JP6492741B2 - Nonaqueous secondary battery functional layer binder composition, nonaqueous secondary battery functional layer slurry composition, nonaqueous secondary battery functional layer, nonaqueous secondary battery and method for producing the same - Google Patents
Nonaqueous secondary battery functional layer binder composition, nonaqueous secondary battery functional layer slurry composition, nonaqueous secondary battery functional layer, nonaqueous secondary battery and method for producing the same Download PDFInfo
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- JP6492741B2 JP6492741B2 JP2015031850A JP2015031850A JP6492741B2 JP 6492741 B2 JP6492741 B2 JP 6492741B2 JP 2015031850 A JP2015031850 A JP 2015031850A JP 2015031850 A JP2015031850 A JP 2015031850A JP 6492741 B2 JP6492741 B2 JP 6492741B2
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- secondary battery
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- polymer
- aqueous secondary
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- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
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- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
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- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
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- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
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- 239000005518 polymer electrolyte Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
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- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
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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
Description
本発明は、非水系二次電池機能層用バインダー組成物、非水系二次電池機能層用スラリー組成物、非水系二次電池用機能層および非水系二次電池、並びに、非水系二次電池の製造方法に関するものである。 The present invention relates to a binder composition for a non-aqueous secondary battery functional layer, a slurry composition for a non-aqueous secondary battery functional layer, a non-aqueous secondary battery functional layer and a non-aqueous secondary battery, and a non-aqueous secondary battery. It is related with the manufacturing method.
リチウムイオン二次電池などの非水系二次電池（以下、単に「二次電池」と略記する場合がある。）は、小型で軽量、且つエネルギー密度が高く、更に繰り返し充放電が可能という特性があり、幅広い用途に使用されている。そして、非水系二次電池は、一般に、正極、負極、および、正極と負極とを隔離して正極と負極との間の短絡を防ぐセパレータなどの電池部材を備えている。 Non-aqueous secondary batteries such as lithium ion secondary batteries (hereinafter sometimes simply referred to as “secondary batteries”) have the characteristics of being small and light, having high energy density, and capable of repeated charge and discharge. Yes, it is used for a wide range of purposes. The non-aqueous secondary battery generally includes a battery member such as a positive electrode, a negative electrode, and a separator that separates the positive electrode and the negative electrode and prevents a short circuit between the positive electrode and the negative electrode.
ここで、近年、二次電池においては、電池部材に所望の性能（例えば、耐熱性や強度など）を付与する機能層を備えた電池部材が使用されている。具体的には、例えば、セパレータ基材上に機能層を形成してなるセパレータや、集電体上に電極合材層を設けてなる電極基材の上に機能層を形成してなる電極が、電池部材として使用されている。また、電池部材の耐熱性や強度などを向上させ得る機能層としては、非導電性粒子をバインダー（結着材）で結着して形成した多孔膜層よりなる機能層が用いられている。 Here, in recent years, in secondary batteries, battery members having a functional layer that imparts desired performance (for example, heat resistance and strength) to the battery members are used. Specifically, for example, a separator in which a functional layer is formed on a separator base material, or an electrode in which a functional layer is formed on an electrode base material in which an electrode mixture layer is provided on a current collector It is used as a battery member. In addition, as a functional layer that can improve the heat resistance and strength of the battery member, a functional layer made of a porous film layer formed by binding non-conductive particles with a binder (binder) is used.
そして、近年では、二次電池の更なる高性能化を目的として、機能層の改良が盛んに行われている（例えば、特許文献１参照）。
具体的には、例えば特許文献１では、粉落ちの発生を抑制し得る機能層として、無機フィラーよりなる非導電性粒子と、ガラス転移温度が２０℃以上のスチレン樹脂およびガラス転移温度が１５℃以下の重合体よりなるバインダーと、スチレン樹脂を均一に溶解し得る有機溶媒とを含むスラリー組成物を基材に塗布し、次いで乾燥することにより形成した多孔膜層よりなる機能層が提案されている。そして、この特許文献１に記載のスラリー組成物を用いて形成した機能層では、スラリー組成物を塗布および乾燥する際に有機溶媒に溶解しているスチレン樹脂がマイグレーションを起こし、機能層の表層に偏在するため、粉落ちの発生が防止される。
In recent years, functional layers have been actively improved for the purpose of further improving the performance of secondary batteries (see, for example, Patent Document 1).
Specifically, for example, in Patent Document 1, as a functional layer capable of suppressing the occurrence of powder falling, non-conductive particles made of an inorganic filler, a styrene resin having a glass transition temperature of 20 ° C. or higher, and a glass transition temperature of 15 ° C. A functional layer composed of a porous film layer formed by applying a slurry composition containing a binder composed of the following polymer and an organic solvent capable of uniformly dissolving a styrene resin to a substrate and then drying is proposed. Yes. And in the functional layer formed using the slurry composition of this patent document 1, when apply | coating and drying a slurry composition, the styrene resin melt | dissolved in the organic solvent raise | generates migration, and it is on the surface layer of a functional layer. Since it is unevenly distributed, occurrence of powder falling is prevented.
しかし、特許文献１に記載の機能層は、機能層の形成時にスチレン樹脂を有機溶媒に溶解してマイグレーションにより表層に偏在させているため、イオン伝導性が低かった。そのため、特許文献１に記載の機能層を備える二次電池には、内部抵抗が増加して電池特性（寿命特性およびレート特性）が低下してしまう虞があった。 However, the functional layer described in Patent Document 1 has low ion conductivity because the styrene resin is dissolved in an organic solvent and is unevenly distributed on the surface layer by migration when the functional layer is formed. Therefore, in the secondary battery including the functional layer described in Patent Document 1, there is a possibility that the internal resistance increases and the battery characteristics (life characteristics and rate characteristics) are deteriorated.
また、近年、二次電池には更なる性能の向上が求められているところ、機能層のバインダーには、電解液への浸漬前だけではなく電解液への浸漬後にも高い接着性を発揮して、電解液浸漬後の機能層の接着強度（ピール強度）および二次電池の電池特性を向上させることも求められていた。 In recent years, secondary batteries have been required to have further improved performance, and the functional layer binder exhibits high adhesion not only before being immersed in the electrolytic solution but also after being immersed in the electrolytic solution. In addition, it has been required to improve the adhesive strength (peel strength) of the functional layer after immersion in the electrolyte and the battery characteristics of the secondary battery.
そこで、本発明は、機能層の形成に用いた際に内部抵抗の増加を抑制しつつ電解液中でも高い接着性を発揮して機能層の電解液浸漬後のピール強度を高めることができる非水系二次電池機能層用バインダー組成物を提供することを目的とする。
また、本発明は、内部抵抗の増加を抑制しつつ電解液浸漬後もピール強度が高い機能層を形成することができる非水系二次電池機能層用スラリー組成物を提供することを目的とする。
更に、本発明は、電解液浸漬後もピール強度が高く、非水系二次電池に優れた電池特性を発揮させることができる非水系二次電池用機能層を提供することを目的とする。
そして、本発明は、電池特性に優れる非水系二次電池およびその製造方法を提供することを目的とする。
Therefore, the present invention is a non-aqueous system that can increase the peel strength of the functional layer after being immersed in the electrolyte while suppressing the increase in internal resistance when used for forming the functional layer and exhibiting high adhesion even in the electrolyte. It aims at providing the binder composition for secondary battery functional layers.
Another object of the present invention is to provide a slurry composition for a non-aqueous secondary battery functional layer that can form a functional layer having high peel strength even after immersion in an electrolyte while suppressing an increase in internal resistance. .
Furthermore, an object of the present invention is to provide a functional layer for a non-aqueous secondary battery that has a high peel strength even after being immersed in an electrolytic solution and can exhibit excellent battery characteristics in the non-aqueous secondary battery.
And an object of this invention is to provide the non-aqueous secondary battery excellent in a battery characteristic, and its manufacturing method.
本発明者は、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者は、非導電性粒子と、所定のガラス転移温度および電解液膨潤度を有する非水溶性の粒子状重合体と、所定のガラス転移温度を有する接着性重合体と、水とを含むスラリー組成物を用いて機能層を形成すれば、内部抵抗の増加を抑制しつつ電解液浸漬後もピール強度が高い機能層を形成することができることを見出し、本発明を完成させた。 The present inventor has intensively studied for the purpose of solving the above problems. The inventor then comprises non-conductive particles, a water-insoluble particulate polymer having a predetermined glass transition temperature and electrolyte swelling degree, an adhesive polymer having a predetermined glass transition temperature, water, The present inventors have found that a functional layer having a high peel strength can be formed even after immersion in an electrolytic solution while suppressing an increase in internal resistance by forming a functional layer using a slurry composition containing the present invention.
即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の非水系二次電池機能層用バインダー組成物は、非水溶性粒子状重合体、接着性重合体および水を含有する非水系二次電池機能層用バインダー組成物であって、前記非水溶性粒子状重合体は、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満であり、前記接着性重合体は、ガラス転移温度が２０℃以下であることを特徴とする。このように、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満である非水溶性粒子状重合体と、ガラス転移温度が２０℃以下である接着性重合体とを含有させれば、機能層の形成に用いた際に、機能層の電解液浸漬後のピール強度を高めることができる。また、非水溶性粒子状重合体の電解液膨潤度を１倍超とし、更に非水溶性粒子状重合体および接着性重合体を含有する水系の組成物とすれば、バインダー組成物を用いて形成した機能層のイオン伝導性が低下するのを抑制して、内部抵抗の増加を抑制することができる。従って、バインダー組成物を用いて形成した機能層を備える二次電池のレート特性を向上させることができる。
なお、本発明において、重合体が「非水溶性」であるとは、２５℃において、その重合体０．５ｇを１００ｇの水に溶解した際に、不溶分が９０質量％以上となることをいう。また、本発明において、重合体の「ガラス転移温度」および「電解液膨潤度」は、本明細書の実施例に記載の測定方法を用いて測定することができる。
That is, the present invention aims to advantageously solve the above-mentioned problems, and the binder composition for a non-aqueous secondary battery functional layer of the present invention comprises a water-insoluble particulate polymer and an adhesive polymer. And a water-containing binder composition for a secondary battery functional layer, wherein the water-insoluble particulate polymer has a glass transition temperature of 50 ° C. or more and an electrolyte swelling degree of more than 1 time. The adhesive polymer has a glass transition temperature of 20 ° C. or lower. Thus, a water-insoluble particulate polymer having a glass transition temperature of 50 ° C. or higher and an electrolyte swelling degree of more than 1 time and less than 3 times, and an adhesive weight having a glass transition temperature of 20 ° C. or less. When the coalescence is contained, the peel strength after immersion of the functional layer in the electrolytic solution can be increased when used for forming the functional layer. Further, if the degree of swelling of the electrolyte solution of the water-insoluble particulate polymer is more than 1 time, and a water-based composition containing a water-insoluble particulate polymer and an adhesive polymer is used, a binder composition is used. It is possible to suppress an increase in internal resistance by suppressing a decrease in ion conductivity of the formed functional layer. Therefore, the rate characteristic of a secondary battery provided with a functional layer formed using the binder composition can be improved.
In the present invention, the polymer being “water-insoluble” means that at 25 ° C., when 0.5 g of the polymer is dissolved in 100 g of water, the insoluble content becomes 90% by mass or more. Say. In the present invention, the “glass transition temperature” and “electrolyte swelling degree” of the polymer can be measured using the measuring methods described in the examples of the present specification.
ここで、本発明の非水系二次電池機能層用バインダー組成物は、前記非水溶性粒子状重合体の体積平均粒子径が５０ｎｍ以上４００ｎｍ以下であることが好ましい。非水溶性粒子状重合体の体積平均粒子径が５０ｎｍ以上であれば、非水溶性粒子状重合体の分散安定性が向上し、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を向上させることができる。また、非水溶性粒子状重合体の体積平均粒子径が４００ｎｍ以下であれば、バインダー組成物を用いて形成した機能層の電解液浸漬後のピール強度を更に高めることができる。
なお、本発明において、重合体の「体積平均粒子径」は、本明細書の実施例に記載の測定方法を用いて測定することができる。
Here, in the binder composition for a non-aqueous secondary battery functional layer of the present invention, the volume average particle diameter of the water-insoluble particulate polymer is preferably 50 nm or more and 400 nm or less. If the volume average particle diameter of the water-insoluble particulate polymer is 50 nm or more, the dispersion stability of the water-insoluble particulate polymer is improved, and the secondary battery having a functional layer formed using the binder composition Life characteristics can be improved. Moreover, if the volume average particle diameter of the water-insoluble particulate polymer is 400 nm or less, the peel strength of the functional layer formed using the binder composition after immersion in the electrolyte can be further increased.
In the present invention, the “volume average particle diameter” of the polymer can be measured using the measuring method described in the examples of the present specification.
また、本発明の非水系二次電池機能層用バインダー組成物は、前記非水溶性粒子状重合体の含有量が、前記接着性重合体１００質量部当たり１質量部以上２０質量部以下であることが好ましい。非水溶性粒子状重合体の含有量を接着性重合体１００質量部当たり１質量部以上２０質量部以下とすれば、機能層の形成に用いた際に、機能層の電解液浸漬前のピール強度と、機能層の電解液浸漬後のピール強度との双方をバランス良く高めることができる。 In the binder composition for a non-aqueous secondary battery functional layer of the present invention, the content of the water-insoluble particulate polymer is 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the adhesive polymer. It is preferable. When the content of the water-insoluble particulate polymer is 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the adhesive polymer, the peel before the electrolyte solution is immersed in the functional layer when used for forming the functional layer. Both the strength and the peel strength after immersion of the functional layer in the electrolytic solution can be improved in a well-balanced manner.
更に、本発明の非水系二次電池機能層用バインダー組成物は、前記非水溶性粒子状重合体が、芳香族モノビニル単量体単位を７０質量％以上９９質量％以下含むことが好ましい。芳香族モノビニル単量体単位を７０質量％以上の割合で含む非水溶性粒子状重合体を使用すれば、バインダー組成物を用いて形成した機能層の電解液浸漬後のピール強度を更に高めることができる。また、芳香族モノビニル単量体単位を９９質量％以下の割合で含む非水溶性粒子状重合体を使用すれば、非水溶性粒子状重合体の分散安定性を向上させて、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を向上させることができる。
なお、本発明において、重合体が「単量体単位を含む」とは、「その単量体を用いて得た重合体中に単量体由来の構造単位が含まれている」ことを意味する。
Furthermore, in the binder composition for a non-aqueous secondary battery functional layer of the present invention, the water-insoluble particulate polymer preferably contains 70% by mass to 99% by mass of an aromatic monovinyl monomer unit. If a water-insoluble particulate polymer containing an aromatic monovinyl monomer unit in a proportion of 70% by mass or more is used, the peel strength after immersion of the electrolyte in the functional layer formed using the binder composition is further increased. Can do. Moreover, if a water-insoluble particulate polymer containing an aromatic monovinyl monomer unit in a proportion of 99% by mass or less is used, the dispersion stability of the water-insoluble particulate polymer is improved, and a binder composition is obtained. The lifetime characteristic of a secondary battery provided with the functional layer formed using can be improved.
In the present invention, the polymer "contains a monomer unit" means "a monomer-derived structural unit is contained in a polymer obtained using the monomer". To do.
また、本発明の非水系二次電池機能層用バインダー組成物は、前記接着性重合体の電解液膨潤度が１倍超３倍未満であることが好ましい。接着性重合体の電解液膨潤度が１倍超３倍未満であれば、機能層の電解液浸漬前のピール強度を十分に高めることができる。また、接着性重合体の電解液膨潤度を１倍超とすれば、バインダー組成物を用いて形成した機能層のイオン伝導性が低下するのを抑制して、内部抵抗の増加を抑制することができる。従って、バインダー組成物を用いて形成した機能層を備える二次電池のレート特性を向上させることができる。 In the binder composition for a non-aqueous secondary battery functional layer of the present invention, the adhesive polymer swelling degree of the adhesive polymer is preferably more than 1 time and less than 3 times. If the degree of swelling of the electrolytic solution of the adhesive polymer is more than 1 time and less than 3 times, the peel strength of the functional layer before immersion in the electrolytic solution can be sufficiently increased. In addition, if the swelling degree of the electrolyte solution of the adhesive polymer is more than 1 time, the decrease in ionic conductivity of the functional layer formed using the binder composition is suppressed, and the increase in internal resistance is suppressed. Can do. Therefore, the rate characteristic of a secondary battery provided with a functional layer formed using the binder composition can be improved.
そして、本発明の非水系二次電池機能層用バインダー組成物は、前記接着性重合体が、（メタ）アクリル酸アルキルエステル単量体単位を３５質量％以上含み、芳香族モノビニル単量体単位を１０質量％以上５５質量％以下含むことが好ましい。（メタ）アクリル酸アルキルエステル単量体単位および芳香族モノビニル単量体単位を上記割合で含有する接着性重合体を使用すれば、機能層の電解液浸漬前のピール強度を十分に高めることができると共に、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を向上させることができる。
なお、本発明において、「（メタ）アクリル」とは、アクリル及び／又はメタクリルを意味する。
In the binder composition for a non-aqueous secondary battery functional layer of the present invention, the adhesive polymer contains 35% by mass or more of a (meth) acrylic acid alkyl ester monomer unit, and an aromatic monovinyl monomer unit. It is preferable that 10 mass% or more and 55 mass% or less are included. If the adhesive polymer containing the (meth) acrylic acid alkyl ester monomer unit and the aromatic monovinyl monomer unit in the above proportion is used, the peel strength of the functional layer before immersion in the electrolyte can be sufficiently increased. In addition, the life characteristics of the secondary battery including the functional layer formed using the binder composition can be improved.
In the present invention, “(meth) acryl” means acryl and / or methacryl.
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の非水系二次電池機能層用スラリー組成物は、上述した非水系二次電池機能層用バインダー組成物の何れかと、非導電性粒子とを含有することを特徴とする。このように、上述した非水系二次電池機能層用バインダー組成物を使用すれば、スラリー組成物を用いて形成した機能層の電解液浸漬後のピール強度を高めることができると共に、機能層のイオン伝導性が低下するのを抑制して、内部抵抗の増加を抑制することができる。従って、スラリー組成物を用いて形成した機能層を備える二次電池のレート特性を向上させることができる。 Moreover, this invention aims at solving the said subject advantageously, The slurry composition for non-aqueous secondary battery functional layers of this invention is the binder composition for non-aqueous secondary battery functional layers mentioned above. It contains any of the objects and non-conductive particles. Thus, when the binder composition for a non-aqueous secondary battery functional layer described above is used, the peel strength after immersion of the functional layer formed using the slurry composition can be increased, and the functional layer It is possible to suppress an increase in internal resistance by suppressing a decrease in ion conductivity. Accordingly, it is possible to improve the rate characteristics of the secondary battery including the functional layer formed using the slurry composition.
更に、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の非水系二次電池用機能層は、上述した非水系二次電池機能層用スラリー組成物から形成されたものであることを特徴とする。このように、上述した非水系二次電池機能層用スラリー組成物を用いれば、電解液浸漬後もピール強度が高く、非水系二次電池に優れた電池特性を発揮させることができる機能層が得られる。 Furthermore, this invention aims at solving the said subject advantageously, The functional layer for non-aqueous secondary batteries of this invention is formed from the slurry composition for non-aqueous secondary battery functional layers mentioned above. It is characterized by being made. Thus, if the slurry composition for a non-aqueous secondary battery functional layer described above is used, a functional layer that has high peel strength even after immersion in an electrolyte and can exhibit excellent battery characteristics in a non-aqueous secondary battery. can get.
そして、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の非水系二次電池は、上述した非水系二次電池用機能層を備えることを特徴とする。このように、上述した非水系二次電池用機能層を用いれば、優れた電池特性を有する二次電池が得られる。 And this invention aims at solving the said subject advantageously, The non-aqueous secondary battery of this invention is equipped with the functional layer for non-aqueous secondary batteries mentioned above, It is characterized by the above-mentioned. Thus, if the functional layer for non-aqueous secondary batteries described above is used, a secondary battery having excellent battery characteristics can be obtained.
また、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の非水系二次電池の製造方法は、上述した非水系二次電池用機能層を加熱プレスする工程を含むことを特徴とする。このように、上述した非水系二次電池用機能層を加熱プレスする工程を経て上述した非水系二次電池を製造すれば、優れた電池特性を有する二次電池が効率的に得られる。 Moreover, this invention aims at solving the said subject advantageously, The manufacturing method of the non-aqueous secondary battery of this invention is the process of heat-pressing the functional layer for non-aqueous secondary batteries mentioned above. It is characterized by including. Thus, if the non-aqueous secondary battery mentioned above is manufactured through the process of heat-pressing the functional layer for non-aqueous secondary batteries mentioned above, the secondary battery which has the outstanding battery characteristic will be obtained efficiently.
本発明によれば、機能層の形成に用いた際に内部抵抗の増加を抑制しつつ電解液中でも高い接着性を発揮して機能層の電解液浸漬後のピール強度を高めることができる非水系二次電池機能層用バインダー組成物を提供することができる。
また、本発明によれば、内部抵抗の増加を抑制しつつ電解液浸漬後もピール強度が高い機能層を形成することができる非水系二次電池機能層用スラリー組成物を提供することができる。
更に、本発明によれば、電解液浸漬後もピール強度が高く、非水系二次電池に優れた電池特性を発揮させることができる非水系二次電池用機能層を提供することができる。
そして、本発明によれば、電池特性に優れる非水系二次電池およびその製造方法を提供することができる。
According to the present invention, when used for the formation of a functional layer, a non-aqueous system capable of increasing the peel strength after immersion of the functional layer by exhibiting high adhesiveness even in the electrolytic solution while suppressing an increase in internal resistance. A binder composition for a secondary battery functional layer can be provided.
