JP2018032627A - Polyamide-imide solution for power storage element electrode, method for manufacturing power storage element electrode, and power storage element electrode - Google Patents
Polyamide-imide solution for power storage element electrode, method for manufacturing power storage element electrode, and power storage element electrode Download PDFInfo
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- JP2018032627A JP2018032627A JP2017158001A JP2017158001A JP2018032627A JP 2018032627 A JP2018032627 A JP 2018032627A JP 2017158001 A JP2017158001 A JP 2017158001A JP 2017158001 A JP2017158001 A JP 2017158001A JP 2018032627 A JP2018032627 A JP 2018032627A
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- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 150
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000003860 storage Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
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- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 239000011149 active material Substances 0.000 claims abstract description 29
- -1 siloxane unit Chemical group 0.000 claims abstract description 17
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 12
- 230000010220 ion permeability Effects 0.000 abstract description 9
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- 238000009835 boiling Methods 0.000 description 16
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- 150000004985 diamines Chemical class 0.000 description 11
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- DDHQTWZKAJOZQL-UHFFFAOYSA-N naphthalene-1,4,5-tricarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O DDHQTWZKAJOZQL-UHFFFAOYSA-N 0.000 description 1
- CYPRBDCCNAZGDN-UHFFFAOYSA-N naphthalene-1,6,7-tricarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 CYPRBDCCNAZGDN-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- 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
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウム二次電池、リチウムイオンキャパシタ、キャパシタ、コンデンサ等の蓄電素子に用いられるポリアミドイミド溶液と、これを用いた電極蓄電素子電極の製造方法および蓄電素子電極とに関する。 The present invention relates to a polyamide-imide solution used for a power storage device such as a lithium secondary battery, a lithium ion capacitor, a capacitor, and a capacitor, a method for manufacturing an electrode power storage device electrode using the same, and a power storage device electrode.
リチウム二次電池等の蓄電素子において、電極表面の傷や凹凸が原因となって、電極に接しているセパレータの電気絶縁性を破壊することがある。その結果、電気的な内部短絡が発生することがある。 In a power storage element such as a lithium secondary battery, the electrical insulation of the separator in contact with the electrode may be destroyed due to scratches or irregularities on the electrode surface. As a result, an electrical internal short circuit may occur.
この内部短絡を防止するため、電極表面に絶縁性の多孔質膜からなる保護層を設けることが提案されている。保護層となる多孔質膜として、特許文献１〜４には、水溶性高分子（セルロース誘導体、ポリアクリル酸誘導体、ポリビニルアルコール誘導体等）、フッ素系樹脂、ゴム系樹脂等にて形成され、かつ、これらにアルミナ、二酸化珪素、ジルコニアなどの微粒子を大量に配合することにより気孔が形成された多孔質膜が提案されている。 保護層を形成させるための別の方法として、特許文献５、６には、保護層形成用の塗膜を電極表面に形成した後、その乾燥前に、貧溶剤を含む凝固浴に浸漬して塗膜の相分離を起こさせて多孔質保護層を得る方法も提案されている。 一方、シリコン等の高容量の活物質を用いたリチウム二次電池においては、正極と負極とをセパレータを介して渦巻状に巻回した巻回電極体を、角形（角筒形）の外装缶やラミネートフィルム外装体の内部に装填して、電池を構成することが一般的である。その場合に、充放電の繰り返しに伴って容量低下が生じたり、電池の膨れにより厚みが大きく増加したりすることがある。このような問題を改善するために、特許文献７には、電極（負極）の活物質層の外表面に、力学的特性、耐熱性に優れたポリイミド（ＰＩ）等のＰＩ系高分子に二酸化珪素、アルミナ等の微粒子を大量に配合した多孔質層を設けることにより、電極の体積変化や変形を緩和する方法が提案されている。しかしながら、前記したような表面に多孔質層が設けられた電極は、活物質層と多孔質層との接着性が低いため、短絡に対する防止効果は、必ずしも充分なものではなかった。 In order to prevent this internal short circuit, it has been proposed to provide a protective layer made of an insulating porous film on the electrode surface. Patent Documents 1 to 4 as porous membranes serving as a protective layer are formed of water-soluble polymers (cellulose derivatives, polyacrylic acid derivatives, polyvinyl alcohol derivatives, etc.), fluorine-based resins, rubber-based resins, and the like. A porous film in which pores are formed by mixing a large amount of fine particles of alumina, silicon dioxide, zirconia or the like with these has been proposed. As another method for forming a protective layer, Patent Documents 5 and 6 describe that after a coating film for forming a protective layer is formed on the electrode surface, it is immersed in a coagulation bath containing a poor solvent before drying. A method of obtaining a porous protective layer by causing phase separation of a coating film has also been proposed. On the other hand, in a lithium secondary battery using a high-capacity active material such as silicon, a wound electrode body in which a positive electrode and a negative electrode are wound in a spiral shape via a separator is used as a rectangular (square tube) outer can. In general, the battery is configured by being loaded inside a laminate film outer package. In that case, the capacity may decrease with repeated charging and discharging, or the thickness may increase greatly due to battery swelling. In order to improve such a problem, Patent Document 7 discloses that an outer surface of an active material layer of an electrode (negative electrode) is coated with a PI polymer such as polyimide (PI) having excellent mechanical properties and heat resistance. There has been proposed a method for relaxing the volume change and deformation of an electrode by providing a porous layer containing a large amount of fine particles such as silicon and alumina. However, an electrode having a porous layer on the surface as described above has a low adhesiveness between the active material layer and the porous layer, and thus the effect of preventing short circuit is not always sufficient.
このような問題を解決する方法として、特許文献８には、金属箔上に電極活物質層を形成させ、その後に、この電極活物質層の表面に、ＰＩ前駆体、ポリアミドイミド（ＰＡＩ）等のＰＩ系高分子と溶媒とを含む塗液を塗布して塗膜を形成し、しかる後、前記塗膜中の溶媒を除去後、必要に応じ、熱イミド化することにより、塗膜内で相分離を起こさせてＰＩ多孔質層を形成せしめることによりリチウム二次電池用電極を製造する方法が提案されている。この方法を用いることにより、耐熱性、力学的特性に優れ、かつ電極活物質層との密着性の高い多孔質ＰＩ層を電極活物質層の表面に形成させることができる。 As a method for solving such a problem, Patent Document 8 discloses that an electrode active material layer is formed on a metal foil, and then a PI precursor, polyamideimide (PAI), or the like is formed on the surface of the electrode active material layer. A coating liquid containing a PI polymer and a solvent is applied to form a coating film, and then, after removing the solvent in the coating film, if necessary, by thermal imidization, A method of manufacturing an electrode for a lithium secondary battery by causing phase separation to form a PI porous layer has been proposed. By using this method, a porous PI layer having excellent heat resistance and mechanical properties and high adhesion to the electrode active material layer can be formed on the surface of the electrode active material layer.
しかしながら、特許文献８で開示された方法において、多孔質ＰＩ層形成用溶液として、ＰＡＩ溶液を用いた場合は、この溶液の粘度がやや低い傾向にあり、そのため電極活物質層への塗布した際に、多孔質である活物質層へＰＡＩ溶液が浸透して、活物質層の気孔を塞ぐことがあり、そのため、活物質層と多孔質ＰＡＩ被膜の界面でイオン透過性が低下することがあり、改良すべき点があった。 また、低粘度であることに起因して、塗膜の厚み斑等が起こりやくなることがあり、塗布の際の塗工性にも改良すべき点があった。 However, in the method disclosed in Patent Document 8, when a PAI solution is used as the porous PI layer forming solution, the viscosity of this solution tends to be somewhat low, and therefore when applied to the electrode active material layer In addition, the PAI solution may permeate into the porous active material layer and block the pores of the active material layer, which may reduce the ion permeability at the interface between the active material layer and the porous PAI coating. There was a point to be improved. In addition, due to the low viscosity, coating thickness unevenness and the like are likely to occur, and there is a point to be improved in the coating property at the time of application.
そこで本発明は、前記課題を解決するものであって、良好なイオン透過性を有する多孔質ＰＡＩ被膜が形成できる、塗工性の良好なＰＡＩ溶液、およびこの被膜が形成された蓄電素子電極とその製造方法の提供を目的とする。 Accordingly, the present invention solves the above-described problems, and can form a porous PAI film having good ion permeability, a PAI solution having good coatability, and a storage element electrode on which the film is formed; It aims at providing the manufacturing method.
