JP2019169272A - Resin current collector and lithium ion battery - Google Patents
Resin current collector and lithium ion battery Download PDFInfo
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- JP2019169272A JP2019169272A JP2018054427A JP2018054427A JP2019169272A JP 2019169272 A JP2019169272 A JP 2019169272A JP 2018054427 A JP2018054427 A JP 2018054427A JP 2018054427 A JP2018054427 A JP 2018054427A JP 2019169272 A JP2019169272 A JP 2019169272A
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- current collector
- resin current
- conductive carbon
- resin
- carbon filler
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- 229920005989 resin Polymers 0.000 title claims abstract description 167
- 239000011347 resin Substances 0.000 title claims abstract description 167
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000000945 filler Substances 0.000 claims abstract description 123
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 114
- 238000010521 absorption reaction Methods 0.000 claims abstract description 67
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 18
- 230000006866 deterioration Effects 0.000 abstract description 7
- 239000000470 constituent Substances 0.000 abstract description 3
- -1 polypropylene Polymers 0.000 description 28
- 229920001155 polypropylene Polymers 0.000 description 23
- 239000004743 Polypropylene Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 239000006230 acetylene black Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000035515 penetration Effects 0.000 description 10
- 239000004020 conductor Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920005629 polypropylene homopolymer Polymers 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000006231 channel black Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000006233 lamp black Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003050 poly-cycloolefin Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical class C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000005590 trimellitic acid group Chemical group 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は、樹脂集電体、及び、リチウムイオン電池に関する。 The present invention relates to a resin current collector and a lithium ion battery.
近年、環境保護のため、二酸化炭素排出量の低減が切に望まれている。自動車業界では、電気自動車（ＥＶ）やハイブリッド電気自動車（ＨＥＶ）の導入による二酸化炭素排出量の低減に期待が集まっており、これらの実用化の鍵を握るモータ駆動用二次電池の開発が鋭意行われている。二次電池としては、高エネルギー密度、高出力密度が達成できるリチウムイオン電池に注目が集まっている。 In recent years, reduction of carbon dioxide emissions has been strongly desired for environmental protection. In the automobile industry, there are high expectations for reducing carbon dioxide emissions by introducing electric vehicles (EVs) and hybrid electric vehicles (HEVs), and we are eager to develop secondary batteries for motor drives that hold the key to their practical application. Has been done. As a secondary battery, attention is focused on a lithium ion battery that can achieve a high energy density and a high output density.
リチウムイオン電池は、一般に、バインダを用いて正極または負極活物質等を正極用または負極用集電体にそれぞれ塗布して電極を構成している。また、バイポーラ（双極）型の電池の場合には、集電体の一方の面にバインダを用いて正極活物質等を塗布して正極層を、反対側の面にバインダを用いて負極活物質等を塗布して負極層を有するバイポーラ（双極）型電極を構成している。 In general, a lithium ion battery forms an electrode by applying a positive electrode or a negative electrode active material or the like to a positive electrode or negative electrode current collector using a binder. In the case of a bipolar battery, a positive electrode active material or the like is applied to one surface of the current collector using a binder, and a positive electrode layer is applied to the opposite surface, and a negative electrode active material using a binder on the opposite surface. To form a bipolar electrode having a negative electrode layer.
このようなリチウムイオン電池においては、従来、集電体として金属箔（金属集電箔）が用いられてきた。近年、金属箔に代わって導電性材料が添加された樹脂から構成される、いわゆる樹脂集電体が提案されている。このような樹脂集電体は、金属集電箔と比較して軽量であり、電池の単位重量あたりの出力向上が期待される。 In such a lithium ion battery, conventionally, a metal foil (metal current collector foil) has been used as a current collector. In recent years, so-called resin current collectors composed of a resin to which a conductive material is added instead of a metal foil have been proposed. Such a resin current collector is lighter than a metal current collector foil, and is expected to improve output per unit weight of the battery.
特許文献１には、樹脂集電体用分散剤、樹脂及び導電性フィラーを含有する樹脂集電体用材料、並びに、該樹脂集電体用材料を有する樹脂集電体が開示されている。 Patent Document 1 discloses a resin current collector material containing a dispersant for a resin current collector, a resin and a conductive filler, and a resin current collector having the resin current collector material.
特許文献１には、樹脂集電体の例として、樹脂としてポリプロピレン樹脂を使用し、導電性フィラーとしてアセチレンブラックを使用した例が記載されている。
このような樹脂集電体を正極用樹脂集電体として使用した場合、アセチレンブラックの比表面積が大きいために、アセチレンブラック界面での電解液の分解が生じやすく、これに伴って樹脂集電体を構成する樹脂が劣化しやすくなることが判明した。
また、アセチレンブラックへの電解液の浸み込み（フィラー膨張）により、樹脂集電体の体積が膨張するという問題もあった。
Patent Document 1 describes an example in which a polypropylene resin is used as a resin and acetylene black is used as a conductive filler as an example of a resin current collector.
When such a resin current collector is used as a positive electrode resin current collector, the acetylene black has a large specific surface area, so that the electrolytic solution is easily decomposed at the acetylene black interface. It has been found that the resin constituting the resin tends to deteriorate.
There is also a problem that the volume of the resin current collector expands due to the penetration of the electrolytic solution into the acetylene black (filler expansion).
以上の状況を踏まえて、本発明は、樹脂集電体を構成する樹脂の劣化を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体を提供することを目的とする。本発明はまた、上記樹脂集電体を用いたリチウムイオン電池を提供することを目的とする。 In view of the above situation, an object of the present invention is to provide a resin current collector that can suppress the deterioration of the resin constituting the resin current collector and is less likely to cause volume expansion. Another object of the present invention is to provide a lithium ion battery using the resin current collector.
本発明者らは、上記課題を解決するために鋭意検討した結果、本発明に想到した。
すなわち、本発明は、ポリオレフィン樹脂及び導電性炭素フィラーを含む樹脂集電体であって、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が０．１０〜０．２６ｍｌであることを特徴とする樹脂集電体；本発明の樹脂集電体を備えることを特徴とするリチウムイオン電池である。
The inventors of the present invention have come up with the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is a resin current collector containing a polyolefin resin and a conductive carbon filler, and the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is 0.10 to 0.26 ml. A lithium ion battery comprising the resin current collector of the present invention.
本発明の樹脂集電体は、構成する樹脂の劣化を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体である。 The resin current collector of the present invention is a resin current collector that can suppress the deterioration of the resin that constitutes it and is less likely to cause volume expansion.
本発明の樹脂集電体は、ポリオレフィン樹脂及び導電性炭素フィラーを含む樹脂集電体であって、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が０．１０〜０．２６ｍｌであることを特徴とする。 The resin current collector of the present invention is a resin current collector containing a polyolefin resin and a conductive carbon filler, and the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is 0.10 to 0.26 ml. It is characterized by being.
本発明の樹脂集電体では、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量を特定の範囲に制御することで、導電性炭素フィラー界面での電解液の分解、及び、導電性炭素フィラーへの電解液の浸み込み（フィラー膨張）を抑制することができる。
その結果、樹脂集電体を構成する樹脂の劣化を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体とすることができる。
In the resin current collector of the present invention, by controlling the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector within a specific range, the decomposition of the electrolytic solution at the conductive carbon filler interface and the conductivity Infiltration of the electrolytic solution into the porous carbon filler (filler expansion) can be suppressed.
As a result, deterioration of the resin constituting the resin current collector can be suppressed, and a resin current collector that hardly causes volume expansion can be obtained.
