JP2014191942A - Binder for electrode of lithium secondary battery, and lithium secondary battery using electrode manufactured using the binder - Google Patents
Binder for electrode of lithium secondary battery, and lithium secondary battery using electrode manufactured using the binder Download PDFInfo
- Publication number
- JP2014191942A JP2014191942A JP2013065370A JP2013065370A JP2014191942A JP 2014191942 A JP2014191942 A JP 2014191942A JP 2013065370 A JP2013065370 A JP 2013065370A JP 2013065370 A JP2013065370 A JP 2013065370A JP 2014191942 A JP2014191942 A JP 2014191942A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- mass
- binder
- active hydrogen
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000011230 binding agent Substances 0.000 title claims abstract description 51
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 90
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- -1 alkoxy silane derivative Chemical class 0.000 claims abstract description 37
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 83
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- 239000013638 trimer Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
本発明は、リチウム二次電池の電極用結着剤、該結着剤を用いて製造された電極を使用したリチウム二次電池に関するものである。 The present invention relates to a binder for an electrode of a lithium secondary battery, and a lithium secondary battery using an electrode manufactured using the binder.
最近、携帯電話、ノートパソコン、携帯情報端末(PDA)、ビデオカメラ、デジタルカメラなど、携帯用電子機器が多く普及し、かかる電子機器の小型化、軽量化が一段と要求されるにつれ、駆動電源である電池の小型化、軽量化、薄型化及び高容量化に対する要求が高まっており、本課題に対する研究が活発に進められている。リチウム二次電池は、高電圧及び良好なエネルギー密度を有しており、携帯用電子機器の電源として広く使われてきた。しかし、小型、軽量化されたディスプレイ産業の発展と共に、さらに小型化されて軽量化された電池が要求されることにより、従来のリチウム二次電池に比べてさらに高い駆動電圧、延長した寿命、及び高いエネルギー密度など、向上した電池特性が要求される。また最近では、車載用、産業用などの中型もしくは大型のリチウム二次電池の開発が進められており、高容量・高出力化向上の開発に期待が寄せられている。従って、このような要求を充足させるために、リチウム電池の各種構成要素の性能を向上させる努力が続けられている。 Recently, portable electronic devices such as mobile phones, notebook computers, personal digital assistants (PDAs), video cameras, digital cameras, etc. have been widely used, and as these electronic devices are increasingly required to be smaller and lighter, drive power supplies There is an increasing demand for a battery that is smaller, lighter, thinner, and has a higher capacity, and research on this issue is actively underway. Lithium secondary batteries have high voltage and good energy density, and have been widely used as power sources for portable electronic devices. However, as the display industry has been reduced in size and weight, there is a need for a battery that is further reduced in size and weight, resulting in higher driving voltage, longer life, and longer life than conventional lithium secondary batteries. Improved battery characteristics such as high energy density are required. Recently, development of medium- or large-sized lithium secondary batteries for in-vehicle use, industrial use, etc. has been promoted, and there is an expectation for the development of high capacity and high output. Therefore, efforts to improve the performance of various components of the lithium battery are continued in order to satisfy such requirements.