本発明者らは、ＰＡＩ溶液組成を特定のものとした上で、ＰＡＩの化学構造を特定のものとしたＰＡＩ溶液を用い、これから得られる多孔質ＰＡＩ被膜を電極活物質層上に積層一体化することにより、前記課題が解決されることを見出し、本発明の完成に至った。 The present inventors specified a PAI solution composition, used a PAI solution having a specific PAI chemical structure, and laminated and integrated a porous PAI film obtained therefrom on the electrode active material layer. As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.
本発明は下記を趣旨とするものである。 The present invention has the following objects.
＜１＞ＰＡＩに対する良溶媒と貧溶媒とを含有するＰＡＩ溶液であって、前記ＰＡＩが、側鎖中にオキシアルキレンユニットおよび／またはシロキサンユニットを含むことを特徴とする蓄電素子電極用ＰＡＩ溶液。
＜２＞前記ＰＡＩ溶液を、活物質層表面に塗布後、乾燥することにより多孔質ＰＡＩ被膜を形成する工程を含む蓄電素子電極の製造方法。
＜３＞活物質層表面に多孔質ＰＡＩ被膜が積層一体化されている電極であって、以下の特徴を有する蓄電素子電極。
１） 前記ＰＡＩの側鎖中に、オキシアルキレンユニットおよび／またはシロキサンユニットを含む。
２） 前記多孔質被膜表面の平均気孔径が１０ｎｍ以上、５０００ｎｍ以下である。
<1> A PAI solution containing a good solvent and a poor solvent for PAI, wherein the PAI contains an oxyalkylene unit and / or a siloxane unit in a side chain.
<2> A method for producing a storage element electrode comprising a step of forming a porous PAI film by applying the PAI solution to the surface of an active material layer and then drying the solution.
<3> An electric storage element electrode in which a porous PAI film is laminated and integrated on the surface of an active material layer and has the following characteristics.
1) The side chain of the PAI contains an oxyalkylene unit and / or a siloxane unit.
2) The average pore diameter of the porous coating surface is 10 nm or more and 5000 nm or less.
本発明のＰＡＩ溶液は、溶液粘度が高められているので、電極活物質層へのＰＡＩ溶液の浸透が起こりにくく、イオン抵抗率を充分に低くすることができる上、塗布の際の塗工性が良好である。 従い、これを活物質層の表面に塗布後、乾燥することにより得られる多孔質ＰＡＩ被膜が活物質層表面に積層一体化された電極は、安全性に優れた蓄電素子電極として好適に用いることができる。 Since the PAI solution of the present invention has an increased solution viscosity, it is difficult for the PAI solution to penetrate into the electrode active material layer, the ionic resistivity can be sufficiently lowered, and the coating property at the time of coating is also high. Is good. Accordingly, an electrode in which a porous PAI film obtained by applying this to the surface of the active material layer and then drying is laminated and integrated on the surface of the active material layer should be suitably used as a storage element electrode with excellent safety. Can do.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明は、ＰＡＩ溶液を用いる。ＰＡＩは、原料であるトリカルボン酸成分とジアミン成分との重縮合物である。 The present invention uses a PAI solution. PAI is a polycondensate of a raw material tricarboxylic acid component and a diamine component.
ＰＡＩのトリカルボン酸成分は、１分子あたり３個のカルボキシル基（その誘導体を含む）を有する有機化合物であって、当該３個のカルボキシル基のうち、少なくとも２個のカルボキシル基が酸無水物形態を形成し得る位置に配置されたものである。 The tricarboxylic acid component of PAI is an organic compound having three carboxyl groups per molecule (including derivatives thereof), and at least two of the three carboxyl groups have an acid anhydride form. It is arranged at a position where it can be formed.
トリカルボン酸成分として、例えば、ベンゼントリカルボン酸成分、ナフタレントリカルボン酸成分が挙げられる。 Examples of the tricarboxylic acid component include a benzene tricarboxylic acid component and a naphthalene tricarboxylic acid component.
ベンゼントリカルボン酸成分の具体例として、例えば、トリメリット酸、ヘミメリット酸、ならびにこれらの無水物およびそのモノクロライドが挙げられる。 Specific examples of the benzenetricarboxylic acid component include, for example, trimellitic acid, hemimellitic acid, anhydrides thereof, and monochlorides thereof.
ナフタレントリカルボン酸成分の具体例として、例えば、１，２，３−ナフタレントリカルボン酸、１，６，７−ナフタレントリカルボン酸、１，４，５−ナフタレントリカルボン酸、ならびにこれらの無水物およびそのモノクロライドが挙げられる。 Specific examples of the naphthalene tricarboxylic acid component include, for example, 1,2,3-naphthalene tricarboxylic acid, 1,6,7-naphthalene tricarboxylic acid, 1,4,5-naphthalene tricarboxylic acid, anhydrides thereof, and monochlorides thereof. Is mentioned.
トリカルボン酸成分の中では、トリメリット酸および無水トリメリット酸クロライド（ＴＡＣ）が好ましい。 Among the tricarboxylic acid components, trimellitic acid and trimellitic anhydride chloride (TAC) are preferable.
トリカルボン酸成分は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 A tricarboxylic acid component may be used independently and may be used in combination of 2 or more type.
また、トリカルボン酸成分は、その一部がテレフタル酸、イソフタル酸、ピロメリット酸、３，３′，４，４′−ビフェニルテトラカルボン酸、３，３′，４，４′−ベンゾフェノンテトラカルボン酸等の成分で置換されたものを用いてもよい。 Some of the tricarboxylic acid components are terephthalic acid, isophthalic acid, pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid. Those substituted with such components may be used.
ＰＡＩのジアミン成分は、１分子あたり２個の１級アミノ基（その誘導体を含む）を有する有機化合物である。 The diamine component of PAI is an organic compound having two primary amino groups (including derivatives thereof) per molecule.
ジアミン成分の具体例として、例えば、４，４′−ジアミノジフェニルエーテル（ＤＡＤＥ）、ｍ−フェニレンジアミン（ＭＤＡ）、ｐ−フェニレンジアミン、４，４′−ジフェニルメタンジアミン（ＤＭＡ）、４，４′−ジフェニルエーテルジアミン、ジフェニルスルホン−４，４′−ジアミン、ジフェニルー４，４′−ジアミン、ｏ−トリジン、２，４−トリレンジアミン、２，６−トリレンジアミン、キシリレンジアミン、ナフタレンジアミン、ならびにこれらのジイソシアネート誘導体が挙げられる。 Specific examples of the diamine component include, for example, 4,4'-diaminodiphenyl ether (DADE), m-phenylenediamine (MDA), p-phenylenediamine, 4,4'-diphenylmethanediamine (DMA), 4,4'-diphenyl ether. Diamine, diphenylsulfone-4,4'-diamine, diphenyl-4,4'-diamine, o-tolidine, 2,4-tolylenediamine, 2,6-tolylenediamine, xylylenediamine, naphthalenediamine, and these A diisocyanate derivative is mentioned.
ジアミン成分の中では、ＤＡＤＥ、ＭＤＡおよびＤＭＡが好ましい。 Of the diamine components, DADE, MDA and DMA are preferred.
ジアミン成分は、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 A diamine component may be used independently and may be used in combination of 2 or more type.
ＰＡＩは、通常、２００℃以上のガラス転移温度を有する。ガラス転移温度は、ＤＳＣ（示差熱分析）により測定された値を用いている。 PAI usually has a glass transition temperature of 200 ° C. or higher. As the glass transition temperature, a value measured by DSC (differential thermal analysis) is used.
ＰＡＩは、熱可塑性であっても非熱可塑性であってもよいが、前記したガラス転移温度を有する芳香族ＰＡＩを好ましく用いることができる。 PAI may be thermoplastic or non-thermoplastic, but aromatic PAI having the glass transition temperature described above can be preferably used.
本発明のＰＡＩは、側鎖中にオキシアルキレンユニットおよび／またはシロキサンユニットを含むＰＡＩ（以下、これらを「ＰＡＩ−Ｍ」と略記することがある）である。このようにすることにより、ＰＡＩ溶液の高粘度化を図ることができる。 The PAI of the present invention is a PAI containing an oxyalkylene unit and / or a siloxane unit in the side chain (hereinafter, these may be abbreviated as “PAI-M”). By doing so, the viscosity of the PAI solution can be increased.