Moreover, according to this invention, the slurry composition for non-aqueous secondary battery functional layers which can form a functional layer with high peel strength even after electrolyte immersion, suppressing the increase in internal resistance can be provided. .
Furthermore, according to the present invention, it is possible to provide a functional layer for a non-aqueous secondary battery that has a high peel strength even after being immersed in an electrolytic solution and can exhibit excellent battery characteristics in the non-aqueous secondary battery.
And according to this invention, the non-aqueous secondary battery excellent in a battery characteristic and its manufacturing method can be provided.
以下、本発明の実施形態について詳細に説明する。
ここで、本発明の非水系二次電池機能層用バインダー組成物（以下、「バインダー組成物」と略記する場合がある。）は、非水系二次電池機能層用スラリー組成物（以下、「スラリー組成物」と略記する場合がある。）を調製する際の材料として用いられる。そして、本発明の非水系二次電池機能層用スラリー組成物は、本発明の非水系二次電池機能層用バインダー組成物と、非導電性粒子とを用いて調製される。また、本発明の非水系二次電池用機能層は、本発明の非水系二次電池機能層用スラリー組成物を用いて形成される。加えて、本発明の非水系二次電池は、例えば本発明の非水系二次電池の製造方法を用いて製造することができ、少なくとも１つの電池部材の表面に本発明の非水系二次電池用機能層を備えるものである。
Hereinafter, embodiments of the present invention will be described in detail.
Here, the non-aqueous secondary battery functional layer binder composition of the present invention (hereinafter sometimes abbreviated as “binder composition”) is a non-aqueous secondary battery functional layer slurry composition (hereinafter “ It may be abbreviated as “slurry composition”.). And the slurry composition for non-aqueous secondary battery functional layers of this invention is prepared using the binder composition for non-aqueous secondary battery functional layers of this invention, and nonelectroconductive particle. Moreover, the functional layer for non-aqueous secondary batteries of this invention is formed using the slurry composition for non-aqueous secondary battery functional layers of this invention. In addition, the non-aqueous secondary battery of the present invention can be manufactured using, for example, the non-aqueous secondary battery manufacturing method of the present invention, and the non-aqueous secondary battery of the present invention is formed on the surface of at least one battery member. Functional layer.
（非水系二次電池機能層用バインダー組成物）
本発明の非水系二次電池機能層用バインダー組成物は、非水溶性粒子状重合体と、接着性重合体と、水とを含み、任意にその他の成分を更に含有する水系の組成物である。そして、本発明の非水系二次電池機能層用バインダー組成物は、非水溶性粒子状重合体として、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満である重合体を使用し、接着性重合体としてガラス転移温度が２０℃以下である重合体を使用することを特徴とする。
そして、本発明の非水系二次電池機能層用バインダー組成物を用いて調製した非水系二次電池機能層用スラリー組成物を使用して機能層を形成すれば、機能層の電解液浸漬後のピール強度を高めることができると共に、機能層のイオン伝導性が低下するのを抑制して機能層を備える非水系二次電池の内部抵抗の増加を抑制することができる。従って、本発明の非水系二次電池機能層用バインダー組成物を使用すれば、二次電池の電池特性（例えば、寿命特性やレート特性など）を向上させることができる。
(Binder composition for non-aqueous secondary battery functional layer)
The binder composition for a non-aqueous secondary battery functional layer of the present invention is a water-based composition containing a water-insoluble particulate polymer, an adhesive polymer, and water, and optionally further containing other components. is there. The binder composition for a non-aqueous secondary battery functional layer of the present invention, as a water-insoluble particulate polymer, has a glass transition temperature of 50 ° C. or higher and an electrolyte swelling degree of more than 1 and less than 3 times. And a polymer having a glass transition temperature of 20 ° C. or lower is used as the adhesive polymer.
And if a functional layer is formed using the slurry composition for non-aqueous secondary battery functional layers prepared using the binder composition for a non-aqueous secondary battery functional layer of the present invention, after the electrolyte solution is immersed in the functional layer The peel strength of the non-aqueous secondary battery including the functional layer can be suppressed by suppressing the ion conductivity of the functional layer from being lowered. Therefore, if the binder composition for a non-aqueous secondary battery functional layer of the present invention is used, battery characteristics (for example, life characteristics and rate characteristics) of the secondary battery can be improved.
ここで、本発明のバインダー組成物を用いることで上述した効果が得られる理由は、明らかではないが、以下の通りであると推察されている。
即ち、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満である非水溶性粒子状重合体は、電解液中において高い接着性を発揮するため、当該非水溶性粒子状重合体を含む本発明のバインダー組成物を使用すれば、機能層の電解液浸漬後のピール強度を高めることができる。従って、本発明のバインダー組成物を使用すれば、例えば二次電池の組立後のエージング中などに機能層が剥離して電極間距離が拡大し、二次電池のレート特性が低下するのを抑制することができる。
また、ガラス転移温度が５０℃以上である非水溶性粒子状重合体は、通常、電解液への浸漬前には大きな接着力を発現しないが、ガラス転移温度が２０℃以下の接着性重合体は電解液への浸漬前でも十分な接着力を発揮する。そのため、接着性重合体を含む本発明のバインダー組成物を使用すれば、主に接着性重合体により非導電性粒子や非水溶性粒子状重合体を結着して機能層を良好に形成することができると共に、機能層の電解液浸漬前のピール強度を確保することができる。
更に、本発明のバインダー組成物は、非水溶性粒子状重合体を含む水系の組成物であるため、粒子状の重合体によって機能層の多孔性を確保してイオン伝導性が低下するのを抑制し、機能層を用いた二次電池の内部抵抗の増加を抑制することができる。従って、本発明のバインダー組成物を使用すれば、レート特性および寿命特性に優れる二次電池を得ることができる。
Here, the reason why the above-described effect is obtained by using the binder composition of the present invention is not clear, but is presumed to be as follows.
That is, a water-insoluble particulate polymer having a glass transition temperature of 50 ° C. or more and an electrolyte solution swelling degree of more than 1 time and less than 3 times exhibits high adhesiveness in the electrolyte solution. If the binder composition of the present invention containing a water-soluble particulate polymer is used, the peel strength after immersion of the functional layer in the electrolytic solution can be increased. Therefore, if the binder composition of the present invention is used, for example, it is possible to prevent the functional layer from being peeled off during aging after the secondary battery is assembled and the interelectrode distance is increased, and the rate characteristics of the secondary battery are deteriorated. can do.
In addition, a water-insoluble particulate polymer having a glass transition temperature of 50 ° C. or higher usually does not exhibit a large adhesive force before being immersed in an electrolytic solution, but an adhesive polymer having a glass transition temperature of 20 ° C. or lower. Exhibits sufficient adhesion even before immersion in the electrolyte. Therefore, if the binder composition of the present invention containing an adhesive polymer is used, the functional layer is satisfactorily formed by binding non-conductive particles and water-insoluble particulate polymer mainly by the adhesive polymer. In addition, the peel strength of the functional layer before immersion in the electrolyte can be ensured.
Furthermore, since the binder composition of the present invention is a water-based composition containing a water-insoluble particulate polymer, the particulate polymer ensures the porosity of the functional layer and decreases the ionic conductivity. It is possible to suppress the increase in internal resistance of the secondary battery using the functional layer. Therefore, if the binder composition of the present invention is used, a secondary battery excellent in rate characteristics and life characteristics can be obtained.
＜非水溶性粒子状重合体＞
非水溶性粒子状重合体は、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満であることを必要とする。そして、非水溶性粒子状重合体は、主に電解液中において優れた接着力を発揮する。
なお、非水溶性粒子状重合体は、水中において粒子状の状態で存在しており、通常、バインダー組成物を用いて形成された機能層中においても粒子状の状態を維持している。
<Water-insoluble particulate polymer>
The water-insoluble particulate polymer needs to have a glass transition temperature of 50 ° C. or higher and an electrolyte swelling degree of more than 1 time and less than 3 times. And a water-insoluble particulate polymer exhibits the outstanding adhesive force mainly in electrolyte solution.
In addition, the water-insoluble particulate polymer exists in a particulate state in water, and usually maintains the particulate state even in a functional layer formed using a binder composition.
［ガラス転移温度］
ここで、非水溶性粒子状重合体のガラス転移温度は、５０℃以上であることが必要であり、７５℃以上であることが好ましく、９０℃以上であることがより好ましい。ガラス転移温度が低すぎると、電解液中において十分な接着力を発揮することができず、機能層の電解液浸漬後のピール強度を高めることができない。なお、非水溶性粒子状重合体のガラス転移温度は、通常、１２０℃以下である。
[Glass-transition temperature]
Here, the glass transition temperature of the water-insoluble particulate polymer needs to be 50 ° C. or higher, preferably 75 ° C. or higher, and more preferably 90 ° C. or higher. If the glass transition temperature is too low, sufficient adhesive strength cannot be exhibited in the electrolytic solution, and the peel strength after the functional layer is immersed in the electrolytic solution cannot be increased. In addition, the glass transition temperature of a water-insoluble particulate polymer is 120 degrees C or less normally.
［電解液膨潤度］
また、非水溶性粒子状重合体の電解液膨潤度は、１倍超３倍未満であることが必要であり、１．２倍以上であることが好ましく、１．５倍以上であることがより好ましく、２．５倍以下であることが好ましく、２．０倍以下であることがより好ましい。電解液膨潤度が１倍超３倍未満であれば、電解液中において十分な接着力を発揮させ、機能層の電解液浸漬後のピール強度を十分に高めることができる。なお、非水溶性粒子状重合体の電解液膨潤度が低すぎると、機能層のイオン伝導性が低下して機能層を用いた二次電池の内部抵抗が増加し、二次電池のレート特性を十分に向上させることができない虞がある。
[Electrolytic solution swelling]
Further, the degree of swelling of the electrolyte solution of the water-insoluble particulate polymer needs to be more than 1 time and less than 3 times, preferably 1.2 times or more, and more preferably 1.5 times or more. More preferably, it is 2.5 times or less, and more preferably 2.0 times or less. When the degree of swelling of the electrolytic solution is more than 1 time and less than 3 times, sufficient adhesive strength can be exhibited in the electrolytic solution, and the peel strength after immersion of the functional layer in the electrolytic solution can be sufficiently increased. In addition, if the electrolyte swelling degree of the water-insoluble particulate polymer is too low, the ionic conductivity of the functional layer is lowered and the internal resistance of the secondary battery using the functional layer is increased, and the rate characteristics of the secondary battery are increased. May not be sufficiently improved.
なお、非水溶性粒子状重合体は、電解液膨潤度が１倍超３倍未満であっても、ガラス転移温度が低い場合には、電解液に膨潤した際に重合体の分子鎖が動き易くなり、強度が低下して電解液中において十分な接着力を発揮することができない。そのため、非水溶性粒子状重合体は、所定のガラス転移温度と所定の電解液膨潤度との双方を有することを必要とする。 Even if the degree of swelling of the electrolyte is more than 1 and less than 3 times, the water-insoluble particulate polymer moves the molecular chain of the polymer when swollen in the electrolyte when the glass transition temperature is low. It becomes easy, strength falls, and sufficient adhesive force cannot be exhibited in electrolyte solution. Therefore, the water-insoluble particulate polymer needs to have both a predetermined glass transition temperature and a predetermined degree of electrolyte solution swelling.
［体積平均粒子径］
更に、非水溶性粒子状重合体の体積平均粒子径は、５０ｎｍ以上であることが好ましく、８０ｎｍ以上であることがより好ましく、１００ｎｍ以上であることが更に好ましく、１３０ｎｍ以上であることが特に好ましく、４００ｎｍ以下であることが好ましく、３５０ｎｍ以下であることがより好ましく、３００ｎｍ以下であることが更に好ましく、２００ｎｍ以下であることが特に好ましい。体積平均粒子径を５０ｎｍ以上とすれば、分散安定性を向上させ、例えば高いせん断力を受けた場合であっても非水溶性粒子状重合体が凝集するのを抑制することができるので、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を向上させることができる。また、体積平均粒子径を４００ｎｍ以下とすれば、電解液中において高い接着力を発揮させ、機能層の電解液浸漬後のピール強度を更に高めることができる。
[Volume average particle diameter]
Further, the volume average particle diameter of the water-insoluble particulate polymer is preferably 50 nm or more, more preferably 80 nm or more, further preferably 100 nm or more, and particularly preferably 130 nm or more. 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, and particularly preferably 200 nm or less. If the volume average particle diameter is 50 nm or more, the dispersion stability can be improved, and for example, the aggregation of the water-insoluble particulate polymer can be suppressed even when subjected to a high shearing force. The lifetime characteristic of a secondary battery provided with the functional layer formed using the composition can be improved. Moreover, if the volume average particle diameter is 400 nm or less, a high adhesive force can be exhibited in the electrolytic solution, and the peel strength after immersion of the functional layer in the electrolytic solution can be further increased.
［組成］
なお、非水溶性粒子状重合体としては、上述したガラス転移温度および電解液膨潤度を有する非水溶性の重合体であれば特に限定されることなく、任意の重合体を用いることができる。中でも、分散安定性および電解液中での接着性を高める観点からは、非水溶性粒子状重合体としては、芳香族モノビニル単量体単位を含む重合体を用いることが好ましく、芳香族モノビニル単量体単位と、酸性基含有単量体単位および／または架橋性単量体単位とを含む共重合体を用いることがより好ましい。
[composition]
The water-insoluble particulate polymer is not particularly limited as long as it is a water-insoluble polymer having the above-described glass transition temperature and electrolyte solution swelling degree, and any polymer can be used. Among these, from the viewpoint of improving dispersion stability and adhesion in the electrolyte, it is preferable to use a polymer containing an aromatic monovinyl monomer unit as the water-insoluble particulate polymer. It is more preferable to use a copolymer containing a monomer unit and an acidic group-containing monomer unit and / or a crosslinkable monomer unit.
[[芳香族モノビニル単量体単位]]
ここで、芳香族モノビニル単量体単位を形成しうる芳香族モノビニル単量体としては、スチレン、スチレンスルホン酸およびその塩（例えば、スチレンスルホン酸ナトリウムなど）、α−メチルスチレン、ビニルトルエン、４−（ｔｅｒｔ−ブトキシ）スチレンなどが挙げられる。これらの中でも、スチレンが好ましい。これらは一種単独で、または、２種以上を組み合わせて用いることができる。
[[Aromatic monovinyl monomer unit]]
Here, examples of the aromatic monovinyl monomer that can form an aromatic monovinyl monomer unit include styrene, styrenesulfonic acid and salts thereof (for example, sodium styrenesulfonate), α-methylstyrene, vinyltoluene, 4 -(Tert-butoxy) styrene etc. are mentioned. Among these, styrene is preferable. These can be used alone or in combination of two or more.
そして、非水溶性粒子状重合体における、芳香族モノビニル単量体単位の含有割合は、好ましくは７０質量％以上であり、より好ましくは８０質量％以上であり、更に好ましくは９４質量％以上であり、好ましくは９９質量％以下であり、より好ましくは９８質量％以下であり、更に好ましくは９７質量％以下である。芳香族モノビニル単量体単位の含有割合を７０質量％以上とすれば、電解液中での接着性を更に高め、バインダー組成物を用いて形成した機能層の電解液浸漬後のピール強度を更に高めることができる。一方、芳香族モノビニル単量体単位の含有割合を９９質量％以下とすれば、分散安定性を更に向上させ、例えば高いせん断力を受けた場合であっても非水溶性粒子状重合体が凝集するのを十分に抑制することができると共に、二次電池の寿命特性を更に向上させることができる。 The content ratio of the aromatic monovinyl monomer unit in the water-insoluble particulate polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 94% by mass or more. Yes, preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 97% by mass or less. If the content ratio of the aromatic monovinyl monomer unit is 70% by mass or more, the adhesion in the electrolytic solution is further improved, and the peel strength after immersion of the functional layer formed using the binder composition is further increased. Can be increased. On the other hand, when the content ratio of the aromatic monovinyl monomer unit is 99% by mass or less, the dispersion stability is further improved. For example, the water-insoluble particulate polymer is aggregated even when subjected to a high shearing force. Can be sufficiently suppressed, and the life characteristics of the secondary battery can be further improved.
[[酸性基含有単量体単位]]
また、酸性基含有単量体単位を形成しうる酸性基含有単量体としては、カルボン酸基含有単量体、スルホン酸基含有単量体、リン酸基含有単量体などを挙げることができる。これらは一種単独で、または、２種以上を組み合わせて用いることができる。
[[Acid group-containing monomer unit]]
Examples of the acidic group-containing monomer that can form an acidic group-containing monomer unit include a carboxylic acid group-containing monomer, a sulfonic acid group-containing monomer, and a phosphoric acid group-containing monomer. it can. These can be used alone or in combination of two or more.
そして、カルボン酸基含有単量体としては、エチレン性不飽和モノカルボン酸及びその誘導体、エチレン性不飽和ジカルボン酸及びその酸無水物並びにそれらの誘導体などが挙げられる。
エチレン性不飽和モノカルボン酸の例としては、アクリル酸、メタクリル酸、クロトン酸などが挙げられる。そして、エチレン性不飽和モノカルボン酸の誘導体の例としては、２−エチルアクリル酸、イソクロトン酸、α−アセトキシアクリル酸、β−ｔｒａｎｓ−アリールオキシアクリル酸、α−クロロ−β−Ｅ−メトキシアクリル酸、β−ジアミノアクリル酸などが挙げられる。
エチレン性不飽和ジカルボン酸の例としては、マレイン酸、フマル酸、イタコン酸、メサコン酸などが挙げられる。そして、エチレン性不飽和ジカルボン酸の酸無水物の例としては、無水マレイン酸、アクリル酸無水物、メチル無水マレイン酸、ジメチル無水マレイン酸などが挙げられる。さらに、エチレン性不飽和ジカルボン酸の誘導体の例としては、メチルマレイン酸、ジメチルマレイン酸、フェニルマレイン酸、クロロマレイン酸、ジクロロマレイン酸、フルオロマレイン酸、マレイン酸ジフェニル、マレイン酸ノニル、マレイン酸デシル、マレイン酸ドデシル、マレイン酸オクタデシル、マレイン酸フルオロアルキルなどが挙げられる。
Examples of the carboxylic acid group-containing monomer include ethylenically unsaturated monocarboxylic acid and derivatives thereof, ethylenically unsaturated dicarboxylic acid and acid anhydrides thereof, and derivatives thereof.
Examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and the like. Examples of the ethylenically unsaturated monocarboxylic acid derivatives include 2-ethylacrylic acid, isocrotonic acid, α-acetoxyacrylic acid, β-trans-aryloxyacrylic acid, α-chloro-β-E-methoxyacrylic. Examples include acid and β-diaminoacrylic acid.
Examples of the ethylenically unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, mesaconic acid and the like. Examples of acid anhydrides of ethylenically unsaturated dicarboxylic acids include maleic anhydride, acrylic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, and the like. In addition, examples of ethylenically unsaturated dicarboxylic acid derivatives include methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, diphenyl maleate, nonyl maleate, decyl maleate , Dodecyl maleate, octadecyl maleate, fluoroalkyl maleate and the like.
スルホン酸基含有単量体としては、ビニルスルホン酸、メチルビニルスルホン酸、（メタ）アリルスルホン酸、（メタ）アクリル酸−２−スルホン酸エチル、２−アクリルアミド−２−メチルプロパンスルホン酸、３−アリロキシ−２−ヒドロキシプロパンスルホン酸などが挙げられる。
なお、本発明において「（メタ）アリル」とは、アリルおよび／またはメタリルを意味する。
Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, methyl vinyl sulfonic acid, (meth) allyl sulfonic acid, (meth) acrylic acid-2-ethyl sulfonate, 2-acrylamido-2-methylpropane sulfonic acid, 3 -Allyloxy-2-hydroxypropane sulfonic acid etc. are mentioned.
In the present invention, “(meth) allyl” means allyl and / or methallyl.
リン酸基含有単量体としては、リン酸−２−（メタ）アクリロイルオキシエチル、リン酸メチル−２−（メタ）アクリロイルオキシエチル、リン酸エチル−（メタ）アクリロイルオキシエチルなどが挙げられる。
なお、本発明において「（メタ）アクリロイル」とは、アクリロイルおよび／またはメタクリロイルを意味する。
Examples of phosphoric acid group-containing monomers include 2- (meth) acryloyloxyethyl phosphate, methyl-2- (meth) acryloyloxyethyl phosphate, ethyl- (meth) acryloyloxyethyl phosphate, and the like.
In the present invention, “(meth) acryloyl” means acryloyl and / or methacryloyl.
これらの中でも、酸性基含有単量体としては、カルボン酸基含有単量体が好ましく、フマル酸、イタコン酸、アクリル酸、メタクリル酸がより好ましく、メタクリル酸が更に好ましい。 Among these, as the acidic group-containing monomer, a carboxylic acid group-containing monomer is preferable, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid are more preferable, and methacrylic acid is further preferable.