電池の特性は、使われる電極、電解質及びその他電池材料により大きく左右されるが、特に、電極の場合は、電極活物質、集電体及びそれらの間に接着力を付与する結着剤により特性が決定される。例えば、使われる活物質の量及び種類が、活物質と結合できるリチウムイオンの量を決定するために、活物質の量が多いほど、そして固有容量の大きい活物質を使用するほど、高容量の電池を得ることができる。また、結着剤が上記活物質間、及び活物質と集電体との間で優秀な接着力を有する場合、電極内で電子及びリチウムイオンの移動が円滑になされ、電極の内部抵抗が減少するので、高効率の充放電が可能になる。そして、高容量電池の場合には、アノード活物質として、カーボン及び黒鉛、カーボン及びケイ素のような複合系電極が必要になるので、充放電時に、活物質の体積膨脹及び収縮が大きく起こるために、上記結着剤は、優秀な接着力以外にも優秀な弾性を有し、電極体積が相当の膨脹及び収縮を繰り返すにもかかわらず、本来の接着力及び復原力を維持できねばならない。このような電極を得るための結着剤としては、有機溶剤中にポリテトラフルオロエチレンやポリフッ化ビニリデン等のフッ素樹脂が溶解されてなるものが知られている。然るに、フッ素樹脂は、集電体を構成する金属との密着性が十分に高いものではない上、柔軟性が十分に高いものではないため、特に倦回型電池を製造する場合には、得られる電極層にクラックが生じたり、得られる電極層と集電体との剥離が生じたりする、という問題がある。十分な接着力を維持するためには、投入量が多くなければならないので、小型化には限界があり、また、有機溶媒と混合して使用するために、製造が複雑であるという短所がある。 The characteristics of the battery are greatly influenced by the electrode, electrolyte and other battery materials used. In particular, in the case of electrodes, the characteristics are determined by the electrode active material, the current collector, and the binder that provides an adhesive force between them. Is determined. For example, the amount and type of active material used can determine the amount of lithium ions that can bind to the active material, the higher the amount of active material and the higher the specific capacity active material, the higher the capacity. A battery can be obtained. In addition, when the binder has an excellent adhesive force between the active materials and between the active material and the current collector, electrons and lithium ions move smoothly in the electrode, and the internal resistance of the electrode is reduced. Therefore, highly efficient charging / discharging becomes possible. In the case of a high-capacity battery, a composite electrode such as carbon and graphite, carbon and silicon is required as an anode active material, so that the volume expansion and contraction of the active material greatly occurs during charging and discharging. The above-mentioned binder has excellent elasticity in addition to excellent adhesive force, and must maintain the original adhesive force and restoring force despite the electrode volume repeatedly expanding and contracting considerably. As a binder for obtaining such an electrode, one obtained by dissolving a fluororesin such as polytetrafluoroethylene or polyvinylidene fluoride in an organic solvent is known. However, since the fluororesin is not sufficiently high in adhesion to the metal constituting the current collector and is not sufficiently high in flexibility, it can be obtained particularly when a wound battery is manufactured. There is a problem that a crack occurs in the obtained electrode layer, or peeling between the obtained electrode layer and the current collector occurs. In order to maintain sufficient adhesive strength, the amount of input must be large, so there is a limit to downsizing, and there is a disadvantage that manufacturing is complicated because it is used in combination with an organic solvent. .
一方、集電体を構成する金属との密着性が高く、しかも、柔軟性が高い電極層を形成することができる結着剤として、スチレン−ブタジエン系ラテックス(SBR)よりなるものが知られている(特許文献1、2、3)。これは弾性特性にはすぐれるが、接着力が弱く、充放電が反復されるにつれて電極の構造を維持できず、電池の寿命が十分とは言えない。そして、近年、電池高容量化の要請から、電極層を構成する材料として、結着剤成分の含有量を低減する傾向にあり、また、電極の製造工程において電極層に対するプレス加工が行われている。然るに、結着剤成分の含有量が低い電極層においては、プレス加工時に電極層が集電体から剥離しやすい。そのため、電極物質によってプレス加工機の汚染が生じるばかりでなく、電極層の一部が剥離した状態で電極が電池に組み込まれ、電池性能の信頼性が低下するという問題が指摘されている。このような問題は、結着剤成分としてガラス転移温度が低くて粘着性の高いポリマーを使用した場合に顕著となるため、ポリマーのガラス転移温度が高い例えば室温以上のラテックスを用いることにより、抑制することができる。しかしながら、ポリマーのガラス転移温度が高い結着剤を用いた場合には、得られる電極層は、柔軟性が低くてクラックが生じやすいものとなる、という問題があるため、電池の容量保持率が低下し、十分な充放電サイクル特性が得られない。 On the other hand, a binder made of styrene-butadiene latex (SBR) is known as a binder capable of forming an electrode layer having high adhesion to the metal constituting the current collector and high flexibility. (Patent Documents 1, 2, and 3). Although this is excellent in elastic characteristics, the adhesive strength is weak, and the structure of the electrode cannot be maintained as charging and discharging are repeated, so that the battery life is not sufficient. In recent years, due to the demand for higher battery capacity, there is a tendency to reduce the content of the binder component as a material constituting the electrode layer, and the electrode layer is subjected to press working in the electrode manufacturing process. Yes. However, in an electrode layer having a low binder component content, the electrode layer is easily peeled off from the current collector during pressing. Therefore, not only does the electrode material contaminate the press machine, but it has been pointed out that the electrode is incorporated in the battery in a state where a part of the electrode layer is peeled off, and the reliability of the battery performance is lowered. Such a problem becomes prominent when a polymer having a low glass transition temperature and a high tackiness is used as a binder component. Therefore, it is suppressed by using a latex having a high glass transition temperature, for example, room temperature or higher. can do. However, when a binder having a high glass transition temperature of the polymer is used, the obtained electrode layer has a problem that it is low in flexibility and easily cracks. The charge / discharge cycle characteristics cannot be obtained.
