JP5446687B2 - Binder resin composition for electrode, electrode mixture paste, and electrode - Google Patents
Binder resin composition for electrode, electrode mixture paste, and electrode Download PDFInfo
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- JP5446687B2 JP5446687B2 JP2009227912A JP2009227912A JP5446687B2 JP 5446687 B2 JP5446687 B2 JP 5446687B2 JP 2009227912 A JP2009227912 A JP 2009227912A JP 2009227912 A JP2009227912 A JP 2009227912A JP 5446687 B2 JP5446687 B2 JP 5446687B2
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- 239000011230 binding agent Substances 0.000 title claims description 118
- 239000011342 resin composition Substances 0.000 title claims description 91
- 239000000203 mixture Substances 0.000 title claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 40
- 229920005575 poly(amic acid) Polymers 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011883 electrode binding agent Substances 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- -1 pyridine compound Chemical class 0.000 claims description 5
- 239000011863 silicon-based powder Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 45
- 239000011521 glass Substances 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 27
- 238000000576 coating method Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 239000012298 atmosphere Substances 0.000 description 26
- 229910001873 dinitrogen Inorganic materials 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 229920001721 polyimide Polymers 0.000 description 14
- 239000009719 polyimide resin Substances 0.000 description 12
- 239000011149 active material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000008961 swelling Effects 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 8
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- NURQLCJSMXZBPC-UHFFFAOYSA-N 3,4-dimethylpyridine Chemical compound CC1=CC=NC=C1C NURQLCJSMXZBPC-UHFFFAOYSA-N 0.000 description 2
- GRFNBEZIAWKNCO-UHFFFAOYSA-N 3-pyridinol Chemical compound OC1=CC=CN=C1 GRFNBEZIAWKNCO-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011530 conductive current collector Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000006358 imidation reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical group C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- JHAWWJQGHKGXHA-UHFFFAOYSA-N 6-tert-butylquinoline Chemical compound N1=CC=CC2=CC(C(C)(C)C)=CC=C21 JHAWWJQGHKGXHA-UHFFFAOYSA-N 0.000 description 1
- ZMPPXANJPWZRRK-UHFFFAOYSA-N CN1C(N(CC1)C)=O.CN1C(CCCCC1)=O Chemical compound CN1C(N(CC1)C)=O.CN1C(CCCCC1)=O ZMPPXANJPWZRRK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910000681 Silicon-tin Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- VXGYRCVTBHVXMZ-UHFFFAOYSA-N quinoline-6-carboxylic acid Chemical compound N1=CC=CC2=CC(C(=O)O)=CC=C21 VXGYRCVTBHVXMZ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、リチウムイオン二次電池、電気二重層キャパシタなどの電気化学素子の電極用のバインダー樹脂組成物に関する。 The present invention relates to a binder resin composition for electrodes of electrochemical devices such as lithium ion secondary batteries and electric double layer capacitors.
リチウムイオン二次電池は、高いエネルギー密度を有し、高容量であるため、移動情報端末の駆動電源などとして広く利用されている。近年は、大容量を必要とする電気・ハイブリッド自動車への搭載など産業用途での使用も広まりつつあり、更なる高容量化や高性能化のための検討がなされている。その試みの一つは、例えば負極活物質として単位体積あたりのリチウム吸蔵量の多いケイ素やスズ、或いはこれらを含む合金を用いて、充放電容量を増大させようとするものである。 Lithium ion secondary batteries have high energy density and high capacity, and are therefore widely used as driving power sources for mobile information terminals. In recent years, use in industrial applications such as mounting on electric / hybrid vehicles that require large capacity is becoming widespread, and studies are being conducted for further increase in capacity and performance. One of the attempts is to increase the charge / discharge capacity by using, for example, silicon or tin having a large amount of lithium occlusion per unit volume or an alloy containing these as a negative electrode active material.
しかし、ケイ素やスズ、或いはこれらを含む合金のような充放電容量の大きな活物質を用いると、充放電に伴って活物質が非常に大きな体積変化を起こすため、これまでの炭素を活物質として用いた電極で広く用いられていたポリフッ化ビニリデンやゴム系の樹脂をバインダー樹脂として用いたのでは、活物質層が破壊され易くなったり、集電体と活物質層との界面で剥離が発生し易くなったりするために、電極内の集電構造が破壊され、電極の電子伝導性が低下して電池のサイクル特性が容易に低下するという問題があった。
このため、非常に大きな体積変化に対しても電極の破壊や剥離を起こしにくい、電池環境下での靭性が高いバインダー樹脂組成物が望まれていた。
However, if an active material with a large charge / discharge capacity such as silicon, tin, or an alloy containing these is used, the active material undergoes a very large volume change along with charge / discharge. If polyvinylidene fluoride or rubber-based resin widely used for the electrode used is used as the binder resin, the active material layer is likely to be broken or peeling occurs at the interface between the current collector and the active material layer Therefore, there is a problem in that the current collecting structure in the electrode is broken, the electron conductivity of the electrode is lowered, and the cycle characteristics of the battery are easily lowered.
For this reason, there has been a demand for a binder resin composition that has high toughness in a battery environment and that does not easily break or peel off an electrode even with a very large volume change.
特許文献１に記載されているとおり、リチウムイオン二次電池の電極用の結着剤にポリイミド樹脂を用いることは公知ある。
特許文献２、特許文献３には、ケイ素合金やスズを含む合金からなる活物質に対して、それぞれ特定の機械的特性を有するバインダー樹脂を用いることが提案されている。しかしながら、ここでは樹脂の具体的な化学構造について開示されていない。
特許文献４には、ケイ素、及びケイ素系合金からなる活物質と、特定の化学構造を有するポリイミド樹脂をバインダーに用いたリチウム二次電池が提案されている。このポリイミド樹脂は、３，３’，４，４’−ベンゾフェノンテトラカルボン酸残基を有するポリイミドであった。
As described in Patent Document 1, it is known to use a polyimide resin as a binder for an electrode of a lithium ion secondary battery.
Patent Documents 2 and 3 propose using binder resins having specific mechanical properties for an active material made of an alloy containing a silicon alloy or tin. However, the specific chemical structure of the resin is not disclosed here.
Patent Document 4 proposes a lithium secondary battery using, as a binder, an active material composed of silicon and a silicon-based alloy and a polyimide resin having a specific chemical structure. This polyimide resin was a polyimide having 3,3 ′, 4,4′-benzophenone tetracarboxylic acid residues.
一方、非特許文献１には、電解液に対する電極用のバインダー樹脂の膨潤度が小さいほど充放電サイクルに伴う放電容量保持率が高くなるので好ましいことが示されている。 On the other hand, Non-Patent Document 1 shows that the smaller the degree of swelling of the binder resin for electrodes with respect to the electrolytic solution, the higher the discharge capacity retention rate associated with the charge / discharge cycle, which is preferable.
本発明の目的は、電池環境下でも膨潤度が小さく高い靱性を保つことができるバインダー樹脂を得ることができる、新たな化学構造からなる電極用バインダー樹脂組成物を提案することである。 An object of the present invention is to propose a binder resin composition for electrodes having a new chemical structure, which can obtain a binder resin having a small degree of swelling and high toughness even in a battery environment.