そして、非水溶性粒子状重合体における、酸性基含有単量体単位の含有割合は、好ましくは０．１質量％以上、より好ましくは１．０質量％以上、更に好ましくは１．５質量％以上であり、好ましくは１０質量％以下、より好ましくは５．０質量％以下、更に好ましくは２．５質量％以下である。酸性基含有単量体単位の含有割合を０．１質量％以上とすれば、分散安定性を更に向上させ、例えば高いせん断力を受けた場合であっても非水溶性粒子状重合体が凝集するのを十分に抑制することができると共に、二次電池の寿命特性を更に向上させることができる。また、酸性基含有単量体単位の含有割合を１０質量％以下とすれば、電解液中での接着性を更に高め、バインダー組成物を用いて形成した機能層の電解液浸漬後のピール強度を更に高めることができる。 The content ratio of the acidic group-containing monomer unit in the water-insoluble particulate polymer is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass. It is above, Preferably it is 10 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is 2.5 mass% or less. When the content ratio of the acidic group-containing monomer unit is 0.1% by mass or more, the dispersion stability is further improved. For example, the water-insoluble particulate polymer aggregates even when subjected to a high shearing force. Can be sufficiently suppressed, and the life characteristics of the secondary battery can be further improved. Moreover, if the content ratio of the acidic group-containing monomer unit is 10% by mass or less, the adhesiveness in the electrolytic solution is further improved, and the peel strength after immersion of the functional layer formed using the binder composition in the electrolytic solution Can be further increased.
[[架橋性単量体単位]]
架橋性単量体単位を形成しうる架橋性単量体としては、重合した際に架橋構造を形成しうる単量体を用いることができる。具体的には、熱架橋性の架橋性基および１分子あたり１つのエチレン性不飽和結合を有する単官能性単量体、並びに、１分子あたり２つ以上のエチレン性不飽和結合を有する多官能性単量体が挙げられる。単官能性単量体に含まれる熱架橋性の架橋性基の例としては、エポキシ基、Ｎ−メチロールアミド基、オキセタニル基、オキサゾリン基およびこれらの組み合わせが挙げられる。架橋性単量体単位を含有させることで、バインダー組成物を用いて形成した機能層の耐粉落ち性を高めつつ、非水溶性粒子状重合体の電解液膨潤度の大きさを適度な大きさとすることができる。
[[Crosslinkable monomer unit]]
As the crosslinkable monomer capable of forming a crosslinkable monomer unit, a monomer capable of forming a crosslinked structure upon polymerization can be used. Specifically, a monofunctional monomer having a thermally crosslinkable crosslinkable group and one ethylenically unsaturated bond per molecule, and a polyfunctional having two or more ethylenically unsaturated bonds per molecule Ionic monomers. Examples of the thermally crosslinkable group contained in the monofunctional monomer include an epoxy group, an N-methylolamide group, an oxetanyl group, an oxazoline group, and combinations thereof. By including a crosslinkable monomer unit, the degree of swelling of the electrolyte solution of the water-insoluble particulate polymer is moderately increased while enhancing the anti-powder resistance of the functional layer formed using the binder composition. It can be.
そして、架橋性単量体は、疎水性であっても親水性であってもよい。
なお、本発明において、架橋性単量体が「疎水性」であるとは、当該架橋性単量体が親水性基を含まないことをいい、架橋性単量体が「親水性」であるとは、当該架橋性単量体が親水性基を含むことをいう。ここで架橋性単量体における「親水性基」とは、カルボン酸基、水酸基、スルホン酸基、リン酸基、エポキシ基、チオール基、アルデヒド基、アミド基、オキセタニル基、オキサゾリン基を指す。
The crosslinkable monomer may be hydrophobic or hydrophilic.
In the present invention, that the crosslinkable monomer is “hydrophobic” means that the crosslinkable monomer does not contain a hydrophilic group, and the crosslinkable monomer is “hydrophilic”. The term “crosslinkable monomer” includes a hydrophilic group. Here, the “hydrophilic group” in the crosslinkable monomer means a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a phosphoric acid group, an epoxy group, a thiol group, an aldehyde group, an amide group, an oxetanyl group, or an oxazoline group.
疎水性の架橋性単量体としては、アリル（メタ）アクリレート、エチレンジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリメチロールプロパン−トリ（メタ）アクリレートなどの多官能（メタ）アクリレート類；ジプロピレングリコールジアリルエーテル、ポリグリコールジアリルエーテル、トリエチレングリコールジビニルエーテル、ヒドロキノンジアリルエーテル、テトラアリルオキシエタンなどの多官能アリル／ビニルエーテル類；そしてジビニルベンゼンなどが挙げられる。
親水性の架橋性単量体としては、ビニルグリシジルエーテル、アリルグリシジルエーテル、Ｎ−メチロールアクリルアミド、アクリルアミド、アリルメタクリルアミドなどが挙げられる。
なお、これらは一種単独で、または、２種以上を組み合わせて用いることができる。
Hydrophobic crosslinkable monomers include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylol Polyfunctional (meth) acrylates such as propane-tri (meth) acrylate; polyfunctional allyl / vinyl ethers such as dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane And divinylbenzene and the like.
Examples of the hydrophilic crosslinkable monomer include vinyl glycidyl ether, allyl glycidyl ether, N-methylol acrylamide, acrylamide, and allyl methacrylamide.
In addition, these can be used individually by 1 type or in combination of 2 or more types.
これらの中でも、バインダー組成物を用いて形成した機能層の耐粉落ち性を高める観点からは、エチレンジメタクリレートが好ましい。 Among these, ethylene dimethacrylate is preferable from the viewpoint of enhancing the powder resistance of the functional layer formed using the binder composition.
そして、非水溶性粒子状重合体における、架橋性単量体単位の含有割合は、好ましくは０．１質量％以上、より好ましくは１．０質量％以上、更に好ましくは１．５質量％以上であり、好ましくは１０質量％以下、より好ましくは５．０質量％以下、更に好ましくは２．５質量％以下である。架橋性単量体単位の含有割合を０．１質量％以上とすれば、非水溶性粒子状重合体の電解液膨潤度の大きさを適度な大きさとし、電解液中での接着性を更に高めることができる。また、架橋性単量体単位の含有割合を１０質量％以下とすれば、バインダー組成物を用いて形成した機能層の耐粉落ち性を高めることができる。 The content of the crosslinkable monomer unit in the water-insoluble particulate polymer is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more. Preferably, it is 10 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is 2.5 mass% or less. If the content ratio of the crosslinkable monomer unit is 0.1% by mass or more, the degree of swelling of the electrolyte solution of the water-insoluble particulate polymer is set to an appropriate level, and the adhesion in the electrolyte solution is further increased. Can be increased. Moreover, if the content rate of a crosslinkable monomer unit shall be 10 mass% or less, the powder-proofing property of the functional layer formed using the binder composition can be improved.
[[その他の単量体単位]]
なお、非水溶性粒子状重合体は、上述した単量体単位以外に、その他の単量体単位を含有していてもよい。そして、その他の単量体単位としては、特に限定されることなく、（メタ）アクリル酸アルキルエステル単量体単位などが挙げられる。
[[Other monomer units]]
The water-insoluble particulate polymer may contain other monomer units in addition to the monomer units described above. The other monomer units are not particularly limited, and examples thereof include (meth) acrylic acid alkyl ester monomer units.
ここで、（メタ）アクリル酸アルキルエステル単量体単位を形成しうる（メタ）アクリル酸アルキルエステル単量体としては、メチルアクリレート、エチルアクリレート、ｎ−プロピルアクリレート、イソプロピルアクリレート、ｎ−ブチルアクリレート、ｔ−ブチルアクリレート、イソブチルアクリレート、ｎ−ペンチルアクリレート、イソペンチルアクリレート、ヘキシルアクリレート、ヘプチルアクリレート、オクチルアクリレート、２−エチルヘキシルアクリレート、ノニルアクリレート、デシルアクリレート、ラウリルアクリレート、ｎ−テトラデシルアクリレート、ステアリルアクリレートなどのアクリル酸アルキルエステル；メチルメタクリレート、エチルメタクリレート、ｎ−プロピルメタクリレート、イソプロピルメタクリレート、ｎ−ブチルメタクリレート、ｔ−ブチルメタクリレート、イソブチルメタクリレート、ｎ−ペンチルメタクリレート、イソペンチルメタクリレート、ヘキシルメタクリレート、ヘプチルメタクリレート、オクチルメタクリレート、２−エチルヘキシルメタクリレート、ノニルメタクリレート、デシルメタクリレート、ラウリルメタクリレート、ｎ−テトラデシルメタクリレート、ステアリルメタクリレート、グリシジルメタクリレートなどのメタクリル酸アルキルエステル；などが挙げられる。
これらの中でも、２−エチルヘキシルアクリレート、エチルアクリレート、ブチルアクリレート、メチルメタクリレートが好ましく、２−エチルヘキシルアクリレートがより好ましい。
Here, as the (meth) acrylic acid alkyl ester monomer that can form a (meth) acrylic acid alkyl ester monomer unit, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate, etc. Acrylic acid alkyl ester; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate Rate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, lauryl methacrylate, n-tetra And methacrylic acid alkyl esters such as decyl methacrylate, stearyl methacrylate, and glycidyl methacrylate;
Among these, 2-ethylhexyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate are preferable, and 2-ethylhexyl acrylate is more preferable.
そして、非水溶性粒子状重合体における、その他の単量体単位の含有割合は、好ましくは３０質量％以下、より好ましくは１０質量％以下であり、非水溶性粒子状重合体は、その他の単量体単位を含有しないことが更に好ましい。その他の単量体単位の含有割合を３０質量％以下とすれば、電解液中での接着性を更に高めることができる。 The content ratio of other monomer units in the water-insoluble particulate polymer is preferably 30% by mass or less, more preferably 10% by mass or less. More preferably, no monomer unit is contained. If the content ratio of other monomer units is 30% by mass or less, the adhesiveness in the electrolytic solution can be further improved.
［非水溶性粒子状重合体の調製方法］
そして、非水溶性粒子状重合体は、例えば、上述した単量体を含む単量体組成物を重合することにより調製することができる。
ここで、単量体組成物中の各単量体の含有割合は、通常、所望の非水溶性粒子状重合体における単量体単位の含有割合と同様にする。
また、非水溶性粒子状重合体の重合様式は、特に限定はされず、例えば、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法を用いてもよい。重合反応としては、イオン重合、ラジカル重合、リビングラジカル重合などの付加重合を用いることができる。そして、重合に使用される乳化剤、分散剤、重合開始剤、重合助剤などは、一般に用いられるものを使用することができ、その使用量も、一般に使用される量とする。
[Method for preparing water-insoluble particulate polymer]
And a water-insoluble particulate polymer can be prepared by polymerizing the monomer composition containing the monomer mentioned above, for example.
Here, the content ratio of each monomer in the monomer composition is usually the same as the content ratio of the monomer unit in the desired water-insoluble particulate polymer.
The polymerization mode of the water-insoluble particulate polymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used. As the polymerization reaction, addition polymerization such as ionic polymerization, radical polymerization, and living radical polymerization can be used. And generally used emulsifiers, dispersants, polymerization initiators, polymerization aids and the like used for the polymerization can be used, and the amount used is also generally used.
＜接着性重合体＞
接着性重合体は、ガラス転移温度が２０℃以下であることを必要とする。そして、接着性重合体は、電解液の浸漬前であっても優れた接着力を発揮する。
なお、機能層の多孔性を確保してイオン伝導性が低下するのを抑制し、機能層を用いた二次電池の内部抵抗の増加を抑制する観点からは、接着性重合体は、水中において粒子状の状態で存在していることが好ましく、バインダー組成物を用いて形成された機能層中においても粒子状の状態を維持していることがより好ましい。即ち、バインダー組成物は、接着性粒子状重合体を含むことが好ましい。
<Adhesive polymer>
The adhesive polymer needs to have a glass transition temperature of 20 ° C. or lower. And an adhesive polymer exhibits the outstanding adhesive force even before immersion of electrolyte solution.
From the standpoint of ensuring the porosity of the functional layer and suppressing the decrease in ionic conductivity, and suppressing the increase in internal resistance of the secondary battery using the functional layer, the adhesive polymer is It is preferable that it exists in a particulate state, and it is more preferable that the particulate state is maintained even in a functional layer formed using the binder composition. That is, the binder composition preferably contains an adhesive particulate polymer.
［ガラス転移温度］
ここで、接着性重合体のガラス転移温度は、２０℃以下であることが必要であり、０℃以下であることが好ましく、−１０℃以下であることがより好ましい。ガラス転移温度が高すぎると、電解液への浸漬前に十分な接着力を発揮することができず、機能層の形成および機能層の電解液浸漬前のピール強度の確保が困難になる。なお、接着性重合体のガラス転移温度は、通常、−６０℃以上である。
[Glass-transition temperature]
Here, the glass transition temperature of the adhesive polymer needs to be 20 ° C. or lower, preferably 0 ° C. or lower, and more preferably −10 ° C. or lower. If the glass transition temperature is too high, sufficient adhesive force cannot be exhibited before immersion in the electrolytic solution, and it becomes difficult to form the functional layer and to ensure the peel strength of the functional layer before immersion in the electrolytic solution. In addition, the glass transition temperature of an adhesive polymer is -60 degreeC or more normally.
［電解液膨潤度］
また、接着性重合体の電解液膨潤度は、１倍超であることが好ましく、１．２倍以上であることがより好ましく、１．５倍以上であることが更に好ましく、３倍未満であることが好ましく、２．５倍以下であることがより好ましく、２．０倍以下であることが更に好ましい。電解液膨潤度が１倍超３倍未満であれば、電解液への浸漬前に十分な接着力を発揮させて、機能層を良好に形成することができると共に、機能層の電解液浸漬前のピール強度を十分に高めることができる。
なお、接着性重合体の電解液膨潤度が低すぎると、機能層のイオン伝導性が低下して機能層を用いた二次電池の内部抵抗が増加し、二次電池のレート特性を十分に向上させることができない虞がある。
[Electrolytic solution swelling]
Moreover, the electrolyte solution swelling degree of the adhesive polymer is preferably more than 1 time, more preferably 1.2 times or more, further preferably 1.5 times or more, and less than 3 times. Preferably, it is 2.5 times or less, more preferably 2.0 times or less. If the degree of swelling of the electrolytic solution is more than 1 and less than 3 times, sufficient functional strength can be exerted before immersion in the electrolytic solution to form the functional layer well, and before the functional layer is immersed in the electrolytic solution The peel strength can be sufficiently increased.
If the swelling degree of the electrolyte solution of the adhesive polymer is too low, the ionic conductivity of the functional layer is lowered, the internal resistance of the secondary battery using the functional layer is increased, and the secondary battery has sufficient rate characteristics. There is a possibility that it cannot be improved.
［体積平均粒子径］
更に、接着性重合体の体積平均粒子径は、５０ｎｍ以上であることが好ましく、１００ｎｍ以上であることがより好ましく、１５０ｎｍ以上であることが更に好ましく、５００ｎｍ以下であることが好ましく、３００ｎｍ以下であることがより好ましく、２５０ｎｍ以下であることが更に好ましい。体積平均粒子径を５０ｎｍ以上とすれば、分散安定性を向上させ、例えば高いせん断力を受けた場合であっても接着性重合体が凝集するのを抑制することができるので、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を向上させることができる。また、体積平均粒子径を５００ｎｍ以下とすれば、電解液への浸漬前に高い接着力を発揮させ、機能層の電解液浸漬前のピール強度を更に高めることができる。
[Volume average particle diameter]
Furthermore, the volume average particle diameter of the adhesive polymer is preferably 50 nm or more, more preferably 100 nm or more, further preferably 150 nm or more, preferably 500 nm or less, and preferably 300 nm or less. More preferably, it is more preferably 250 nm or less. If the volume average particle diameter is 50 nm or more, the dispersion stability is improved, and for example, the adhesive polymer can be prevented from aggregating even when subjected to a high shearing force. The lifetime characteristic of a secondary battery provided with the functional layer formed using can be improved. Further, when the volume average particle diameter is 500 nm or less, a high adhesive force can be exhibited before immersion in the electrolytic solution, and the peel strength of the functional layer before immersion in the electrolytic solution can be further increased.
［組成］
なお、接着性重合体としては、上述したガラス転移温度を有する重合体であれば特に限定されることなく、任意の重合体を用いることができる。中でも、分散安定性および電解液への浸漬前の接着性を高める観点からは、接着性重合体としては、（メタ）アクリル酸アルキルエステル単量体単位と芳香族モノビニル単量体単位とを含む共重合体を用いることが好ましく、（メタ）アクリル酸アルキルエステル単量体単位と芳香族モノビニル単量体単位とを含むランダム共重合体を用いることがより好ましい。
[composition]
In addition, as an adhesive polymer, if it is a polymer which has the glass transition temperature mentioned above, it will not specifically limit, An arbitrary polymer can be used. Among them, from the viewpoint of improving dispersion stability and adhesion before immersion in the electrolyte, the adhesive polymer includes a (meth) acrylic acid alkyl ester monomer unit and an aromatic monovinyl monomer unit. It is preferable to use a copolymer, and it is more preferable to use a random copolymer containing a (meth) acrylic acid alkyl ester monomer unit and an aromatic monovinyl monomer unit.
[[（メタ）アクリル酸アルキルエステル単量体単位]]
ここで、（メタ）アクリル酸アルキルエステル単量体単位を形成しうる（メタ）アクリル酸アルキルエステル単量体としては、上述した非水溶性粒子状重合体において、その他の単量体単位としての（メタ）アクリル酸アルキルエステル単量体単位を形成しうる（メタ）アクリル酸アルキルエステル単量体と同様のものが挙げられる。
中でも、２−エチルヘキシルアクリレート、エチルアクリレート、ブチルアクリレート、メチルメタクリレートが好ましく、２−エチルヘキシルアクリレートがより好ましい。
[[(Meth) acrylic acid alkyl ester monomer unit]]
Here, as the (meth) acrylic acid alkyl ester monomer that can form the (meth) acrylic acid alkyl ester monomer unit, in the above-described water-insoluble particulate polymer, The same thing as the (meth) acrylic-acid alkylester monomer which can form a (meth) acrylic-acid alkylester monomer unit is mentioned.
Among these, 2-ethylhexyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate are preferable, and 2-ethylhexyl acrylate is more preferable.
そして、接着性重合体における、（メタ）アクリル酸アルキルエステル単量体単位の含有割合は、好ましくは３５質量％以上、より好ましくは４５質量％以上、更に好ましくは５５質量％以上であり、好ましくは８０質量％以下、より好ましくは７５質量％以下、更に好ましくは７０質量％以下である。（メタ）アクリル酸アルキルエステル単量体単位の含有割合を３５質量％以上とすれば、電解液への浸漬前の接着性を更に高め、バインダー組成物を用いて形成した機能層の電解液浸漬前のピール強度を更に高めることができる。一方、（メタ）アクリル酸アルキルエステル単量体単位の含有割合を８０質量％以下とすれば、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を高めることができる。 The content ratio of the (meth) acrylic acid alkyl ester monomer unit in the adhesive polymer is preferably 35% by mass or more, more preferably 45% by mass or more, and further preferably 55% by mass or more. Is 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less. If the content ratio of the (meth) acrylic acid alkyl ester monomer unit is 35% by mass or more, the adhesion before immersion in the electrolytic solution is further improved, and the functional layer formed using the binder composition is immersed in the electrolytic solution. The previous peel strength can be further increased. On the other hand, when the content ratio of the (meth) acrylic acid alkyl ester monomer unit is 80% by mass or less, the life characteristics of the secondary battery including the functional layer formed using the binder composition can be improved.
[[芳香族モノビニル単量体単位]]
また、芳香族モノビニル単量体単位を形成しうる芳香族モノビニル単量体としては、上述した非水溶性粒子状重合体において芳香族モノビニル単量体単位を形成しうる芳香族モノビニル単量体と同様のものが挙げられる。
中でも、芳香族モノビニル単量体としては、スチレンが好ましい。
[[Aromatic monovinyl monomer unit]]
The aromatic monovinyl monomer that can form an aromatic monovinyl monomer unit includes an aromatic monovinyl monomer that can form an aromatic monovinyl monomer unit in the water-insoluble particulate polymer described above. The same thing is mentioned.
Among them, styrene is preferable as the aromatic monovinyl monomer.
そして、接着性重合体における、芳香族モノビニル単量体単位の含有割合は、好ましくは１０質量％以上であり、より好ましくは２０質量％以上であり、更に好ましくは２７質量％以上であり、好ましくは５５質量％以下であり、より好ましくは４５質量％以下であり、更に好ましくは３５質量％以下である。芳香族モノビニル単量体単位の含有割合を１０質量％以上とすれば、バインダー組成物を用いて形成した機能層を備える二次電池の寿命特性を高めることができる。一方、芳香族モノビニル単量体単位の含有割合を５５質量％以下とすれば、電解液への浸漬前の接着性を更に高め、バインダー組成物を用いて形成した機能層の電解液浸漬前のピール強度を更に高めることができる。 The content of the aromatic monovinyl monomer unit in the adhesive polymer is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 27% by mass or more, preferably Is 55% by mass or less, more preferably 45% by mass or less, and still more preferably 35% by mass or less. When the content ratio of the aromatic monovinyl monomer unit is 10% by mass or more, the life characteristics of the secondary battery including the functional layer formed using the binder composition can be improved. On the other hand, if the content ratio of the aromatic monovinyl monomer unit is 55% by mass or less, the adhesiveness before immersion in the electrolytic solution is further improved, and the functional layer formed using the binder composition before immersion in the electrolytic solution. Peel strength can be further increased.