オキシアルキレンユニットとしては、具体的には、オキシエチレンユニット、オキシプロピレンユニット、オキシブチレンユニット等が挙げられる。 オキシアルキレンユニットを含むＰＡＩは、例えば、ＰＡＩとオキシアルキレンユニットを有するジアミン（以下、「ＤＡ−１」と略記することがある）とを、溶媒中で反応させることにより得ることができる。 Specific examples of the oxyalkylene unit include an oxyethylene unit, an oxypropylene unit, and an oxybutylene unit. PAI containing an oxyalkylene unit can be obtained, for example, by reacting PAI and a diamine having an oxyalkylene unit (hereinafter sometimes abbreviated as “DA-1”) in a solvent.
ＤＡ−１の具体例としては、エチレングリコールビス（２−アミノエチル）エーテル、ジエチレングリコールビス（２−アミノエチル）エーテル、トリエチレングリコールビス（２−アミノエチル）エーテル、テトラエチレングリコールビス（２−アミノエチル）エーテル、ポリエチレングリコールビス（２−アミノエチル）エーテル（ＰＥＧＭＥ）、プロピレングリコールビス（２−アミノエチル）エーテル、ジプロピレングリコールビス（２−アミノエチル）エーテル、トリプロピレングリコールビス（２−アミノエチル）エーテル、テトラプロピレングリコールビス（２−アミノエチル）エーテル、ポリプロピレングリコールビス（２−アミノエチル）エーテル（ＰＰＧＭＥ）等が挙げられる。これらの中で、数平均分子量が、３００〜５０００のものが好ましい。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらの中で、ＰＥＧＭＥ、ＰＰＧＭＥが好ましい。これらの化合物は市販品を利用することができる。 Specific examples of DA-1 include ethylene glycol bis (2-aminoethyl) ether, diethylene glycol bis (2-aminoethyl) ether, triethylene glycol bis (2-aminoethyl) ether, tetraethylene glycol bis (2-amino). Ethyl) ether, polyethylene glycol bis (2-aminoethyl) ether (PEGME), propylene glycol bis (2-aminoethyl) ether, dipropylene glycol bis (2-aminoethyl) ether, tripropylene glycol bis (2-aminoethyl) ) Ether, tetrapropylene glycol bis (2-aminoethyl) ether, polypropylene glycol bis (2-aminoethyl) ether (PPGME) and the like. Among these, those having a number average molecular weight of 300 to 5,000 are preferable. These may be used alone or in combination of two or more. Among these, PEGME and PPGME are preferable. These compounds can use a commercial item.
シロキサンユニット含むＰＡＩは、例えば、ＰＡＩとシロキサンユニットを有するジアミン（以下、「ＤＡ−２」と略記することがある）とを、溶媒中で反応させることにより得ることができる。 PAI containing a siloxane unit can be obtained, for example, by reacting PAI with a diamine having a siloxane unit (hereinafter sometimes abbreviated as “DA-2”) in a solvent.
ＤＡ−２の具体例としては、１，３−ビス（３−アミノプロピル）−１，１，３，３−テトラメチルジシロキサン、１，３−ビス（４−アミノブチル）−１，１，３，３−テトラメチルジシロキサン、ビス（４−アミノフェノキシ）ジメチルシラン、１，３−ビス（４−アミノフェノキシ）−１，１，３，３−テトラメチルジシロキサン等、および下記一般式（１）で表されるものが挙げられる。これらは単独で用いてもよく、２種以上を組み合わせて用いてもよい。これらのなかで、下記一般式（１）において、Ｒ１およびＲ２がトリメチレン基、Ｒ３、Ｒ４、Ｒ５およびＲ６がメチル基、ｎは３〜１００であるもの（以下、「ＤＡＳＭ」と略記することがある）が好ましく、これらの中で、数平均分子量が、３００〜５０００のものがより好ましい。 これらのＤＡＳＭは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。なお、ＤＡＳＭは市販品を用いることができる。 Specific examples of DA-2 include 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1, 3,3-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (4-aminophenoxy) -1,1,3,3-tetramethyldisiloxane, and the following general formula ( What is represented by 1) is mentioned. These may be used alone or in combination of two or more. Among them, in the following general formula (1), R1 and R2 are trimethylene groups, R3, R4, R5 and R6 are methyl groups, and n is 3 to 100 (hereinafter abbreviated as “DASM”). Among them, those having a number average molecular weight of 300 to 5,000 are more preferable. These DASMs may be used alone or in combination of two or more. DASM can be a commercially available product.
ＰＡＩ−Ｍを含むＰＡＩ溶液（以下、「ＰＡＩ−Ｍ溶液」と略記することがある）には、溶質であるＰＡＩ−Ｍを溶解する良溶媒と、溶質には貧溶媒となる溶媒とを混合した混合溶媒が含有されている。ここで、良溶媒とは、２５℃において、ＰＡＩ−Ｍに対する溶解度が１質量％以上の溶媒をいい、貧溶媒とは、２５℃において、ＰＡＩ−Ｍに対する溶解度が１質量％未満の溶媒をいう。貧溶媒は、良溶媒よりも高沸点であることが好ましい。また、その沸点差は、５℃以上が好ましく、２０℃以上がより好ましく、５０℃以上がさらに好ましい。 In a PAI solution containing PAI-M (hereinafter sometimes abbreviated as “PAI-M solution”), a good solvent that dissolves PAI-M as a solute and a solvent that is a poor solvent for a solute are mixed. The mixed solvent is contained. Here, the good solvent means a solvent having a solubility in PAI-M of 1% by mass or more at 25 ° C., and the poor solvent means a solvent having a solubility in PAI-M of less than 1% by mass at 25 ° C. . The poor solvent preferably has a higher boiling point than the good solvent. Moreover, the boiling point difference is preferably 5 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 50 ° C. or higher.
良溶媒としては、アミド系溶媒または尿素系溶媒が好ましく用いられる。アミド系溶媒としては、例えば、Ｎ−メチル−２−ピロリドン（ＮＭＰ 沸点：２０２℃）、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ 沸点：１５３℃）、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ 沸点：１６６℃）が挙げられる。また、尿素系溶媒としては、例えば、テトラメチル尿素（ＴＭＵ 沸点：１７７℃）、ジメチルエチレン尿素（沸点：２２０℃）が挙げられる。これらの良溶媒は単独で用いてもよく、２種以上を組み合わせて用いてもよい。 As the good solvent, an amide solvent or a urea solvent is preferably used. Examples of the amide solvent include N-methyl-2-pyrrolidone (NMP boiling point: 202 ° C.), N, N-dimethylformamide (DMF boiling point: 153 ° C.), N, N-dimethylacetamide (DMAc boiling point: 166 ° C.). Is mentioned. Examples of the urea solvent include tetramethylurea (TMU boiling point: 177 ° C.) and dimethylethylene urea (boiling point: 220 ° C.). These good solvents may be used alone or in combination of two or more.
貧溶媒としては、エーテル系溶媒が好ましく用いられる。エーテル系溶媒としては、例えば、ジエチレングリコールジメチルエーテル（沸点：１６２℃）、トリエチレングリコールジメチルエーテル（Ｇ３ 沸点：２１６℃）、テトラエチレングリコールジメチルエーテル（Ｇ４ 沸点：２７５℃）、ジエチレングリコール（沸点：２４４℃）、トリエチレングリコール（沸点：２８７℃） トリプロピレングリコール（沸点：２７３℃）、ジエチレングルコールモノメチルエーテル（沸点：１９４℃）、トリプロピレングリコールモノメチルエーテル（沸点：２４２℃）、トリエチレングルコールモノメチルエーテル（沸点：２４９℃）等の溶媒を挙げることができる。これらを単独で用いてもよく、２種以上を組み合わせて用いてもよい。貧溶媒の配合量は、全溶媒量に対して１５〜９５質量％であることが好ましく、６０〜９０質量％であることがより好ましい。このような溶媒組成とすることにより、活物質層への塗布後の乾燥工程において、効率よく相分離が起こり、高い気孔率を有するイオン透過性の良好な多孔質ＰＡＩ被膜を得ることができる。 As the poor solvent, an ether solvent is preferably used. Examples of ether solvents include diethylene glycol dimethyl ether (boiling point: 162 ° C), triethylene glycol dimethyl ether (G3 boiling point: 216 ° C), tetraethylene glycol dimethyl ether (G4 boiling point: 275 ° C), diethylene glycol (boiling point: 244 ° C), triethylene glycol. Ethylene glycol (boiling point: 287 ° C) Tripropylene glycol (boiling point: 273 ° C), diethylene glycol monomethyl ether (boiling point: 194 ° C), tripropylene glycol monomethyl ether (boiling point: 242 ° C), triethylene glycol monomethyl ether (boiling point) : 249 ° C.). These may be used alone or in combination of two or more. The blending amount of the poor solvent is preferably 15 to 95% by mass and more preferably 60 to 90% by mass with respect to the total amount of the solvent. By setting it as such a solvent composition, in the drying process after application | coating to an active material layer, a phase separation occurs efficiently and the porous PAI film with favorable ion permeability which has high porosity can be obtained.