本発明の樹脂集電体で用いるポリオレフィン樹脂としては、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、ポリメチルペンテン（ＰＭＰ）及びポリシクロオレフィン（ＰＣＯ）等の混合物が挙げられる。また、これらのポリオレフィン樹脂は、変性物（以下、変性ポリオレフィンという）であってもよい。 Examples of the polyolefin resin used in the resin current collector of the present invention include mixtures of polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polycycloolefin (PCO), and the like. These polyolefin resins may be modified products (hereinafter referred to as modified polyolefins).
ポリオレフィン樹脂の中でも、防湿特性や機械的強度の点で、ポリエチレン、ポリプロピレンが好ましい。
ポリプロピレンとしては、例えば、ホモポリプロピレン、ランダムポリプロピレン、ブロックポリプロピレン、長鎖分岐構造を有するポリプロピレン及び酸変性ポリプロピレン等が挙げられる。
ホモポリプロピレンは、プロピレンの単独重合体である。ランダムポリプロピレンは、不規則に導入された少量（好ましくは４．５重量％以下）のエチレン単位を含有する共重合体である。ブロックポリプロピレンは、ホモポリプロピレンの中にエチレンプロピレンゴム（ＥＰＲ）が分散している組成物であり、ホモポリプロピレンの「海」の中にＥＰＲを含む「島」が浮かぶ「海島構造」を有している。長鎖分岐構造を有するポリプロピレンとしては、特開２００１−２５３９１０号公報等に記載されたポリプロピレン等が挙げられる。酸変性ポリプロピレンは、カルボキシル基を導入したポリプロピレンであり、無水マレイン酸等の不飽和カルボン酸とポリプロピレンとを有機過酸化物の存在下で反応する等の公知の方法で反応して得ることができる。
Among the polyolefin resins, polyethylene and polypropylene are preferable in terms of moisture-proof properties and mechanical strength.
Examples of the polypropylene include homopolypropylene, random polypropylene, block polypropylene, polypropylene having a long chain branched structure, and acid-modified polypropylene.
Homopolypropylene is a homopolymer of propylene. Random polypropylene is a copolymer containing a small amount (preferably 4.5 wt% or less) of ethylene units introduced randomly. Block polypropylene is a composition in which ethylene propylene rubber (EPR) is dispersed in homopolypropylene, and has a “sea-island structure” in which “islands” including EPR float in the “sea” of homopolypropylene. Yes. Examples of the polypropylene having a long chain branched structure include polypropylenes described in JP-A No. 2001-253910. The acid-modified polypropylene is a polypropylene having a carboxyl group introduced, and can be obtained by reacting an unsaturated carboxylic acid such as maleic anhydride with polypropylene in the presence of an organic peroxide by a known method. .
ポリオレフィン樹脂としては、例えば、以下のものが市場から入手できる。
ＰＥ：「ノバテックＬＬ ＵＥ３２０」「ノバテックＬＬ ＵＪ９６０」いずれも日本ポリエチレン（株）製
ＰＰ：「サンアロマーＰＭ８５４Ｘ」「サンアロマーＰＣ６８４Ｓ」「サンアロマーＰＬ５００Ａ」「サンアロマーＰＣ６３０Ｓ」「サンアロマーＰＣ６３０Ａ」「サンアロマーＰＢ５２２Ｍ」「クオリアＣＭ６８８Ａ」いずれもサンアロマー（株）製、「プライムポリマーＪ−２０００ＧＰ」（株）プライムポリマー製、「ウィンテックＷＦＸ４Ｔ」日本ポリプロ（株）製
ＰＭＰ：「ＴＰＸ」三井化学（株）製
As polyolefin resin, the following can be obtained from the market, for example.
PE: “Novatech LL UE320” and “Novatech LL UJ960” are all manufactured by Nippon Polyethylene Co., Ltd. PP: “Sun Allomer PM854X” “Sun Allomer PC684S” “Sun Allomer PL500A” “Sun Allomer PC630S” “Sun Allomer PC630A” “Sun Allomer PB522M” “Qualia CM688A” All are manufactured by Sun Allomer Co., Ltd., “Prime Polymer J-2000GP” manufactured by Prime Polymer Co., Ltd., “Wintech WFX4T” manufactured by Nippon Polypro Co., Ltd. PMP: “TPX” manufactured by Mitsui Chemicals, Inc.
変性ポリオレフィンとしては、ポリエチレン、ポリプロピレン又はこれらの共重合体に極性官能基を導入したものが挙げられ、極性官能基としては、カルボキシル基、１，３−ジオキソ−２−オキサプロピレン基、ヒドロキシル基、アミノ基、アミド基及びイミド基等が挙げられる。 Examples of the modified polyolefin include those obtained by introducing a polar functional group into polyethylene, polypropylene, or a copolymer thereof. Examples of the polar functional group include a carboxyl group, a 1,3-dioxo-2-oxapropylene group, a hydroxyl group, An amino group, an amide group, an imide group, etc. are mentioned.
ポリエチレン、ポリプロピレン又はこれらの共重合体に極性官能基を導入した変性ポリオレフィンは、樹脂用分散剤及び相溶化剤等として市販されており、三洋化成工業株式会社製ユーメックスシリーズ及び三井化学株式会社製アドマーシリーズ等として入手可能である。 Modified polyolefins in which polar functional groups are introduced into polyethylene, polypropylene, or copolymers thereof are commercially available as dispersants and compatibilizers for resins, etc., Umex series manufactured by Sanyo Chemical Industries, Ltd. It is available as a series.
本発明の樹脂集電体では、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が０．１０〜０．２６ｍｌである。
樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が０．１０ｍｌ未満であると、電気抵抗値が高くなりすぎ、０．２６ｍｌを超えると、導電性炭素フィラー界面での電解液の分解や、導電性炭素フィラーへの電解液の浸み込み（フィラー膨張）が起こる。
導電性炭素フィラーの吸油量は、「ＪＩＳ Ｋ６２１７−４ ２００８ ゴム用カーボンブラック基本特性」に準じて、ＤＢＰ（フタル酸ジブチル）の吸収量を測定した値である。
In the resin current collector of the present invention, the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is 0.10 to 0.26 ml.
When the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is less than 0.10 ml, the electric resistance value becomes too high, and when it exceeds 0.26 ml, the electrolyte solution at the interface of the conductive carbon filler Decomposition and penetration of the electrolyte into the conductive carbon filler (filler expansion) occur.
The oil absorption amount of the conductive carbon filler is a value obtained by measuring the absorption amount of DBP (dibutyl phthalate) according to “JIS K6217-4 2008 Carbon black basic characteristics for rubber”.
樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量は、以下の式で算出される。
樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量（ｍｌ）
＝樹脂集電体１ｇ中の導電性炭素フィラーの重量（ｇ）×導電性炭素フィラーの吸油量（ｍｌ／ｇ）
The total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is calculated by the following equation.
Total oil absorption of conductive carbon filler contained in 1 g of resin current collector (ml)
= Weight of conductive carbon filler in 1 g of resin current collector (g) × oil absorption of conductive carbon filler (ml / g)
樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量は、以下の方法等により分析することができる。
まず、樹脂集電体から導電性炭素フィラーを分離する必要がある。導電性炭素フィラーの分離には、樹脂集電体を構成する樹脂を溶解することができる溶媒で樹脂集電体を溶解し、樹脂集電体を構成する樹脂と導電性炭素フィラーを分離する等の方法を用いることができる。
分離前の樹脂集電体の重量（ｇ）と、分離された導電性炭素フィラーの重量（ｇ）から、樹脂集電体１ｇ中の導電性炭素フィラーの重量（ｇ）を求めることができ、上記式により樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量を求めることができる。
なお、導電性炭素フィラーの種類は、走査電子顕微鏡（ＳＥＭ）観察や、元素分析等により特定することができる。
The total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector can be analyzed by the following method or the like.