[[その他の単量体単位]]
なお、接着性重合体は、上述した単量体単位以外に、その他の単量体単位を含有していてもよい。そして、その他の単量体単位としては、特に限定されることなく、酸性基含有単量体単位、架橋性単量体単位などが挙げられる。
なお、その他の単量体単位である酸性基含有単量体単位および架橋性単量体単位は、上述した（メタ）アクリル酸アルキルエステル単量体単位および芳香族モノビニル単量体単位以外の単量体単位である。従って、酸性基含有単量体単位を形成しうる酸性基含有単量体および架橋性単量体単位を形成しうる架橋性単量体には、上述した（メタ）アクリル酸アルキルエステル単量体および芳香族モノビニル単量体（例えば、スチレンスルホン酸およびその塩など）は含まれない。
[[Other monomer units]]
The adhesive polymer may contain other monomer units in addition to the monomer units described above. The other monomer units are not particularly limited, and examples thereof include acidic group-containing monomer units and crosslinkable monomer units.
Other monomer units, such as acidic group-containing monomer units and crosslinkable monomer units, are units other than the above-mentioned (meth) acrylic acid alkyl ester monomer units and aromatic monovinyl monomer units. It is a unit of mass. Accordingly, the acidic group-containing monomer that can form an acidic group-containing monomer unit and the crosslinkable monomer that can form a crosslinkable monomer unit include the above-mentioned (meth) acrylic acid alkyl ester monomers. And aromatic monovinyl monomers (such as styrene sulfonic acid and its salts) are not included.
−酸性基含有単量体単位−
ここで、酸性基含有単量体単位を形成しうる酸性基含有単量体としては、上述した非水溶性粒子状重合体において酸性基含有単量体単位を形成しうる酸性基含有単量体と同様のものが挙げられる。
中でも、酸性基含有単量体としては、カルボン酸基含有単量体が好ましく、フマル酸、イタコン酸、アクリル酸、メタクリル酸がより好ましく、アクリル酸が更に好ましい。
-Acid group-containing monomer unit-
Here, as the acidic group-containing monomer that can form an acidic group-containing monomer unit, the acidic group-containing monomer that can form an acidic group-containing monomer unit in the water-insoluble particulate polymer described above. The same thing is mentioned.
Especially, as an acidic group containing monomer, a carboxylic acid group containing monomer is preferable, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid are more preferable, and acrylic acid is still more preferable.
そして、接着性重合体における、酸性基含有単量体単位の含有割合は、好ましくは１質量％以上、より好ましくは２質量％以上、更に好ましくは３質量％以上であり、好ましくは１０質量％以下、より好ましくは６質量％以下、更に好ましくは５質量％以下である。酸性基含有単量体単位の含有割合を１質量％以上とすれば、分散安定性を向上させ、例えば高いせん断力を受けた場合であっても接着性重合体が凝集するのを抑制することができると共に、二次電池の寿命特性を更に向上させることができる。また、酸性基含有単量体単位の含有割合を１０質量％以下とすれば、電解液への浸漬前の接着性を更に高め、バインダー組成物を用いて形成した機能層の電解液浸漬前のピール強度を更に高めることができる。 The content ratio of the acidic group-containing monomer unit in the adhesive polymer is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and preferably 10% by mass. Hereinafter, it is more preferably 6% by mass or less, still more preferably 5% by mass or less. When the content ratio of the acidic group-containing monomer unit is 1% by mass or more, the dispersion stability is improved, for example, the aggregation of the adhesive polymer is suppressed even when subjected to a high shearing force. In addition, the life characteristics of the secondary battery can be further improved. Moreover, if the content rate of an acidic group containing monomer unit shall be 10 mass% or less, the adhesiveness before immersion to electrolyte solution will further be improved, and before the electrolyte solution immersion of the functional layer formed using the binder composition Peel strength can be further increased.
−架橋性単量体単位−
また、架橋性単量体単位を形成しうる架橋性単量体としては、上述した非水溶性粒子状重合体において架橋性単量体単位を形成しうる架橋性単量体と同様のものが挙げられる。
中でも、架橋性単量体としては、親水性の架橋性単量体と疎水性の架橋性単量体とを併用することが好ましく、アリルグリシジルエーテルとアリルメタクリレートとを併用することがより好ましい。
-Crosslinkable monomer unit-
The crosslinkable monomer that can form a crosslinkable monomer unit is the same as the crosslinkable monomer that can form a crosslinkable monomer unit in the water-insoluble particulate polymer described above. Can be mentioned.
Among these, as the crosslinkable monomer, it is preferable to use a hydrophilic crosslinkable monomer and a hydrophobic crosslinkable monomer in combination, and it is more preferable to use allyl glycidyl ether and allyl methacrylate in combination.
そして、接着性重合体における、架橋性単量体単位の含有割合は、好ましくは０．２質量％以上、より好ましくは０．５質量％以上、更に好ましくは０．８質量％以上であり、好ましくは５質量％以下、より好ましくは２質量％以下である。架橋性単量体単位の含有割合を０．２質量％以上５質量％以下とすれば、電解液への浸漬前の接着性を更に高め、バインダー組成物を用いて形成した機能層の電解液浸漬前のピール強度を更に高めることができる。 The content of the crosslinkable monomer unit in the adhesive polymer is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more. Preferably it is 5 mass% or less, More preferably, it is 2 mass% or less. When the content ratio of the crosslinkable monomer unit is 0.2% by mass or more and 5% by mass or less, the adhesiveness before immersion in the electrolytic solution is further improved, and the electrolytic solution of the functional layer formed using the binder composition The peel strength before immersion can be further increased.
［接着性重合体の調製方法］
そして、接着性重合体は、例えば、上述した単量体を含む単量体組成物を重合することにより調製することができる。
ここで、単量体組成物中の各単量体の含有割合は、通常、所望の接着性重合体における単量体単位の含有割合と同様にする。
また、接着性重合体の重合様式は、特に限定はされず、例えば、溶液重合法、懸濁重合法、塊状重合法、乳化重合法などのいずれの方法を用いてもよい。重合反応としては、イオン重合、ラジカル重合、リビングラジカル重合などの付加重合を用いることができる。そして、重合に使用される乳化剤、分散剤、重合開始剤、重合助剤などは、一般に用いられるものを使用することができ、その使用量も、一般に使用される量とする。
ここで、ランダム共重合体よりなる接着性重合体を調製する場合には、単量体組成物中の単量体をある程度重合したオリゴマーの状態でなく、単量体の状態で重合を開始することで、ブロック共重合体およびグラフト共重合体の生成を抑制すればよい。
[Method for Preparing Adhesive Polymer]
And an adhesive polymer can be prepared by superposing | polymerizing the monomer composition containing the monomer mentioned above, for example.
Here, the content ratio of each monomer in the monomer composition is usually the same as the content ratio of the monomer unit in the desired adhesive polymer.
The polymerization mode of the adhesive polymer is not particularly limited, and any method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method may be used. As the polymerization reaction, addition polymerization such as ionic polymerization, radical polymerization, and living radical polymerization can be used. And generally used emulsifiers, dispersants, polymerization initiators, polymerization aids and the like used for the polymerization can be used, and the amount used is also generally used.
Here, when preparing an adhesive polymer made of a random copolymer, the polymerization is started not in the form of an oligomer obtained by polymerizing the monomer in the monomer composition to some extent but in the monomer state. Thus, the generation of the block copolymer and the graft copolymer may be suppressed.
＜その他の成分＞
なお、バインダー組成物は、上述した成分以外にも、その他の任意の成分を含んでいてもよい。前記任意の成分は、機能層を用いた二次電池における電池反応に過度に好ましくない影響を及ぼさないものであれば、特に制限は無い。また、前記任意の成分の種類は、１種類でもよく、２種類以上でもよい。
前記任意の成分としては、例えば、濡れ剤、レベリング剤、電解液分解抑制剤、水溶性重合体などの、機能層の形成に使用される既知の添加剤が挙げられる。
<Other ingredients>
In addition, the binder composition may contain other arbitrary components in addition to the components described above. The optional component is not particularly limited as long as it does not have an excessively unfavorable influence on the battery reaction in the secondary battery using the functional layer. Further, the kind of the arbitrary component may be one kind or two or more kinds.
Examples of the optional component include known additives used for forming a functional layer, such as a wetting agent, a leveling agent, an electrolytic solution decomposition inhibitor, and a water-soluble polymer.
＜非水系二次電池機能層用バインダー組成物の調製＞
本発明のバインダー組成物は、上述した成分を分散媒としての水中に分散させることにより調製することができる。具体的には、ボールミル、サンドミル、ビーズミル、顔料分散機、らい潰機、超音波分散機、ホモジナイザー、プラネタリーミキサー、フィルミックスなどの混合機を用いて上述した成分と水とを混合することにより、バインダー組成物を調製することができる。
なお、非水溶性粒子状重合体や接着性重合体は、水系溶媒中で単量体組成物を重合して調製した場合には、水分散体の状態でそのまま他の成分と混合することができる。また、非水溶性粒子状重合体や接着性重合体を水分散体の状態で混合する場合には、水分散体中の水を分散媒として使用してもよい。
<Preparation of binder composition for non-aqueous secondary battery functional layer>
The binder composition of the present invention can be prepared by dispersing the above-described components in water as a dispersion medium. Specifically, by mixing the above-described components and water using a mixer such as a ball mill, sand mill, bead mill, pigment disperser, crushed grinder, ultrasonic disperser, homogenizer, planetary mixer, fill mix, etc. A binder composition can be prepared.
In addition, when the water-insoluble particulate polymer or adhesive polymer is prepared by polymerizing the monomer composition in an aqueous solvent, it can be mixed with other components as it is in the state of an aqueous dispersion. it can. Moreover, when mixing a water-insoluble particulate polymer and adhesive polymer in the state of an aqueous dispersion, you may use the water in an aqueous dispersion as a dispersion medium.
［非水溶性粒子状重合体および接着性重合体の配合比］
ここで、バインダー組成物の調製に当たり、非水溶性粒子状重合体および接着性重合体の配合比は、非水溶性粒子状重合体の含有量が、接着性重合体１００質量部当たり１質量部以上２０質量部以下となるようにすることが好ましい。そして、バインダー組成物中の非水溶性粒子状重合体の含有量は、接着性重合体１００質量部当たり、１．５質量部以上であることがより好ましく、２．０質量部以上であることが更に好ましく、３．０質量部以上であることが特に好ましく、１５質量部以下であることがより好ましく、１２質量部以下であることが更に好ましく、９．０質量部以下であることが特に好ましい。非水溶性粒子状重合体の量を接着性重合体１００質量部当たり１質量部以上とすれば、電解液中での接着力を十分に向上させ、機能層の電解液浸漬後のピール強度を十分に高めることができる。一方、非水溶性粒子状重合体の量を接着性重合体１００質量部当たり２０質量部以下とすれば、電解液への浸漬前の接着力を十分に向上させ、機能層の電解液浸漬前のピール強度を十分に高めることができる。また、非水溶性粒子状重合体は、通常、電解液への浸漬前には大きな接着力を発現しないところ、非水溶性粒子状重合体の量を接着性重合体１００質量部当たり２０質量部以下とすれば、機能層の耐粉落ち性を高めることができると共に、電解液への浸漬前に機能層から非水溶性粒子状重合体が脱落するのを抑制して、機能層の電解液浸漬後のピール強度を十分に高めることができる。
[Blending ratio of water-insoluble particulate polymer and adhesive polymer]
Here, in preparing the binder composition, the mixing ratio of the water-insoluble particulate polymer and the adhesive polymer is such that the content of the water-insoluble particulate polymer is 1 part by mass per 100 parts by mass of the adhesive polymer. It is preferable that the amount is 20 parts by mass or less. The content of the water-insoluble particulate polymer in the binder composition is more preferably 1.5 parts by mass or more, and 2.0 parts by mass or more per 100 parts by mass of the adhesive polymer. Is more preferably 3.0 parts by mass or more, more preferably 15 parts by mass or less, still more preferably 12 parts by mass or less, and particularly preferably 9.0 parts by mass or less. preferable. If the amount of the water-insoluble particulate polymer is 1 part by mass or more per 100 parts by mass of the adhesive polymer, the adhesive strength in the electrolyte is sufficiently improved, and the peel strength of the functional layer after immersion in the electrolyte is increased. It can be raised enough. On the other hand, if the amount of the water-insoluble particulate polymer is 20 parts by mass or less per 100 parts by mass of the adhesive polymer, the adhesive force before immersion in the electrolyte is sufficiently improved, and the functional layer before immersion in the electrolyte The peel strength can be sufficiently increased. In addition, the water-insoluble particulate polymer usually does not develop a large adhesive force before being immersed in the electrolytic solution, but the amount of the water-insoluble particulate polymer is 20 parts by mass per 100 parts by mass of the adhesive polymer. If it is as follows, the anti-powder resistance of the functional layer can be improved, and the non-water-soluble particulate polymer can be prevented from falling off from the functional layer before being immersed in the electrolytic solution. The peel strength after immersion can be sufficiently increased.
（非水系二次電池機能層用スラリー組成物）
本発明の非水系二次電池機能層用スラリー組成物は、上述した非水系二次電池機能層用バインダー組成物と、非導電性粒子とを含み、任意にその他の成分を更に含有する水系のスラリー組成物である。即ち、本発明の非水系二次電池機能層用スラリー組成物は、非導電性粒子と、非水溶性粒子状重合体と、接着性重合体と、水と含み、任意にその他の成分を更に含有する。
そして、本発明の非水系二次電池機能層用スラリー組成物を使用して機能層を形成すれば、機能層の電解液浸漬後のピール強度を高めることができると共に、機能層のイオン伝導性が低下するのを抑制して、二次電池の内部抵抗の増加を抑制することができる。従って、本発明の非水系二次電池機能層用スラリー組成物を用いて形成した機能層を使用すれば、二次電池のレート特性を向上させることができる。
(Slurry composition for non-aqueous secondary battery functional layer)
The slurry composition for a non-aqueous secondary battery functional layer of the present invention comprises an aqueous system containing the above-mentioned binder composition for a non-aqueous secondary battery functional layer and non-conductive particles, and optionally further containing other components. It is a slurry composition. That is, the slurry composition for a non-aqueous secondary battery functional layer of the present invention includes non-conductive particles, a water-insoluble particulate polymer, an adhesive polymer, and water, and optionally further contains other components. contains.
And if a functional layer is formed using the slurry composition for non-aqueous secondary battery functional layers of this invention, while the peel strength after electrolyte solution immersion of a functional layer can be raised, the ion conductivity of a functional layer Can be suppressed, and an increase in the internal resistance of the secondary battery can be suppressed. Therefore, if the functional layer formed using the slurry composition for a non-aqueous secondary battery functional layer of the present invention is used, the rate characteristics of the secondary battery can be improved.
＜非導電性粒子＞
ここで、非導電性粒子は、水および二次電池の非水系電解液に溶解せず、それらの中においても、その形状が維持される粒子である。そして、非導電性粒子は、電気化学的にも安定であるため、二次電池の使用環境下で機能層中に安定に存在する。
<Non-conductive particles>
Here, the non-conductive particles are particles that do not dissolve in water and the non-aqueous electrolyte solution of the secondary battery, and maintain the shape thereof. And since a nonelectroconductive particle is electrochemically stable, it exists stably in a functional layer under the use environment of a secondary battery.
そして、非導電性粒子としては、例えば各種の無機微粒子や有機微粒子を使用することができる。
具体的には、非導電性粒子としては、無機微粒子と、上述した非水溶性粒子状重合体および接着性重合体以外の有機微粒子との双方を用いることができるが、通常は無機微粒子が用いられる。なかでも、非導電性粒子の材料としては、非水系二次電池の使用環境下で安定に存在し、電気化学的に安定である材料が好ましい。このような観点から非導電性粒子の材料の好ましい例を挙げると、酸化アルミニウム（アルミナ）、水和アルミニウム酸化物（ベーマイト）、酸化ケイ素、酸化マグネシウム（マグネシア）、酸化カルシウム、酸化チタン（チタニア）、ＢａＴｉＯ3、ＺｒＯ、アルミナ−シリカ複合酸化物等の酸化物粒子；窒化アルミニウム、窒化ホウ素等の窒化物粒子；シリコン、ダイヤモンド等の共有結合性結晶粒子；硫酸バリウム、フッ化カルシウム、フッ化バリウム等の難溶性イオン結晶粒子；タルク、モンモリロナイト等の粘土微粒子；などが挙げられる。また、これらの粒子は必要に応じて元素置換、表面処理、固溶体化等が施されていてもよい。
なお、上述した非導電性粒子は、１種類を単独で使用してもよいし、２種類以上を組み合わせて用いてもよい。
As the nonconductive particles, for example, various inorganic fine particles and organic fine particles can be used.
Specifically, as the non-conductive particles, both inorganic fine particles and organic fine particles other than the above-described water-insoluble particulate polymer and adhesive polymer can be used. Usually, inorganic fine particles are used. It is done. Especially, as a material of nonelectroconductive particle, the material which exists stably in the use environment of a non-aqueous secondary battery and is electrochemically stable is preferable. From this point of view, preferable examples of the non-conductive particle material include aluminum oxide (alumina), hydrated aluminum oxide (boehmite), silicon oxide, magnesium oxide (magnesia), calcium oxide, titanium oxide (titania). Oxide particles such as BaTiO 3 , ZrO, alumina-silica composite oxide; nitride particles such as aluminum nitride and boron nitride; covalently bonded crystal particles such as silicon and diamond; barium sulfate, calcium fluoride, barium fluoride Insoluble ion crystal particles such as; clay fine particles such as talc and montmorillonite; In addition, these particles may be subjected to element substitution, surface treatment, solid solution, and the like as necessary.
In addition, the nonelectroconductive particle mentioned above may be used individually by 1 type, and may be used in combination of 2 or more types.
＜非水系二次電池機能層用バインダー組成物の配合比＞
ここで、非水系二次電池機能層用スラリー組成物中における、非導電性粒子と非水系二次電池機能層用バインダー組成物との配合比は、特に限定されないが、スラリー組成物中における非水溶性粒子状重合体および接着性重合体の含有量の合計は、非導電性粒子１００質量部当たり、好ましくは１質量部以上、より好ましくは１．５質量部以上、更に好ましくは２質量部以上であり、好ましくは１０質量部以下、より好ましくは８質量部以下、更に好ましくは５質量部以下である。非水溶性粒子状重合体の含有量と接着性重合体の含有量との合計を、非導電性粒子１００質量部当たり１質量部以上とすれば、電解液への浸漬前と浸漬後との双方の接着性を十分に確保して、機能層の電解液浸漬前のピール強度および機能層の電解液浸漬後のピール強度の双方を十分に高めることができる。また、非水溶性粒子状重合体の含有量と接着性重合体の含有量との合計を、非導電性粒子１００質量部当たり１０質量部以下とすれば、二次電池の内部抵抗の増加を抑制して、二次電池のレート特性および寿命特性を向上させることができる。
<Combination ratio of binder composition for non-aqueous secondary battery functional layer>
Here, the mixing ratio of the non-conductive particles and the binder composition for the non-aqueous secondary battery functional layer in the slurry composition for the non-aqueous secondary battery functional layer is not particularly limited. The total content of the water-soluble particulate polymer and the adhesive polymer is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and further preferably 2 parts by mass, per 100 parts by mass of the non-conductive particles. It is above, Preferably it is 10 mass parts or less, More preferably, it is 8 mass parts or less, More preferably, it is 5 mass parts or less. If the total of the content of the water-insoluble particulate polymer and the content of the adhesive polymer is 1 part by mass or more per 100 parts by mass of the non-conductive particles, before and after the immersion in the electrolyte solution Both adhesivenesses can be sufficiently secured, and both the peel strength before immersion of the functional layer in the electrolytic solution and the peel strength after immersion of the functional layer in the electrolytic solution can be sufficiently increased. Further, if the total content of the water-insoluble particulate polymer and the content of the adhesive polymer is 10 parts by mass or less per 100 parts by mass of the non-conductive particles, the internal resistance of the secondary battery is increased. It can suppress and can improve the rate characteristic and lifetime characteristic of a secondary battery.
＜その他の成分＞
なお、スラリー組成物は、上述した成分以外にも、その他の任意の成分を含んでいてもよい。前記任意の成分は、機能層を用いた二次電池における電池反応に過度に好ましくない影響を及ぼさないものであれば、特に制限は無い。また、前記任意の成分の種類は、１種類でもよく、２種類以上でもよい。
前記任意の成分としては、上述したバインダー組成物に配合し得るその他の成分と同様のものが挙げられる。
<Other ingredients>
In addition, the slurry composition may contain other arbitrary components in addition to the components described above. The optional component is not particularly limited as long as it does not have an excessively unfavorable influence on the battery reaction in the secondary battery using the functional layer. Further, the kind of the arbitrary component may be one kind or two or more kinds.
As said arbitrary component, the thing similar to the other component which can be mix | blended with the binder composition mentioned above is mentioned.
＜非水系二次電池機能層用スラリー組成物の調製＞
スラリー組成物の調製方法は、特に限定はされないが、通常は、上述したバインダー組成物と、非導電性粒子と、必要に応じて用いられる任意の成分とを、分散媒としての水の存在下で混合して得られる。なお、分散媒として使用される水には、バインダー組成物が含有していた水も含まれ得る。
<Preparation of slurry composition for non-aqueous secondary battery functional layer>
The method for preparing the slurry composition is not particularly limited, but usually, the binder composition described above, non-conductive particles, and optional components used as necessary, in the presence of water as a dispersion medium. It is obtained by mixing with. In addition, the water used as the dispersion medium may include the water contained in the binder composition.