本発明のＰＡＩ溶液は、例えば、以下のような製造方法で製造することができる。すなわち、固体状のＰＡＩを前記混合溶媒に溶解せしめてＰＡＩ溶液とし、しかる後、この溶液にＤＡ−１および／またはＤＡ−２を加え、６０℃〜１５０℃程度に加熱することにより、ＰＡＩの側鎖にオキシアルキレンユニットおよび／またはシロキサンユニットが導入されたＰＡＩ−Ｍ溶液とすることができる。この反応においては、ＰＡＩのイミド環の一部がジアミンのアミノリシスにより開環して、アミド結合を生成するので、溶液状態を維持したまま、ＰＡＩ溶液の高粘度化を図ることができる。 すなわち、ＤＡ−１やＤＡ−２は、アミド結合を介したＰＡＩのリンカとして作用して、高粘度化に寄与するが、完全に架橋ゲル化することはないので、溶液状態を維持することができる。 なお、このような反応が起こっていることは、ＰＡＩ溶液の粘度上昇によって、確認することができるが、ＮＭＲやＩＲ等の分光学的手法を用いて確認することもできる。
ＤＡ−１またはＤＡ−２の添加量としては、ＰＡＩに対し、５〜４０質量％とすることが好ましく、１０〜３５質量％とすることが好ましい。 また、この反応の際の固形分濃度としては、ＰＡＩ−Ｍの固形分濃度として１０〜２０質量％とすることが好ましい。
The PAI solution of the present invention can be produced, for example, by the following production method. That is, solid PAI is dissolved in the mixed solvent to obtain a PAI solution, and then DA-1 and / or DA-2 is added to the solution and heated to about 60 ° C. to 150 ° C. A PAI-M solution in which an oxyalkylene unit and / or a siloxane unit is introduced into the side chain can be obtained. In this reaction, a part of the imide ring of PAI is opened by aminolysis of diamine to generate an amide bond, so that the viscosity of the PAI solution can be increased while maintaining the solution state. That is, DA-1 or DA-2 acts as a PAI linker through an amide bond and contributes to high viscosity, but does not completely cross-link and gel, so that the solution state can be maintained. it can. The occurrence of such a reaction can be confirmed by an increase in the viscosity of the PAI solution, but can also be confirmed using a spectroscopic technique such as NMR or IR.
The addition amount of DA-1 or DA-2 is preferably 5 to 40% by mass, and preferably 10 to 35% by mass with respect to PAI. Moreover, as solid content concentration in this reaction, it is preferable to set it as 10-20 mass% as solid content concentration of PAI-M.
ＰＡＩ−Ｍ溶液の粘度（３０℃）としては、１０〜１００Ｐａ・ｓとすることが好ましく、１５〜５０Ｐａ・ｓとすることがより好ましい。 このようにすることにより、塗工性が良好で、かつイオン透過性の良好なＰＡＩ被膜が形成可能な溶液とすることができる。 The viscosity (30 ° C.) of the PAI-M solution is preferably 10 to 100 Pa · s, and more preferably 15 to 50 Pa · s. By doing in this way, it can be set as the solution which can form a PAI film with favorable coating property and favorable ion permeability.
前記固体状のＰＡＩとしては、例えば、市販のＰＡＩ粉体（例えば、ソルベイアドバンストポリマーズ株式会社製トーロン４０００Ｔシリーズ、トーロン４０００ＴＦ、トーロンＡＩ−１０シリーズ等）を利用することができる。 As the solid PAI, for example, commercially available PAI powder (for example, Torlon 4000T series, Torlon 4000TF, Torlon AI-10 series, etc. manufactured by Solvay Advanced Polymers Co., Ltd.) can be used.
ＰＡＩ溶液を得るには、前記したような固体状のＰＡＩを用いて製造する方法が好ましいが、原料である前記芳香族トリカルボン酸成分および前記ジアミン成分（各種ジアミンもしくはそのジイソシアネート誘導体）を略等モルで配合し、それを前記混合溶媒中で重合反応させて得られる溶液も用いることができる。また、良溶媒中のみで重合反応して溶液を得た後、これに貧溶媒を加える方法や、貧溶媒中のみで重合反応して懸濁液を得た後、これに良溶媒を加える方法で、ＰＡＩ溶液を得ることができる。 In order to obtain a PAI solution, a method using a solid PAI as described above is preferred, but the aromatic tricarboxylic acid component and the diamine component (various diamines or diisocyanate derivatives thereof) as raw materials are approximately equimolar. It is also possible to use a solution obtained by blending in the above and polymerizing the mixture in the mixed solvent. In addition, after a polymerization reaction only in a good solvent to obtain a solution, a method of adding a poor solvent thereto, or after a polymerization reaction only in a poor solvent to obtain a suspension, a method of adding a good solvent thereto. Thus, a PAI solution can be obtained.
ＰＡＩ−Ｍ溶液には、フィラを配合することができる。フィラの配合により形成される多孔質構造と、前記貧溶媒の作用により形成される多孔質構造の相乗効果により、多孔質ＰＡＩ層のイオン透過性をより高めることができる。 Filler can be mix | blended with a PAI-M solution. Due to the synergistic effect of the porous structure formed by blending the filler and the porous structure formed by the action of the poor solvent, the ion permeability of the porous PAI layer can be further increased.
フィラの種類に制限は無く、有機フィラ、無機フィラおよびその混合物等を用いることができる。有機フィラの具体例としては、例えば、スチレン、ビニルケトン、アクリロニトリル、メタクリル酸メチル、メタクリル酸エチル、グリシジルメタクリレート、グリシジルアクリレート、アクリル酸メチル等の単独または２種類以上の共重合体、ポリテトラフルオロエチレン、４フッ化エチレン−６フッ化プロピレン共重合体、４フッ化エチレン−エチレン共重合体、ポリビニリデンフルオライド等のフッ素系樹脂等の重合体からなる粉体を挙げることができる。有機フィラは、単独または２種以上を混合して用いることができる。無機フィラとしては、例えば、金属酸化物、金属窒化物、金属炭化物、金属水酸化物、炭酸塩、硫酸塩等の無機物からなる粉体を挙げることができる。具体例としては、アルミナ、ベーマイト（酸化水酸化アルミニウム）、カオリン（ケイ酸アルミニウム）、シリカ、二酸化チタン、硫酸バリウム、または炭酸カルシウム等からなる粉体を挙げることができる。無機フィラは、単独または２種以上を混合して用いることができる。これらの無機フィラの中でも、化学的安定性の観点から、アルミナ粉体、ベーマイト粉体が好ましい。 There is no restriction | limiting in the kind of filler, An organic filler, an inorganic filler, its mixture, etc. can be used. Specific examples of the organic filler include, for example, styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, methyl acrylate alone, or a copolymer of two or more kinds, polytetrafluoroethylene, Examples thereof include a powder made of a polymer such as a fluororesin such as a tetrafluoroethylene-6 fluoropropylene copolymer, a tetrafluoroethylene-ethylene copolymer, and polyvinylidene fluoride. An organic filler can be used individually or in mixture of 2 or more types. Examples of inorganic fillers include powders made of inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates and sulfates. Specific examples include powders made of alumina, boehmite (aluminum oxide hydroxide), kaolin (aluminum silicate), silica, titanium dioxide, barium sulfate, calcium carbonate, or the like. An inorganic filler can be used individually or in mixture of 2 or more types. Among these inorganic fillers, alumina powder and boehmite powder are preferable from the viewpoint of chemical stability.
フィラの形状に制限はなく、略球状、板状、柱状、針状、ウィスカー状、繊維状等の粒子を用いることができ、略球状粒子が好ましい。略球状粒子のアスペクト比（粒子の長径／粒子の短径）は１以上、１．５以下とすることが好ましい。 There is no restriction | limiting in the shape of a filler, Particle | grains, such as substantially spherical shape, plate shape, columnar shape, needle shape, whisker shape, fiber shape, can be used, and a substantially spherical particle is preferable. The aspect ratio of the substantially spherical particles (particle major axis / particle minor axis) is preferably 1 or more and 1.5 or less.