本発明願発明者らは、種々検討した結果、特定の化学構造からなる樹脂組成物を用いると、電池環境下でも膨潤度が小さく、高い靱性（大きな破断伸度及び破断エネルギー）を有する、新たな電極用バインダー樹脂組成物を得ることを見出して、本発明に至った。 As a result of various investigations, the inventors of the present invention have found that when a resin composition having a specific chemical structure is used, the degree of swelling is small even in a battery environment, and the toughness (large breaking elongation and breaking energy) is high. The present inventors have found that a binder resin composition for an electrode can be obtained, and have reached the present invention.
すなわち、本発明は以下の項に関する。
１． 下記化学式（１）で表される繰返し単位からなるポリアミック酸（ポリアミド酸）と溶剤とからなる電極用バインダー樹脂組成物。
That is, the present invention relates to the following items.
1. A binder resin composition for an electrode comprising a polyamic acid (polyamic acid) comprising a repeating unit represented by the following chemical formula (1) and a solvent.
２． さらに、ピリジン類化合物を含有することを特徴とする前記項１に記載の電極用バインダー樹脂組成物。
３． 加熱処理して得られるバインダー樹脂が、２５℃で２４時間ジメチルカーボネートに浸漬したときの質量増加が３質量％以下であることを特徴とする前記項１〜２のいずれかに記載の電極用バインダー樹脂組成物。
４． 加熱処理して得られるバインダー樹脂の引張破断エネルギーが１００ＭＪ／ｍ３以上であり、且つ２５℃で２４時間ジメチルカーボネートに浸漬した後の引張破断エネルギーの保持率が７０％以上であることを特徴とする前記項１〜３のいずれかに記載の電極用バインダー樹脂組成物。
2. The binder resin composition for an electrode according to item 1, further comprising a pyridine compound.
3. Item 3. The binder for an electrode according to any one of Items 1 to 2, wherein the binder resin obtained by heat treatment has a mass increase of 3% by mass or less when immersed in dimethyl carbonate at 25 ° C. for 24 hours. Resin composition.
4). The binder resin obtained by heat treatment has a tensile breaking energy of 100 MJ / m 3 or more, and a retention of tensile breaking energy after being immersed in dimethyl carbonate at 25 ° C. for 24 hours is 70% or more. The binder resin composition for electrodes according to any one of Items 1 to 3.
５． 電極活物質と前記項１〜４のいずれかに記載の電極用バインダー樹脂組成物とを含む電極合剤ペースト。
６． 電極活物質が炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末であることを特徴とする前記項５に記載の電極合剤ペースト。
5. The electrode mixture paste containing an electrode active material and the binder resin composition for electrodes according to any one of Items 1 to 4.
6). Item 6. The electrode mixture paste according to Item 5, wherein the electrode active material is carbon powder, silicon powder, tin powder, or an alloy powder containing silicon or tin.
７． 前記項５〜６のいずれかに記載の電極合剤ペーストを集電体上に塗布し、加熱処理して溶媒を除去するとともにイミド化反応することにより得られることを特徴とする電極。
８． 加熱処理温度が２５０℃以下であることを特徴とする前記項７に記載の電極。
９． リチウムイオン二次電池用負極であることを特徴とする前記項７〜８のいずれかに記載の電極。
7). 7. An electrode obtained by applying the electrode mixture paste according to any one of Items 5 to 6 on a current collector, removing the solvent by heat treatment, and imidizing.
8). 8. The electrode according to item 7, wherein the heat treatment temperature is 250 ° C. or lower.
9. Item 9. The electrode according to any one of Items 7 to 8, which is a negative electrode for a lithium ion secondary battery.
本発明によれば、電池環境下でも膨潤度が小さく、高い靱性（大きな破断伸度及び破断エネルギー）を有するバインダー樹脂を得ることが可能な、新たな化学構造からなる電極用バインダー樹脂組成物を得ることができる。 According to the present invention, there is provided a binder resin composition for an electrode having a new chemical structure, which is capable of obtaining a binder resin having a low degree of swelling even under a battery environment and having high toughness (large breaking elongation and breaking energy). Can be obtained.
本発明の電極用バインダー樹脂組成物は、特定の繰返し単位からなるポリアミック酸と溶剤とからなる。
本発明のポリアミック酸を構成するテトラカルボン酸成分は、実質的に３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、及びその加水分解物やエステル化物などの誘導体を用いて構成される。本発明の効果の範囲内で他のテトラカルボン酸成分を少量用いても構わないが、概ね全テトラカルボン酸成分の１０モル％以下、好ましくは５モル％以下、より好ましくは０モル％である。
The binder resin composition for electrodes of the present invention comprises a polyamic acid composed of a specific repeating unit and a solvent.
The tetracarboxylic acid component constituting the polyamic acid of the present invention is substantially composed of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and derivatives such as hydrolysates and esterified products thereof. Is done. A small amount of other tetracarboxylic acid components may be used within the scope of the effect of the present invention, but is generally 10 mol% or less, preferably 5 mol% or less, more preferably 0 mol% of the total tetracarboxylic acid components. .
本発明のポリアミック酸を構成するジアミン成分は、その１０〜９０モル％、好ましくは２０〜８０モル％、より好ましくは３０〜７０モル％のパラフェニレンジアミンと、その９０〜１０モル％、好ましくは８０〜２０モル％、より好ましくは７０〜３０モル％の４，４’−ジアミノジフェニルエーテルを用いて構成される。この範囲内では、得られるポリイミド樹脂の電解液に対する樹脂の膨潤度が小さく、破断伸度及び破断エネルギーが大きくなるので電極用バインダー樹脂として極めて好適である。なお、本発明の効果の範囲内で他のジアミン成分を少量用いても構わないが、概ね全ジアミン成分の１０モル％以下、好ましくは５モル％以下、より好ましくは０モル％である。 The diamine component constituting the polyamic acid of the present invention is 10 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol% paraphenylenediamine, and 90 to 10 mol%, preferably It is composed of 80 to 20 mol%, more preferably 70 to 30 mol% of 4,4'-diaminodiphenyl ether. Within this range, the degree of swelling of the resulting polyimide resin with respect to the electrolyte solution is small, and the elongation at break and the energy at break are large, making it extremely suitable as a binder resin for electrodes. Although a small amount of other diamine components may be used within the scope of the effect of the present invention, it is generally 10 mol% or less, preferably 5 mol% or less, more preferably 0 mol% of the total diamine components.
本発明のポリアミック酸を構成するテトラカルボン酸成分とジアミン成分とのモル比［テトラカルボン酸成分／ジアミン成分］は略等モル、具体的には０．９５〜１．０５好ましくは０．９７〜１．０３になるようにすることが重要である。このモル比の範囲外では、得られるポリイミド樹脂の靭性が低くなる恐れがある。 The molar ratio of the tetracarboxylic acid component and the diamine component constituting the polyamic acid of the present invention [tetracarboxylic acid component / diamine component] is approximately equimolar, specifically 0.95 to 1.05, preferably 0.97 to It is important to make it 1.03. Outside the range of this molar ratio, the toughness of the resulting polyimide resin may be reduced.