ここで、上述した成分の混合方法は特に制限されないが、各成分を効率よく分散させるべく、混合装置として分散機を用いて混合を行うことが好ましい。そして、分散機は、上記成分を均一に分散および混合できる装置が好ましい。例を挙げると、ボールミル、サンドミル、顔料分散機、擂潰機、超音波分散機、ホモジナイザー、プラネタリーミキサーなどが挙げられる。なかでも、高い分散シェアを加えることができることから、ビーズミル、ロールミル、フィルミックス等の高分散装置が特に好ましい。 Here, although the mixing method of the component mentioned above is not restrict | limited in particular, In order to disperse | distribute each component efficiently, it is preferable to mix using a disperser as a mixing apparatus. The disperser is preferably an apparatus capable of uniformly dispersing and mixing the above components. Examples include a ball mill, a sand mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, and a planetary mixer. Among them, a high dispersion apparatus such as a bead mill, a roll mill, or a fill mix is particularly preferable because a high dispersion share can be added.
（非水系二次電池用機能層）
本発明の非水系二次電池用機能層は、上述した非水系二次電池機能層用スラリー組成物から形成されたものであり、例えば、上述したスラリー組成物を適切な基材の表面に塗布して塗膜を形成した後、形成した塗膜を乾燥することにより、形成することができる。
そして、本発明の非水系二次電池用機能層は、上述した非水系二次電池機能層用スラリー組成物を用いて形成しているので、電解液浸漬後であってもピール強度が高く、非水系二次電池に優れた電池特性を発揮させることができる。特に、本発明の非水系二次電池用機能層は、非水溶性粒子状重合体を含む水系のスラリー組成物を用いて形成されており、層内に粒子状の重合体が存在しているので、重合体を有機溶剤に溶解させてなる溶剤系のスラリー組成物を用いて形成した、層内で重合体が膜状化し易い機能層と比較し、多孔性が高く、イオン伝導性に優れている。従って、本発明の機能層を使用すれば、レート特性などの電池特性に優れる非水系二次電池を得ることができる。
(Functional layer for non-aqueous secondary batteries)
The functional layer for a non-aqueous secondary battery of the present invention is formed from the above-described slurry composition for a non-aqueous secondary battery functional layer. For example, the above-described slurry composition is applied to the surface of an appropriate substrate. And after forming a coating film, it can form by drying the formed coating film.
And since the non-aqueous secondary battery functional layer of the present invention is formed using the slurry composition for non-aqueous secondary battery functional layer described above, the peel strength is high even after the electrolyte is immersed, Excellent battery characteristics can be exhibited in the non-aqueous secondary battery. In particular, the functional layer for a non-aqueous secondary battery of the present invention is formed using an aqueous slurry composition containing a water-insoluble particulate polymer, and the particulate polymer is present in the layer. Therefore, compared with a functional layer formed by using a solvent-based slurry composition obtained by dissolving a polymer in an organic solvent, the polymer is easily formed into a film in the layer, and has high porosity and excellent ionic conductivity. ing. Therefore, if the functional layer of the present invention is used, a nonaqueous secondary battery excellent in battery characteristics such as rate characteristics can be obtained.
＜基材＞
ここで、スラリー組成物を塗布する基材に制限は無く、例えば離型基材の表面にスラリー組成物の塗膜を形成し、その塗膜を乾燥して機能層を形成し、機能層から離型基材を剥がすようにしてもよい。このように、離型基材から剥がされた機能層を自立膜として二次電池の電池部材の形成に用いることもできる。具体的には、離型基材から剥がした機能層をセパレータ基材の上に積層して機能層を備えるセパレータを形成してもよいし、離型基材から剥がした機能層を電極基材の上に積層して機能層を備える電極を形成してもよい。
しかし、機能層を剥がす工程を省略して電池部材の製造効率を高める観点からは、基材としてセパレータ基材または電極基材を用いることが好ましい。セパレータ基材および電極基材上に設けられた機能層は、セパレータおよび電極の耐熱性や強度などを向上させる保護層（耐熱層）として好適に使用することができる。
<Base material>
Here, there is no restriction | limiting in the base material which apply | coats a slurry composition, for example, forms the coating film of a slurry composition on the surface of a mold release base material, dries the coating film, forms a functional layer, The release substrate may be peeled off. Thus, the functional layer peeled off from the release substrate can be used as a self-supporting film for forming a battery member of a secondary battery. Specifically, the functional layer peeled off from the release substrate may be laminated on the separator substrate to form a separator having the functional layer, or the functional layer peeled off from the release substrate may be used as the electrode substrate. An electrode provided with a functional layer may be formed by stacking on the substrate.
However, from the viewpoint of improving the production efficiency of the battery member by omitting the step of peeling off the functional layer, it is preferable to use a separator substrate or an electrode substrate as the substrate. The functional layer provided on the separator substrate and the electrode substrate can be suitably used as a protective layer (heat resistant layer) for improving the heat resistance and strength of the separator and the electrode.
［セパレータ基材］
ここで、セパレータ基材としては、特に限定されないが、有機セパレータ基材などの既知のセパレータ基材が挙げられる。有機セパレータ基材は、有機材料からなる多孔性部材であり、有機セパレータ基材の例を挙げると、ポリエチレン、ポリプロピレン等のポリオレフィン樹脂、芳香族ポリアミド樹脂などを含む微多孔膜または不織布などが挙げられ、強度に優れることからポリエチレン製の微多孔膜や不織布が好ましい。なお、有機セパレータ基材の厚さは、任意の厚さとすることができ、通常０．５μｍ以上、好ましくは５μｍ以上であり、通常４０μｍ以下、好ましくは３０μｍ以下、より好ましくは２０μｍ以下である。
[Separator substrate]
Here, although it does not specifically limit as a separator base material, Known separator base materials, such as an organic separator base material, are mentioned. The organic separator base material is a porous member made of an organic material. Examples of the organic separator base material include microporous films or nonwoven fabrics including polyolefin resins such as polyethylene and polypropylene, aromatic polyamide resins, and the like. From the viewpoint of excellent strength, a polyethylene microporous film or nonwoven fabric is preferred. In addition, the thickness of an organic separator base material can be made into arbitrary thickness, Usually, 0.5 micrometer or more, Preferably it is 5 micrometers or more, Usually, 40 micrometers or less, Preferably it is 30 micrometers or less, More preferably, it is 20 micrometers or less.
［電極基材］
電極基材（正極基材および負極基材）としては、特に限定されないが、集電体上に電極合材層が形成された電極基材が挙げられる。
ここで、集電体、電極合材層中の電極活物質（正極活物質、負極活物質）および電極合材層用結着材（正極合材層用結着材、負極合材層用結着材）、並びに、集電体上への電極合材層の形成方法は、既知のものを用いることができ、例えば特開２０１３−１４５７６３号公報に記載のものが挙げられる。
[Electrode substrate]
Although it does not specifically limit as an electrode base material (a positive electrode base material and a negative electrode base material), The electrode base material with which the electrode compound-material layer was formed on the electrical power collector is mentioned.
Here, the current collector, the electrode active material in the electrode mixture layer (positive electrode active material, negative electrode active material) and the binder for electrode mixture layer (binder for positive electrode mixture layer, binder for negative electrode mixture layer) As a method for forming the electrode mixture layer on the current collector and the current collector, known methods can be used, and examples thereof include those described in JP2013-145663A.
＜非水系二次電池用機能層の形成方法＞
上述したセパレータ基材、電極基材などの基材上に機能層を形成する方法としては、以下の方法が挙げられる。
１）スラリー組成物をセパレータ基材または電極基材の表面（電極基材の場合は電極合材層側の表面、以下同じ）に塗布し、次いで乾燥する方法；
２）スラリー組成物にセパレータ基材または電極基材を浸漬後、これを乾燥する方法；
３）スラリー組成物を離型基材上に塗布、乾燥して機能層を製造し、得られた機能層をセパレータ基材または電極基材の表面に転写する方法；
これらの中でも、前記１）の方法が、機能層の膜厚制御をしやすいことから特に好ましい。前記１）の方法は、詳細には、スラリー組成物を基材上に塗布する工程（塗布工程）、基材上に塗布されたスラリー組成物を乾燥させて機能層を形成する工程（機能層形成工程）を備える。
<Method for forming functional layer for non-aqueous secondary battery>
Examples of the method for forming a functional layer on a substrate such as the separator substrate and electrode substrate described above include the following methods.
1) A method in which the slurry composition is applied to the surface of a separator substrate or an electrode substrate (in the case of an electrode substrate, the surface on the electrode mixture layer side, the same shall apply hereinafter) and then dried;
2) A method of drying a separator substrate or an electrode substrate after immersing them in a slurry composition;
3) A method in which the slurry composition is applied onto a release substrate and dried to produce a functional layer, and the obtained functional layer is transferred to the surface of a separator substrate or an electrode substrate;
Among these, the method 1) is particularly preferable because the thickness of the functional layer can be easily controlled. Specifically, the method 1) includes a step of applying the slurry composition onto the substrate (application step), and a step of forming the functional layer by drying the slurry composition applied onto the substrate (functional layer). Forming step).
［塗布工程］
塗布工程において、スラリー組成物を基材上に塗布する方法としては、特に制限は無く、例えば、ドクターブレード法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗り法などの方法が挙げられる。
[Coating process]
In the coating process, the method of coating the slurry composition on the substrate is not particularly limited, and examples thereof include a doctor blade method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, and a brush coating method. Is mentioned.
［機能層形成工程］
また、機能層形成工程において、基材上のスラリー組成物を乾燥する方法としては、特に限定されず公知の方法を用いることができ、例えば温風、熱風、低湿風による乾燥、真空乾燥、赤外線や電子線などの照射による乾燥法が挙げられる。乾燥条件は特に限定されないが、乾燥温度は好ましくは５０〜１５０℃で、乾燥時間は好ましくは５〜３０分である。
[Functional layer formation process]
In the functional layer forming step, the method for drying the slurry composition on the substrate is not particularly limited, and a known method can be used. For example, drying with hot air, hot air, low-humidity air, vacuum drying, infrared ray And a drying method by irradiation with electron beam or the like. The drying conditions are not particularly limited, but the drying temperature is preferably 50 to 150 ° C., and the drying time is preferably 5 to 30 minutes.
（機能層を備える電池部材）
本発明の機能層を備える電池部材（セパレータおよび電極）は、本発明の効果を著しく損なわない限り、セパレータ基材または電極基材と、本発明の機能層との他に、上述した本発明の機能層以外の構成要素を備えていてもよい。例えば、必要に応じて、セパレータ基材または電極基材と、本発明の機能層との間に他の機能層を有していてもよい。この場合、本発明の機能層は、セパレータ基材または電極基材の表面に間接的に設けられることになる。また、本発明の機能層を備える電池部材は、本発明の機能層の表面に他の機能層を有していてもよい。
(Battery member having a functional layer)
The battery member (separator and electrode) provided with the functional layer of the present invention is not limited to the separator base or electrode base and the functional layer of the present invention as long as the effects of the present invention are not significantly impaired. You may provide components other than a functional layer. For example, you may have another functional layer between the separator base material or the electrode base material, and the functional layer of this invention as needed. In this case, the functional layer of the present invention is indirectly provided on the surface of the separator substrate or the electrode substrate. Moreover, the battery member provided with the functional layer of the present invention may have another functional layer on the surface of the functional layer of the present invention.
ここで、他の機能層としては、本発明の機能層に該当しないものであれば特に限定されることなく、本発明の機能層上に設けられて電池部材同士の接着に用いられる接着層などが挙げられる。
なお、本発明の機能層上に他の機能層として接着層を設ける場合、特に、他の機能層として電解液中において優れた接着力を発揮する接着層を設ける場合には、本発明の機能層の電解液中でのピール強度が十分に高くないと、他の機能層（接着層）の接着力が優れていても、本発明の機能層部分で剥離が生じ、電池特性が低下する虞がある。しかし、本発明の機能層は、電解液中でのピール強度も高いため、本発明の機能層を使用すれば、電解液中において優れた接着力を発揮する接着層を更に積層して電池部材同士の接着に用いた場合であっても、接着層に所期の性能を発揮させて電池部材同士を良好に接着させることができる。因みに、電解液中において優れた接着力を発揮する接着層としては、特に限定されることなく、電解液膨潤度が５倍以上３０倍以下の重合体からなるコア部と、電解液膨潤度が１倍超４倍以下の重合体からなるシェル部とを有するコアシェル構造の重合体を用いて形成した接着層、例えば特開２０１５−２８８４２号公報に記載の接着層などが挙げられる。
Here, the other functional layer is not particularly limited as long as it does not correspond to the functional layer of the present invention, and an adhesive layer provided on the functional layer of the present invention and used for bonding battery members to each other. Is mentioned.
In addition, when providing an adhesive layer as another functional layer on the functional layer of the present invention, in particular, when providing an adhesive layer that exhibits excellent adhesive force in the electrolyte as the other functional layer, the function of the present invention. If the peel strength of the layer in the electrolyte is not sufficiently high, even if the adhesive strength of the other functional layer (adhesive layer) is excellent, peeling may occur in the functional layer portion of the present invention, and the battery characteristics may deteriorate. There is. However, since the functional layer of the present invention also has high peel strength in the electrolytic solution, if the functional layer of the present invention is used, an adhesive layer that exhibits excellent adhesive force in the electrolytic solution is further laminated to form a battery member. Even if it is a case where it uses for adhesion | attachment of each other, a battery member can be adhere | attached favorably by making the adhesive layer exhibit expected performance. Incidentally, the adhesive layer exhibiting excellent adhesive force in the electrolytic solution is not particularly limited, and the core portion made of a polymer having an electrolytic solution swelling degree of 5 times or more and 30 times or less, and the electrolytic solution swelling degree is Examples include an adhesive layer formed using a polymer having a core-shell structure having a shell portion made of a polymer that is greater than 1 time and less than 4 times, such as an adhesive layer described in JP-A-2015-28842.
そして、本発明の機能層の厚みは、好ましくは０．０１μｍ以上、より好ましくは０．１μｍ以上、更に好ましくは１μｍ以上であり、好ましくは２０μｍ以下、より好ましくは１０μｍ以下、更に好ましくは５μｍ以下である。機能層の厚みが０．０１μｍ以上であることで、機能層の強度を十分に確保することができ、２０μｍ以下であることで、電解液の拡散性を確保し、機能層を用いた二次電池のレート特性を向上させることができる。 The thickness of the functional layer of the present invention is preferably 0.01 μm or more, more preferably 0.1 μm or more, still more preferably 1 μm or more, preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. It is. When the thickness of the functional layer is 0.01 μm or more, the strength of the functional layer can be sufficiently ensured, and when it is 20 μm or less, the diffusibility of the electrolytic solution is secured, and the secondary using the functional layer The rate characteristics of the battery can be improved.
（非水系二次電池）
本発明の非水系二次電池は、上述した本発明の非水系二次電池用機能層を備えるものである。より具体的には、本発明の非水系二次電池は、正極、負極、セパレータ、および電解液を備え、上述した非水系二次電池用機能層が、電池部材である正極、負極およびセパレータの少なくとも一つに含まれる。そして、本発明の非水系二次電池は、本発明のスラリー組成物から得られる機能層を備えているので、優れた電池特性を発揮する。
(Non-aqueous secondary battery)
The non-aqueous secondary battery of the present invention includes the above-described functional layer for a non-aqueous secondary battery of the present invention. More specifically, the non-aqueous secondary battery of the present invention includes a positive electrode, a negative electrode, a separator, and an electrolyte solution, and the functional layer for the non-aqueous secondary battery described above is a battery member of the positive electrode, the negative electrode, and the separator. Included in at least one. And since the non-aqueous secondary battery of this invention is equipped with the functional layer obtained from the slurry composition of this invention, it exhibits the outstanding battery characteristic.
＜正極、負極およびセパレータ＞
本発明の二次電池に用いる正極、負極およびセパレータは、少なくとも一つが本発明の機能層を含む。具体的には、機能層を有する正極および負極としては、集電体上に電極合材層を形成してなる電極基材の上に本発明の機能層を設けてなる電極を用いることができる。また、機能層を有するセパレータとしては、セパレータ基材の上に本発明の機能層を設けてなるセパレータを用いることができる。なお、電極基材およびセパレータ基材としては、「非水系二次電池用機能層」の項で挙げたものと同様のものを用いることができる。
また、機能層を有さない正極、負極およびセパレータとしては、特に限定されることなく、上述した電極基材よりなる電極および上述したセパレータ基材よりなるセパレータを用いることができる。
<Positive electrode, negative electrode and separator>
At least one of the positive electrode, the negative electrode, and the separator used for the secondary battery of the present invention includes the functional layer of the present invention. Specifically, as a positive electrode and a negative electrode having a functional layer, an electrode in which the functional layer of the present invention is provided on an electrode substrate formed by forming an electrode mixture layer on a current collector can be used. . Moreover, as a separator which has a functional layer, the separator which provides the functional layer of this invention on a separator base material can be used. In addition, as an electrode base material and a separator base material, the thing similar to what was mentioned by the term of the "functional layer for non-aqueous secondary batteries" can be used.
Moreover, as a positive electrode, a negative electrode, and a separator which do not have a functional layer, it does not specifically limit, The electrode which consists of an electrode base material mentioned above, and the separator which consists of a separator base material mentioned above can be used.
＜電解液＞
電解液としては、通常、有機溶媒に支持電解質を溶解した有機電解液が用いられる。支持電解質としては、例えば、リチウムイオン二次電池においてはリチウム塩が用いられる。リチウム塩としては、例えば、ＬｉＰＦ6、ＬｉＡｓＦ6、ＬｉＢＦ4、ＬｉＳｂＦ6、ＬｉＡｌＣｌ4、ＬｉＣｌＯ4、ＣＦ3ＳＯ3Ｌｉ、Ｃ4Ｆ9ＳＯ3Ｌｉ、ＣＦ3ＣＯＯＬｉ、（ＣＦ3ＣＯ）2ＮＬｉ、（ＣＦ3ＳＯ2）2ＮＬｉ、（Ｃ2Ｆ5ＳＯ2）ＮＬｉなどが挙げられる。なかでも、溶媒に溶けやすく高い解離度を示すので、ＬｉＰＦ6、ＬｉＣｌＯ4、ＣＦ3ＳＯ3Ｌｉが好ましい。なお、電解質は１種類を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。通常は、解離度の高い支持電解質を用いるほどリチウムイオン伝導度が高くなる傾向があるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。
<Electrolyte>
As the electrolytic solution, an organic electrolytic solution in which a supporting electrolyte is dissolved in an organic solvent is usually used. As the supporting electrolyte, for example, a lithium salt is used in a lithium ion secondary battery. Examples of the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like. Among these, LiPF 6 , LiClO 4 , and CF 3 SO 3 Li are preferable because they are easily dissolved in a solvent and exhibit a high degree of dissociation. In addition, electrolyte may be used individually by 1 type and may be used in combination of 2 or more types. Usually, the lithium ion conductivity tends to increase as the supporting electrolyte having a higher degree of dissociation is used, so that the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
電解液に使用する有機溶媒としては、支持電解質を溶解できるものであれば特に限定されないが、例えばリチウムイオン二次電池においては、ジメチルカーボネート（ＤＭＣ）、エチレンカーボネート（ＥＣ）、ジエチルカーボネート（ＤＥＣ）、プロピレンカーボネート（ＰＣ）、ブチレンカーボネート（ＢＣ）、メチルエチルカーボネート（ＭＥＣ）等のカーボネート類；γ−ブチロラクトン、ギ酸メチル等のエステル類；１，２−ジメトキシエタン、テトラヒドロフラン等のエーテル類；スルホラン、ジメチルスルホキシド等の含硫黄化合物類；などが好適に用いられる。また、これらの溶媒の混合液を用いてもよい。中でも、誘電率が高く、安定な電位領域が広いので、カーボネート類が好ましい。通常、用いる溶媒の粘度が低いほどリチウムイオン伝導度が高くなる傾向があるので、溶媒の種類によりリチウムイオン伝導度を調節することができる。
なお、電解液中の電解質の濃度は適宜調整することができる。また、電解液には、既知の添加剤を添加してもよい。
The organic solvent used in the electrolytic solution is not particularly limited as long as it can dissolve the supporting electrolyte. For example, in a lithium ion secondary battery, dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC). Carbonates such as propylene carbonate (PC), butylene carbonate (BC), and methyl ethyl carbonate (MEC); esters such as γ-butyrolactone and methyl formate; ethers such as 1,2-dimethoxyethane and tetrahydrofuran; sulfolane, Sulfur-containing compounds such as dimethyl sulfoxide; are preferably used. Moreover, you may use the liquid mixture of these solvents. Among these, carbonates are preferable because they have a high dielectric constant and a wide stable potential region. Usually, the lower the viscosity of the solvent used, the higher the lithium ion conductivity tends to be, so the lithium ion conductivity can be adjusted depending on the type of solvent.
The concentration of the electrolyte in the electrolytic solution can be adjusted as appropriate. Moreover, you may add a known additive to electrolyte solution.
（非水系二次電池の製造方法）
上述した本発明の非水系二次電池は、例えば、正極と負極とをセパレータを介して重ね合わせ、これを必要に応じて、巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口することで製造することができ、好ましくは以下に詳細に説明する本発明の非水系二次電池の製造方法を用いて製造される。なお、正極、負極、セパレータのうち、少なくとも一つの部材を機能層付きの部材とする。また、電池容器には、必要に応じてエキスパンドメタルや、ヒューズ、ＰＴＣ素子などの過電流防止素子、リード板などを入れ、電池内部の圧力上昇、過充放電の防止をしてもよい。電池の形状は、例えば、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、何れであってもよい。
(Method for producing non-aqueous secondary battery)
In the non-aqueous secondary battery of the present invention described above, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is placed in a battery container by winding or folding as necessary. It can manufacture by inject | pouring and sealing, Preferably it manufactures using the manufacturing method of the non-aqueous secondary battery of this invention demonstrated in detail below. Of the positive electrode, the negative electrode, and the separator, at least one member is a member with a functional layer. In addition, an expanded metal, an overcurrent prevention element such as a fuse or a PTC element, a lead plate, or the like may be placed in the battery container to prevent an increase in pressure inside the battery or overcharge / discharge. The shape of the battery may be any of a coin shape, a button shape, a sheet shape, a cylindrical shape, a square shape, a flat shape, and the like.