First, it is necessary to separate the conductive carbon filler from the resin current collector. For the separation of the conductive carbon filler, the resin current collector is dissolved in a solvent capable of dissolving the resin constituting the resin current collector, and the resin constituting the resin current collector and the conductive carbon filler are separated. This method can be used.
From the weight (g) of the resin current collector before separation and the weight (g) of the separated conductive carbon filler, the weight (g) of the conductive carbon filler in 1 g of the resin current collector can be obtained. The total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector can be obtained from the above formula.
In addition, the kind of conductive carbon filler can be specified by scanning electron microscope (SEM) observation, elemental analysis, or the like.
なお、樹脂集電体が、導電性炭素フィラーとして２種以上の導電性炭素フィラーを含む場合は、導電性炭素フィラーの吸油量はそれぞれ分離して測定される。２種以上の導電性炭素フィラーの分離は、遠心分離機等を用いて行うことができる。
導電性炭素フィラーを２種類以上含む場合は樹脂集電体１ｇ中に含まれるそれぞれの導電性炭素フィラーの重量にそれぞれの導電性炭素フィラーの吸油量を掛けることにより、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量を計算することとする。
In addition, when the resin current collector contains two or more kinds of conductive carbon fillers as the conductive carbon filler, the oil absorption amount of the conductive carbon filler is measured separately. Separation of two or more kinds of conductive carbon fillers can be performed using a centrifuge or the like.
When two or more kinds of conductive carbon fillers are included, the weight of each conductive carbon filler contained in 1 g of the resin current collector is multiplied by the oil absorption amount of each conductive carbon filler to be included in 1 g of the resin current collector. The total oil absorption of the conductive carbon filler is calculated.
導電性炭素フィラーとしては、黒鉛（グラファイト）、カーボンブラック（アセチレンブラック、ケッチェンブラック、ファーネスブラック、チャンネルブラック、サーマルランプブラック等）、カーボンナノチューブ、グラフェン及びこれらの混合物等が挙げられるが、これらに限定されるわけではない。 Examples of the conductive carbon filler include graphite (graphite), carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), carbon nanotube, graphene, and a mixture thereof. It is not limited.
導電性炭素フィラーとしては、その体積平均粒子径は特に限定されず、例えば、３ｎｍ〜１１．５μｍのものを適宜選択して用いることができる。
本明細書において、導電性炭素フィラーの体積平均粒子径は、マイクロトラック法（レーザー回折・散乱法）によって求めた粒度分布における積算値５０％での粒径（Ｄｖ５０）を意味する。マイクロトラック法とは、レーザー光を粒子に照射することによって得られる散乱光を利用して粒度分布を求める方法である。なお、体積平均粒子径の測定には、日機装（株）製のマイクロトラック等を用いることができる。
As a conductive carbon filler, the volume average particle diameter is not specifically limited, For example, a 3 nm-11.5 micrometer thing can be selected suitably, and can be used.
In the present specification, the volume average particle diameter of the conductive carbon filler means a particle diameter (Dv50) at an integrated value of 50% in the particle size distribution obtained by the microtrack method (laser diffraction / scattering method). The microtrack method is a method for obtaining a particle size distribution using scattered light obtained by irradiating particles with laser light. In addition, Nikkiso Co., Ltd. microtrack etc. can be used for the measurement of a volume average particle diameter.
本発明の樹脂集電体は、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量を０．２６ｍｌ以下と小さくすることにより、樹脂集電体を構成する樹脂の劣化を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体とすることができるが、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量を小さくするためには、吸油量の小さい導電性炭素フィラーを使用する方法を採用することができる。
その一方で、吸油量の小さい導電性炭素フィラーを用いると樹脂集電体は比較的電気抵抗が高くなるため、必要な電気抵抗値を得るためには導電性炭素フィラーの配合量を増やす必要がある。
そして、導電性炭素フィラーの配合量を増やすと、樹脂集電体の薄膜化が困難になることがある。
樹脂集電体を薄膜化することができないと、電池内における集電体の体積が大きいことに起因して、電池容量の低下につながるために好ましくない。
The resin current collector of the present invention suppresses deterioration of the resin constituting the resin current collector by reducing the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector to 0.26 ml or less. However, in order to reduce the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector, a conductive material having a small oil absorption amount can be obtained. A method using a conductive carbon filler can be employed.
On the other hand, if a conductive carbon filler with a small oil absorption is used, the resin current collector has a relatively high electrical resistance, so it is necessary to increase the blending amount of the conductive carbon filler in order to obtain a required electrical resistance value. is there.
And if the compounding quantity of a conductive carbon filler is increased, it may become difficult to make the resin current collector thinner.
If the resin current collector cannot be made thin, it is not preferable because the capacity of the current collector in the battery is large, leading to a decrease in battery capacity.
そこで、本発明の樹脂集電体の好ましい態様として、吸油量の小さい導電性炭素フィラーと、吸油量が大きく、導電性の高い導電性炭素フィラーを混合して使用する態様が考えられる。
吸油量の小さい導電性炭素フィラーと、吸油量の大きい導電性炭素フィラーを併用することによって、構成する樹脂の劣化を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体を得ることができ、さらに薄膜化の要請にも応えることができる。
Therefore, as a preferred embodiment of the resin current collector of the present invention, an embodiment in which a conductive carbon filler having a small oil absorption amount and a conductive carbon filler having a large oil absorption amount and high conductivity are used in combination is conceivable.
By using together a conductive carbon filler with a small oil absorption amount and a conductive carbon filler with a large oil absorption amount, a resin current collector can be obtained in which deterioration of the constituent resin can be suppressed and volume expansion is unlikely to occur. In addition, it is possible to meet the demand for thin film.
具体的には、本発明の樹脂集電体が、導電性炭素フィラーが、吸油量が１．５ｍｌ／ｇ未満である第１の導電性炭素フィラー（Ａ１）と、吸油量が１．５〜４．０ｍｌ／ｇである第２の導電性炭素フィラー（Ａ２）とを含むことが好ましい。 Specifically, the resin current collector of the present invention includes a conductive carbon filler, a first conductive carbon filler (A1) having an oil absorption of less than 1.5 ml / g, and an oil absorption of 1.5 to It is preferable to contain the 2nd electroconductive carbon filler (A2) which is 4.0 ml / g.
吸油量が大きく、導電性の高い第２の導電性炭素フィラー（Ａ２）を含むことにより低い電気抵抗値が得られるため、樹脂集電体を薄膜化することに適している。
一方、吸油量が大きい第２の導電性炭素フィラー（Ａ２）は副反応の反応場にもなるので、吸油量が小さい第１の導電性炭素フィラー（Ａ１）を使用することにより、導電性炭素フィラー界面での電解液の分解、及び、導電性炭素フィラーへの電解液の浸み込み（フィラー膨張）を抑制することができる。
すなわち、２種類の導電性炭素フィラーのそれぞれの働きにより、構成する樹脂の劣化を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体を得ることができ、さらに薄膜化に適した樹脂集電体を提供することができる。
By including the second conductive carbon filler (A2) having a large oil absorption amount and high conductivity, a low electrical resistance value can be obtained, which is suitable for thinning the resin current collector.
On the other hand, since the second conductive carbon filler (A2) having a large oil absorption amount also serves as a side reaction reaction field, the conductive carbon filler can be obtained by using the first conductive carbon filler (A1) having a small oil absorption amount. It is possible to suppress decomposition of the electrolytic solution at the filler interface and penetration of the electrolytic solution into the conductive carbon filler (filler expansion).