ポリアミック酸は、ジアミン成分とテトラカルボン酸成分とを溶剤中で反応させることで容易に調製することができる。限定するものではないが、好ましくはジアミン成分を溶剤に溶解した溶液にテトラカルボン酸成分を一度に、或いは多段階で添加し、攪拌することにより好適に行うことができる。反応温度は１０℃〜６０℃が好ましく、１５℃〜５５℃がさらに好ましく、１５℃〜５０℃が特に好ましい。反応温度が１０℃より低いと反応が遅くなることから好ましくなく、６０℃より高いと溶液の粘度が低くなることがあり好ましくない。反応時間は、０．５時間〜７２時間の範囲が好ましく、１時間〜６０時間がさらに好ましく、１．５時間〜４８時間が特に好ましい。反応時間が０．５時間より短いと反応が十分進行せず、合成されたポリアミック酸溶液の粘度が不安定になることがある。一方、７２時間以上の時間をかけるのは生産性の面から好ましくない。 A polyamic acid can be easily prepared by reacting a diamine component and a tetracarboxylic acid component in a solvent. Although it does not limit, Preferably, it can carry out suitably by adding the tetracarboxylic acid component to the solution which melt | dissolved the diamine component in the solvent at once or in multistep, and stirring. The reaction temperature is preferably 10 ° C to 60 ° C, more preferably 15 ° C to 55 ° C, and particularly preferably 15 ° C to 50 ° C. When the reaction temperature is lower than 10 ° C, the reaction is slow, which is not preferable. The reaction time is preferably in the range of 0.5 to 72 hours, more preferably 1 to 60 hours, and particularly preferably 1.5 to 48 hours. When the reaction time is shorter than 0.5 hours, the reaction does not proceed sufficiently, and the viscosity of the synthesized polyamic acid solution may become unstable. On the other hand, taking 72 hours or more is not preferable from the viewpoint of productivity.
ポリアミック酸の調製には従来ポリアミック酸を調製する際に用いられる公知の有機溶剤を使用することができる。例えば、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、Ｎ−メチルカプロラクタム、ヘキサメチルホスホロトリアミド、１，２−ジメトキシエタン、ビス（２−メトキシエチル）エーテル、１，２−ビス（２−メトキシエトキシ）エタン、テトラヒドロフラン、ビス［２−（２−メトキシエトキシ）エチル］エーテル、１，４−ジオキサン、ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、ｍ−クレゾール、フェノール、γ−ブチロラクトンが挙げられる。これらの溶剤は、単独または２種以上混合して使用しても差し支えない。これらのうち、ポリアミック酸の溶解性、および安全性から、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン、γ−ブチロラクトンが好ましく、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドン、γ−ブチロラクトンが特に好ましい。 For the preparation of the polyamic acid, a known organic solvent conventionally used for preparing a polyamic acid can be used. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone N-methylcaprolactam, hexamethylphosphorotriamide, 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2- Methoxyethoxy) ethyl] ether, 1,4-dioxane, dimethylsulfoxide, dimethylsulfone, diphenylether, sulfolane, diphenylsulfone, tetramethylurea, anisole, m-cresol, phenol, γ-butyrolactone. These solvents may be used alone or in combination of two or more. Of these, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,3-dimethyl are considered because of the solubility and safety of polyamic acid. 2-Imidazolidinone and γ-butyrolactone are preferable, and N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are particularly preferable.
本発明の電池用バインダー樹脂組成物は、前記ポリアミック酸を溶剤に均一に溶解してなる。この組成物は、ポリアミック酸に起因する固形分濃度が、溶剤とポリアミック酸との合計量に対して５質量％超〜４５質量％、好ましくは１０質量％超〜４０質量％、より好ましくは１５質量％超〜３０質量％の組成物として好適に用いることができる。ポリアミック酸に起因する固形分濃度が５質量％より低いと溶液の粘度が低くなりすぎ、４５質量％より高いと溶液の流動性がなくなることがある。また溶液粘度は、３０℃における溶液粘度が、好ましくは１０００Ｐａ・ｓｅｃ以下、より好ましくは０．５〜５００Ｐａ・ｓｅｃ、さらに好ましくは１〜３００Ｐａ・ｓｅｃ、特に好ましくは３〜２００Ｐａ・ｓｅｃである。
溶液粘度が１０００Ｐａ・ｓｅｃを超えると、電極活物質粉末の混合や集電体上への均一な塗布が困難となり、また、０．５Ｐａ・ｓｅｃよりも低いと、電極活物質粉末の混合や集電体上への塗布時にたれなどが生じ、加熱乾燥、イミド化後のポリイミド樹脂の靭性が低くなる恐れがある。
The binder resin composition for a battery of the present invention is obtained by uniformly dissolving the polyamic acid in a solvent. This composition has a solid content concentration due to the polyamic acid of more than 5% by mass to 45% by mass, preferably more than 10% by mass to 40% by mass, more preferably 15%, based on the total amount of the solvent and the polyamic acid. It can be suitably used as a composition of more than 30% by mass to 30% by mass. If the solid content concentration resulting from polyamic acid is lower than 5% by mass, the viscosity of the solution becomes too low, and if it is higher than 45% by mass, the fluidity of the solution may be lost. The solution viscosity at 30 ° C. is preferably 1000 Pa · sec or less, more preferably 0.5 to 500 Pa · sec, still more preferably 1 to 300 Pa · sec, and particularly preferably 3 to 200 Pa · sec.
When the solution viscosity exceeds 1000 Pa · sec, it becomes difficult to mix the electrode active material powder and uniformly apply it onto the current collector. When the solution viscosity is lower than 0.5 Pa · sec, the electrode active material powder is mixed and collected. There is a risk that dripping or the like occurs during coating on the electric body, and the toughness of the polyimide resin after heat drying and imidization is lowered.
本発明の電極用バインダー樹脂組成物を調製する際に用いるポリアミック酸は、ジアミン成分とテトラカルボン酸成分とを溶剤中で反応させて得られたポリアミック酸溶液を、例えば貧溶媒に投入して析出させる方法などにより単離して（それを、所定の溶剤に再度溶解させることによって）使用しても良いし、得られたポリアミック酸溶液を単離することなく、調製したものをそのままで、或いは単に希釈するなどして使用してもよい。生産性、コストの点から、得られたポリアミック酸溶液を単離することなくそのまま使用することが好ましい。 The polyamic acid used in preparing the electrode binder resin composition of the present invention is deposited by pouring a polyamic acid solution obtained by reacting a diamine component and a tetracarboxylic acid component in a solvent, for example, into a poor solvent. May be used (by re-dissolving it in a predetermined solvent), and the prepared polyamic acid solution may be used as it is without isolation, or simply It may be used after being diluted. From the viewpoint of productivity and cost, it is preferable to use the obtained polyamic acid solution as it is without isolation.