ここで、本発明の非水系二次電池の製造方法では、上述した本発明の非水系二次電池用機能層を加熱プレスする工程を経て非水系二次電池を製造する。具体的には、本発明の製造方法では、例えば、少なくとも一つが本発明の機能層を備えている電池部材（正極、負極およびセパレータ）を準備する工程（電池部材準備工程）と、準備した正極と負極とをセパレータを介して重ね合わせ、これを必要に応じて捲回または折り曲げて積層体を形成する工程（積層体形成工程）と、積層体を電池容器に入れ、電池容器に電解液を注入して封口する工程（封入工程）と、積層体ごと本発明の機能層を加熱プレスする工程（加熱プレス工程）とを実施して、非水系二次電池を製造する。
そして、本発明の製造方法では、本発明の機能層を加熱プレスしているので、機能層の電解液中でのピール強度を更に高め、優れた電池特性を有する二次電池を効率的に製造することができる。
Here, in the manufacturing method of the non-aqueous secondary battery of the present invention, the non-aqueous secondary battery is manufactured through the step of heat-pressing the above-described functional layer for the non-aqueous secondary battery of the present invention. Specifically, in the production method of the present invention, for example, a step (battery member preparation step) of preparing a battery member (positive electrode, negative electrode and separator) at least one having the functional layer of the present invention, and a prepared positive electrode And a negative electrode are stacked with a separator interposed between them and wound or bent as necessary to form a laminated body (laminated body forming process), and the laminated body is put into a battery container, and an electrolytic solution is put into the battery container. A non-aqueous secondary battery is manufactured by carrying out a step of filling and sealing (sealing step) and a step of heating and pressing the functional layer of the present invention together with the laminate (heat pressing step).
And in the manufacturing method of this invention, since the functional layer of this invention is heat-pressed, the peel strength in the electrolyte solution of a functional layer is further raised and the secondary battery which has the outstanding battery characteristic is manufactured efficiently. can do.
なお、本発明の製造方法では、加熱プレス工程は封入工程の前に実施してもよいが、積層された電池部材の位置ズレが加熱プレス時に発生するのを抑制する観点からは、加熱プレス工程は封入工程の後に実施することが好ましい。
また、加熱プレス工程は、機能層と電解液とを接触させた状態で（例えば、電解液中で）行うことが好ましい。機能層と電解液とを接触させ、非水溶性粒子状重合体などを電解液に膨潤させた状態で加熱プレスを行えば、機能層の電解液中でのピール強度を更に高めることができる。
In the production method of the present invention, the hot pressing step may be performed before the enclosing step, but from the viewpoint of suppressing the occurrence of misalignment of the stacked battery members during the hot pressing, the hot pressing step Is preferably carried out after the encapsulation step.
Moreover, it is preferable to perform a heat press process in the state which contacted the functional layer and electrolyte solution (for example, in electrolyte solution). If the pressing is performed in a state where the functional layer and the electrolytic solution are in contact with each other and the water-insoluble particulate polymer or the like is swollen in the electrolytic solution, the peel strength of the functional layer in the electrolytic solution can be further increased.
ここで、本発明の製造方法の加熱プレス工程を封入工程の前に行う場合には、機能層を加熱プレスする際の温度を、非水溶性粒子状重合体のガラス転移温度（Ｔｇ）を超える温度としてもよい。非水溶性粒子状重合体のガラス転移温度（Ｔｇ）を超える温度で加熱プレスを行えば、電解液浸漬前であっても非水溶性粒子状重合体にある程度の接着力を発揮させ、機能層を良好に形成することができる。なお、非水溶性粒子状重合体が流動化して機能層中で膜状化するのを抑制し、二次電池の電池特性が低下するのを抑制する観点からは、加熱プレス工程を封入工程の前に行う場合には、機能層を加熱プレスする際の温度を、非水溶性粒子状重合体のガラス転移温度（Ｔｇ）より３０℃高い温度（Ｔｇ＋３０℃）以下とすることが好ましい。
一方、本発明の製造方法の加熱プレス工程を封入工程の後に行う場合には、機能層を加熱プレスする際の温度を、非水溶性粒子状重合体のガラス転移温度（Ｔｇ）より４０℃低い温度（Ｔｇ−４０℃）以上とすることが好ましく、Ｔｇより３５℃低い温度（Ｔｇ−３５℃）以上とすることがより好ましく、Ｔｇより３０℃低い温度（Ｔｇ−３０℃）以上とすることが更に好ましい。また、加熱プレス工程を封入工程の後に行う場合には、加熱プレス工程では、機能層を加熱プレスする際の温度を、非水溶性粒子状重合体のガラス転移温度（Ｔｇ）以下とすることが好ましく、Ｔｇより５℃低い温度（Ｔｇ−５℃）以下とすることがより好ましく、Ｔｇより１０℃低い温度（Ｔｇ−１０℃）以下とすることが更に好ましい。加熱プレス工程を封入工程の後に行う場合に、機能層を加熱プレスする際の温度をＴｇより４０℃低い温度以上とすれば、電解液中において非水溶性粒子状重合体に高い接着力を発揮させ、機能層のピール強度を更に高めることができる。また、加熱プレス工程を封入工程の後に行う場合に、機能層を加熱プレスする際の温度をＴｇ以下とすれば、基材の劣化を防止することができると共に、加熱プレス中に非水溶性粒子状重合体が流動化して機能層中で膜状化するのを抑制し、二次電池の電池特性が低下するのを抑制することができる。
なお、加熱プレス工程において機能層を加熱プレスする際の圧力は、特に限定されることなく、例えば０．７ＭＰａ以上５ＭＰａ以下とすることができる。
Here, when performing the heat press process of the manufacturing method of this invention before an enclosure process, the temperature at the time of heat-pressing a functional layer exceeds the glass transition temperature (Tg) of a water-insoluble particulate polymer. It is good also as temperature. If heat-pressing is performed at a temperature exceeding the glass transition temperature (Tg) of the water-insoluble particulate polymer, the water-insoluble particulate polymer can exhibit a certain degree of adhesive force even before being immersed in the electrolyte, and the functional layer Can be formed satisfactorily. From the viewpoint of suppressing the water-insoluble particulate polymer from fluidizing and forming into a film in the functional layer, and suppressing the deterioration of the battery characteristics of the secondary battery, the heating press process is included in the encapsulation process. When performing before, it is preferable to make temperature at the time of carrying out the heat press of a functional layer below 30 degreeC higher than the glass transition temperature (Tg) of a water-insoluble particulate polymer (Tg + 30 degreeC).
On the other hand, when the heating press step of the production method of the present invention is performed after the encapsulation step, the temperature when the functional layer is hot pressed is 40 ° C. lower than the glass transition temperature (Tg) of the water-insoluble particulate polymer. It is preferable to set the temperature (Tg-40 ° C) or higher, more preferably 35 ° C lower than Tg (Tg-35 ° C) or higher, and 30 ° C lower than Tg (Tg-30 ° C) or higher. Is more preferable. Moreover, when performing a heat press process after an enclosure process, in the heat press process, the temperature at the time of carrying out the heat press of a functional layer shall be below the glass transition temperature (Tg) of a water-insoluble particulate polymer. Preferably, the temperature is 5 ° C. lower than Tg (Tg−5 ° C.) or lower, and more preferably 10 ° C. lower than Tg (Tg−10 ° C.) or lower. When the hot pressing process is performed after the sealing process, if the temperature at which the functional layer is hot pressed is set to 40 ° C. or lower than Tg, high adhesion to the water-insoluble particulate polymer is exhibited in the electrolytic solution. The peel strength of the functional layer can be further increased. In addition, when the heating press process is performed after the encapsulation process, if the temperature at which the functional layer is heated and pressed is Tg or less, the deterioration of the substrate can be prevented, and water-insoluble particles can be prevented during the heating press. It is possible to suppress the fluidized polymer from fluidizing and forming into a film in the functional layer, and to suppress the deterioration of the battery characteristics of the secondary battery.
In addition, the pressure at the time of carrying out the heat press of the functional layer in a heat press process is not specifically limited, For example, it can be 0.7 MPa or more and 5 MPa or less.
以下、本発明について実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下の説明において、量を表す「％」および「部」は、特に断らない限り、質量基準である。
また、複数種類の単量体を共重合して製造される重合体において、ある単量体を重合して形成される構造単位の前記重合体における割合は、別に断らない限り、通常は、その重合体の重合に用いる全単量体に占める当該ある単量体の比率(仕込み比)と一致する。
実施例および比較例において、重合体の電解液膨潤度、ガラス転移温度および体積平均粒子径、非水系二次電池機能層用スラリー組成物の高せん断下での安定性、非水系二次電池用機能層の電解液浸漬前のピール強度および電解液浸漬後のピール強度、並びに、二次電池のレート特性および寿命特性は、下記の方法で測定および評価した。
EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified.
In addition, in a polymer produced by copolymerizing a plurality of types of monomers, the proportion of the structural unit formed by polymerizing a certain monomer in the polymer is usually that unless otherwise specified. This coincides with the ratio (preparation ratio) of the certain monomer in the total monomers used for polymerization of the polymer.
In Examples and Comparative Examples, polymer electrolyte swelling degree, glass transition temperature and volume average particle diameter, stability of slurry composition for non-aqueous secondary battery functional layer under high shear, for non-aqueous secondary battery The peel strength of the functional layer before immersion in the electrolyte solution, the peel strength after immersion of the electrolyte solution, and the rate characteristics and life characteristics of the secondary battery were measured and evaluated by the following methods.
＜電解液膨潤度＞
重合体の水分散液を、電解銅箔（古河電工製ＮＣ−ＷＳ（登録商標））に対してテーブルコーターを用いて塗布し、５０℃で２０分、１２０℃で２０分、熱風乾燥器で乾燥させ、１ｃｍ×１ｃｍのフィルム（厚さ５００μｍ）を作製し、重量Ｍ０を測定した。その後、得られたフィルムを非水系電解液に６０℃で７２時間浸漬した。ここで、非水系電解液としては、エチレンカーボネート（ＥＣ）と、ジエチルカーボネート（ＤＥＣ）と、ビニレンカーボネート（ＶＣ）との混合溶媒（体積混合比：ＥＣ／ＤＥＣ／ＶＣ＝６８．５／３０／１．５）に、支持電解質としてＬｉＰＦ6を混合溶媒に対して１ｍｏｌ／Ｌの濃度で溶かしたものを用いた。その後、浸漬後のフィルムの表面の非水系電解液をふき取り重量Ｍ１を測定した。そして、下記式に従って、電解液膨潤度を算出した。
電解液膨潤度＝Ｍ１／Ｍ０
＜ガラス転移温度＞
重合体を含む水分散液を５０％湿度、２３〜２５℃の環境下で３日間乾燥させて、厚み１±０．３ｍｍのフィルムを得た。このフィルムを、１２０℃の熱風オーブンで１時間乾燥させた。その後、乾燥させたフィルムをサンプルとして、ＪＩＳ Ｋ７１２１に準拠して、測定温度−１００℃〜１８０℃、昇温速度５℃／分にて、示差走査熱量分析計（ＤＳＣ６２２０ＳＩＩ、ナノテクノロジー社製）を用いてガラス転移温度（℃）を測定した。
＜体積平均粒子径＞
重合体を含む水分散液をイオン交換水で希釈して、固形分濃度２質量％の測定試料を作成し、レーザー回折・光散乱方式粒度分布測定装置（ＬＳ２３０、ベックマンコールター社製）を用いて、粒子状の重合体の体積平均粒子径（Ｄ５０）を測定した。
＜高せん断下での安定性＞
スラリー組成物を、グラビアロール（線数９５）を用いて、搬送速度５０ｍ／分、グラビア回転比１００％の条件で、セパレータ基材（ポリエチレン製）上に塗布し、塗布後のセパレータ基材を切り出し、単位面積当たりの塗布量Ｑ０（ｍｇ／ｃｍ2）を算出した。また、塗布開始から１時間後に、同様に塗布量Ｑ１（ｍｇ／ｃｍ2）を算出した。そして、ΔＱ＝（｜Ｑ０−Ｑ１｜）／Ｑ０×１００（％）の式を用いて塗布量変化率ΔＱ（％）を算出し、下記の基準で評価した。塗布量変化率ΔＱが小さいほど、塗布量の変化が少なく、スラリー組成物の高せん断下での安定性が高いことを示す。
Ａ：塗布量変化率ΔＱが５％未満
Ｂ：塗布量変化率ΔＱが５％以上１０％未満
Ｃ：塗布量変化率ΔＱが１０％以上２０％未満
Ｄ：塗布量変化率ΔＱが２０％以上
＜電解液浸漬前のピール強度＞
ポリエチレン製の多孔基材からなる有機セパレータ基材（セルガード社製、厚み１６μｍ）を用意した。用意した有機セパレータ基材の片面にスラリー組成物を塗布し、６０℃で１０分乾燥させ、厚み１８μｍの機能層（多孔膜層）付きセパレータを得た。そして、長さ１００ｍｍ、幅１０ｍｍの長方形に切り出して試験片とした。また、予め試験台にセロハンテープを固定した。このセロハンテープとしては、ＪＩＳ Ｚ１５２２に規定されるものを用いた。
そして、セパレータから切り出した試験片を、機能層（多孔膜層）を下にしてセロハンテープに貼り付けた。その後、セパレータの一端を垂直方向に引張り速度１００ｍｍ／分で引っ張って剥がしたときの応力を測定した。測定を３回行い、測定した応力の平均値を求めて、これを機能層の電解液浸漬前のピール強度とした。そして、下記の基準で評価した。
Ａ：ピール強度が５０Ｎ／ｍ以上
Ｂ：ピール強度が３５Ｎ／ｍ以上５０Ｎ／ｍ未満
Ｃ：ピール強度が２０Ｎ／ｍ以上３５Ｎ／ｍ未満
Ｄ：ピール強度が２０Ｎ／ｍ未満
＜電解液浸漬後のピール強度＞
ポリエチレン製の多孔基材からなる有機セパレータ基材（セルガード社製、厚み１６μｍ）を２枚用意した。一方の有機セパレータ基材の片面にスラリー組成物を塗布し、塗布面に他方の有機セパレータ基材を重ねた。そして、６０℃で１０分乾燥させ、厚み３４μｍの積層体（有機セパレータ基材、機能層、有機セパレータ基材の積層体）を得た。その後、積層体を長さ１００ｍｍ、幅１０ｍｍの長方形に切り出し、試験片とした。
得られた試験片を非水系電解液中に温度６０℃で３日間浸漬した。ここで、非水系電解液としては、エチレンカーボネート（ＥＣ）と、ジエチルカーボネート（ＤＥＣ）と、ビニレンカーボネート（ＶＣ）との混合溶媒（体積混合比：ＥＣ／ＤＥＣ／ＶＣ＝６８．５／３０／１．５）に、支持電解質としてＬｉＰＦ6を混合溶媒に対して１ｍｏｌ／Ｌの濃度で溶かしたものを用いた。
その後、電解液に浸漬した試験片を１ＭＰａ、８０℃の条件で２分間プレスした後、一方の有機セパレータ基材を固定し、他方の有機セパレータ基材の一端を鉛直上方に引張り速度５０ｍｍ／分で引っ張って剥がしたときの応力を測定した。測定を３回行い、測定した応力の平均値を求めて、これを機能層の電解液浸漬後のピール強度とした。そして、下記の基準で評価した。
Ａ：ピール強度が９．０Ｎ／ｍ以上
Ｂ：ピール強度が８．０Ｎ／ｍ以上９．０Ｎ／ｍ未満
Ｃ：ピール強度が６．０Ｎ／ｍ以上８．０Ｎ／ｍ未満
Ｄ：ピール強度が６．０Ｎ／ｍ未満
＜レート特性＞
作製した二次電池を、２０％充電状態で、６０℃の環境下、１２時間静置した後に、２５℃の環境下で、４．３５Ｖ、０．１Ｃの充電、２．７５Ｖ、０．１Ｃの放電にて充放電の操作を行い、初期容量Ｃ０を測定した。その後、２５℃の環境下で、４．３５Ｖ、０．１Ｃの充電、２．７５Ｖ、２Ｃの放電にて充放電の操作を行い、容量Ｃ１を測定した。そして、ΔＣ＝｛（Ｃ０−Ｃ１）／Ｃ０｝×１００（％）を算出し、下記の基準で評価した。ΔＣが大きいほど、レート特性に優れていることを示す。
Ａ：ΔＣが９０％以上
Ｂ：ΔＣが８５％以上９０％未満
Ｃ：ΔＣが８０％以上８５％未満
Ｄ：ΔＣが８０％未満
＜寿命特性＞
作製した二次電池を、２０％充電状態で、６０℃の環境下、１２時間静置した後に、２５℃の環境下で４．３５Ｖ、０．１Ｃの充電、２．７５Ｖ、０．１Ｃの放電にて充放電の操作を行った。その後、４．３５Ｖ、０．１Ｃで充電し、そのまま６０℃で１６８時間（７日間）放置し、その後２５℃でセル電圧Ｖ２（Ｖ）を測定した。電圧降下ΔＶ（ｍＶ）をΔＶ＝｛４．３５−Ｖ２｝×１０００の式を用いて算出し、下記のように評価した。この値が小さいほど寿命特性（自己放電特性）に優れていることを示す。
Ａ：電圧降下ΔＶが２００ｍＶ以下
Ｂ：電圧降下ΔＶが２００ｍＶ超４００ｍＶ以下
Ｃ：電圧降下ΔＶが４００ｍＶ超６００ｍＶ以下
Ｄ：電圧降下ΔＶが６００ｍＶ超
<Electrolytic solution swelling>
The aqueous dispersion of the polymer is applied to an electrolytic copper foil (NC-WS (registered trademark) manufactured by Furukawa Electric) using a table coater, 20 minutes at 50 ° C, 20 minutes at 120 ° C, with a hot air dryer. The film was dried to produce a 1 cm × 1 cm film (thickness: 500 μm), and the weight M0 was measured. Thereafter, the obtained film was immersed in a nonaqueous electrolytic solution at 60 ° C. for 72 hours. Here, as the non-aqueous electrolyte, a mixed solvent of ethylene carbonate (EC), diethyl carbonate (DEC), and vinylene carbonate (VC) (volume mixing ratio: EC / DEC / VC = 68.5 / 30 / In 1.5), LiPF 6 dissolved in a mixed solvent at a concentration of 1 mol / L was used as a supporting electrolyte. Thereafter, the non-aqueous electrolyte solution on the surface of the film after immersion was wiped off, and the weight M1 was measured. And according to the following formula, electrolyte solution swelling degree was computed.
Electrolyte swelling degree = M1 / M0
<Glass transition temperature>
The aqueous dispersion containing the polymer was dried for 3 days in an environment of 50% humidity and 23 to 25 ° C. to obtain a film having a thickness of 1 ± 0.3 mm. The film was dried in a 120 ° C. hot air oven for 1 hour. Then, using the dried film as a sample, a differential scanning calorimeter (DSC6220SII, manufactured by Nanotechnology Co., Ltd.) is used at a measurement temperature of −100 ° C. to 180 ° C. and a temperature increase rate of 5 ° C./min according to JIS K7121. The glass transition temperature (° C) was measured.
<Volume average particle diameter>
An aqueous dispersion containing a polymer is diluted with ion-exchanged water to prepare a measurement sample having a solid content concentration of 2% by mass, and a laser diffraction / light scattering type particle size distribution analyzer (LS230, manufactured by Beckman Coulter, Inc.) is used. The volume average particle diameter (D50) of the particulate polymer was measured.
<Stability under high shear>
The slurry composition was applied onto a separator substrate (made of polyethylene) using a gravure roll (number of lines: 95) under the conditions of a conveyance speed of 50 m / min and a gravure rotation ratio of 100%. Cut out and the coating amount Q0 (mg / cm 2 ) per unit area was calculated. Further, the coating amount Q1 (mg / cm 2 ) was similarly calculated 1 hour after the start of coating. Then, a coating amount change rate ΔQ (%) was calculated using an equation of ΔQ = (| Q0−Q1 |) / Q0 × 100 (%), and evaluated according to the following criteria. The smaller the coating amount change rate ΔQ, the smaller the change in the coating amount and the higher the stability of the slurry composition under high shear.
A: Application rate change rate ΔQ is less than 5% B: Application rate change rate ΔQ is 5% or more and less than 10% C: Application rate change rate ΔQ is 10% or more and less than 20% D: Application rate change rate ΔQ is 20% or more <Peel strength before immersion in electrolyte>
An organic separator substrate made of a polyethylene porous substrate (manufactured by Celgard, thickness 16 μm) was prepared. The slurry composition was applied to one side of the prepared organic separator substrate and dried at 60 ° C. for 10 minutes to obtain a separator with a functional layer (porous membrane layer) having a thickness of 18 μm. And it cut out into the rectangle of length 100mm and width 10mm, and it was set as the test piece. Moreover, the cellophane tape was fixed to the test stand beforehand. As this cellophane tape, the one specified in JIS Z1522 was used.
And the test piece cut out from the separator was affixed on the cellophane tape with the functional layer (porous membrane layer) facing down. Thereafter, the stress was measured when one end of the separator was pulled in the vertical direction at a pulling speed of 100 mm / min and peeled off. The measurement was performed three times, the average value of the measured stress was determined, and this was defined as the peel strength before immersion of the functional layer in the electrolyte solution. And it evaluated on the following reference | standard.