本発明は、以上のような事情に基づいてなされたものであって、その目的は、集電体に対する密着性が高くてプレス加工時に剥離が生じることがなく、高い柔軟性を有し、結着性及び耐電解液性に優れた結着剤と、該結着剤を用いて製造された電極を使用した充放電特性に優れたリチウム二次電池を提供することにある。 The present invention has been made on the basis of the circumstances as described above, and its purpose is to have high adhesion to the current collector, no peeling during press working, high flexibility, An object of the present invention is to provide a lithium secondary battery excellent in charge and discharge characteristics using a binder excellent in adhesion and electrolyte resistance and an electrode manufactured using the binder.
上記の目的を達成するために、本発明は、(A成分)ポリイソシアネート、(B成分)2個以上の活性水素基を有する化合物、(C成分)1個以上の活性水素基と親水性基を有する化合物、及び(D成分)鎖伸長剤、からなるポリウレタン水分散体を含有するリチウム二次電池の電極用結着剤であって、前記(D成分)がアルコキシシラン誘導体を含有する事を特徴とするリチウム二次電池の電極用結着剤を第1の要旨とする。
前記(B成分)がカーボネートポリオール、芳香環を有するポリエステルポリオール、及び/または芳香環を有するポリエーテルポリオールを含有する事が好ましい。
前記(A成分)が脂環族系及び/または芳香族系イソシアネートを含有することが好ましい。
本発明の第2の要旨は前記リチウム二次電池の電極用結着剤を用いた電極を使用するリチウム二次電池である。
すなわち、本発明者らは、集電体に対する密着性が高くてプレス加工時に剥離が生じることがなく、高い柔軟性を有し、結着性及び耐電解液性に優れた結着剤を得るために鋭意研究を重ねた。その研究の過程で(A成分)ポリイソシアネート、(B成分)2個以上の活性水素基を有する化合物、(C成分)1個以上の活性水素基と親水性基を有する化合物、及び(D成分)鎖伸長剤、からなるポリウレタン水分散体を含有するリチウム二次電池の電極用結着剤であって、前記(D成分)がアルコキシシラン誘導体を含有するポリウレタン水分散体を使用した電極用結着剤により所期の目的を達成することを見出し、本発明に到達した。
In order to achieve the above object, the present invention comprises (A component) polyisocyanate, (B component) a compound having two or more active hydrogen groups, (C component) one or more active hydrogen groups and a hydrophilic group. A binder for an electrode of a lithium secondary battery comprising a polyurethane water dispersion consisting of a compound having the formula (D) and a chain extender, wherein the (D) contains an alkoxysilane derivative. A feature of the binder for an electrode of a lithium secondary battery is a first gist.
The (Component B) preferably contains a carbonate polyol, a polyester polyol having an aromatic ring, and / or a polyether polyol having an aromatic ring.
The component (A) preferably contains an alicyclic and / or aromatic isocyanate.
The second gist of the present invention is a lithium secondary battery using an electrode using the binder for an electrode of the lithium secondary battery.