本発明の電極用バインダー樹脂組成物で用いられる溶剤は、ポリアミック酸を溶解し得る従来公知の有機溶媒を好適に用いることができる。常圧での沸点が３００℃以下の有機極性溶媒が好ましく、ポリアミック酸の調製の際に用いられる前記溶剤を好適に用いることができる。 As the solvent used in the binder resin composition for an electrode of the present invention, a conventionally known organic solvent capable of dissolving polyamic acid can be suitably used. An organic polar solvent having a boiling point of 300 ° C. or less at normal pressure is preferable, and the solvent used in the preparation of the polyamic acid can be suitably used.
本発明の電極用バインダー樹脂組成物においては、さらにピリジン類化合物を含有することが、得られるポリイミド樹脂の電解液に対する膨潤度をより小さくし、破断伸度及び破断エネルギーをより大きくすることができ、さらに電極を得るための加熱処理温度を低く抑えることができるので、好適である。
ピリジン類化合物は、化学構造中にピリジン骨格を有する化合物のことであり、例えばピリジン、３−ピリジノール、キノリン、イソキノリン、キノキサリン、６−ｔｅｒｔ−ブチルキノリン、アクリジン、６−キノリンカルボン酸、３，４−ルチジン、ピリダジン、などを好適に挙げることができる。これらのピリジン類化合物は、単独または２種以上併用して使用しても差し支えない。
In the binder resin composition for an electrode of the present invention, further containing a pyridine compound can further reduce the degree of swelling of the resulting polyimide resin with respect to the electrolyte and increase the elongation at break and the energy at break. Furthermore, the heat treatment temperature for obtaining the electrode can be kept low, which is preferable.
The pyridine compound is a compound having a pyridine skeleton in the chemical structure. For example, pyridine, 3-pyridinol, quinoline, isoquinoline, quinoxaline, 6-tert-butylquinoline, acridine, 6-quinolinecarboxylic acid, 3,4 -Lutidine, pyridazine, etc. can be mentioned preferably. These pyridine compounds may be used alone or in combination of two or more.
電極用バインダー樹脂組成物においてピリジン類化合物の添加量は、限定するものではないが、ポリアミック酸のアミック酸構造に対して（アミック酸構造１モル当たり）、好ましくは０．０５〜２．０モル当量、より好ましくは０．１〜１．０モル当量である。添加量がこの範囲外では、電解液に対する樹脂の膨潤度をより小さくし、得られるポリイミド樹脂の破断伸度及び破断エネルギーをより大きくし、さらに電極を得るための加熱処理温度を低く抑えるというピリジン類化合物の添加効果を得ることが難しい場合があり好ましくない。 The addition amount of the pyridine compound in the binder resin composition for electrodes is not limited, but is preferably 0.05 to 2.0 mol with respect to the amic acid structure of the polyamic acid (per mol of the amic acid structure). Equivalent, more preferably 0.1 to 1.0 molar equivalent. If the addition amount is outside this range, the degree of swelling of the resin with respect to the electrolyte solution is further reduced, the breaking elongation and the breaking energy of the resulting polyimide resin are further increased, and further the heat treatment temperature for obtaining the electrode is kept low. It is difficult to obtain the effect of adding a compound, which is not preferable.
本発明の電極用バインダー樹脂組成物は、加熱処理或いはイミド化剤などの化学的処理によって、容易にポリイミド樹脂になる。例えば、電極用バインダー樹脂組成物を基材上に流延あるいは塗布して１２０℃〜１８０℃の範囲で加熱乾燥後、自己支持性となったフィルムを基材から剥離し、金属枠などに固定して、さらに２００℃〜４００℃で５分〜１０時間加熱してポリイミド樹脂フィルムを好適にあることができる。
本発明の電極用バインダー樹脂組成物は、前記のような加熱処理によって得られたポリイミド樹脂が、ジメチルカーボネートに２５℃で２４時間浸漬したときに、その質量増加が好ましくは３質量％以下、より好ましくは２質量％以下になるので、電池用バインダー樹脂組成物として好適に用いることができる。
また、本発明の電極用バインダー樹脂組成物は、前記のような加熱処理によって得られたポリイミド樹脂の引張破断エネルギーが１００ＭＪ／ｍ３以上、より好ましくは１１０ＭＪ／ｍ３以上、さらに好ましくは１２０ＭＪ／ｍ３以上であり、且つジメチルカーボネートに２５℃で２４時間浸漬した後の引張破断エネルギーの保持率が７０％以上、より好ましくは７５％以上、さらに好ましくは８０％以上であり、優れた靱性を有するので、電池用バインダー樹脂組成物として好適に用いることができる。
The binder resin composition for an electrode of the present invention easily becomes a polyimide resin by a heat treatment or a chemical treatment such as an imidizing agent. For example, a binder resin composition for electrodes is cast or coated on a base material, heat-dried in the range of 120 ° C to 180 ° C, and then the self-supporting film is peeled off from the base material and fixed to a metal frame or the like. Further, the polyimide resin film can be suitably obtained by heating at 200 ° C. to 400 ° C. for 5 minutes to 10 hours.
When the polyimide resin obtained by the heat treatment as described above is immersed in dimethyl carbonate at 25 ° C. for 24 hours, the increase in mass is preferably 3% by mass or less. Since it becomes 2 mass% or less preferably, it can be used suitably as a binder resin composition for batteries.
Further, electrode binder resin composition of the present invention has a tensile energy to break of the polyimide resin obtained by the heat treatment as described above is 100 MJ / m 3 or more, more preferably 110 mJ / m 3 or more, more preferably 120 MJ / m 3 or more, and the retention of tensile fracture energy after being immersed in dimethyl carbonate at 25 ° C. for 24 hours is 70% or more, more preferably 75% or more, and still more preferably 80% or more, and has excellent toughness. Therefore, it can be suitably used as a battery binder resin composition.
本発明の電極用バインダー樹脂組成物に、少なくとも電極活物質を、限定するものではないが、好ましくは１０℃〜６０℃の温度範囲で混合することにより、電極合剤ペーストを好適に調製することができる。電極活物質は公知のものを好適に用いることができるが、リチウム含有金属複合酸化物、炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末が好ましい。電極合剤ペースト中の電極活物質の量は、格別限定されないが、通常、ポリアミック酸に起因する固形分質量に対して、質量基準で０．１〜１０００倍、好ましくは１〜１０００倍、より好ましくは５〜１０００倍、さらに好ましくは１０〜１０００倍である。活物質量が少なすぎると、集電体に形成された活物質層に不活性な部分が多くなり、電極としての機能が不十分になることがある。また、活物質量が多すぎると活物質が集電体に十分に結着されずに脱落しやくなる。なお、電極合剤ペースト中には、必要に応じて界面活性剤や粘度調整剤や導電補助剤などの添加剤を加えることができる。また、ポリアミック酸がペーストの全固形分中の１〜１５質量％となるよう混合することが好ましい。この範囲外では電極の性能が低下することがある。 Although at least an electrode active material is not limited to the binder resin composition for electrodes of this invention, Preferably it mixes in the temperature range of 10 to 60 degreeC, and prepares an electrode mixture paste suitably. Can do. Known electrode active materials can be preferably used, but lithium-containing metal composite oxides, carbon powders, silicon powders, tin powders, or alloy powders containing silicon or tin are preferable. The amount of the electrode active material in the electrode mixture paste is not particularly limited, but is usually 0.1 to 1000 times, preferably 1 to 1000 times, on a mass basis with respect to the solid mass due to the polyamic acid. Preferably it is 5-1000 times, More preferably, it is 10-1000 times. When the amount of the active material is too small, an inactive portion is increased in the active material layer formed on the current collector, and the function as an electrode may be insufficient. On the other hand, when the amount of the active material is too large, the active material is not sufficiently bound to the current collector and easily falls off. In the electrode mixture paste, additives such as a surfactant, a viscosity modifier and a conductive additive can be added as necessary. Moreover, it is preferable to mix so that a polyamic acid may be 1-15 mass% in the total solid of a paste. Outside this range, the electrode performance may deteriorate.