That is, by the action of each of the two types of conductive carbon fillers, it is possible to obtain a resin current collector that can suppress the deterioration of the constituent resin and that is less likely to cause volume expansion. Resin current collectors can be provided.
導電性炭素フィラーとして（Ａ１）と（Ａ２）を含む場合、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量（ｍｌ）は以下の式で算出される。
樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量（ｍｌ）
＝樹脂集電体１ｇ中の（Ａ１）の重量（ｇ）×（Ａ１）の吸油量（ｍｌ／ｇ）＋樹脂集電体１ｇ中の（Ａ２）の重量（ｇ）×（Ａ２）の吸油量（ｍｌ／ｇ）
なお、（Ａ１）又は（Ａ２）を２種類以上含む場合は樹脂集電体１ｇ中に含まれるそれぞれの導電性炭素フィラーの重量にそれぞれの導電性炭素フィラーの吸油量を掛けて計算することとする。
When (A1) and (A2) are included as the conductive carbon filler, the total oil absorption amount (ml) of the conductive carbon filler contained in 1 g of the resin current collector is calculated by the following formula.
Total oil absorption of conductive carbon filler contained in 1 g of resin current collector (ml)
= Weight (g) of (A1) in 1 g of resin current collector × oil absorption amount (ml / g) of (A1) + oil absorption of weight (g) of (A2) in 1 g of resin current collector × (A2) Amount (ml / g)
In addition, when two or more types of (A1) or (A2) are included, the weight of each conductive carbon filler contained in 1 g of the resin current collector is multiplied by the oil absorption amount of each conductive carbon filler. To do.
第１の導電性炭素フィラー（Ａ１）はその吸油量が１．５ｍｌ／ｇ未満の導電性炭素フィラーであることが好ましい。第１の導電性炭素フィラー（Ａ１）はその吸油量が１．３ｍｌ／ｇ以下であることがより好ましい。
また、第１の導電性炭素フィラー（Ａ１）はその吸油量が０．１ｍｌ／ｇ以上であることが好ましい。
The first conductive carbon filler (A1) is preferably a conductive carbon filler having an oil absorption of less than 1.5 ml / g. More preferably, the first conductive carbon filler (A1) has an oil absorption of 1.3 ml / g or less.
The first conductive carbon filler (A1) preferably has an oil absorption of 0.1 ml / g or more.
第１の導電性炭素フィラー（Ａ１）としては、天然又は人造の黒鉛（グラファイト）、ハードカーボン（難黒鉛化炭素）、カーボンブラック（アセチレンブラック）、カーボンナノチューブ及びこれらの混合物等が挙げられるが、これらに限定されるわけではない。これらの中では黒鉛が好ましい。また、形状は球状、鱗片状及び塊状のいずれであっても良いが、球状が好ましい。 Examples of the first conductive carbon filler (A1) include natural or artificial graphite (graphite), hard carbon (non-graphitizable carbon), carbon black (acetylene black), carbon nanotube, and a mixture thereof. However, it is not limited to these. Of these, graphite is preferred. Further, the shape may be any of a spherical shape, a scale shape and a lump shape, but a spherical shape is preferable.
第１の導電性炭素フィラー（Ａ１）としては、その吸油量が１．５ｍｌ／ｇ未満である限り、その種類、吸油量が異なる２種類以上の導電性炭素フィラーを含んでいてもよい。 As the first conductive carbon filler (A1), as long as the oil absorption is less than 1.5 ml / g, two or more types of conductive carbon fillers having different types and oil absorption may be included.
第１の導電性炭素フィラー（Ａ１）として市場から入手できるものとしては、商品名「デンカブラックＬｉ−４００（１．４０ｍｌ／ｇ）」［デンカ(株)製］、商品名「ＶＧＣＦ（１．１０ｍｌ／ｇ）」［昭和電工（株）製］、商品名「ＳＮＧ−ＷＸＡ１（０．１５ｍｌ／ｇ）」［ＪＦＥケミカル(株)製］等が挙げられる。
なお、品名の後の括弧内に記載した値は、そのフィラーの吸油量である。
As the first conductive carbon filler (A1), those available on the market are trade name “Denka Black Li-400 (1.40 ml / g)” [manufactured by Denka Co., Ltd.], trade name “VGCF (1. 10 ml / g) ”[manufactured by Showa Denko KK], trade name“ SNG-WXA1 (0.15 ml / g) ”[manufactured by JFE Chemical Co., Ltd.], and the like.
In addition, the value described in parentheses after the product name is the oil absorption amount of the filler.
第２の導電性炭素フィラー（Ａ２）はその吸油量が１．５〜４．０ｍｌ／ｇの導電性炭素フィラーであることが好ましい。
第２の導電性炭素フィラー（Ａ２）はその吸油量が１．７〜３．６ｍｌ／ｇであることがより好ましい。
The second conductive carbon filler (A2) is preferably a conductive carbon filler having an oil absorption of 1.5 to 4.0 ml / g.
More preferably, the second conductive carbon filler (A2) has an oil absorption of 1.7 to 3.6 ml / g.
第２の導電性炭素フィラー（Ａ２）としては、カーボンブラック（アセチレンブラック、ケッチェンブラック、ファーネスブラック、チャンネルブラック、サーマルランプブラック等）、カーボンナノチューブ、グラフェン等が挙げられるが、これらに限定されるわけではない。これらの中ではアセチレンブラックが好ましい。 Examples of the second conductive carbon filler (A2) include, but are not limited to, carbon black (acetylene black, ketjen black, furnace black, channel black, thermal lamp black, etc.), carbon nanotube, graphene, and the like. Do not mean. Of these, acetylene black is preferred.
第２の導電性炭素フィラー（Ａ２）としては、その吸油量が１．５〜４．０ｍｌ／ｇである限り、その種類、吸油量が異なる２種類以上の導電性炭素フィラーを含んでいてもよい。 As a 2nd electroconductive carbon filler (A2), as long as the oil absorption is 1.5-4.0 ml / g, even if it contains the 2 or more types of conductive carbon filler from which the kind and oil absorption differ. Good.
第２の導電性炭素フィラー（Ａ２）として市場から入手できるものとしては、商品名「デンカブラック（１．７５ｍｌ／ｇ）」［デンカ(株)製］、商品名「エンサコ２５０Ｇ（１．９０ｍｌ／ｇ）」［Ｉｍｅｒｙｓ製］、商品名「ケッチェンブラックＥＣ３００Ｊ（３．６０ｍｌ／ｇ）」［ライオン・スペシャリティ・ケミカルズ（株）製］、商品名「ＡＭＣ（３．３０ｍｌ／ｇ）［宇部興産（株）製］、商品名「ｉｇｒａｆｅｎ−αＳ（２．５０ｍｌ／ｇ）」［アイテック（株）製］等が挙げられる。
なお、品名の後の括弧内に記載した値は、そのフィラーの吸油量である。
Examples of commercially available second conductive carbon filler (A2) include the trade name “Denka Black (1.75 ml / g)” [manufactured by Denka Co., Ltd.], and the trade name “Ensaco 250G (1.90 ml / g). g) ”[manufactured by Imerys], trade name“ Ketjen Black EC300J (3.60 ml / g) ”[manufactured by Lion Specialty Chemicals Co., Ltd.], trade name“ AMC (3.30 ml / g) [Ube Industries ( Product name) ", trade name" igrafen-αS (2.50 ml / g) "[product of ITEC Co., Ltd.], and the like.
In addition, the value described in parentheses after the product name is the oil absorption amount of the filler.