A: Peel strength is 50 N / m or more B: Peel strength is 35 N / m or more and less than 50 N / m C: Peel strength is 20 N / m or more and less than 35 N / m D: Peel strength is less than 20 N / m <After electrolytic solution immersion Peel strength>
Two organic separator substrates made of a polyethylene porous substrate (manufactured by Celgard, thickness 16 μm) were prepared. The slurry composition was applied to one surface of one organic separator substrate, and the other organic separator substrate was stacked on the coated surface. And it was made to dry for 10 minutes at 60 degreeC, and the laminated body (laminated body of an organic separator base material, a functional layer, and an organic separator base material) with a thickness of 34 micrometers was obtained. Thereafter, the laminate was cut into a rectangle having a length of 100 mm and a width of 10 mm to obtain a test piece.
The obtained test piece was immersed in a non-aqueous electrolyte at a temperature of 60 ° C. for 3 days. Here, as the non-aqueous electrolyte, a mixed solvent of ethylene carbonate (EC), diethyl carbonate (DEC), and vinylene carbonate (VC) (volume mixing ratio: EC / DEC / VC = 68.5 / 30 / In 1.5), LiPF 6 dissolved in a mixed solvent at a concentration of 1 mol / L was used as a supporting electrolyte.
Thereafter, the test piece immersed in the electrolytic solution was pressed under conditions of 1 MPa and 80 ° C. for 2 minutes, one organic separator substrate was fixed, and one end of the other organic separator substrate was pulled vertically upward at a speed of 50 mm / min. The stress when it was pulled and peeled off was measured. The measurement was performed three times, the average value of the measured stress was determined, and this was taken as the peel strength after the functional layer was immersed in the electrolytic solution. And it evaluated on the following reference | standard.
A: Peel strength is 9.0 N / m or more B: Peel strength is 8.0 N / m or more and less than 9.0 N / m C: Peel strength is 6.0 N / m or more and less than 8.0 N / m D: Peel strength is <6.0 N / m <Rate characteristics>
The produced secondary battery was allowed to stand for 12 hours in an environment at 60 ° C. in a 20% charged state, and then charged at 4.35 V and 0.1 C in an environment at 25 ° C., 2.75 V and 0.1 C. The initial capacity C0 was measured by performing a charge / discharge operation. Thereafter, in a 25 ° C. environment, 4.35 V, 0.1 C charge, 2.75 V, and 2 C discharge were performed, and the capacity C1 was measured. Then, ΔC = {(C0−C1) / C0} × 100 (%) was calculated and evaluated according to the following criteria. It shows that it is excellent in a rate characteristic, so that (DELTA) C is large.
A: ΔC is 90% or more B: ΔC is 85% or more and less than 90% C: ΔC is 80% or more and less than 85% D: ΔC is less than 80% <lifetime characteristics>
The produced secondary battery was left in a 20% charged state at 60 ° C. for 12 hours, and then charged at 4.35 V and 0.1 C in an environment at 25 ° C., 2.75 V and 0.1 C. The charging / discharging operation was performed by discharging. Thereafter, the battery was charged at 4.35 V and 0.1 C, and allowed to stand at 60 ° C. for 168 hours (7 days). Thereafter, the cell voltage V2 (V) was measured at 25 ° C. The voltage drop ΔV (mV) was calculated using the equation: ΔV = {4.35−V2} × 1000 and evaluated as follows. It shows that it is excellent in the lifetime characteristic (self-discharge characteristic), so that this value is small.
A: Voltage drop ΔV is 200 mV or less B: Voltage drop ΔV is more than 200 mV and 400 mV or less C: Voltage drop ΔV is more than 400 mV and 600 mV or less D: Voltage drop ΔV is more than 600 mV
（実施例１）
＜非水溶性粒子状重合体の調製＞
撹拌機を備えた反応器に、イオン交換水１５０部、乳化剤としてのラウリル硫酸ナトリウム（花王ケミカル社製、製品名「エマール２Ｆ」）０．１部、および、重合開始剤としての過流酸アンモニウム０．３部を、それぞれ供給し、気相部を窒素ガスで置換し、８０℃に昇温した。
一方、別の容器で、イオン交換水４０部、分散剤としてのドデシルベンゼンスルホン酸ナトリウム０．２部、並びに、芳香族モノビニル単量体としてのスチレン９６部、酸性基含有単量体としてのメタクリル酸２部、架橋性単量体としてのエチレンジメタクリレート２部を混合して単量体組成物を得た。そして、得られた単量体組成物を３時間かけて前記反応器に連続的に添加し、重合を行った。なお、単量体組成物の添加中は、８０℃で反応を行った。添加終了後、さらに８０℃で２時間撹拌して反応を終了し、非水溶性粒子状重合体の水分散液を得た。
そして、得られた非水溶性粒子状重合体について、電解液膨潤度、ガラス転移温度および体積平均粒子径を測定した。結果を表１に示す。
＜接着性重合体の調製＞
撹拌機を備えた反応器に、イオン交換水９０部、重合開始剤としての過流酸アンモニウム０．５部を、それぞれ供給し、気相部を窒素ガスで置換し、８０℃に昇温した。
一方、別の容器で、イオン交換水４０部、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム０．８部、並びに、（メタ）アクリル酸アルキルエステル単量体としての２−エチルヘキシルアクリレート６５．１部、芳香族モノビニル単量体としてのスチレン３０部、酸性基含有単量体としてのアクリル酸３部、架橋性単量体としてのアリルグリシジルエーテル１．７部およびアリルメタクリレート０．２部を混合して単量体組成物を得た。そして、得られた単量体組成物を４時間かけて前記反応器に連続的に添加し、重合を行った。なお、単量体組成物の添加中は、８０℃で反応を行った。添加終了後、さらに８０℃で３時間撹拌して反応を終了し、粒子状の接着性重合体の水分散液を得た。
そして、得られた接着性重合体について、電解液膨潤度、ガラス転移温度および体積平均粒子径を測定した。結果を表１に示す。
＜非水系二次電池機能層用バインダー組成物の調製＞
非水溶性粒子状重合体の水分散液と、接着性重合体の水分散液とを、接着性重合体１００部（固形分換算）当たり、非水溶性粒子状重合体の量が５部（固形分換算）となるように混合し、２５℃で３０分間撹拌してバインダー組成物を得た。
＜非水系二次電池機能層用スラリー組成物の調製＞
非導電性粒子としてのベーマイトフィラー（河合石灰工業社製、ＢＭＭ−Ｗ）１００部と、非水溶性粒子状重合体および接着性重合体の合計量（固形分換算）が３部となる量のバインダー組成物と、増粘剤としてのカルボキシメチルセルロース（ダイセル１２２０）１．０部と、ポリエチレングリコール型界面活性剤（サンノプコＳＮウェット３６６）０．２部と、イオン交換水とを混合し、スラリー組成物を得た。
そして、得られたスラリー組成物について、高せん断下での安定性を評価した。また、得られたスラリー組成物を用いて、機能層の電解液浸漬前のピール強度および電解液浸漬後のピール強度を評価した。結果を表１に示す。
＜その他の機能層用組成物の調製＞
−コアシェル構造を有する有機粒子の調製−
攪拌機付き５ＭＰａ耐圧容器に、コア部形成用として、（メタ）アクリル酸エステル単量体としてのメタクリル酸メチル７５部、酸基含有単量体としてのメタクリル酸４部、架橋性単量体としてのエチレングリコールジメタクリレート１部；乳化剤としてのドデシルベンゼンスルホン酸ナトリウム１部；イオン交換水１５０部、並びに、重合開始剤としての過硫酸カリウム０．５部を入れ、十分に攪拌した。その後、６０℃に加温して重合を開始した。重合転化率が９６％になるまで重合を継続させて、コア部を構成する粒子状の重合体を含む水分散液を得た。
この水分散液に、シェル部形成用として、芳香族モノビニル単量体としてのスチレン１９部および酸基含有単量体としてのメタクリル酸１部の混合物を連続添加し、７０℃に加温して重合を継続した。重合転化率が９６％になった時点で、冷却して反応を停止し、コア部の外表面が部分的にシェル部で覆われたコアシェル構造を有する有機粒子を含む水分散液を調製した。
なお、得られた有機粒子の体積平均粒子径は、０．４５μｍであった。
−結着材の調製−
撹拌機を備えた反応器に、イオン交換水７０部、乳化剤としてのラウリル硫酸ナトリウム（花王ケミカル社製、製品名「エマール２Ｆ」）０．１５部、および重合開始剤としての過流酸アンモニウム０．５部を、それぞれ供給し、気相部を窒素ガスで置換し、６０℃に昇温した。
一方、別の容器で、イオン交換水５０部、分散剤としてのドデシルベンゼンスルホン酸ナトリウム０．５部、および、アクリル酸ブチル９４部、アクリロニトリル２部、メタクリル酸２部、Ｎ−メチロールアクリルアミド１部、アクリルアミド１部を混合して単量体組成物を得た。この単量体組成物を４時間かけて前記反応器に連続的に添加して重合を行った。単量体組成物の添加中は、６０℃で反応を行った。添加終了後、さらに７０℃で３時間撹拌して反応を終了し、粒子状の結着材（アクリル重合体）を含む水分散液を調製した。
なお、得られた結着材のガラス転移温度は−４０℃であった。
−組成物の調製−
前記のコアシェル構造を有する有機粒子を含む水分散液を固形分換算で１００部に対し、前記の結着材を含む水分散液を固形分換算で１５部、濡れ剤としてのエチレンオキサイド−プロピレンオキサイド共重合体（固形分濃度７０質量％、重合比：５／５（質量比））を固形分換算で１．９部混合し、さらにイオン交換水を固形分濃度が１５質量％になるように混合し、スラリー状の組成物を調製した。
＜機能層を備える非水系二次電池用セパレータの作製＞
ポリエチレン製の多孔基材からなる有機セパレータ基材（セルガード社製、厚み１６μｍ）を用意した。用意した有機セパレータ基材の片面に、非水系二次電池機能層用スラリー組成物を塗布し、６０℃で１０分乾燥させた。これにより、機能層（多孔膜層）を備える厚み１８μｍのセパレータを得た。
機能層（多孔膜層）を備えるセパレータに対し、その他の機能層用組成物を厚さ１μｍとなるように両面に塗布し、６０℃で１０分乾燥させた。これにより、機能層（多孔膜層）およびその他の機能層（接着層）を備える厚み２０μｍのセパレータを得た。
＜非水系二次電池用正極の作製＞
正極活物質としてのＬｉＣｏＯ2（体積平均粒子径：１２μｍ）を１００部、導電材としてのアセチレンブラック（電気化学工業社製「ＨＳ−１００」）を２部、正極合材層用の結着材としてのポリフッ化ビニリデン（クレハ社製、＃７２０８）を固形分換算で２部と、溶媒としてのＮ−メチルピロリドンとを混合し、全固形分濃度を７０％とした。これらをプラネタリーミキサーにより混合し、正極用スラリー組成物を調製した。
前述のようにして得られた正極用スラリー組成物を、コンマコーターで、集電体である厚さ２０μｍのアルミ箔の上に、乾燥後の膜厚が１５０μｍ程度になるように塗布し、乾燥させた。この乾燥は、アルミ箔を０．５ｍ／分の速度で６０℃のオーブン内を２分間かけて搬送することにより行った。その後、１２０℃にて２分間加熱処理して、正極原反を得た。このプレス前の正極原反をロールプレスで圧延して、正極合材層の厚さが８０μｍのプレス後の正極を得た。
＜非水系二次電池用負極の作製＞
攪拌機付き５ＭＰａ耐圧容器に、１，３−ブタジエン３３部、イタコン酸３．５部、スチレン６３．５部、乳化剤としてのドデシルベンゼンスルホン酸ナトリウム０．４部、イオン交換水１５０部および重合開始剤としての過硫酸カリウム０．５部を入れ、十分に攪拌した後、５０℃に加温して重合を開始した。重合転化率が９６％になった時点で冷却して反応を停止して、負極合材層用の粒子状結着材（ＳＢＲ）を含む混合物を得た。上記粒子状結着材を含む混合物に、５％水酸化ナトリウム水溶液を添加して、ｐＨ８に調整後、加熱減圧蒸留によって未反応単量体の除去を行った。その後、３０℃以下まで冷却し、所望の粒子状結着材を含む水分散液を得た。
次に、負極活物質としての人造黒鉛（体積平均粒子径：１５．６μｍ）１００部、増粘剤としてのカルボキシメチルセルロースナトリウム塩（日本製紙社製、「ＭＡＣ３５０ＨＣ」）の２％水溶液を固形分換算で１部、および、イオン交換水を混合して固形分濃度が６８％となるように調整した後、２５℃で６０分間混合した。次いで、固形分濃度が６２％となるようにイオン交換水で調整し、さらに２５℃で１５分間混合した。その後、得られた混合液に、前述の粒子状結着材を含む水分散液を固形分換算で１．５部、およびイオン交換水を入れ、最終固形分濃度が５２％となるように調整し、さらに１０分間混合した。これを減圧下で脱泡処理し、流動性の良い負極用スラリー組成物を得た。
そして、前述のようにして得られた負極用スラリー組成物を、コンマコーターで、集電体である厚さ２０μｍの銅箔の上に、乾燥後の膜厚が１５０μｍ程度になるように塗布し、乾燥させた。この乾燥は、銅箔を０．５ｍ／分の速度で６０℃のオーブン内を２分間かけて搬送することにより行った。その後、１２０℃にて２分間加熱処理してプレス前の負極原反を得た。このプレス前の負極原反をロールプレスで圧延して、負極合材層の厚さが８０μｍのプレス後の負極を得た。
＜非水系二次電池の製造＞
上記で得られたプレス後の正極を４９ｃｍ×５ｃｍに切り出して正極合材層側の表面が上側になるように置き、その上に１２０ｃｍ×５．５ｃｍに切り出した非水系二次電池用セパレータ（機能層およびその他の機能層を備えるセパレータ）を、正極がセパレータの長手方向左側に位置するように配置した。さらに、上記で得られたプレス後の負極を、５０ｃｍ×５．２ｃｍに切り出し、これをセパレータ上に、負極合材層側の表面がセパレータに向かい合うように、かつ、負極がセパレータの長手方向右側に位置するように配置した。これを捲回機により、セパレータの長手方向の真ん中を中心に捲回し、捲回体（積層体）を得た。この捲回体を６０℃、０．５ＭＰａでプレスし、扁平体とした後、電池の外装としてのアルミ包材外装で包み、電解液（溶媒：ＥＣ／ＤＥＣ／ＶＣ（体積混合比）＝６８．５／３０／１．５、電解質：濃度１ＭのＬｉＰＦ6）を空気が残らないように注入した。さらに、アルミ包材外装の開口を密封するために、１５０℃のヒートシールをしてアルミ包材外装を閉口した。その後、アルミ包材外装に封入した捲回体をアルミ包材外装ごと温度８０℃、圧力１ＭＰａで２分間プレスし、非水系二次電池として放電容量１０００ｍＡｈの捲回型リチウムイオン二次電池を製造した。
そして、得られた二次電池について、レート特性および寿命特性を評価した。結果を表１に示す。
Example 1
<Preparation of water-insoluble particulate polymer>
In a reactor equipped with a stirrer, 150 parts of ion-exchanged water, 0.1 part of sodium lauryl sulfate (product name “Emar 2F”, manufactured by Kao Chemical Co., Ltd.) as an emulsifier, and ammonium persulfate as a polymerization initiator 0.3 parts were respectively supplied, the gas phase part was replaced with nitrogen gas, and the temperature was raised to 80 ° C.
On the other hand, in a separate container, 40 parts of ion exchange water, 0.2 part of sodium dodecylbenzenesulfonate as a dispersant, 96 parts of styrene as an aromatic monovinyl monomer, and methacrylic acid as an acidic group-containing monomer. 2 parts of acid and 2 parts of ethylene dimethacrylate as a crosslinkable monomer were mixed to obtain a monomer composition. And the obtained monomer composition was continuously added to the said reactor over 3 hours, and superposition | polymerization was performed. In addition, reaction was performed at 80 degreeC during addition of a monomer composition. After completion of the addition, the reaction was terminated by further stirring at 80 ° C. for 2 hours to obtain an aqueous dispersion of a water-insoluble particulate polymer.
And about the obtained water-insoluble particulate polymer, electrolyte solution swelling degree, glass transition temperature, and volume average particle diameter were measured. The results are shown in Table 1.
<Preparation of adhesive polymer>
In a reactor equipped with a stirrer, 90 parts of ion-exchanged water and 0.5 part of ammonium persulfate as a polymerization initiator were supplied, the gas phase part was replaced with nitrogen gas, and the temperature was raised to 80 ° C. .
On the other hand, in a separate container, 40 parts of ion-exchanged water, 0.8 part of sodium dodecylbenzenesulfonate as an emulsifier, and 65.1 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid alkyl ester monomer, aroma 30 parts of styrene as an aromatic monovinyl monomer, 3 parts of acrylic acid as an acidic group-containing monomer, 1.7 parts of allyl glycidyl ether as a crosslinkable monomer and 0.2 part of allyl methacrylate A mass composition was obtained. And the obtained monomer composition was continuously added to the said reactor over 4 hours, and superposition | polymerization was performed. In addition, reaction was performed at 80 degreeC during addition of a monomer composition. After completion of the addition, the reaction was further terminated by stirring at 80 ° C. for 3 hours to obtain an aqueous dispersion of a particulate adhesive polymer.
And about the obtained adhesive polymer, electrolyte solution swelling degree, glass transition temperature, and volume average particle diameter were measured. The results are shown in Table 1.
<Preparation of binder composition for non-aqueous secondary battery functional layer>
The aqueous dispersion of the water-insoluble particulate polymer and the aqueous dispersion of the adhesive polymer were mixed in an amount of 5 parts of water-insoluble particulate polymer per 100 parts of the adhesive polymer (in terms of solid content) ( Solid content conversion) and stirred at 25 ° C. for 30 minutes to obtain a binder composition.
<Preparation of slurry composition for non-aqueous secondary battery functional layer>
Boehmite filler (BMM-W, manufactured by Kawai Lime Industry Co., Ltd.) as non-conductive particles and a total amount (in terms of solid content) of the water-insoluble particulate polymer and adhesive polymer is 3 parts. A binder composition, 1.0 part of carboxymethyl cellulose (Daicel 1220) as a thickener, 0.2 part of a polyethylene glycol type surfactant (San Nopco SN wet 366), and ion-exchanged water are mixed together to form a slurry composition. I got a thing.
And about the obtained slurry composition, stability under high shear was evaluated. Moreover, the peel strength before electrolyte solution immersion of the functional layer and the peel strength after electrolyte solution immersion were evaluated using the obtained slurry composition. The results are shown in Table 1.
<Preparation of other functional layer compositions>
-Preparation of organic particles having a core-shell structure-
In a 5 MPa pressure vessel with a stirrer, 75 parts of methyl methacrylate as a (meth) acrylic acid ester monomer, 4 parts of methacrylic acid as an acid group-containing monomer, 1 part of ethylene glycol dimethacrylate; 1 part of sodium dodecylbenzenesulfonate as an emulsifier; 150 parts of ion-exchanged water and 0.5 part of potassium persulfate as a polymerization initiator were added and sufficiently stirred. Then, it heated to 60 degreeC and superposition | polymerization was started. Polymerization was continued until the polymerization conversion rate reached 96% to obtain an aqueous dispersion containing a particulate polymer constituting the core portion.
To this aqueous dispersion, a mixture of 19 parts of styrene as an aromatic monovinyl monomer and 1 part of methacrylic acid as an acid group-containing monomer was continuously added to form a shell part, and heated to 70 ° C. Polymerization was continued. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to prepare an aqueous dispersion containing organic particles having a core-shell structure in which the outer surface of the core part was partially covered with the shell part.
In addition, the volume average particle diameter of the obtained organic particles was 0.45 μm.
-Preparation of binder-
In a reactor equipped with a stirrer, 70 parts of ion-exchanged water, 0.15 part of sodium lauryl sulfate (product name “Emar 2F”, manufactured by Kao Chemical Co., Ltd.) as an emulsifier, and ammonium persulfate 0 as a polymerization initiator .5 parts were respectively supplied, the gas phase part was replaced with nitrogen gas, and the temperature was raised to 60 ° C.
On the other hand, in a separate container, 50 parts of ion exchange water, 0.5 part of sodium dodecylbenzenesulfonate as a dispersant, 94 parts of butyl acrylate, 2 parts of acrylonitrile, 2 parts of methacrylic acid, 1 part of N-methylolacrylamide 1 part of acrylamide was mixed to obtain a monomer composition. This monomer composition was continuously added to the reactor over 4 hours for polymerization. During the addition of the monomer composition, the reaction was performed at 60 ° C. After completion of the addition, the reaction was further terminated by stirring at 70 ° C. for 3 hours to prepare an aqueous dispersion containing a particulate binder (acrylic polymer).
The obtained binder had a glass transition temperature of −40 ° C.
-Preparation of composition-
The aqueous dispersion containing the organic particles having the core-shell structure is 100 parts in terms of solid content, and the aqueous dispersion containing the binder is 15 parts in terms of solid content, ethylene oxide-propylene oxide as a wetting agent. Copolymer (solid content concentration 70% by mass, polymerization ratio: 5/5 (mass ratio)) is mixed with 1.9 parts in terms of solid content, and ion exchange water is further added so that the solid content concentration becomes 15% by mass. By mixing, a slurry-like composition was prepared.