充放電により可逆的にリチウムイオンを挿入・放出できる例えばリチウム含有金属複合酸化物のような電極活物質を用いて得られる電極合剤ペーストを、アルミニウムなどの導電性の集電体上に流延あるいは塗布して、８０〜４００℃、より好ましくは１２０〜３８０℃、特に好ましくは１５０〜３５０℃の温度範囲で加熱処理して溶媒を除去するとともにイミド化反応することにより電極を得ることができる。
加熱処理温度が上記の範囲外の場合、イミド化反応が十分に進行しなかったり、電極成形体の物性が低下したりすることがある。加熱処理は発泡や粉末化を防ぐために多段で行ってもよい。また、加熱処理時間は３分〜４８時間の範囲が好ましい。４８時間以上は生産性の点から好ましくなく、３分より短いとイミド化反応や溶媒の除去が不十分となることがあり好ましくない。
得られる電極はリチウムイオン二次電池の正極として特に好適に用いることができる。
An electrode mixture paste obtained by using an electrode active material such as a lithium-containing metal composite oxide capable of reversibly inserting and releasing lithium ions by charging and discharging is cast on a conductive current collector such as aluminum. Alternatively, the electrode can be obtained by coating and removing the solvent by heat treatment at a temperature range of 80 to 400 ° C., more preferably 120 to 380 ° C., particularly preferably 150 to 350 ° C., and imidization reaction. .
When the heat treatment temperature is outside the above range, the imidization reaction may not proceed sufficiently, or the physical properties of the electrode molded body may decrease. The heat treatment may be performed in multiple stages to prevent foaming or powdering. The heat treatment time is preferably in the range of 3 minutes to 48 hours. 48 hours or longer is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, imidation reaction or solvent removal may be insufficient, which is not preferable.
The obtained electrode can be particularly suitably used as a positive electrode of a lithium ion secondary battery.
また、充放電により可逆的にリチウムイオンを挿入・放出できる例えば炭素粉末、ケイ素粉末、スズ粉末、またはケイ素若しくはスズを含む合金粉末のような電極活物質を用いて得られる電極合剤ペーストを、銅などの導電性の集電体上に流延あるいは塗布する場合、８０〜３００℃、より好ましくは１２０〜２８０℃、特に好ましくは１５０〜２５０℃の温度範囲で加熱処理して溶媒を除去するとともにイミド化反応することにより電極を得ることができる。加熱処理温度が８０℃よりも低い場合、イミド化反応が十分に進行せずに電極成形体の物性が低下することがある。３００℃よりも高い温度で熱処理すると銅が変形などをしてしまい、電極として使用できなくなることがある。この場合も加熱処理は発泡や粉末化を防ぐために多段で行ってもよい。また、加熱処理時間は３分〜４８時間の範囲が好ましい。４８時間以上は生産性の点から好ましくなく、３分より短いとイミド化反応や溶媒の除去が不十分となることがあり好ましくない。
得られる電極はリチウムイオン二次電池の負極として好適に用いることができる。
Further, an electrode mixture paste obtained by using an electrode active material such as carbon powder, silicon powder, tin powder, or an alloy powder containing silicon or tin capable of reversibly inserting and releasing lithium ions by charging and discharging, When cast or coated on a conductive current collector such as copper, the solvent is removed by heat treatment at a temperature of 80 to 300 ° C., more preferably 120 to 280 ° C., particularly preferably 150 to 250 ° C. An electrode can be obtained by imidization reaction together. When the heat treatment temperature is lower than 80 ° C., the imidization reaction does not proceed sufficiently and the physical properties of the electrode molded body may be lowered. If heat treatment is performed at a temperature higher than 300 ° C., copper may be deformed and cannot be used as an electrode. Also in this case, the heat treatment may be performed in multiple stages in order to prevent foaming and powdering. The heat treatment time is preferably in the range of 3 minutes to 48 hours. 48 hours or longer is not preferable from the viewpoint of productivity, and if it is shorter than 3 minutes, imidation reaction or solvent removal may be insufficient, which is not preferable.
The obtained electrode can be suitably used as a negative electrode of a lithium ion secondary battery.
以下、本発明を実施例により更に具体的に説明するが、本発明は、これらの実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
実施例で用いた特性の測定方法を以下に示す。
＜固形分濃度＞
試料溶液（その質量をｗ１とする）を、熱風乾燥機中１２０℃で１０分間、２５０℃で１０分間、次いで３５０℃で３０分間加熱処理して、加熱処理後の質量（その質量をｗ２とする）を測定する。固形分濃度［質量％］は、次式によって算出した。
固形分濃度［質量％］＝（ｗ２／ｗ１）×１００
A method for measuring the characteristics used in the examples is shown below.
<Concentration of solid content>
The sample solution (whose mass is designated as w1) is heat-treated in a hot air dryer at 120 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then at 350 ° C. for 30 minutes. Measure). Solid content concentration [mass%] was computed by the following formula.
Solid content concentration [% by mass] = (w2 / w1) × 100
＜対数粘度＞
試料溶液を、固形分濃度に基づいて濃度が０．５ｇ／ｄｌ（溶媒はＮＭＰ）になるように希釈した。この希釈液を、３０℃にて、キャノンフェンスケＮｏ．１００を用いて流下時間（Ｔ１）を測定した。対数粘度は、ブランクのＮＭＰの流下時間（Ｔ０）を用いて、次式から算出した。
対数粘度＝｛ｌｎ（Ｔ１／Ｔ０）｝／０．５
<Logarithmic viscosity>
The sample solution was diluted to a concentration of 0.5 g / dl (solvent is NMP) based on the solid content concentration. This diluted solution was added to Cannon Fenceke No. The flow-down time (T 1 ) was measured using 100. The logarithmic viscosity was calculated from the following equation using the flow time (T 0 ) of blank NMP.
Logarithmic viscosity = {ln (T 1 / T 0 )} / 0.5
＜溶液粘度（回転粘度）＞
トキメック社製Ｅ型粘度計を用いて３０℃で測定した。
<Solution viscosity (rotational viscosity)>
It measured at 30 degreeC using the Tokimec E-type viscosity meter.