フィラの平均粒子径に制限はないが、０．０１μｍ以上、２μｍ以下であることが好ましい。平均粒子径はレーザ回折散乱法に基づく測定装置により測定することができる。 Although there is no restriction | limiting in the average particle diameter of a filler, It is preferable that they are 0.01 micrometer or more and 2 micrometers or less. The average particle diameter can be measured by a measuring device based on the laser diffraction scattering method.
フィラは、その表面が、界面活性剤やシランカップラのような表面処理剤で処理されていてもよい。 The surface of the filler may be treated with a surface treatment agent such as a surfactant or a silane coupler.
フィラ配合量は、ＰＡＩ−Ｍの固形分との質量比（ＰＡＩ−Ｍ／フィラ）で、８０／２０〜１０／９０とすることが好ましく、７０／３０〜２０／８０とすることがより好ましい。 Filler blending amount is preferably 80/20 to 10/90, more preferably 70/30 to 20/80, by mass ratio (PAI-M / filler) to the solid content of PAI-M. .
ＰＡＩ溶液には、必要に応じて、各種界面活性剤や有機シランカップリング剤のような公知の添加物を、本発明の効果を損なわない範囲で添加してもよい。また、必要に応じて、ＰＡＩ以外の他のポリマーを、本発明の効果を損なわない範囲で添加してもよい。 If necessary, known additives such as various surfactants and organic silane coupling agents may be added to the PAI solution as long as the effects of the present invention are not impaired. Moreover, you may add other polymers other than PAI in the range which does not impair the effect of this invention as needed.
ＰＡＩ−Ｍ溶液を、電極活物質層の表面に塗布し、１００〜２００℃の温度で乾燥を行うことにより、相分離を誘起させて多孔質ＰＡＩ被膜を形成させることができ、電極活物質層と、この多孔質ＰＡＩ被膜とが積層一体化される。 By applying the PAI-M solution to the surface of the electrode active material layer and drying at a temperature of 100 to 200 ° C., it is possible to induce phase separation to form a porous PAI film, And the porous PAI coating are laminated and integrated.
電極活物質層へのＰＡＩ溶液の塗布方法としては、ロールツーロールにより連続的に塗布する方法、枚様で塗布する方法が採用でき、いずれの方法でもよい。塗布装置としては、ダイコータ、多層ダイコータ、グラビアコータ、コンマコータ、リバースロールコータ、ドクタブレードコータ等を用いる公知の方法で行うことができる。 As a method for applying the PAI solution to the electrode active material layer, a method of applying continuously by roll-to-roll or a method of applying in sheet form can be adopted, and any method may be used. As the coating apparatus, a known method using a die coater, a multilayer die coater, a gravure coater, a comma coater, a reverse roll coater, a doctor blade coater or the like can be used.
多孔質ＰＡＩ被膜表面の平均気孔径は、１０ｎｍ以上、５０００ｎｍ以下であり、２０ｎｍ以上、３０００ｎｍ以下がより好ましい。平均気孔径をこのようにすることにより、ＰＡＩ被膜のイオン抵抗率を充分に低くすることができる。 平均気孔径は、多孔質ＰＡＩ被膜表面のＳＥＭ（走査型電子顕微鏡）像を倍率５０００〜２００００倍で取得し、市販の画像処理ソフトで解析することにより確認することができる。 The average pore diameter on the surface of the porous PAI coating is 10 nm or more and 5000 nm or less, and more preferably 20 nm or more and 3000 nm or less. By making the average pore diameter in this way, the ionic resistivity of the PAI film can be made sufficiently low. The average pore diameter can be confirmed by acquiring an SEM (scanning electron microscope) image on the surface of the porous PAI film at a magnification of 5000 to 20000 and analyzing it with commercially available image processing software.
多孔質ＰＡＩ被膜の気孔率は、３０〜９０体積％であることが好ましく、４０〜８０体積％であることがより好ましく、４５〜８０体積％であることがさらに好ましい。気孔率をこのように設定することにより、良好な力学的特性と、活物質の体積変化に伴う応力緩和のための良好なクッション性とが同時に確保される。このため、安全性に優れ、かつ良好なサイクル特性を有する電極を得ることができる。多孔質ＰＡＩ被膜の気孔率は、多孔質ＰＡＩ被膜の見掛け密度と、被膜を構成するＰＡＩの真密度（比重）とから算出される値である。詳細には、気孔率（体積％）は、ＰＡＩ被膜の見掛け密度がＡ（ｇ／ｃｍ３）、ＰＡＩの真密度がＢ（ｇ／ｃｍ３）の場合、次式により算出される。
気孔率（体積％） ＝ １００−Ａ＊（１００／Ｂ）
The porosity of the porous PAI coating is preferably 30 to 90% by volume, more preferably 40 to 80% by volume, and still more preferably 45 to 80% by volume. By setting the porosity in this way, good mechanical properties and good cushioning properties for stress relaxation accompanying the volume change of the active material can be ensured at the same time. For this reason, the electrode which is excellent in safety | security and has a favorable cycling characteristic can be obtained. The porosity of the porous PAI coating is a value calculated from the apparent density of the porous PAI coating and the true density (specific gravity) of the PAI constituting the coating. Specifically, the porosity (volume%) is calculated by the following formula when the apparent density of the PAI film is A (g / cm 3 ) and the true density of the PAI is B (g / cm 3 ).
Porosity (volume%) = 100−A * (100 / B)
多孔質ＰＡＩ被膜は、充分なイオン透過性を有していることが好ましい。 すなわち、そのイオン抵抗率が、２．５Ωｃｍ２以下であることが好ましい。イオン抵抗率が、上記範囲であると、本発明の電極を用いたリチウム二次電池の良好な充放電特性を確保することができる。
ここでＰＡＩ被膜のイオン抵抗率（Ｒｓ−ＰＡＩ）は、例えば、以下のような方法を用いて、算出することができる。すなわち、集電体上に形成された活物質層のみのイオン抵抗率をＲｓ−１、その表面に多孔質ＰＡＩ被膜が形成された積層体のイオン抵抗率をＲｓ−２とすると、Ｒｓ−ＰＡＩは、Ｒｓ−２からＲｓ−１を減じることにより算出する。
Ｒｓ−１およびＲｓ−２は、これらの表面に、電解液の存在下で、市販セパレータ、対極となるリチウム箔を順次積層して、測定用セルを構成し、前記リチウム箔および前記集電体を電極として、２５℃で、１００ＫＨｚでのインピーダンスを測定することに決定することができる。
The porous PAI film preferably has sufficient ion permeability. That is, the ion resistivity is preferably 2.5 Ωcm 2 or less. When the ionic resistivity is within the above range, good charge / discharge characteristics of the lithium secondary battery using the electrode of the present invention can be ensured.
Here, the ionic resistivity (Rs-PAI) of the PAI film can be calculated using, for example, the following method. That is, assuming that the ionic resistivity of only the active material layer formed on the current collector is Rs-1, and the ionic resistivity of the laminate having the porous PAI film formed on the surface thereof is Rs-2, Rs-PAI Is calculated by subtracting Rs-1 from Rs-2.
Rs-1 and Rs-2 are formed by sequentially laminating a commercially available separator and a lithium foil as a counter electrode in the presence of an electrolytic solution on these surfaces to constitute a measurement cell, and the lithium foil and the current collector Can be determined to measure the impedance at 25 kHz and 100 KHz.
多孔質ＰＡＩ被膜は活物質層と強固に接着していることが好ましい。すなわち、電池の安全性向上の観点から、電極活物質層と多孔質ＰＡＩ被膜の接着強度が、電極活物質層の強度よりも高いことが好ましい。接着強度が、電極活物質層の強度よりも高いかどうかは、電極活物質層をＰＡＩ被膜から剥離した時、その界面で、凝集破壊が起こるか、界面剥離が起こるかで判定することができる。凝集破壊が起こったときに、接着界面の強度が、電極活物質層の強度よりも高いと判定される。剥離後のＰＡＩ被膜の表面（電極活物質層との接着面）の一部に活物質層の断片が付着している場合に凝集破壊と判定される。本発明の電極では、このような高い接着力が電池の安全性の向上に大きく寄与する。 The porous PAI film is preferably firmly bonded to the active material layer. That is, from the viewpoint of improving battery safety, the adhesive strength between the electrode active material layer and the porous PAI film is preferably higher than the strength of the electrode active material layer. Whether the adhesive strength is higher than the strength of the electrode active material layer can be determined by whether cohesive failure or interface peeling occurs at the interface when the electrode active material layer is peeled from the PAI coating. . When cohesive failure occurs, it is determined that the strength of the adhesive interface is higher than the strength of the electrode active material layer. A cohesive failure is determined when a fragment of the active material layer adheres to a part of the surface of the PAI film after peeling (adhesive surface with the electrode active material layer). In the electrode of the present invention, such high adhesive strength greatly contributes to the improvement of battery safety.