本発明の樹脂集電体では、樹脂集電体中の第１の導電性炭素フィラー（Ａ１）の重量割合が７〜６５重量％であることが好ましい。
また、樹脂集電体中の第２の導電性炭素フィラー（Ａ２）の重量割合が１〜３５重量％であることが好ましい。
In the resin current collector of the present invention, the weight ratio of the first conductive carbon filler (A1) in the resin current collector is preferably 7 to 65% by weight.
Moreover, it is preferable that the weight ratio of the 2nd electroconductive carbon filler (A2) in a resin electrical power collector is 1-35 weight%.
本発明の樹脂集電体では、樹脂集電体に含まれる第１の導電性炭素フィラー（Ａ１）と第２の導電性炭素フィラー（Ａ２）との重量比率が、［第１の導電性炭素フィラー（Ａ１）／第２の導電性炭素フィラー（Ａ２）］＝５５／４５〜９０／１０であることが好ましい。
上記比率が５５／４５以上であると、吸油量が大きい第２の導電性炭素フィラー（Ａ２）の比率が相対的に少ないため、導電性炭素フィラー界面での電解液の分解、及び、導電性炭素フィラーへの電解液の浸み込み（フィラー膨張）を好適に抑制することができる。
また、上記比率が９０／１０以下であると、吸油量が小さく、比較的導電性が低い第１の導電性炭素フィラー（Ａ１）の比率が多過ぎないため、樹脂集電体の電気抵抗値を低くするために必要なフィラーの量を減らすことができ、樹脂集電体の薄膜化がより容易になる。
In the resin current collector of the present invention, the weight ratio of the first conductive carbon filler (A1) and the second conductive carbon filler (A2) contained in the resin current collector is [first conductive carbon filler]. Filler (A1) / second conductive carbon filler (A2)] = 55/45 to 90/10 is preferable.
When the ratio is 55/45 or more, the ratio of the second conductive carbon filler (A2) having a large oil absorption is relatively small, so that the decomposition of the electrolytic solution at the conductive carbon filler interface and the conductivity Infiltration of the electrolyte into the carbon filler (filler expansion) can be suitably suppressed.
Further, when the ratio is 90/10 or less, the ratio of the first conductive carbon filler (A1) having a small oil absorption amount and relatively low conductivity is not too large, so that the electric resistance value of the resin current collector The amount of filler necessary for reducing the thickness of the resin current collector can be reduced, and the resin current collector can be made thinner.
本発明の樹脂集電体では、導電性炭素フィラーの重量割合が樹脂集電体の重量に対して１３〜７０重量％であることが好ましい。
上記重量割合が１３重量％以上であると、樹脂集電体に含まれる導電性炭素フィラーの量が充分であるため電気抵抗値をより低くすることができる。また、上記重量割合が７０重量％未満であると、樹脂集電体に含まれるポリオレフィン樹脂の割合が低くなりすぎないため、樹脂集電体の成形性への影響が少なく、樹脂集電体の薄膜化により適している。
In the resin current collector of the present invention, the weight ratio of the conductive carbon filler is preferably 13 to 70% by weight with respect to the weight of the resin current collector.
When the weight ratio is 13% by weight or more, since the amount of the conductive carbon filler contained in the resin current collector is sufficient, the electric resistance value can be further reduced. Further, when the weight ratio is less than 70% by weight, the ratio of the polyolefin resin contained in the resin current collector does not become too low, so that there is little influence on the moldability of the resin current collector. More suitable for thinning.
樹脂集電体は、導電性炭素フィラーとは異なる導電材料を含有していてもよい。
導電材料の材質としては、金属［ニッケル、アルミニウム、ステンレス（ＳＵＳ）、銀、銅及びチタン等］及びこれらの合金、並びにこれらの混合物が挙げられる。電気的安定性の観点から、好ましくはニッケルである。
また、導電材料として、粒子系セラミック材料や樹脂材料の周りに導電材料（上記した導電材料のうち金属のもの）をめっき等でコーティングしたものでもよい。
The resin current collector may contain a conductive material different from the conductive carbon filler.
Examples of the material of the conductive material include metals [nickel, aluminum, stainless steel (SUS), silver, copper, titanium, and the like], alloys thereof, and mixtures thereof. From the viewpoint of electrical stability, nickel is preferred.
In addition, as the conductive material, a particle ceramic material or a resin material may be coated with a conductive material (metal among the above-described conductive materials) by plating or the like.
樹脂集電体は、ポリオレフィン樹脂と、導電性炭素フィラーとの他に、さらに必要に応じ、その他の成分［導電材料用分散剤、着色剤、紫外線吸収剤、汎用の可塑剤（フタル酸骨格含有化合物、トリメリット酸骨格含有化合物、リン酸基含有化合物及びエポキシ骨格含有化合物等）］等を適宜含んでいてもよい。その他の成分の合計添加量は、電気的安定性の観点から、樹脂集電体１００重量部中０．００１〜５重量部であることが好ましく、さらに好ましくは０．００１〜３重量部である。 In addition to the polyolefin resin and conductive carbon filler, the resin current collector contains other components [dispersants for conductive materials, colorants, ultraviolet absorbers, general-purpose plasticizers (including phthalic acid skeletons) as necessary. A compound, a trimellitic acid skeleton-containing compound, a phosphoric acid group-containing compound, an epoxy skeleton-containing compound, etc.)] and the like. From the viewpoint of electrical stability, the total amount of other components added is preferably 0.001 to 5 parts by weight, more preferably 0.001 to 3 parts by weight, in 100 parts by weight of the resin current collector. .
導電材料用分散剤としては、三洋化成工業株式会社製ユーメックスシリーズ、東洋紡株式会社製ハードレンシリーズ、トーヨータックシリーズ等が使用可能である。 As the dispersant for the conductive material, the Yumex series manufactured by Sanyo Kasei Kogyo Co., Ltd., the Hardren series manufactured by Toyobo Co., Ltd., the Toyotack series, etc. can be used.
樹脂集電体に含まれるポリオレフィン樹脂の割合が２５〜８２重量％であることが好ましい。ポリオレフィン樹脂の割合が上記範囲であると、成形性が良好であり、樹脂集電体の薄膜化に適している。 The ratio of the polyolefin resin contained in the resin current collector is preferably 25 to 82% by weight. When the proportion of the polyolefin resin is within the above range, the moldability is good and suitable for thinning the resin current collector.
本発明の樹脂集電体では、樹脂集電体の膜厚は、５０〜１１０μｍであることが好ましく、５０〜１００μｍがより好ましい。
樹脂集電体の膜厚が１１０μｍ以下であると、樹脂集電体としての厚さが薄く、薄膜化された樹脂集電体であるといえる。このような樹脂集電体は電池内における体積が小さいため、電池の電池容量を高くするために適している。
また、樹脂集電体の膜厚が５０μｍ以上であると、樹脂集電体の強度が充分となるため好ましい。
In the resin current collector of the present invention, the thickness of the resin current collector is preferably 50 to 110 μm, and more preferably 50 to 100 μm.
When the resin current collector has a film thickness of 110 μm or less, it can be said that the resin current collector is thin and has a thinned resin current collector. Since such a resin current collector has a small volume in the battery, it is suitable for increasing the battery capacity of the battery.
Moreover, it is preferable that the film thickness of the resin current collector is 50 μm or more because the strength of the resin current collector is sufficient.