＜溶液安定性＞
電極用バインダー樹脂組成物を、２５℃の温度に調整された雰囲気中に保管し、１ヶ月後の溶液粘度変化が±１０％以内のものを○、±１０％を超えたものを×とした。
<Solution stability>
The binder resin composition for electrodes was stored in an atmosphere adjusted to a temperature of 25 ° C., and the change in solution viscosity after 1 month was within ± 10%, and the one exceeding ± 10% was evaluated as x. .
＜機械的物性（引張試験）＞
引張試験は、引張り試験機（オリエンテック社製ＲＴＣ−１２２５Ａ）を用いて、ＡＳＴＭ Ｄ８８２に準拠して測定した。
<Mechanical properties (tensile test)>
The tensile test was measured according to ASTM D882 using a tensile tester (Orientec RTC-1225A).
＜膨潤試験＞
電極用バインダー樹脂組成物から得られたポリイミドフィルムを５ｃｍ角（厚さ：５０μｍ）に切り出したものを用いた。６０℃で２４時間真空乾燥後の質量を乾燥質量（Ｗｄ）、ジメチルカーボネート溶液に２５℃で２４時間浸漬後の質量を膨潤質量（Ｗｗ）とし、次式により膨潤度Ｓを計算した。
Ｓ［質量％］＝（Ｗｗ−Ｗｄ）／Ｗｗ×１００
<Swelling test>
The polyimide film obtained from the binder resin composition for electrodes was cut into 5 cm square (thickness: 50 μm). The mass after vacuum drying at 60 ° C. for 24 hours was defined as dry mass (Wd), and the mass after immersion in dimethyl carbonate solution at 25 ° C. for 24 hours was defined as swelling mass (Ww).
S [mass%] = (Ww−Wd) / Ww × 100
＜破断エネルギー保持率＞
ジメチルカーボネート溶液での膨潤試験前後のサンプルについて引張試験を行い、次式により破断エネルギーの保持率を算出した。
破断エネルギー保持率[％]
＝浸漬後の破断エネルギー／浸漬前の破断エネルギー×１００
<Break energy retention>
A tensile test was performed on the samples before and after the swelling test with the dimethyl carbonate solution, and the retention rate of the breaking energy was calculated by the following formula.
Breaking energy retention [%]
= Breaking energy after immersion / Breaking energy before immersion x 100
以下の例で使用した化合物の略号について説明する。
ｓ−ＢＰＤＡ：３，３’，４，４’−ビフェニルテトラカルボン酸二無水物
ＯＤＡ：４，４’−ジアミノジフェニルエーテル
ＰＰＤ：ｐ−フェニレンジアミン
ＮＭＰ：Ｎ−メチル−２−ピロリドン
ＤＭＡｃ：Ｎ，Ｎ−ジメチルアセトアミド
The abbreviations of the compounds used in the following examples are described.
s-BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ODA: 4,4′-diaminodiphenyl ether PPD: p-phenylenediamine NMP: N-methyl-2-pyrrolidone DMAc: N, N -Dimethylacetamide
〔実施例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの３７．１４ｇ（０．１８５モル）及びＰＰＤの２．２３ｇ（０．０２１モル）と、ｓ−ＢＰＤＡの６０．６３ｇ（０．２０６モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．２質量％、溶液粘度４．８Ｐａ・ｓ、対数粘度０．７１の電極用バインダー樹脂組成物を得た。
[Example 1]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 400 g of NMP was added as a solvent, and 37.14 g (0.185 mol) of ODA and 2.23 g of PPD ( 0.021 mol) and 60.63 g (0.206 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.2% by mass, a solution viscosity of 4.8 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 0.71 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物４．７７ｇ（イミド化後の固形分質量０．８ｇ）と３００メッシュのケイ素粉末９．２ｇを乳鉢中で磨り潰すように混練し、電極合剤ペーストを調製した。得られたペーストは、ガラス棒で銅箔上に薄く延ばすことが可能であった。ペーストを塗布した銅箔を基板上に固定し、窒素雰囲気下で、１２０℃で１時間、２００℃で１０分、２２０℃で１０分、２５０℃で１０分、３００℃で１０分、３５０℃で１０分加熱することにより、活物質層の厚みが１００μｍの電極を好適に作成することができた。 Further, 4.77 g of the obtained binder resin composition for electrodes (solid content mass after imidization 0.8 g) and 9.2 g of 300 mesh silicon powder were kneaded so as to be ground in a mortar, and electrode mixture paste Was prepared. The obtained paste could be thinly spread on the copper foil with a glass rod. The copper foil coated with the paste was fixed on the substrate, and under a nitrogen atmosphere, 120 ° C. for 1 hour, 200 ° C. for 10 minutes, 220 ° C. for 10 minutes, 250 ° C. for 10 minutes, 300 ° C. for 10 minutes, 350 ° C. By heating for 10 minutes, an electrode having an active material layer thickness of 100 μm could be suitably produced.
〔実施例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの３３．６５ｇ（０．１６８モル）及びＰＰＤの４．５４ｇ（０．０４２モル）と、ｓ−ＢＰＤＡの６１．０８ｇ（０．２１０モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．０質量％、溶液粘度４．９Ｐａ・ｓ、対数粘度０．６９の電極用バインダー樹脂組成物を得た。
[Example 2]
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 400 g of NMP was added as a solvent, and 33.65 g (0.168 mol) of ODA and 4.54 g of PPD ( 0.042 mol) and 61.08 g (0.210 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.0% by mass, a solution viscosity of 4.9 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 0.69 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例３〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの２００ｇと、ＤＭＡｃの２００ｇとを加え、これにＯＤＡの３０．０３ｇ（０．１５０モル）及びＰＰＤの６．９５ｇ（０．０６４モル）と、ｓ−ＢＰＤＡの６３．０２ｇ（０．２１４モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．３質量％、溶液粘度５．０Ｐａ・ｓ、対数粘度０．７５の電極用バインダー樹脂組成物を得た。
Example 3
200 g of NMP and 200 g of DMAc were added as solvents to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 30.03 g (0.150 mol) of ODA and 6.95 g (0.064 mol) of PPD and 63.02 g (0.214 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.3% by mass and a solution viscosity. An electrode binder resin composition having 5.0 Pa · s and a logarithmic viscosity of 0.75 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例４〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの２２．３３ｇ（０．１１２モル）及びＰＰＤの１２．０６ｇ（０．１１２モル）と、ｓ−ＢＰＤＡの６５．６１ｇ（０．２２３モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．５質量％、溶液粘度４．９Ｐａ・ｓ、対数粘度０．６６の電極用バインダー樹脂組成物を得た。
Example 4
400 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 22.33 g (0.112 mol) of ODA and 12.06 g of PPD were added thereto. 0.112 mol) and 65.61 g (0.223 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.5% by mass, a solution viscosity of 4.9 Pa · s, A binder resin composition for electrodes having a logarithmic viscosity of 0.66 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例５〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの１３．９７ｇ（０．０７０モル）及びＰＰＤの１７．６１ｇ（０．１６３モル）と、ｓ−ＢＰＤＡの６８．４２ｇ（０．２３３モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．３質量％、溶液粘度５．２Ｐａ・ｓ、対数粘度０．６５の電極用バインダー樹脂組成物を得た。
Example 5
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 400 g of NMP was added as a solvent, and 13.97 g (0.070 mol) of ODA and 17.61 g of PPD ( 0.163 mol) and 68.42 g (0.233 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.3% by mass, a solution viscosity of 5.2 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 0.65 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例６〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの９．５２ｇ（０．０４８モル）及びＰＰＤの２０．５６ｇ（０．１９０モル）と、ｓ−ＢＰＤＡの６９．９２ｇ（０．２３８モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．２質量％、溶液粘度４．８Ｐａ・ｓ、対数粘度０．６３の電極用バインダー樹脂組成物を得た。
Example 6
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 400 g of NMP was added as a solvent, and 9.52 g (0.048 mol) of ODA and 20.56 g of PPD ( 0.190 mol) and 69.92 g (0.238 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.2% by mass, a solution viscosity of 4.8 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 0.63 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例７〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの４．８７ｇ（０．０２４モル）及びＰＰＤの２３．６５ｇ（０．２１９モル）と、ｓ−ＢＰＤＡの７１．４８ｇ（０．２４３モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．１質量％、溶液粘度５．１Ｐａ・ｓ、対数粘度０．６２の電極用バインダー樹脂組成物を得た。
Example 7
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas inlet / outlet tube, 400 g of NMP was added as a solvent, and 4.87 g (0.024 mol) of ODA and 23.65 g of PPD ( 0.219 mol) and 71.48 g (0.243 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours to obtain a solid content concentration of 18.1% by mass, a solution viscosity of 5.1 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 0.62 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例８〕