多孔質ＰＡＩ被膜の厚さは０．５〜１００μｍが好ましく、１〜２０μｍがより好ましい。 The thickness of the porous PAI coating is preferably 0.5 to 100 μm, more preferably 1 to 20 μm.
多孔質ＰＡＩ被膜が積層される電極活物質層とは、本発明の蓄電素子（例えばリチウム二次電池）電極の集電体上に形成された層であり、正極活物質層と負極活物質層の総称である。 The electrode active material layer on which the porous PAI film is laminated is a layer formed on the current collector of the storage element (for example, lithium secondary battery) electrode of the present invention, and includes a positive electrode active material layer and a negative electrode active material layer. Is a general term.
集電体としては、銅箔、ステンレス箔、ニッケル箔、アルミ箔等の金属箔を使用することができる。正極にはアルミ箔が、負極には銅箔が好ましく用いられる。これらの金属箔の厚みは５〜５０μｍが好ましく、９〜１８μｍがより好ましい。これらの金属箔の表面は、活物質層との接着性を向上させるための粗面化処理や防錆処理がされていてもよい。 As the current collector, a metal foil such as a copper foil, a stainless steel foil, a nickel foil, or an aluminum foil can be used. Aluminum foil is preferably used for the positive electrode, and copper foil is used for the negative electrode. The thickness of these metal foils is preferably 5 to 50 μm, more preferably 9 to 18 μm. The surface of these metal foils may be subjected to a roughening treatment or an antirust treatment for improving the adhesiveness with the active material layer.
正極活物質層は、例えば、正極活物質粒子を樹脂バインダで結着して得られる層である。正極活物質粒子として用いられる材料としては、リチウムイオンを吸蔵保存できるものが好ましく、例えば、酸化物系（ＬｉＣｏＯ２、ＬｉＮｉＯ２等）、リン酸鉄系（ＬｉＦｅＰＯ４等）、高分子化合物系（ポリアニリン、ポリチオフェン等）等の活物質粒子を挙げることができる。この中でも、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＦｅＰＯ４が好ましい。正極活物質層には、その内部抵抗を低下させるため、カーボン（黒鉛、カーボンブラック等）粒子や金属（銀、銅、ニッケル等）粒子等の導電性粒子が、１〜３０質量％程度配合されていてもよい。 The positive electrode active material layer is, for example, a layer obtained by binding positive electrode active material particles with a resin binder. The material used as the positive electrode active material particles is preferably a material capable of occluding and storing lithium ions. For example, an oxide system (LiCoO 2 , LiNiO 2 etc.), an iron phosphate system (LiFePO 4 etc.), a polymer compound system ( Active material particles such as polyaniline and polythiophene). Among these, LiCoO 2 , LiNiO 2 , and LiFePO 4 are preferable. In order to reduce the internal resistance of the positive electrode active material layer, conductive particles such as carbon (graphite, carbon black, etc.) particles and metal (silver, copper, nickel, etc.) particles are blended in an amount of about 1 to 30% by mass. It may be.
負極活物質層は、例えば、負極活物質粒子を樹脂バインダで結着して得られる層である。負極活物質粒子として用いられる材料としては、リチウムイオンを吸蔵保存できるものが好ましく、例えば黒鉛、アモルファスカーボン、シリコン系、錫系等の活物質粒子を挙げることができる。この中でも黒鉛粒子、シリコン系粒子が好ましい。シリコン系粒子としては、例えば、シリコン単体、シリコン合金、シリコン・二酸化珪素複合体等の粒子を挙げることができる。これらシリコン系粒子の中でも、シリコン単体の粒子が好ましい。シリコン単体とは、純度が９５質量％以上の結晶質または非晶質のシリコンをいう。負極活物質層には、その内部抵抗を低下させるため、カーボン（黒鉛、カーボンブラック等）粒子や金属（銀、銅、ニッケル等）粒子等の導電性粒子が、１〜３０質量％程度配合されていてもよい。また、負極活物質層として、リチウム箔やリチウム合金箔を用いることができる。 The negative electrode active material layer is, for example, a layer obtained by binding negative electrode active material particles with a resin binder. The material used as the negative electrode active material particles is preferably a material capable of occluding and storing lithium ions. Examples thereof include graphite, amorphous carbon, silicon-based, and tin-based active material particles. Among these, graphite particles and silicon-based particles are preferable. Examples of the silicon-based particles include particles of silicon alone, a silicon alloy, a silicon / silicon dioxide composite, and the like. Among these silicon-based particles, particles of silicon alone are preferable. Silicon alone means crystalline or amorphous silicon having a purity of 95% by mass or more. In order to reduce the internal resistance of the negative electrode active material layer, conductive particles such as carbon (graphite, carbon black, etc.) particles and metal (silver, copper, nickel, etc.) particles are blended in an amount of about 1 to 30% by mass. It may be. Further, a lithium foil or a lithium alloy foil can be used as the negative electrode active material layer.
活物質粒子や導電性粒子の粒子径は、正極、負極いずれも５０μｍ以下が好ましく、１０μｍ以下がさらに好ましい。粒子径は、小さすぎても樹脂バインダによる結着が難しくなるので、通常０．１μｍ以上、好ましくは０．５μｍ以上である。 The particle diameter of the active material particles and the conductive particles is preferably 50 μm or less for both the positive electrode and the negative electrode, and more preferably 10 μm or less. Even if the particle diameter is too small, binding with a resin binder becomes difficult, so it is usually 0.1 μm or more, preferably 0.5 μm or more.
電極活物質層の気孔率は、正極、負極いずれも５〜５０体積％が好ましく、１０〜４０体積％がより好ましい。 As for the porosity of an electrode active material layer, 5-50 volume% is preferable in both a positive electrode and a negative electrode, and 10-40 volume% is more preferable.
電極活物質層の層厚は、通常２０〜２００μｍ程度である。 The layer thickness of the electrode active material layer is usually about 20 to 200 μm.
前述の、活物質粒子を結着させるための樹脂バインダとしては、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ビニリデンフロライド−ヘキサフルオロプロピレン共重合体、ビニリデンフロライド−テトラフルオロエチレン共重合体、スチレン・ブタジエン共重合ゴム（ＳＢＲ）、ポリテトラフルオロエチレン、ポリプロピレン、ポリエチレン、ＰＡＩ等を挙げることができる。この中でも、ＰＶＤＦ、ＳＢＲ、ＰＡＩが好ましい。 Examples of the resin binder for binding the active material particles include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, styrene- Examples thereof include butadiene copolymer rubber (SBR), polytetrafluoroethylene, polypropylene, polyethylene, and PAI. Among these, PVDF, SBR, and PAI are preferable.
前記したような集電体上に活物質層が形成された積層体は市販品を利用することもできるが、例えば以下のような公知の方法で製造することができる。 A commercial product can be used for the laminate in which the active material layer is formed on the current collector as described above, but it can be produced by, for example, the following known methods.
すなわち、集電体である金属箔の表面に、前述のバインダと活物質粒子と溶媒とを含む分散体（以下、「活物質分散体」と略記することがある）を塗布後、乾燥して金属箔上に電極活物質層を形成させることができる。 That is, a dispersion containing the above binder, active material particles, and solvent (hereinafter sometimes abbreviated as “active material dispersion”) is applied to the surface of a metal foil as a current collector, and then dried. An electrode active material layer can be formed on the metal foil.
以下に、実施例を挙げて、本発明をさらに詳細に説明する。なお本発明は実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the examples.
下記の実施例及び比較例で使用した、集電体上に形成された電極活物質層（負極用）を以下のようにして得た。 The electrode active material layer (for negative electrode) formed on the current collector used in the following Examples and Comparative Examples was obtained as follows.