That is, the present inventors obtain a binder that has high adhesion to the current collector, does not cause peeling during press processing, has high flexibility, and has excellent binding properties and electrolyte resistance. In order to achieve this, we have conducted extensive research. (A component) polyisocyanate, (B component) a compound having two or more active hydrogen groups, (C component) a compound having one or more active hydrogen groups and a hydrophilic group, and (D component) A binder for an electrode of a lithium secondary battery containing a polyurethane water dispersion comprising a chain extender, wherein the component (D) is a binder for an electrode using a polyurethane water dispersion containing an alkoxysilane derivative. The inventors have found that the intended purpose can be achieved by the adhesive, and have reached the present invention.
本発明のリチウム二次電池の電極用結着剤は、集電体に対する密着性が高くてプレス加工時に剥離が生じることがなく、高い柔軟性を有し、結着性及び耐電解液性に優れており、該結着剤を用いた電極を用いることで充放電特性に優れたリチウム二次電池を得ることができる。 The binder for the electrode of the lithium secondary battery of the present invention has high adhesion to the current collector, does not cause peeling at the time of pressing, has high flexibility, and has binding properties and electrolyte resistance. It is excellent and a lithium secondary battery excellent in charge / discharge characteristics can be obtained by using an electrode using the binder.
つぎに、本発明の実施の形態を詳しく説明する。
本発明のリチウム二次電池の電極用結着剤は、(A成分)ポリイソシアネート、(B成分)2個以上の活性水素基を有する化合物、(C成分)1個以上の活性水素基と親水性基を有する化合物、及び(D成分)鎖伸長剤、からなるポリウレタン水分散体であって、前記(D成分)がアルコキシシラン誘導体を含有するポリウレタン水分散体を含有するものである。
Next, embodiments of the present invention will be described in detail.
The binder for an electrode of the lithium secondary battery of the present invention includes (A component) polyisocyanate, (B component) a compound having two or more active hydrogen groups, (C component) one or more active hydrogen groups and a hydrophilic group. A polyurethane water dispersion comprising a compound having a functional group and a (D component) chain extender, wherein the (D component) contains a polyurethane water dispersion containing an alkoxysilane derivative.
前記(A成分)のポリイソシアネートは特に限定されること無く当該技術分野で一般的に使用されるポリイソシアネートを使用することができる。具体的には、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香族ポリイソシアネート、芳香脂肪族ポリイソシアネートを挙げることができる。脂肪族ポリイソシアネートとしては、テトラメチレンジイソシアネート、ドデカメチレンジイソシアネート、ヘキサメチレンジイソシアネート、2,2,4−トリメチルヘキサメチレンジイソシアネート、2,4,4−トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、2−メチルペンタン−1,5−ジイソシアネート、3−メチルペンタン−1,5−ジイソシアネート等を挙げることができる。脂環族ポリイソシアネートとしては、イソホロンジイソシアネート、水添キシリレンジイソシアネート、4,4’−ジシクロヘキシルメタンジイソシアネート、1,4−シクロヘキサンジイソシアネート、メチルシクロヘキシレンジイソシアネート、1,3−ビス(イソシアネートメチル)シクロヘキサン等を挙げることができる。芳香族ポリイソシアネートとしては、トリレンジイソシアネート、2,2’−ジフェニルメタンジイソシアネート、2,4’−ジフェニルメタンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート(MDI)、4,4’−ジベンジルジイソシアネート、1,5−ナフチレンジイソシアネート、キシリレンジイソシアネート、1,3−フェニレンジイソシアネート、1,4−フェニレンジイソシアネート等を挙げることができる。芳香脂肪族ポリイソシアネートとしては、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、α,α,α,α−テトラメチルキシリレンジイソシアネート等を挙げることができる。また、これらの有機ポリイソシアネートの2量体、3量体やビュレット化イソシアネート等の変性体を挙げることができる。これらは、単独で又は2種以上を併用して用いることもできる。前記ポリイソシアネートの内、結着性及び耐電解液性の点から脂環族系及び/または芳香族系イソシアネートが好ましく、具体的には、4,4’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、1,3−ビス(イソシアネートメチル)シクロヘキサンが好ましい。 The polyisocyanate of (Component A) is not particularly limited, and polyisocyanates generally used in the art can be used. Specific examples include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Aliphatic polyisocyanates include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1 , 5-diisocyanate, 3-methylpentane-1,5-diisocyanate and the like. Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. Can be mentioned. Aromatic polyisocyanates include tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5 -A naphthylene diisocyanate, a xylylene diisocyanate, a 1, 3- phenylene diisocyanate, a 1, 4- phenylene diisocyanate etc. can be mentioned. Examples of the araliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate, and the like. Moreover, modified bodies, such as a dimer, a trimer of these organic polyisocyanate, and a buret-ized isocyanate, can be mentioned. These may be used alone or in combination of two or more. Of the polyisocyanates, alicyclic and / or aromatic isocyanates are preferred from the viewpoint of binding properties and resistance to electrolytic solution. Specifically, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane is preferred.