実施例１で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
Example 8
To the binder resin composition for an electrode obtained in Example 1, 0.1 molar equivalent of isoquinoline with respect to the amic acid structure of the polyamic acid was added, and the binder resin composition for an electrode was stirred at 25 ° C. for 4 hours. The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A heat treatment was performed at 30 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例９〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの３０．０３ｇ（０．１５０モル）及びＰＰＤの６．９５ｇ（０．０６４モル）と、ｓ−ＢＰＤＡの６３．０２ｇ（０．２１４モル）とを加え、５０℃で１０時間撹拌した。２５℃に冷却後にポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌して、固形分濃度１８．１質量％、溶液粘度５．１Ｐａ・ｓ、対数粘度０．６８の電極用バインダー樹脂組成物を得た。
Example 9
To a 500 mL glass reaction vessel equipped with a stirrer and a nitrogen gas introduction / discharge tube, 400 g of NMP was added as a solvent, to which 30.03 g (0.150 mol) of ODA and 6.95 g of PPD ( 0.064 mol) and 63.02 g (0.214 mol) of s-BPDA were added and stirred at 50 ° C. for 10 hours. After cooling to 25 ° C., 0.1 molar equivalent of isoquinoline is added to the amic acid structure of the polyamic acid, and stirred at 25 ° C. for 4 hours to obtain a solid content concentration of 18.1% by mass, a solution viscosity of 5.1 Pa · s, A binder resin composition for an electrode having a logarithmic viscosity of 0.68 was obtained.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例１０〕
実施例４で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表１に示した。
Example 10
To the binder resin composition for an electrode obtained in Example 4, 0.1 molar equivalent of isoquinoline with respect to the amic acid structure of the polyamic acid was added, and the binder resin composition for an electrode was stirred at 25 ° C. for 4 hours. The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A heat treatment was performed at 30 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 1.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例１１〕
実施例４で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 11
The binder resin composition for an electrode obtained by adding 0.1 molar equivalent of quinoline to the amic acid structure of the polyamic acid to the binder resin composition for an electrode obtained in Example 4, and stirring at 25 ° C. for 4 hours, The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A heat treatment was performed at 30 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂前駆体溶液組成物を実施例１と同様に処理して、電極を作成することが可能であった。 Moreover, it was possible to process the obtained binder resin precursor solution composition for electrodes similarly to Example 1, and to produce an electrode.
〔実施例１２〕
実施例４で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のキノキサリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 12
To the binder resin composition for an electrode obtained in Example 4, 0.1 molar equivalent of quinoxaline was added to the amic acid structure of the polyamic acid, and the binder resin composition for an electrode was stirred at 25 ° C. for 4 hours. The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A heat treatment was performed at 30 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例１３〕
実施例５で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂前駆体溶液組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 13
The binder resin precursor solution composition for an electrode obtained by adding 0.1 molar equivalent of isoquinoline to the binder resin composition for an electrode obtained in Example 5 and stirring at 25 ° C. for 4 hours. Was applied to the glass plate of the substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. Then, a heat treatment was performed at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例１４〕
実施例７で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 14
To the binder resin composition for an electrode obtained in Example 7, 0.1 molar equivalent of isoquinoline with respect to the amic acid structure of the polyamic acid was added, and the binder resin composition for an electrode was stirred at 25 ° C. for 4 hours. The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A heat treatment was performed at 30 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を実施例１と同様に処理して、電極を好適に作成することができた。 Moreover, the obtained binder resin composition for electrodes was treated in the same manner as in Example 1 to suitably prepare electrodes.
〔実施例１５〕
実施例８で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 15
After applying the binder resin composition for an electrode obtained in Example 8 on a glass plate of a substrate by a bar coater, and defoaming and pre-drying the coating film at 25 ° C. under reduced pressure for 30 minutes, It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を、熱処理温度を１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間にしたこと以外は実施例１と同様に処理して、電極を好適に作成することができた。 Further, the obtained electrode binder resin composition was treated in the same manner as in Example 1 except that the heat treatment temperature was 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then 200 ° C. for 10 minutes. Was successfully created.
〔実施例１６〕
実施例９で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 16
The electrode binder resin composition obtained in Example 9 was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes. It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を、熱処理温度を１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間にしたこと以外は実施例１と同様に処理して、電極を好適に作成することができた。 Further, the obtained electrode binder resin composition was treated in the same manner as in Example 1 except that the heat treatment temperature was 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then 200 ° C. for 10 minutes. Was successfully created.
〔実施例１７〕
実施例１０で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 17
After applying the binder resin composition for an electrode obtained in Example 10 onto a glass plate of a substrate by a bar coater, and defoaming and predrying the coating film at 25 ° C. for 30 minutes under reduced pressure, It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を、熱処理温度を１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間にしたこと以外は実施例１と同様に処理して、電極を好適に作成することができた。 Further, the obtained electrode binder resin composition was treated in the same manner as in Example 1 except that the heat treatment temperature was 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then 200 ° C. for 10 minutes. Was successfully created.
〔実施例１８〕
実施例１３で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 18
After applying the binder resin composition for an electrode obtained in Example 13 on a glass plate of a base material with a bar coater, and defoaming and predrying the coating film at 25 ° C. under reduced pressure for 30 minutes, It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を、熱処理温度を１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間にしたこと以外は実施例１と同様に処理して、電極を好適に作成することができた。 Further, the obtained electrode binder resin composition was treated in the same manner as in Example 1 except that the heat treatment temperature was 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then 200 ° C. for 10 minutes. Was successfully created.