また、本発明の樹脂集電体では、樹脂集電体の厚さ方向の電気抵抗値（貫通抵抗値）が、１〜１５０Ω・ｃｍ２であることが好ましい。厚さ方向の電気抵抗値は以下の方法で測定することができる。
＜厚さ方向の電気抵抗値の測定＞
３ｃｍ×１０ｃｍの短冊状に裁断した樹脂集電体を測定用試験片とし、抵抗計［ＲＭ３５４８、ＨＩＯＫＩ製］を接続した電気抵抗測定器［ＩＭＣ−０２４０型、井元製作所（株）製］の電極間に試験片を挟み、電極に２．１６ｋｇの荷重をかけながら抵抗値を測定する。加重をかけてから６０秒後の値に電極と試験片との接触面積（３．１４ｃｍ２）をかけた値を厚さ方向の電気抵抗値とすることができる。なお、電気抵抗測定器［ＩＭＣ−０２４０型、井元製作所（株）製］は、ＪＩＳＫ６３７８−５において厚さ方向の体積電気抵抗の測定に用いる装置に準拠した試験片を正負電極間に挟んで抵抗値の測定を行うための装置である。
In the resin current collector of the present invention, it is preferable that the electric resistance value (penetration resistance value) in the thickness direction of the resin current collector is 1 to 150 Ω · cm 2 . The electric resistance value in the thickness direction can be measured by the following method.
<Measurement of electrical resistance in the thickness direction>
An electrode of an electrical resistance measuring instrument [IMC-0240 type, manufactured by Imoto Seisakusho Co., Ltd.] to which a resin current collector cut into a 3 cm × 10 cm strip was used as a test specimen for measurement, and a resistance meter [RM3548, manufactured by HIOKI] was connected. A test piece is sandwiched between the electrodes, and the resistance value is measured while applying a load of 2.16 kg to the electrodes. A value obtained by multiplying the value 60 seconds after applying the weight by the contact area (3.14 cm 2 ) between the electrode and the test piece can be used as the electric resistance value in the thickness direction. In addition, an electrical resistance measuring instrument [IMC-0240 type, manufactured by Imoto Seisakusho Co., Ltd.] has a resistance in which a test piece compliant with a device used for measuring volumetric electrical resistance in the thickness direction is sandwiched between positive and negative electrodes in JISK6378-5. It is a device for measuring values.
本発明の樹脂集電体は、好ましくは、以下の方法で製造することができる。
まず、ポリオレフィン樹脂、導電性炭素フィラー、及び、必要に応じてその他の成分を混合することにより、樹脂集電体用材料を得る。
混合の方法としては、導電性炭素フィラーのマスターバッチを得てからさらにポリオレフィン樹脂と混合する方法、ポリオレフィン樹脂、導電性炭素フィラー、及び、必要に応じてその他の成分のマスターバッチを用いる方法、及び、全ての原料を一括して混合する方法等があり、その混合にはペレット状又は粉体状の成分を適切な公知の混合機、例えばニーダー、インターナルミキサー、バンバリーミキサー及びロール等を用いることができる。
The resin current collector of the present invention can be preferably produced by the following method.
First, a resin current collector material is obtained by mixing a polyolefin resin, a conductive carbon filler, and other components as required.
As a mixing method, after obtaining a master batch of conductive carbon filler, a method of further mixing with a polyolefin resin, a method of using a polyolefin resin, a conductive carbon filler, and, if necessary, a master batch of other components, and There is a method of mixing all the raw materials at once, and the mixing is performed by using an appropriate known mixer such as a kneader, an internal mixer, a Banbury mixer, and a roll, etc. Can do.
混合時の各成分の添加順序には特に限定はない。得られた混合物は、さらにペレタイザーなどによりペレット化又は粉末化してもよい。 There is no particular limitation on the order of addition of each component during mixing. The obtained mixture may be further pelletized or powdered with a pelletizer or the like.
得られた樹脂集電体用材料を例えばフィルム状に成形することにより、本発明の樹脂集電体が得られる。フィルム状に成形する方法としては、Ｔダイ法、インフレーション法及びカレンダー法等の公知のフィルム成形法が挙げられる。なお、本発明の樹脂集電体は、フィルム成形以外の成形方法によっても得ることができる。 The resin current collector of the present invention is obtained by molding the obtained resin current collector material into a film, for example. Examples of the method for forming a film include known film forming methods such as a T-die method, an inflation method, and a calendar method. The resin current collector of the present invention can also be obtained by a molding method other than film molding.
本発明の樹脂集電体は、リチウムイオン電池の集電体として使用することが好ましい。
正極用樹脂集電体として用いることもでき、負極用樹脂集電体として用いることもできるが、リチウムイオン電池の正極用樹脂集電体として用いることが好ましい。
The resin current collector of the present invention is preferably used as a current collector for a lithium ion battery.
Although it can be used as a resin current collector for a positive electrode or a resin current collector for a negative electrode, it is preferably used as a resin current collector for a positive electrode of a lithium ion battery.
本発明の樹脂集電体は、リチウムイオン電池のバイポーラ電極用の樹脂集電体として好ましく用いることもできる。
バイポーラ電極とは、リチウムイオン電池用電極であって、一つの集電体の一方の面に正極が形成され他方の面に負極が形成された電極を意味する。
集電体の一方の面に正極が形成され他方の面に負極が形成されたバイポーラ電極の少なくとも一方の面が本発明の樹脂集電体であることが好ましい。
The resin current collector of the present invention can be preferably used as a resin current collector for a bipolar electrode of a lithium ion battery.
The bipolar electrode is an electrode for a lithium ion battery, and means an electrode in which a positive electrode is formed on one surface of one current collector and a negative electrode is formed on the other surface.
It is preferable that at least one surface of the bipolar electrode in which the positive electrode is formed on one surface of the current collector and the negative electrode is formed on the other surface is the resin current collector of the present invention.
本発明のリチウムイオン電池は、本発明の樹脂集電体を備えることを特徴とする。
本発明のリチウムイオン電池が本発明の樹脂集電体を正極用樹脂集電体として備える場合、本発明のリチウムイオン電池は、上述した本発明の樹脂集電体と、樹脂集電体の表面に形成された正極活物質層とを備える。正極活物質層は、正極活物質とともに、必要に応じてバインダ、導電助剤等の添加剤を含む。
The lithium ion battery of the present invention includes the resin current collector of the present invention.
When the lithium ion battery of the present invention includes the resin current collector of the present invention as a positive electrode resin current collector, the lithium ion battery of the present invention includes the above-described resin current collector of the present invention and the surface of the resin current collector. And a positive electrode active material layer formed on the substrate. A positive electrode active material layer contains additives, such as a binder and a conductive support agent, as needed with a positive electrode active material.
本発明のリチウムイオン電池が本発明の樹脂集電体を負極用樹脂集電体として備える場合、本発明のリチウムイオン電池は、上述した本発明の樹脂集電体と、樹脂集電体の表面に形成された負極活物質層とを備える。負極活物質層は、負極活物質とともに、必要に応じてバインダ、導電助剤等の添加剤を含む。 When the lithium ion battery of the present invention includes the resin current collector of the present invention as a negative electrode resin current collector, the lithium ion battery of the present invention includes the above-described resin current collector of the present invention and the surface of the resin current collector. And a negative electrode active material layer formed on the substrate. A negative electrode active material layer contains additives, such as a binder and a conductive support agent, as needed with a negative electrode active material.