負極活物質である黒鉛粒子（平均粒径８μｍ）８８質量部と、導電助剤のカーボンブラック（アセチレンブラック）５質量部と、バインダ樹脂であるＰＶＤＦ７質量部とを、ＮＭＰ中に均一に分散して、固形分濃度２５質量％の負極活物質分散体を得た。この分散体を負極集電体である厚さ１８μｍの銅箔に塗布し、得られた塗膜を１５０℃で２０分乾燥後、熱プレスして、厚みが５０μｍの負極活物質層を得た。 A negative active material graphite particle (average particle size 8 μm) 88 parts by mass, a conductive auxiliary agent carbon black (acetylene black) 5 parts by mass, and a binder resin PVDF 7 parts by mass are uniformly dispersed in NMP. Thus, a negative electrode active material dispersion having a solid content concentration of 25% by mass was obtained. This dispersion was applied to a copper foil having a thickness of 18 μm as a negative electrode current collector, and the obtained coating film was dried at 150 ° C. for 20 minutes and then hot pressed to obtain a negative electrode active material layer having a thickness of 50 μm. .
下記の実施例及び比較例において得られた電極の特性は、以下の方法で評価した。 The characteristics of the electrodes obtained in the following examples and comparative examples were evaluated by the following methods.
電極を直径１６ｍｍの円形に打ち抜き、その多孔質ＰＡＩ被膜面側に、ポリエチレン製多孔膜からなるセパレータと、リチウム箔とを順に積層し、これをステンレス製のコイン型外装容器中に収納した。この外装容器中に電解液（溶媒：エチレンカーボネートとジメチルカーボネートとを体積比で１：１の割合で混合した混合溶媒、電解質：１ＭＬｉＰＦ６）を注入し、外装容器にパッキンを介してステンレス製のキャップをかぶせて固定し、電池缶を封止して、評価用のセルを得た。このセルを用い、前記した方法で、１００ＫＨｚでのインピーダンスを測定することにより、イオン抵抗率（Ｒｓ−ＰＡＩ）を算出した。 The electrode was punched into a circle having a diameter of 16 mm, and a separator made of a polyethylene porous film and a lithium foil were sequentially laminated on the porous PAI coating surface side, and this was stored in a stainless steel coin-type outer container. An electrolytic solution (solvent: mixed solvent in which ethylene carbonate and dimethyl carbonate are mixed at a volume ratio of 1: 1, electrolyte: 1 M LiPF 6 ) is poured into the outer container, and the outer container is made of stainless steel through a packing. The cap was covered and fixed, the battery can was sealed, and the cell for evaluation was obtained. Using this cell, the ion resistivity (Rs-PAI) was calculated by measuring the impedance at 100 KHz by the method described above.
＜実施例１＞
ＴＡＣと、ＤＡＤＥおよびＭＤＡと、を共重合（共重合モル比：ＤＡＤＥ／ＭＤＡ＝７／３）して得られるＰＡＩ粉体（ソルベイアドバンストポリマーズ株式会社製トーロン４０００Ｔ−ＨＶ、ガラス転移温度２８０℃）を、ＮＭＰとＧ４とからなる混合溶媒（質量比 ＮＭＰ／Ｇ４＝３０／７０）に、８０℃で溶解して、ＰＡＩの固形分濃度が１５質量％の均一なＰＡＩ溶液（Ｓ−０）を得た。次に、このＰＡＩ溶液に、ＰＡＩ質量に対し２４質量％相当のＰＰＧＭＥ（数平均分子量２０００：ハンツマン社製ジェファーミンＤ２０００）を添加し、攪拌下、８０℃で４時間反応させて均一な固形分濃度が１８．０質量％のＰＡＩ溶液（Ｓ−１）を得た。 Ｓ−１の粘度は、３０℃で３４．５Ｐａ・ｓであった。
<Example 1>
PAI powder obtained by copolymerizing TAC, DADE and MDA (copolymerization molar ratio: DADE / MDA = 7/3) (Tolon 4000T-HV, Solvay Advanced Polymers Co., Ltd., glass transition temperature 280 ° C.) Is dissolved in a mixed solvent composed of NMP and G4 (mass ratio NMP / G4 = 30/70) at 80 ° C. to obtain a uniform PAI solution (S-0) having a solid content concentration of PAI of 15% by mass. Obtained. Next, to this PAI solution, PPGME (number average molecular weight 2000: Jeffamine D2000 manufactured by Huntsman) equivalent to 24% by mass with respect to the mass of PAI is added and reacted at 80 ° C. for 4 hours with stirring to obtain a uniform solid content. A PAI solution (S-1) having a concentration of 18.0% by mass was obtained. The viscosity of S-1 was 34.5 Pa · s at 30 ° C.
＜実施例２＞
ＰＰＧＭＥの添加量を、ＰＡＩ質量に対し１２質量％相当としたこと以外は、実施例１と同様に行い、固形分濃度が１６．５質量％の均一なＰＡＩ溶液（Ｓ−２）を得た。Ｓ−２の粘度は、３０℃で１１．７Ｐａ・ｓであった。
<Example 2>
Except that the amount of PPGME added was equivalent to 12% by mass relative to the PAI mass, the same procedure as in Example 1 was performed to obtain a uniform PAI solution (S-2) having a solid content concentration of 16.5% by mass. . The viscosity of S-2 was 11.7 Pa · s at 30 ° C.
＜実施例３＞
実施例１で得られたＰＡＩ溶液（Ｓ−０）に、ＰＡＩ質量に対し６質量％相当のＤＡＳＭ（数平均分子量８６０：信越化学社製 ＫＦ−８０１０）を用いたこと以外は、実施例１と同様に行い、固形分濃度が１５．８質量％の均一なＰＡＩ溶液（Ｓ−３）を得た。Ｓ−３の粘度は、３０℃で１０．５Ｐａ・ｓであった。
<Example 3>
Example 1 except that DASM (number average molecular weight 860: KF-8010 manufactured by Shin-Etsu Chemical Co., Ltd.) corresponding to 6% by mass of PAI mass was used for the PAI solution (S-0) obtained in Example 1. And a uniform PAI solution (S-3) having a solid content concentration of 15.8% by mass was obtained. The viscosity of S-3 was 10.5 Pa · s at 30 ° C.
＜実施例４＞
実施例２で得られたＰＡＩ溶液（Ｓ−２）に、ＰＡＩ質量に対し４０質量％相当の市販球状アルミナ（平均粒子径：０．５μｍ）を加え、ボールミルで混錬混合することにより、固形分濃度が１９．８質量％のＰＡＩ懸濁液（Ｓ−４）を得た。
<Example 4>
A commercial spherical alumina equivalent to 40% by mass (average particle size: 0.5 μm) was added to the PAI solution (S-2) obtained in Example 2 and kneaded and mixed with a ball mill to obtain a solid. A PAI suspension (S-4) having a partial concentration of 19.8% by mass was obtained.
＜比較例１＞
ＴＡＣと、ＤＡＤＥおよびＭＤＡと、を共重合（共重合モル比：ＤＡＤＥ／ＭＤＡ＝７／３）して得られるＰＡＩ粉体（ソルベイアドバンストポリマーズ株式会社製トーロン４０００Ｔ−ＨＶ、ガラス転移温度２８０℃）を、ＮＭＰとＧ４とからなる混合溶媒（質量比 ＮＭＰ／Ｇ４＝３０／７０）に、８０℃で溶解して、ＰＡＩの固形分濃度が１６．５質量％の均一なＰＡＩ溶液（Ｓ−５）を得た。Ｓ−５の粘度は、３０℃で８．６Ｐａ・ｓであった。
<Comparative Example 1>
PAI powder obtained by copolymerizing TAC, DADE and MDA (copolymerization molar ratio: DADE / MDA = 7/3) (Tolon 4000T-HV, Solvay Advanced Polymers Co., Ltd., glass transition temperature 280 ° C.) Is dissolved in a mixed solvent consisting of NMP and G4 (mass ratio NMP / G4 = 30/70) at 80 ° C. to obtain a uniform PAI solution (S-5 with a solid content concentration of PAI of 16.5% by mass). ) The viscosity of S-5 was 8.6 Pa · s at 30 ° C.