〔実施例１９〕
実施例１４で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表２に示した。
Example 19
The electrode binder resin composition obtained in Example 14 was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes. It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 2.
また、得られた電極用バインダー樹脂組成物を、熱処理温度を１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間にしたこと以外は実施例１と同様に処理して、電極を好適に作成することができた。 Further, the obtained electrode binder resin composition was treated in the same manner as in Example 1 except that the heat treatment temperature was 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then 200 ° C. for 10 minutes. Was successfully created.
〔比較例１〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＯＤＡの４０．５０ｇ（０．２０２モル）と、ｓ−ＢＰＤＡの５９．５０ｇ（０．２０２モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．５質量％、溶液粘度５．１Ｐａ・ｓ、対数粘度０．７１の電極用バインダー樹脂組成物を得た。
[Comparative Example 1]
400 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge pipe, and 40.50 g (0.202 mol) of ODA and 59 of s-BPDA were added thereto. .50 g (0.202 mol) was added and stirred at 50 ° C. for 10 hours to obtain a binder resin composition for an electrode having a solid concentration of 18.5% by mass, a solution viscosity of 5.1 Pa · s, and a logarithmic viscosity of 0.71. Got.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で６０分間、１５０℃で３０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表３に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air drier in a gas atmosphere, heat treatment at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 350 ° C. for 10 minutes, thickness 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 3.
〔比較例２〕
攪拌機、窒素ガス導入・排出管を備えた内容積５００ｍＬのガラス製の反応容器に、溶媒としてＮＭＰの４００ｇを加え、これにＰＰＤの２６．８８ｇ（０．２４９モル）と、ｓ−ＢＰＤＡの７３．１２ｇ（０．２４９モル）とを加え、５０℃で１０時間撹拌して、固形分濃度１８．０質量％、溶液粘度５．０Ｐａ・ｓ、対数粘度０．６１の電極用バインダー樹脂組成物を得た。
[Comparative Example 2]
400 g of NMP was added as a solvent to a glass reaction vessel having an internal volume of 500 mL equipped with a stirrer and a nitrogen gas introduction / discharge tube, and 26.88 g (0.249 mol) of PPD and 73 of s-BPDA were added thereto. .12 g (0.249 mol) was added, and the mixture was stirred at 50 ° C. for 10 hours. Got.
得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで４００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表３に示した。
The obtained binder resin composition for an electrode was applied onto a glass plate of a substrate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then subjected to nitrogen under normal pressure. Put in a hot air dryer under gas atmosphere, heat treatment at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, then 400 ° C. for 10 minutes, thickness of 50 μm The binder resin film was formed.
The properties of the obtained film are shown in Table 3.
〔比較例３〕
比較例１で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、２００℃で１０分間、２５０℃で１０分間、次いで３５０℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表３に示した。
[Comparative Example 3]
To the binder resin composition for an electrode obtained in Comparative Example 1, 0.1 molar equivalent of isoquinoline with respect to the amic acid structure of the polyamic acid was added, and the binder resin composition for an electrode was stirred at 25 ° C. for 4 hours. The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A heat treatment was performed at 30 ° C. for 30 minutes, 150 ° C. for 10 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 350 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 3.
〔比較例４〕
比較例２で得られた電極用バインダー樹脂組成物に、ポリアミック酸のアミック酸構造に対して０．１モル当量のイソキノリンを加え、２５℃で４時間撹拌した電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で６０分間、１５０℃で３０分間、２００℃で１０分間、２５０℃で１０分間、次いで４００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表３に示した。
[Comparative Example 4]
To the binder resin composition for electrodes obtained in Comparative Example 2, 0.1 molar equivalent of isoquinoline with respect to the amic acid structure of the polyamic acid was added, and the binder resin composition for electrodes stirred for 4 hours at 25 ° C. The coating was applied on a glass plate of the material by a bar coater, defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes, and then placed in a hot air drier under normal pressure and nitrogen gas atmosphere. A binder resin film having a thickness of 50 μm was formed by heat treatment at 60 ° C. for 60 minutes, 150 ° C. for 30 minutes, 200 ° C. for 10 minutes, 250 ° C. for 10 minutes, and then 400 ° C. for 10 minutes.
The properties of the obtained film are shown in Table 3.
〔比較例５〕
比較例３で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で３０分間、１５０℃で１０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表３に示した。
[Comparative Example 5]
After applying the binder resin composition for an electrode obtained in Comparative Example 3 on a glass plate of a base material with a bar coater, the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes. It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 30 minutes, 150 ° C. for 10 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 3.
〔比較例６〕
比較例４で得られた電極用バインダー樹脂組成物を、基材のガラス板上にバーコーターによって塗布し、その塗膜を、減圧下２５℃で３０分間、脱泡及び予備乾燥した後で、常圧下、窒素ガス雰囲気下に熱風乾燥器に入れて、１２０℃で６０分間、１５０℃で３０分間、次いで２００℃で１０分間加熱処理して、厚さが５０μｍのバインダー樹脂フィルムを形成した。
得られたフィルムの特性を表３に示した。
[Comparative Example 6]
The electrode binder resin composition obtained in Comparative Example 4 was applied onto a base glass plate by a bar coater, and the coating film was defoamed and pre-dried at 25 ° C. under reduced pressure for 30 minutes. It was put into a hot air drier under normal pressure and nitrogen gas atmosphere, and heat-treated at 120 ° C. for 60 minutes, 150 ° C. for 30 minutes, and then at 200 ° C. for 10 minutes to form a binder resin film having a thickness of 50 μm.
The properties of the obtained film are shown in Table 3.
本発明によれば、リチウムイオン二次電池、電気二重層キャパシタなどの電気化学素子の電極のバインダー用途として好適な、電池環境下でも膨潤度が小さく、高い靱性（大きな破断伸度及び破断エネルギー）を有する、新たな化学構造からなる電極用バインダー樹脂組成物を得ることができる。 According to the present invention, it is suitable as a binder for electrodes of electrochemical elements such as lithium ion secondary batteries and electric double layer capacitors, and has low swelling and high toughness (high breaking elongation and breaking energy) even in battery environments. It is possible to obtain a binder resin composition for an electrode having a new chemical structure.
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| PCT/JP2010/066419 WO2011040308A1 (en) | 2009-09-30 | 2010-09-22 | Binder resin composition for electrode, electrode mix paste, and electrode |
| CN201080039038.XA CN102484254B (en) | 2009-09-30 | 2010-09-22 | Binder resin composition for electrode, electrode mix paste, and electrode |
| KR1020127004992A KR101713060B1 (en) | 2009-09-30 | 2010-09-22 | Binder resin composition for electrode, electrode mix paste, and electrode |
| EP10820427.2A EP2485307B1 (en) | 2009-09-30 | 2010-09-22 | Binder resin composition for electrode, electrode mixture paste, and electrode |
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