本発明のリチウムイオン電池は、さらに、電解液と、セパレータとを備える。本発明のリチウムイオン電池において、正極活物質、負極活物質、電解液、セパレータ等の材料としては、公知の材料を使用することができる。正極活物質及び負極活物質は、アクリル系樹脂等の樹脂で被覆された被覆活物質であってもよい。正極用集電体又は負極用集電体が本発明の樹脂集電体でない場合、これらの集電体は、金属集電箔であってもよいし、樹脂集電体であってもよい。 The lithium ion battery of the present invention further includes an electrolytic solution and a separator. In the lithium ion battery of the present invention, known materials can be used as the positive electrode active material, the negative electrode active material, the electrolytic solution, the separator, and the like. The positive electrode active material and the negative electrode active material may be a coated active material coated with a resin such as an acrylic resin. When the positive electrode current collector or the negative electrode current collector is not the resin current collector of the present invention, these current collectors may be metal current collector foils or resin current collectors.
次に本発明を実施例によって具体的に説明するが、本発明の主旨を逸脱しない限り本発明は実施例に限定されるものではない。なお、特記しない限り部は重量部、％は重量％を意味する。 EXAMPLES Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples without departing from the gist of the present invention. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
以下の実施例で使用した材料は下記の通りである。
ポリオレフィン樹脂：ブロックポリプロピレン［商品名「サンアロマーＰＭ８５４Ｘ」、サンアロマー（株）製］
第１の導電性炭素フィラー（Ａ１）
Ａ１−１：アセチレンブラック［吸油量１．４０ｍｌ／ｇ、商品名「デンカブラックＬｉ−４００」、デンカ(株)製］
Ａ１−２：カーボンナノチューブ［吸油量１．１０ｍｌ／ｇ、商品名「ＶＧＣＦ」、昭和電工（株）製］
Ａ１−３：黒鉛粒子［吸油量０．１５ｍｌ／ｇ、商品名「ＳＮＧ−ＷＸＡ１」、ＪＦＥケミカル(株)製］
第２の導電性炭素フィラー（Ａ２）
Ａ２−１：アセチレンブラック［吸油量１．７５ｍｌ／ｇ、商品名「デンカブラック」、デンカ（株）製］
Ａ２−２：アセチレンブラック［吸油量１．９０ｍｌ／ｇ、商品名「エンサコ２５０Ｇ」、Ｉｍｅｒｙｓ製］
Ａ２−３：ケッチェンブラック［吸油量３．６０ｍｌ／ｇ、商品名「ケッチェンブラックＥＣ３００Ｊ」、ライオン・スペシャリティ・ケミカルズ（株）製］
Ａ２−４：カーボンナノチューブ［吸油量３．３０ｍｌ／ｇ、商品名「ＡＭＣ」、宇部興産（株）製］
Ａ２−５：グラフェン［吸油量２．５０ｍｌ／ｇ、商品名「ｉｇｒａｆｅｎ−αＳ」、アイテック（株）製］
なお、各導電性炭素フィラーの吸油量は、「ＪＩＳ Ｋ６２１７−４ ２００８ ゴム用カーボンブラック基本特性」に準じて、ＤＢＰ（フタル酸ジブチル）の吸収量を測定した値である。
分散剤
［商品名「ユーメックス１００１（酸変性ポリプロピレン）」、三洋化成工業（株）製］
The materials used in the following examples are as follows.
Polyolefin resin: Block polypropylene [trade name "Sun Allomer PM854X", manufactured by Sun Allomer Co., Ltd.]
First conductive carbon filler (A1)
A1-1: Acetylene black [oil absorption 1.40 ml / g, trade name “DENKA BLACK Li-400”, manufactured by DENKA CORPORATION]
A1-2: Carbon nanotube [oil absorption 1.10 ml / g, trade name “VGCF”, manufactured by Showa Denko KK]
A1-3: Graphite particles [oil absorption amount 0.15 ml / g, trade name “SNG-WXA1”, manufactured by JFE Chemical Co., Ltd.]
Second conductive carbon filler (A2)
A2-1: Acetylene black [oil absorption 1.75 ml / g, trade name “DENKA BLACK”, manufactured by DENKA CORPORATION]
A2-2: Acetylene black [oil absorption 1.90 ml / g, trade name “Ensaco 250G”, manufactured by Imerys]
A2-3: Ketjen Black [Oil absorption 3.60 ml / g, trade name “Ketjen Black EC300J”, manufactured by Lion Specialty Chemicals Co., Ltd.]
A2-4: Carbon nanotube [oil absorption 3.30 ml / g, trade name “AMC”, manufactured by Ube Industries, Ltd.]
A2-5: Graphene [Oil absorption amount 2.50 ml / g, trade name “igrafen-αS”, manufactured by ITEC Co., Ltd.]
The oil absorption amount of each conductive carbon filler is a value obtained by measuring the absorption amount of DBP (dibutyl phthalate) according to “JIS K6217-4 2008 Carbon black basic characteristics for rubber”.
Dispersant [trade name “Yumex 1001 (acid-modified polypropylene)”, manufactured by Sanyo Chemical Industries, Ltd.]
＜実施例１＞
２軸押出機にて、ポリオレフィン樹脂８０部、Ａ１−１「デンカブラックＬｉ−４００」１５部及び分散剤５部を１８０℃、１００ｒｐｍ、滞留時間５分の条件で溶融混練して樹脂集電体用材料を得た。
得られた樹脂集電体用材料をＴダイから押し出し、５０℃に温調した冷却ロールで圧延することで、膜厚１００μｍの樹脂集電体を得た。
<Example 1>
Resin current collector by melt-kneading 80 parts of polyolefin resin, 15 parts of A1-1 “Denka Black Li-400” and 5 parts of dispersing agent at 180 ° C., 100 rpm, residence time of 5 minutes in a twin screw extruder. Material was obtained.
The obtained resin current collector material was extruded from a T die and rolled with a cooling roll adjusted to 50 ° C. to obtain a resin current collector with a film thickness of 100 μm.
＜実施例２〜１２、比較例１〜６＞
ポリオレフィン樹脂の配合量、並びに、第１の導電性炭素フィラー（Ａ１）及び第２の導電性炭素フィラー（Ａ２）の種類及び配合量を表１に示すように変更して、実施例１と同様の方法により樹脂集電体用材料及び樹脂集電体を得た。
<Examples 2-12, Comparative Examples 1-6>
As in Example 1, the blending amount of the polyolefin resin and the types and blending amounts of the first conductive carbon filler (A1) and the second conductive carbon filler (A2) were changed as shown in Table 1. Thus, a resin current collector material and a resin current collector were obtained.
＜酸化電流量の測定＞
＜耐電位試験用コインセルの作製＞
２０３２型コインセルの負極缶にガスケット、φ１６ｍｍに裁断したＬｉ箔、φ１７ｍｍに裁断したセパレータ（厚さ２５μｍのポリプロピレン製）を順に重ね、電解液を１００μＬ添加した。その上にφ１５ｍｍに裁断した樹脂集電体を乗せ、さらにカーボンコートアルミ［昭和電工（株）製、ＳＤＸ］、スペーサー（厚さ５００μｍ）を２つ、皿バネ、正極缶を順に重ねて封をし、評価用のコインセルを作製した。なお、電解液として、１Ｍ ＬｉＰＦ６をエチレンカーボネートとジメチルカーボネートとの混合溶媒（体積比１：１）に溶解した溶液を準備した。
<Measurement of oxidation current>
<Production of coin cell for electric potential resistance test>
A gasket, a Li foil cut to φ16 mm, and a separator (made of polypropylene having a thickness of 25 μm) cut to φ17 mm were sequentially stacked on a negative electrode can of a 2032 type coin cell, and 100 μL of an electrolytic solution was added. A resin current collector cut to φ15 mm is placed on it, and carbon coated aluminum [Showa Denko Co., Ltd., SDX], two spacers (thickness: 500 μm), disc springs, and positive electrode cans are stacked in order. Then, a coin cell for evaluation was produced. As the electrolyte, a mixed solvent of a 1M LiPF 6 ethylene carbonate and dimethyl carbonate (volume ratio 1: 1) dissolved solution was prepared in the.