前記(B成分)は、分子末端または分子内に2個以上のヒドロキシル基、アミノ基またはメルカプト基を有する化合物で、具体的には公知のポリエーテル、ポリエステル、ポリエーテルエステル、ポリカーボネート、ポリチオエーテル、ポリアセタール、ポリオレフィン、ポリシロキサン、フッ素系、植物油系等を使用することができる。 より具体的には、エチレングリコール、プロピレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、3-メチル-1,5-ペンタンジオール、ヘキサンジオール、ネオペチルグリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,4−シクロヘキサンジメタノール、ビスフェノールA、ビスフェノールF、ビスフェノールS、水素添加ビスフェノールA、ジブロモビスフェノールA、1,4-シクロヘキサンジメタノール、ジヒドロキシエチルテレフタレート、ハイドロキノンジヒドロキシエチルエーテル、トリメチロールプロパン、グリセリン、ペンタエリスリトール等の多価アルコール、それらのオキシアルキレン誘導体又はそれらの多価アルコール及びオキシアルキレン誘導体と多価カルボン酸、多価カルボン酸無水物、若しくは多価カルボン酸エステルからのエステル化合物、ポリカーボネートポリオール、ポリカプロラクトンポリオール、ポリエステルポリオ−ル、ポリチオエーテルポリオ−ル、ポリアセタールポリオ−ル、ポリテトラメチレングリコ−ル、ポリブタジエンポリオ−ル、ヒマシ油ポリオ−ル、大豆油ポリオール、フッ素ポリオール、シリコンポリオール等のポリオ−ル化合物やその変性体が挙げられる。アルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどが挙げられる。これら2個以上の活性水素基を有する基を有する化合物は、単独で使用してもよく、2種以上を併用してもよい。 The component (B) is a compound having two or more hydroxyl groups, amino groups or mercapto groups at the molecular end or in the molecule, specifically, known polyethers, polyesters, polyether esters, polycarbonates, polythioethers, Polyacetal, polyolefin, polysiloxane, fluorine-based, vegetable oil-based and the like can be used. More specifically, ethylene glycol, propylene glycol, propanediol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopetyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene Glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A, 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxy Polyhydric alcohols such as ethyl ether, trimethylolpropane, glycerin, pentaerythritol, and their oxy Alkylene derivatives or their polyhydric alcohols and oxyalkylene derivatives and polycarboxylic acids, polyhydric carboxylic acid anhydrides, or ester compounds from polycarboxylic esters, polycarbonate polyols, polycaprolactone polyols, polyester polyols, polythioethers Polyol compounds such as polyols, polyacetal polyols, polytetramethylene glycols, polybutadiene polyols, castor oil polyols, soybean oil polyols, fluorine polyols, silicone polyols, and modified products thereof may be mentioned. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. These compounds having a group having two or more active hydrogen groups may be used alone or in combination of two or more.