<Preparation of separator for non-aqueous secondary battery including functional layer>
An organic separator substrate made of a polyethylene porous substrate (manufactured by Celgard, thickness 16 μm) was prepared. The slurry composition for non-aqueous secondary battery functional layers was applied to one side of the prepared organic separator substrate, and dried at 60 ° C. for 10 minutes. As a result, a separator having a functional layer (porous membrane layer) having a thickness of 18 μm was obtained.
To the separator provided with the functional layer (porous membrane layer), other functional layer compositions were applied on both sides to a thickness of 1 μm and dried at 60 ° C. for 10 minutes. Thereby, a separator having a thickness of 20 μm provided with a functional layer (porous membrane layer) and other functional layers (adhesive layer) was obtained.
<Preparation of positive electrode for non-aqueous secondary battery>
100 parts of LiCoO 2 (volume average particle diameter: 12 μm) as the positive electrode active material, 2 parts of acetylene black (“HS-100” manufactured by Denki Kagaku Kogyo Co., Ltd.) as the conductive material, binder for the positive electrode mixture layer As a solid content, 2 parts of polyvinylidene fluoride (manufactured by Kureha Co., Ltd., # 7208) and N-methylpyrrolidone as a solvent were mixed to give a total solid content concentration of 70%. These were mixed by a planetary mixer to prepare a positive electrode slurry composition.
The positive electrode slurry composition obtained as described above was applied onto a 20 μm-thick aluminum foil as a current collector with a comma coater so that the film thickness after drying was about 150 μm and dried. I let you. This drying was performed by transporting the aluminum foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a positive electrode raw material. The positive electrode raw material before pressing was rolled with a roll press to obtain a positive electrode after pressing with a positive electrode mixture layer thickness of 80 μm.
<Preparation of negative electrode for non-aqueous secondary battery>
In a 5 MPa pressure vessel with a stirrer, 33 parts of 1,3-butadiene, 3.5 parts of itaconic acid, 63.5 parts of styrene, 0.4 part of sodium dodecylbenzenesulfonate as an emulsifier, 150 parts of ion-exchanged water and a polymerization initiator After adding 0.5 parts of potassium persulfate as a mixture and sufficiently stirring, the mixture was heated to 50 ° C. to initiate polymerization. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain a mixture containing a particulate binder (SBR) for the negative electrode mixture layer. A 5% aqueous sodium hydroxide solution was added to the mixture containing the particulate binder and the pH was adjusted to 8, and then the unreacted monomer was removed by heating under reduced pressure. Then, it cooled to 30 degrees C or less, and obtained the water dispersion liquid containing a desired particulate-form binder.
Next, 100 parts of artificial graphite (volume average particle diameter: 15.6 μm) as a negative electrode active material and a 2% aqueous solution of carboxymethylcellulose sodium salt (manufactured by Nippon Paper Industries Co., Ltd., “MAC350HC”) as a thickener 1 part and ion-exchanged water were mixed to adjust the solid content concentration to 68%, and then mixed at 25 ° C. for 60 minutes. Subsequently, it adjusted with ion-exchange water so that solid content concentration might be 62%, and also mixed for 15 minutes at 25 degreeC. After that, 1.5 parts of the aqueous dispersion containing the particulate binder described above and ion-exchanged water are added to the obtained mixed liquid and adjusted so that the final solid content concentration is 52%. And mixed for another 10 minutes. This was defoamed under reduced pressure to obtain a negative electrode slurry composition having good fluidity.
Then, the negative electrode slurry composition obtained as described above was applied on a copper foil having a thickness of 20 μm, which is a current collector, with a comma coater so that the film thickness after drying was about 150 μm. , Dried. This drying was performed by conveying the copper foil in an oven at 60 ° C. at a speed of 0.5 m / min for 2 minutes. Thereafter, heat treatment was performed at 120 ° C. for 2 minutes to obtain a negative electrode raw material before pressing. The negative electrode raw material before pressing was rolled with a roll press to obtain a negative electrode after pressing with a negative electrode mixture layer thickness of 80 μm.
<Manufacture of non-aqueous secondary batteries>
The pressed positive electrode obtained above was cut out to 49 cm × 5 cm and placed so that the surface of the positive electrode mixture layer side was on the upper side, and a separator for a non-aqueous secondary battery cut out to 120 cm × 5.5 cm ( The separator provided with the functional layer and other functional layers) was disposed so that the positive electrode was located on the left side in the longitudinal direction of the separator. Further, the pressed negative electrode obtained above was cut out into 50 cm × 5.2 cm, and this was cut on the separator so that the surface on the negative electrode mixture layer side faced the separator, and the negative electrode was on the right side in the longitudinal direction of the separator. It arranged so that it may be located in. This was wound by a winding machine around the middle in the longitudinal direction of the separator to obtain a wound body (laminate). The wound body was pressed at 60 ° C. and 0.5 MPa to form a flat body, and then wrapped with an aluminum packaging exterior as a battery exterior. Electrolyte (solvent: EC / DEC / VC (volume mixing ratio) = 68 5/30 / 1.5, electrolyte: LiPF 6 ) with a concentration of 1M was injected so that no air remained. Furthermore, in order to seal the opening of the aluminum packaging material exterior, heat sealing at 150 ° C. was performed to close the aluminum packaging material exterior. Thereafter, the wound body enclosed in the aluminum packaging material exterior is pressed together with the aluminum packaging material exterior at a temperature of 80 ° C. and a pressure of 1 MPa for 2 minutes to produce a wound lithium ion secondary battery with a discharge capacity of 1000 mAh as a non-aqueous secondary battery. did.
And the rate characteristic and lifetime characteristic were evaluated about the obtained secondary battery. The results are shown in Table 1.
（実施例２〜４）
非水系二次電池機能層用バインダー組成物の調製時に、非水溶性粒子状重合体の水分散液と、接着性重合体の水分散液との配合比を変更し、接着性重合体１００部（固形分換算）当たりの非水溶性粒子状重合体の量（固形分換算）が表１に示す量となるようにした以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Examples 2 to 4)
At the time of preparing the binder composition for the non-aqueous secondary battery functional layer, the mixing ratio of the water dispersion of the water-insoluble particulate polymer and the water dispersion of the adhesive polymer was changed, and 100 parts of the adhesive polymer was obtained. In the same manner as in Example 1 except that the amount of the water-insoluble particulate polymer (in terms of solid content) (in terms of solid content) was as shown in Table 1, a water-insoluble particulate polymer, An adhesive polymer, a binder composition, a slurry composition, other functional layer compositions, a separator, a positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（実施例５）
非水溶性粒子状重合体の調製時に、芳香族モノビニル単量体としてのスチレンの量を７０部に変更し、（メタ）アクリル酸アルキルエステル単量体としての２−エチルヘキシルアクリレート２６部を更に添加して単量体組成物を得た以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Example 5)
When preparing the water-insoluble particulate polymer, the amount of styrene as the aromatic monovinyl monomer was changed to 70 parts, and 26 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid alkyl ester monomer was further added. In the same manner as in Example 1 except that the monomer composition was obtained, a water-insoluble particulate polymer, an adhesive polymer, a binder composition, a slurry composition, other functional layer compositions, a separator A positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（実施例６）
非水溶性粒子状重合体の調製時に、重合開始剤としての過流酸アンモニウムの量を０．４部に変更した以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Example 6)
The water-insoluble particulate polymer, adhesiveness was the same as in Example 1 except that the amount of ammonium persulfate as a polymerization initiator was changed to 0.4 part during the preparation of the water-insoluble particulate polymer. A polymer, a binder composition, a slurry composition, other functional layer compositions, a separator, a positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（実施例７）
非水溶性粒子状重合体の調製時に、重合開始剤としての過流酸アンモニウムの量を０．２部に変更した以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Example 7)
The water-insoluble particulate polymer, adhesiveness was the same as in Example 1 except that the amount of ammonium persulfate as a polymerization initiator was changed to 0.2 parts when preparing the water-insoluble particulate polymer. A polymer, a binder composition, a slurry composition, other functional layer compositions, a separator, a positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（実施例８〜９）
接着性重合体の調製時に、（メタ）アクリル酸アルキルエステル単量体としての２−エチルヘキシルアクリレートの量および芳香族モノビニル単量体としてのスチレンの量を表１に示すように変更して単量体組成物を得た以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Examples 8 to 9)
When preparing the adhesive polymer, the amount of 2-ethylhexyl acrylate as the (meth) acrylic acid alkyl ester monomer and the amount of styrene as the aromatic monovinyl monomer were changed as shown in Table 1 A water-insoluble particulate polymer, an adhesive polymer, a binder composition, a slurry composition, other functional layer compositions, a separator, a positive electrode, and a negative electrode in the same manner as in Example 1 except that a body composition was obtained. A secondary battery was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（実施例１０〜１１）
非水系二次電池機能層用スラリー組成物の調製時に、バインダー組成物の配合量を変更し、非水溶性粒子状重合体および接着性重合体の合計量（固形分換算）が表１に示す量となるようにした以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Examples 10 to 11)
When preparing the slurry composition for the non-aqueous secondary battery functional layer, the blending amount of the binder composition is changed, and the total amount (in terms of solid content) of the water-insoluble particulate polymer and the adhesive polymer is shown in Table 1. In the same manner as in Example 1 except that the amount was changed, the water-insoluble particulate polymer, adhesive polymer, binder composition, slurry composition, other functional layer composition, separator, positive electrode, negative electrode A secondary battery was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（比較例１）
非水溶性粒子状重合体の調製時に、芳香族モノビニル単量体としてのスチレンおよび架橋性単量体としてのエチレンジメタクリレートを使用せず、（メタ）アクリル酸アルキルエステル単量体としてのブチルアクリレート９６部および架橋性単量体としてのＮ−メチロールアクリルアミド２部を更に添加して単量体組成物を得た以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Comparative Example 1)
When preparing water-insoluble particulate polymer, styrene as an aromatic monovinyl monomer and ethylene dimethacrylate as a crosslinkable monomer are not used, but butyl acrylate as a (meth) acrylic acid alkyl ester monomer In the same manner as in Example 1, except that 96 parts and 2 parts of N-methylolacrylamide as a crosslinkable monomer were further added to obtain a monomer composition, a water-insoluble particulate polymer, adhesive weight A coalescence, a binder composition, a slurry composition, other functional layer compositions, a separator, a positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（比較例２）
非水溶性粒子状重合体の調製時に、芳香族モノビニル単量体としてのスチレンの量を５５部に変更し、（メタ）アクリル酸アルキルエステル単量体としての２−エチルヘキシルアクリレート４１部を更に添加して単量体組成物を得た以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Comparative Example 2)
When preparing the water-insoluble particulate polymer, the amount of styrene as the aromatic monovinyl monomer was changed to 55 parts, and 41 parts of 2-ethylhexyl acrylate as a (meth) acrylic acid alkyl ester monomer was further added. In the same manner as in Example 1 except that the monomer composition was obtained, a water-insoluble particulate polymer, an adhesive polymer, a binder composition, a slurry composition, other functional layer compositions, a separator A positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（比較例３）
非水溶性粒子状重合体の調製時に、芳香族モノビニル単量体としてのスチレンの量を５７．５部に変更し、酸性基含有単量体としてのメタクリル酸の量を０．５部に変更し、（メタ）アクリル酸アルキルエステル単量体としてのメチルメタクリレート４０部を更に添加して単量体組成物を得た以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Comparative Example 3)
When preparing the water-insoluble particulate polymer, the amount of styrene as the aromatic monovinyl monomer was changed to 57.5 parts, and the amount of methacrylic acid as the acidic group-containing monomer was changed to 0.5 parts. In the same manner as in Example 1, except that 40 parts of methyl methacrylate as a (meth) acrylic acid alkyl ester monomer was further added to obtain a monomer composition, a water-insoluble particulate polymer, adhesive A functional polymer, a binder composition, a slurry composition, other functional layer compositions, a separator, a positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
（比較例４）
非水系二次電池機能層用スラリー組成物の調製時に、増粘剤等を使用せず、非導電性粒子としてのベーマイトフィラー（河合石灰工業社製、ＢＭＭ−Ｗ）１００部と、非水溶性粒子状重合体および接着性重合体の合計量（固形分換算）が３部となる量のバインダー組成物と、Ｎ−メチルピロリドンとを混合し、その後水を除去して、非水溶性粒子状重合体がＮ−メチルピロリドンに溶解したスラリー組成物を得た以外は実施例１と同様にして、非水溶性粒子状重合体、接着性重合体、バインダー組成物、スラリー組成物、その他の機能層用組成物、セパレータ、正極、負極および二次電池を調製し、実施例１と同様にして評価を行った。結果を表１に示す。
(Comparative Example 4)
When preparing a slurry composition for a non-aqueous secondary battery functional layer, 100 parts of boehmite filler (BMM-W, manufactured by Kawai Lime Industry Co., Ltd.) as non-conductive particles without using a thickener or the like and water-insoluble A binder composition in which the total amount of the particulate polymer and the adhesive polymer (in terms of solid content) is 3 parts and N-methylpyrrolidone are mixed, and then water is removed to form a water-insoluble particulate form. A water-insoluble particulate polymer, an adhesive polymer, a binder composition, a slurry composition, and other functions in the same manner as in Example 1 except that a slurry composition in which the polymer was dissolved in N-methylpyrrolidone was obtained. A layer composition, a separator, a positive electrode, a negative electrode, and a secondary battery were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
なお、以下に示す表１中、
「Ｓｔ」は、スチレンを示し
「ＭＡＡ］は、メタクリル酸を示し、
「２−ＥＨＡ」は、２−エチルヘキシルアクリレートを示し
「ＢＡ」は、ブチルアクリレートを示し、
「ＭＭＡ」は、メチルメタクリレートを示し、
「ＥＤＭＡ」は、エチレンジメタクリレートを示し、
「ＮＭＡ」は、Ｎ−メチロールアクリルアミドを示し、
「ＡＡ」は、アクリル酸を示し、
「ＡＧＥ」は、アリルグリシジルエーテルを示し、
「ＡＭＡ」は、アリルメタクリレートを示し、
「ＮＭＰ」は、Ｎ−メチルピロリドンを示す。
In Table 1 shown below,
“St” represents styrene, “MAA” represents methacrylic acid,
“2-EHA” represents 2-ethylhexyl acrylate, “BA” represents butyl acrylate,
“MMA” indicates methyl methacrylate;
“EDMA” refers to ethylene dimethacrylate,
“NMA” indicates N-methylolacrylamide,
“AA” indicates acrylic acid;
“AGE” refers to allyl glycidyl ether;
“AMA” indicates allyl methacrylate,
“NMP” refers to N-methylpyrrolidone.
表１より、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満である非水溶性粒子状重合体と、ガラス転移温度が２０℃以下である接着性重合体とを用いた実施例１〜１１では、機能層の電解液浸漬前後のピール強度が高く、電池特性に優れる二次電池が得られることが分かる。また、表１より、ガラス転移温度が低く、かつ、電解液膨潤度が大きい非水溶性粒子状重合体を用いた比較例１、ガラス転移温度が低い非水溶性粒子状重合体を用いた比較例２および電解液膨潤度が大きい非水溶性粒子状重合体を用いた比較例３では、機能層の電解液浸漬後のピール強度が低く、二次電池のレート特性が低下してしまうことが分かる。更に、表１より、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満である重合体をＮ−メチルピロリドンに溶解して用いた比較例４では、機能層中で重合体が膜状化して内部抵抗が増加し、二次電池のレート特性および寿命特性が低下してしまうことが分かる。
また、実施例１〜４より、非水溶性粒子状重合体と接着性重合体の配合比を調整することで、機能層の電解液浸漬前のピール強度と電解液浸漬後のピール強度とをバランス良く高められることが分かる。
更に、実施例１および実施例５より、非水溶性粒子状重合体の組成を調整することで、機能層の電解液浸漬後のピール強度を高めて二次電池のレート特性を向上させ得ることが分かる。また、電解液中において非水溶性粒子状重合体のガラス転移温度以下の温度で機能層の加熱プレスを行うことにより、電池特性に優れる二次電池が得られることが分かる。
また、実施例１および実施例６〜７より、非水溶性粒子状重合体の粒子径を調整することで、スラリー組成物の安定性と、機能層の電解液浸漬後のピール強度と、二次電池の寿命特性とをバランスよく高められることが分かる。
更に、実施例１および実施例８〜９より、接着性重合体の組成を調整することで、機能層の電解液浸漬前のピール強度および二次電池の寿命特性を向上させ得ることが分かる。
そして、実施例１および実施例１０〜１１より、バインダー組成物の配合量を調整することで、機能層の電解液浸漬前後のピール強度と二次電池の電池特性とをバランス良く高められることが分かる。
From Table 1, a water-insoluble particulate polymer having a glass transition temperature of 50 ° C. or higher and an electrolyte solution swelling degree of more than 1 and less than 3 times, and an adhesive weight having a glass transition temperature of 20 ° C. or less. In Examples 1 to 11 using the union, it can be seen that a secondary battery having high peel strength before and after immersion of the functional layer in the electrolyte solution and excellent in battery characteristics can be obtained. Further, from Table 1, Comparative Example 1 using a water-insoluble particulate polymer having a low glass transition temperature and a large degree of electrolyte swelling, Comparison using a water-insoluble particulate polymer having a low glass transition temperature In Example 2 and Comparative Example 3 using a water-insoluble particulate polymer having a high degree of electrolyte swelling, the peel strength of the functional layer after immersion in the electrolyte is low, and the rate characteristics of the secondary battery may be reduced. I understand. Furthermore, from Table 1, in Comparative Example 4 in which a polymer having a glass transition temperature of 50 ° C. or higher and an electrolyte swelling degree of more than 1 time and less than 3 times was dissolved in N-methylpyrrolidone, It can be seen that the polymer becomes a film in the layer, the internal resistance increases, and the rate characteristics and life characteristics of the secondary battery are degraded.
In addition, from Examples 1 to 4, by adjusting the blending ratio of the water-insoluble particulate polymer and the adhesive polymer, the peel strength of the functional layer before immersion in the electrolyte and the peel strength after immersion of the electrolyte are obtained. It can be seen that the balance can be improved.
Furthermore, from Example 1 and Example 5, by adjusting the composition of the water-insoluble particulate polymer, it is possible to increase the peel strength after immersion of the functional layer in the electrolyte and improve the rate characteristics of the secondary battery. I understand. Moreover, it turns out that the secondary battery which is excellent in a battery characteristic is obtained by performing the heat press of a functional layer in the electrolyte solution at the temperature below the glass transition temperature of a water-insoluble particulate polymer.
Moreover, from Example 1 and Examples 6-7, by adjusting the particle diameter of the water-insoluble particulate polymer, the stability of the slurry composition, the peel strength after immersion of the functional layer in the electrolyte solution, and two It can be seen that the life characteristics of the secondary battery can be improved in a well-balanced manner.
Furthermore, it can be seen from Example 1 and Examples 8 to 9 that by adjusting the composition of the adhesive polymer, the peel strength of the functional layer before immersion in the electrolyte and the life characteristics of the secondary battery can be improved.
And from Example 1 and Examples 10-11, by adjusting the compounding quantity of a binder composition, the peel strength before and behind the electrolyte solution of a functional layer and the battery characteristic of a secondary battery can be improved with good balance. I understand.
本発明によれば、機能層の形成に用いた際に内部抵抗の増加を抑制しつつ電解液中でも高い接着性を発揮して機能層の電解液浸漬後のピール強度を高めることができる非水系二次電池機能層用バインダー組成物を提供することができる。
また、本発明によれば、内部抵抗の増加を抑制しつつ電解液浸漬後もピール強度が高い機能層を形成することができる非水系二次電池機能層用スラリー組成物を提供することができる。
更に、本発明によれば、電解液浸漬後もピール強度が高く、非水系二次電池に優れた電池特性を発揮させることができる非水系二次電池用機能層を提供することができる。
そして、本発明によれば、電池特性に優れる非水系二次電池およびその製造方法を提供することができる。
According to the present invention, when used for the formation of a functional layer, a non-aqueous system capable of increasing the peel strength after immersion of the functional layer by exhibiting high adhesiveness even in the electrolytic solution while suppressing an increase in internal resistance. A binder composition for a secondary battery functional layer can be provided.
Moreover, according to this invention, the slurry composition for non-aqueous secondary battery functional layers which can form a functional layer with high peel strength even after electrolyte immersion, suppressing the increase in internal resistance can be provided. .
Furthermore, according to the present invention, it is possible to provide a functional layer for a non-aqueous secondary battery that has a high peel strength even after being immersed in an electrolytic solution and can exhibit excellent battery characteristics in the non-aqueous secondary battery.
And according to this invention, the non-aqueous secondary battery excellent in a battery characteristic and its manufacturing method can be provided.
Claims (9)
前記非水溶性粒子状重合体は、ガラス転移温度が５０℃以上であり、かつ、電解液膨潤度が１倍超３倍未満であり、
前記接着性重合体は、ガラス転移温度が２０℃以下であり、
前記非水溶性粒子状重合体の含有量が、前記接着性重合体１００質量部当たり１質量部以上２０質量部以下である、非水系二次電池機能層用バインダー組成物。 A binder composition for a non-aqueous secondary battery functional layer containing a water-insoluble particulate polymer, an adhesive polymer, and water,
The water-insoluble particulate polymer has a glass transition temperature of 50 ° C. or higher and an electrolyte swelling degree of more than 1 time and less than 3 times,
The adhesive polymer state, and are the glass transition temperature of 20 ° C. or less,
The binder composition for a nonaqueous secondary battery functional layer , wherein the content of the water-insoluble particulate polymer is 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the adhesive polymer .
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