＜樹脂集電体の耐電位試験評価＞
充放電測定装置「ＨＪ１００１ＳＭ８Ａ」［北斗電工製］を用いて、評価用コインセルを電圧４．２Ｖまで充電し、そのまま２００時間電圧をかけた状態での発生電流を計測した。本試験での結果は、４．２Ｖの電圧をかけ続けた状態で流れた電流量の総和としている。
なお、酸化電流量が少ないと電池の構成部材として用いた際の部材由来の容量ロスが低減でき、優れた長期の信頼性を有することを示す。
酸化電流量が０．９ｍＡｈ／φ１５以下である場合良好と判断して表１において酸化電流量判定の欄に○と表示し、酸化電流量が０．９ｍＡｈ／φ１５を超える場合を×と表示した。
<Evaluation of potential resistance of resin current collector>
Using the charge / discharge measuring device “HJ1001SM8A” (Hokuto Denko), the coin cell for evaluation was charged to a voltage of 4.2 V, and the generated current was measured with the voltage applied for 200 hours. The result of this test is the sum of the amount of current that flowed while 4.2V voltage was applied.
In addition, when there is little oxidation current amount, the capacity | capacitance loss derived from the member at the time of using as a structural member of a battery can be reduced, and it has shown having the outstanding long-term reliability.
When the oxidation current amount is 0.9 mAh / φ15 or less, it is judged as good, and in Table 1, “O” is displayed in the oxidation current amount determination column, and “x” is displayed when the oxidation current amount exceeds 0.9 mAh / φ15. .
＜体積膨張率の評価＞
本発明の系では、樹脂集電体の体積変化を重量変化と読み替えることが可能であるので、以下の方法により樹脂集電体の膨潤率（重量％）を測定して、体積膨張率を評価した。
樹脂集電体を１０×４０×０．２ｍｍの寸法に切り出した試験片とし、この試験片を上記電解液に５０℃で３日間浸漬させて飽和吸液状態の樹脂集電体を準備した。
試験片の吸液前後の重量変化から下記式によって膨潤率（重量％）を求めた。結果を表１に示す。
膨潤率［重量％］＝［（吸液後の試験片重量−吸液前の試験片重量）／吸液前の試験片重量］×１００
膨潤率が０．１％以下である場合良好と判断して表１において体積膨張率判定の欄に○と表示し、膨潤率が０．１％を超える場合を×と表示した。
<Evaluation of volume expansion coefficient>
Since the volume change of the resin current collector can be read as the weight change in the system of the present invention, the swelling rate (% by weight) of the resin current collector is measured by the following method to evaluate the volume expansion rate. did.
The resin current collector was used as a test piece cut out to a size of 10 × 40 × 0.2 mm, and this test piece was immersed in the electrolyte at 50 ° C. for 3 days to prepare a saturated current-absorbing resin current collector.
From the change in weight of the test piece before and after liquid absorption, the swelling ratio (% by weight) was determined by the following formula. The results are shown in Table 1.
Swelling ratio [% by weight] = [(weight of test piece after liquid absorption−weight of test piece before liquid absorption) / weight of test piece before liquid absorption] × 100
When the swelling rate was 0.1% or less, it was judged as good, and in Table 1, “◯” was displayed in the column of volume expansion rate determination, and “x” was shown when the swelling rate exceeded 0.1%.
＜貫通抵抗値の測定＞
樹脂集電体を３ｃｍ×１０ｃｍ程度の短冊に裁断し、電気抵抗測定器［ＩＭＣ−０２４０型、井元製作所（株）製］及び抵抗計［ＲＭ３５４８、ＨＩＯＫＩ製］を用いて各樹脂集電体の貫通抵抗値を測定した。
電気抵抗測定器に２．１６ｋｇの荷重をかけた状態での樹脂集電体の抵抗値を測定し、２．１６ｋｇの荷重をかけてから６０秒後の値をその樹脂集電体の抵抗値とした。下記の式に示すように、抵抗測定時の冶具の接触表面の面積（３．１４ｃｍ２）をかけた値を貫通抵抗値（Ω・ｃｍ２）とした。
貫通抵抗値（Ω・ｃｍ２）＝抵抗値（Ω）×３．１４（ｃｍ２）
貫通抵抗値が１５０Ω・ｃｍ２以下である場合良好と判断して表１において電気抵抗値判定の欄に○と表示し、貫通抵抗値が１５０Ω・ｃｍ２を超える場合を×と表示した。
<Measurement of penetration resistance value>
The resin current collector is cut into a strip of about 3 cm × 10 cm, and each of the resin current collectors is measured using an electrical resistance measuring instrument [IMC-0240 type, manufactured by Imoto Seisakusho Co., Ltd.] and a resistance meter [RM3548, manufactured by HIOKI]. The penetration resistance value was measured.
Measure the resistance value of the resin current collector with a load of 2.16 kg applied to the electrical resistance measuring instrument. The value 60 seconds after applying the load of 2.16 kg is the resistance value of the resin current collector. It was. As shown in the following equation, and the area of the contact surface of the jig at the time of resistance measurement (3.14 cm 2) was subjected value of penetration resistance value (Ω · cm 2).
Penetration resistance value (Ω · cm 2 ) = resistance value (Ω) × 3.14 (cm 2 )
When the penetration resistance value was 150 Ω · cm 2 or less, it was judged good, and in Table 1, “◯” was displayed in the electric resistance value determination column, and “×” was indicated when the penetration resistance value exceeded 150 Ω · cm 2 .
表１より、実施例１〜１２では、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が好適な範囲となっているため、酸化電流量を抑制することができ、かつ、体積の膨張が起こりにくい樹脂集電体を得ることができた。
一方で、比較例１〜６では、樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が少なすぎる、又は、大きすぎるために、酸化電流量、体積膨張率、及び、電気抵抗値のいずれかの評価結果が悪くなっていた。
From Table 1, in Examples 1-12, since the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is within a suitable range, the amount of oxidation current can be suppressed, and the volume A resin current collector in which the expansion of the resin hardly occurs was obtained.
On the other hand, in Comparative Examples 1-6, since the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is too small or too large, the amount of oxidation current, the volume expansion coefficient, and the electrical resistance value One of the evaluation results was getting worse.
本発明の樹脂集電体は、特に、携帯電話、パーソナルコンピューター及びハイブリッド自動車、電気自動車用に用いられるリチウムイオン電池用の集電体として有用である。 The resin current collector of the present invention is particularly useful as a current collector for lithium ion batteries used for mobile phones, personal computers, hybrid vehicles, and electric vehicles.
Claims (7)
樹脂集電体１ｇに含まれる導電性炭素フィラーの合計吸油量が０．１０〜０．２６ｍｌであることを特徴とする樹脂集電体。 A resin current collector comprising a polyolefin resin and a conductive carbon filler,
A resin current collector, wherein the total oil absorption amount of the conductive carbon filler contained in 1 g of the resin current collector is 0.10 to 0.26 ml.
吸油量が１．５ｍｌ／ｇ未満である第１の導電性炭素フィラー（Ａ１）と、
吸油量が１．５〜４．０ｍｌ／ｇである第２の導電性炭素フィラー（Ａ２）とを含む請求項１に記載の樹脂集電体。 The conductive carbon filler is
A first conductive carbon filler (A1) having an oil absorption of less than 1.5 ml / g;
The resin current collector according to claim 1, comprising a second conductive carbon filler (A2) having an oil absorption of 1.5 to 4.0 ml / g.
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