＜実施例５＞
実施例１で得られたＳ−１を前記負極活物質層の表面に塗布し、１３０℃で１０分乾燥して、厚みが１１μｍのＰＡＩ被膜が負極活物質層の表面に形成された電極（負極）「ＡＮ−１」を得た。 塗布の際の塗工性は極めて良好であった。この多孔質ＰＡＩ被膜は、負極活物質層の表面に強固に接着されていた。 多孔質ＰＡＩ被膜の平均気孔径（表面）は２１００ｎｍであり、気孔率は、６１体積％であった。
負極「ＡＮ−１」を用いて、前記した方法でセルを作成し、イオン抵抗率を測定した所、このＰＡＩ被膜のＲｓ−ＰＡＩは、２．２Ωｃｍ２であった。
<Example 5>
S-1 obtained in Example 1 was applied to the surface of the negative electrode active material layer, dried at 130 ° C. for 10 minutes, and an electrode in which a PAI film having a thickness of 11 μm was formed on the surface of the negative electrode active material layer ( Negative electrode) “AN-1” was obtained. The coating property at the time of application was very good. This porous PAI film was firmly bonded to the surface of the negative electrode active material layer. The average pore diameter (surface) of the porous PAI coating was 2100 nm, and the porosity was 61% by volume.
When a cell was prepared by the above-described method using the negative electrode “AN-1” and the ionic resistivity was measured, the Rs-PAI of this PAI film was 2.2 Ωcm 2 .
＜実施例６＞
ＰＡＩ溶液として、Ｓ−２を用いたこと以外は、実施例５と同様にして、厚みが１２μｍのＰＡＩ被膜が負極活物質層の表面に形成された電極（負極）「ＡＮ−２」を得た。 塗布の際の塗工性は良好であった。 この多孔質ＰＡＩ被膜は、負極活物質層の表面に強固に接着されていた。 多孔質ＰＡＩ被膜の平均気孔径（表面）は２２００ｎｍであり、気孔率は、６２体積％であった。 負極「ＡＮ−２」を用いて、前記した方法でセルを作成し、イオン抵抗率を測定した所、このＰＡＩ被膜のＲｓ−ＰＡＩは、２．４Ωｃｍ２であった。
<Example 6>
An electrode (negative electrode) “AN-2” having a PAI film having a thickness of 12 μm formed on the surface of the negative electrode active material layer was obtained in the same manner as in Example 5 except that S-2 was used as the PAI solution. It was. The coating property at the time of application was good. This porous PAI film was firmly bonded to the surface of the negative electrode active material layer. The average pore diameter (surface) of the porous PAI coating was 2200 nm, and the porosity was 62% by volume. When a cell was prepared by the above-described method using the negative electrode “AN-2” and the ionic resistivity was measured, Rs-PAI of this PAI film was 2.4 Ωcm 2 .
＜実施例７＞
ＰＡＩ溶液として、Ｓ−３を用いたこと以外は、実施例５と同様にして、厚みが１３μｍのＰＡＩ被膜が負極活物質層の表面に形成された電極（負極）「ＡＮ−３」を得た。 塗布の際の塗工性は良好であった。 この多孔質ＰＡＩ被膜は、負極活物質層の表面に強固に接着されていた。 多孔質ＰＡＩ被膜の平均気孔径（表面）は２５００ｎｍであり、気孔率は、６１体積％であった。 負極「ＡＮ−３」を用いて、前記した方法でセルを作成し、イオン抵抗率を測定した所、このＰＡＩ被膜のＲｓ−ＰＡＩは、２．３Ωｃｍ２であった。
<Example 7>
An electrode (negative electrode) “AN-3” in which a PAI film having a thickness of 13 μm was formed on the surface of the negative electrode active material layer was obtained in the same manner as in Example 5 except that S-3 was used as the PAI solution. It was. The coating property at the time of application was good. This porous PAI film was firmly bonded to the surface of the negative electrode active material layer. The average pore diameter (surface) of the porous PAI film was 2500 nm, and the porosity was 61% by volume. A cell was prepared by the above-described method using the negative electrode “AN-3” and the ionic resistivity was measured. As a result, Rs-PAI of this PAI film was 2.3 Ωcm 2 .
＜実施例８＞
ＰＡＩ懸濁液として、Ｓ−４を用いたこと以外は、実施例５と同様にして、厚みが１１μｍのＰＡＩ被膜が負極活物質層の表面に形成された電極（負極）「ＡＮ−４」を得た。 塗布の際の塗工性は良好であった。 この多孔質ＰＡＩ被膜は、負極活物質層の表面に強固に接着されていた。 多孔質ＰＡＩ被膜の平均気孔径（表面）は１５００ｎｍであり、気孔率は、６８体積％であった。 負極「ＡＮ−４」を用いて、前記した方法でセルを作成し、イオン抵抗率を測定した所、このＰＡＩ被膜のＲｓ−ＰＡＩは、１．９Ωｃｍ２であった。
<Example 8>
An electrode (negative electrode) “AN-4” in which a PAI film having a thickness of 11 μm was formed on the surface of the negative electrode active material layer in the same manner as in Example 5 except that S-4 was used as the PAI suspension. Got. The coating property at the time of application was good. This porous PAI film was firmly bonded to the surface of the negative electrode active material layer. The average pore diameter (surface) of the porous PAI coating was 1500 nm, and the porosity was 68% by volume. A cell was prepared by the above-described method using the negative electrode “AN-4”, and the ionic resistivity was measured. As a result, the Rs-PAI of this PAI film was 1.9 Ωcm 2 .
＜比較例２＞
ＰＡＩ溶液として、Ｓ−５を用いたこと以外は、実施例５と同様にして、厚みが１２μｍのＰＡＩ被膜が負極活物質層の表面に形成された電極（負極）「ＡＮ−５」を得た。 塗布の際には、ＰＡＩ溶液の一部が活物質層の周辺部に流れでることがあった。 この多孔質ＰＡＩ被膜は、負極活物質層の表面に強固に接着されていた。 多孔質ＰＡＩ被膜の平均気孔径（表面）は１９００ｎｍであり、気孔率は、６０体積％であった。 負極「ＡＮ−５」を用いて、前記した方法でセルを作成し、イオン抵抗率を測定した所、このＰＡＩ被膜のＲｓ−ＰＡＩは、２．９Ωｃｍ２であった。
<Comparative example 2>
An electrode (negative electrode) “AN-5” in which a PAI film having a thickness of 12 μm was formed on the surface of the negative electrode active material layer was obtained in the same manner as in Example 5 except that S-5 was used as the PAI solution. It was. At the time of application, a part of the PAI solution may flow to the periphery of the active material layer. This porous PAI film was firmly bonded to the surface of the negative electrode active material layer. The average pore diameter (surface) of the porous PAI coating was 1900 nm, and the porosity was 60% by volume. When a cell was prepared by the above-described method using the negative electrode “AN-5” and the ionic resistivity was measured, Rs-PAI of this PAI film was 2.9 Ωcm 2 .
実施例、比較例で示したように、本発明のＰＡＩ溶液は、高粘度化されているので、塗工性が良好である。 さらにこれを用いて、電極活物質上に形成された多孔質ＰＡＩ塗膜は、イオン抵抗率が低く、良好なイオン透過性が確保できる。 As shown in the Examples and Comparative Examples, the PAI solution of the present invention has a high viscosity, and thus has good coating properties. Furthermore, using this, the porous PAI coating film formed on the electrode active material has low ionic resistivity and can ensure good ion permeability.
本発明のＰＡＩ溶液は、高粘度化されているので、塗工性が良好であり、これから得られる多孔質ＰＡＩ被膜はイオン透過性に優れる。 従い、これを活物質層の表面に塗布後、乾燥することにより得られる多孔質ＰＡＩ被膜が活物質層表面に積層一体化された電極は、安全性に優れた蓄電素子電極として好適に用いることができる。
Since the PAI solution of the present invention has a high viscosity, the coating property is good, and the porous PAI film obtained therefrom is excellent in ion permeability. Accordingly, an electrode in which a porous PAI film obtained by applying this to the surface of the active material layer and then drying is laminated and integrated on the surface of the active material layer should be suitably used as a storage element electrode with excellent safety. Can do.
Claims (3)
１） 前記ポリアミドイミドの側鎖中に、オキシアルキレンユニットおよび／またはシロキサンユニットを含む。
２) 前記多孔質ポリアミドイミド被膜表面の平均気孔径が１０ｎｍ以上、５０００ｎｍ以下である。
An electrode in which a porous polyamideimide coating is laminated and integrated on the surface of an active material layer, and has the following characteristics.
1) The side chain of the polyamideimide contains oxyalkylene units and / or siloxane units.
2) The average pore diameter of the porous polyamideimide coating surface is 10 nm or more and 5000 nm or less.
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