５個（５個×５個）のマス目を有する碁盤目を形成した。この碁盤目に粘着テープを貼着して直ちに引き剥がし、フィラーの脱落の程度を目視評価した。結果を表４、５および６に示す。
◎：剥離なし。
○：１〜３個のマス目が剥離。
△：４〜１０個のマス目が剥離。
×：１１個以上のマス目が剥離。
Measurement of binding force of heat-resistant protective layer Surface of active material coating layer from heat-resistant protective layer using knife on surface of positive and negative electrode sheet of each example and comparative example, and separator surface having heat-resistant protective layer Alternatively, 6 cuts were made to reach the depth of the separator surface at intervals of 2 mm to form grids having 25 (5 × 5) squares. Adhesive tape was applied to the grid and immediately peeled off, and the degree of filler falling off was visually evaluated. The results are shown in Tables 4, 5 and 6.
A: No peeling.
○: 1 to 3 squares peeled off.
Δ: 4-10 squares peeled off.
X: 11 or more squares peeled off.
耐熱保護層の耐電解液性の測定
エチレンカーボネートとジエチルカーボネートを体積比１：１で混合した溶媒にＬｉＰＦ６を１ｍｏｌ／Ｌで溶解した電解液に、各実施例および各比較例の耐熱保護層を有した正・負極電極シートまたはセパレータより１００ｃｍ２の試験片を切り出し、４８時間浸漬させる。試験片を取り出した後、１２０℃で真空乾燥を行った後に秤量し、下記の式により、溶出減量を測定した。結果を表４、５および６に示す。
溶出減量（％）＝１００×｛（電解液浸漬前の重量）−（電解液浸漬後の重量）｝／（電解液浸漬前の重量）
◎：溶出減量が０．０１％未満。
○：溶出減量が０．０１％以上、０．０５％未満。
△：溶出減量が０．０５％以上、０．１％未満。
×：溶出減量が０．１％以上。
Measurement of Electrolytic Solution Resistance of Heat-resistant Protective Layer The heat-resistant protective layer of each example and each comparative example was added to an electrolytic solution in which LiPF6 was dissolved at 1 mol / L in a solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1. A test piece of 100 cm 2 is cut out from the positive / negative electrode sheet or separator, and is immersed for 48 hours. After the test piece was taken out, it was weighed after vacuum drying at 120 ° C., and the dissolution loss was measured by the following formula. The results are shown in Tables 4, 5 and 6.
Loss of dissolution (%) = 100 × {(weight before immersion in electrolyte) − (weight after immersion in electrolyte)} / (weight before immersion in electrolyte)
A: Elution loss is less than 0.01%.
○: Elution loss is 0.01% or more and less than 0.05%.
Δ: Elution loss is 0.05% or more and less than 0.1%.
X: Elution loss is 0.1% or more.
表３記載の耐熱保護層用組成物を塗工した耐熱保護層の物性評価結果を示す。
負極に塗工した場合の物性評価結果を表４に、正極に塗工した場合の結果を表５に、セパレータに塗工した場合の結果を表６に示す。
The physical-property evaluation result of the heat-resistant protective layer which coated the composition for heat-resistant protective layers of Table 3 is shown.
Table 4 shows the physical property evaluation results when applied to the negative electrode, Table 5 shows the results when applied to the positive electrode, and Table 6 shows the results when applied to the separator.
上記の通り、本発明の二次電池耐熱保護層用バインダーは、フィラーとの結着力および耐電解液性に優れる二次電池耐熱保護装用組成物を得ることができ、当該組成物を用いることにより、塗工欠陥の少ない耐熱保護層を得ることができる。その結果として、安全性の良好な電池を得ることが可能である。
As described above, the binder for a secondary battery heat-resistant protective layer of the present invention can provide a secondary battery heat-resistant protective composition excellent in binding power with a filler and electrolyte solution resistance, and by using the composition. A heat-resistant protective layer with few coating defects can be obtained. As a result, it is possible to obtain a battery with good safety.
Claims (16)
The composition for a heat-resistant protective layer of a lithium ion secondary battery according to claim 15 , wherein the average particle diameter (volume basis D50) of alumina is 0.1 to 10 µm.
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| WO2012011555A1 (en) * | 2010-07-23 | 2012-01-26 | 日本ゼオン株式会社 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| KR101927700B1 (en) * | 2010-10-28 | 2018-12-11 | 제온 코포레이션 | Secondary battery porous membrane, slurry for secondary battery porous membrane, and secondary battery |
| KR101852657B1 (en) * | 2011-09-26 | 2018-04-26 | 스미또모 가가꾸 가부시끼가이샤 | Adhesive resin composition for secondary battery |
| JP6336703B2 (en) * | 2011-10-05 | 2018-06-06 | 日産自動車株式会社 | Separator with heat-resistant insulation layer |
| JP5803628B2 (en) * | 2011-12-05 | 2015-11-04 | 東亞合成株式会社 | Method for producing aqueous resin emulsion composition |
| US9758629B2 (en) | 2012-09-11 | 2017-09-12 | Jsr Corporation | Composition for producing protective film, protective film, and electrical storage device |
| KR102053259B1 (en) * | 2012-10-31 | 2019-12-09 | 아사히 가세이 이-매터리얼즈 가부시키가이샤 | Multilayer porous film and method for manufacturing same, and separator for non-aqueous electrolyte cell |
| JP2015151445A (en) * | 2014-02-13 | 2015-08-24 | 三菱樹脂株式会社 | Laminated porous film, separator for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
| HUE046528T2 (en) | 2014-07-25 | 2020-03-30 | Zeon Corp | Porous membrane for lithium ion secondary battery, and lithium ion secondary battery |
| HUE055163T2 (en) | 2014-09-30 | 2021-11-29 | Zeon Corp | Composition for lithium ion secondary battery porous membrane, porous membrane for lithium ion secondary battery, and lithium ion secondary battery |
| JP6737182B2 (en) | 2014-11-28 | 2020-08-05 | 日本ゼオン株式会社 | Non-aqueous secondary battery functional layer composition, non-aqueous secondary battery functional layer and non-aqueous secondary battery |
| WO2018173717A1 (en) * | 2017-03-24 | 2018-09-27 | 日本ゼオン株式会社 | Binder composition for nonaqueous secondary batteries and slurry composition for nonaqueous secondary batteries |
| KR101970648B1 (en) * | 2018-01-04 | 2019-04-22 | 주식회사 엘지화학 | Binder composition for secondary battery, electrode slurry compositon comprising the same, electrode and secondary battery |
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