前記化合物は、分子末端に2個以上のヒドロキシル基を有する化合物であることが好ましい。該化合物としてはエチレングリコール、プロピレングリコール、プロパンジオール、ブタンジオール、ペンタンジオール、3-メチル-1,5-ペンタンジオール、ヘキサンジオール、ネオペチルグリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,4―シクロヘキサンジメタノール、ビスフェノールA、ビスフェノールF、ビスフェノールS、水素添加ビスフェノールA、ジブロモビスフェノールA、1,4―シクロヘキサンジメタノール、ジヒドロキシエチルテレフタレート、ハイドロキノンジヒドロキシエチルエーテル、及びそれらのオキシアルキレン誘導体ポリカーボネートポリオール、ポリカプロラクトンポリオール、ポリエステルポリオ−ル、ポリチオエーテルポリオ−ル、ポリアセタールポリオ−ル、ポリテトラメチレングリコ−ル、ポリブタジエンポリオ−ルが挙げられ、前記アルキレン誘導体のアルキレンオキサイドはエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどが挙げられる。これらの内、前記(B成分)にはポリカーボネートポリオール、芳香環を有するポリエステルポリオール、及び/または芳香環を有するポリエーテルポリオールを含有することが好ましい。 The compound is preferably a compound having two or more hydroxyl groups at the molecular terminals. Examples of the compound include ethylene glycol, propylene glycol, propanediol, butanediol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopetyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, Dipropylene glycol, tripropylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A, 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether , And their oxyalkylene derivative polycarbonate polyol, polycaprolactone poly All, polyester polyol, polythioether polyol, polyacetal polyol, polytetramethylene glycol, polybutadiene polyol, and the alkylene oxides of the above-mentioned alkylene derivatives include ethylene oxide, propylene oxide, butylene oxide and the like. Can be mentioned. Among these, the (component B) preferably contains a polycarbonate polyol, a polyester polyol having an aromatic ring, and / or a polyether polyol having an aromatic ring.
前記ポリカーボネートポリオールとしては、特に限定されること無く当該技術分野で一般的に使用されるポリカーボネートポリオールを使用することができる。具体的には、1,6−ヘキサンジオールのカーボネートポリオール、1,4−ブタンジオール及び1,6−ヘキサンジオールのカーボネートポリオール、1,5−ペンタンジオール及び1,6−ヘキサンジオールのカーボネート、3−メチル−1,5−ペンタンジオール及び1,6−ヘキサンジオールのカーボネートポリオール、1,9−ノナンジオール及び2−メチル−1,8−オクタンジオールのカーボネート、1,4−シクロヘキサンジメタノール及び1,6−ヘキサンジオールのカーボネート、1,4−シクロヘキサンジメタノールのカーボネートが挙げられ、これらは旭化成ケミカルズ(株)製のPCDL T−6001、T−6002、T−5651、T−5652、T−5650J、T−4671、T−4672、やクラレ(株)製のクラレポリオールC−590、C−1050、C−1050R,C−1090,C−2050、C−2050R,C−2070、C−2070R、C−2090、C−2090R、C−3090、C−3090R、C−4090、C−4090R、C−5090、C−5090R、C−1065N、C−2065N、C−1015N、C−2015Nや宇部興産(株)製のETERNACOLL UH−50、UH−100、UH−200、UH−300、UM−90(3/1)、UM−90(1/1)、UM−90(1/3)、UC−100などが挙げられる。 The polycarbonate polyol is not particularly limited, and a polycarbonate polyol generally used in the technical field can be used. Specifically, carbonate polyol of 1,6-hexanediol, carbonate polyol of 1,4-butanediol and 1,6-hexanediol, carbonate of 1,5-pentanediol and 1,6-hexanediol, 3- Carbonate polyols of methyl-1,5-pentanediol and 1,6-hexanediol, carbonates of 1,9-nonanediol and 2-methyl-1,8-octanediol, 1,4-cyclohexanedimethanol and 1,6 -Hexanediol carbonate, 1,4-cyclohexanedimethanol carbonate, and these are PCDL T-6001, T-6002, T-5651, T-5651, T-5650J, T manufactured by Asahi Kasei Chemicals Corporation. -4671, T-4672, Kuraray ( ) Kuraray polyol C-590, C-1050, C-1050R, C-1090, C-2050, C-2050R, C-2070, C-2070R, C-2090, C-2090R, C-3090, C -3090R, C-4090, C-4090R, C-5090, C-5090R, C-1065N, C-2065N, C-1015N, C-2015N and Ube Industries ETERNACOLL UH-50, UH-100 , UH-200, UH-300, UM-90 (3/1), UM-90 (1/1), UM-90 (1/3), UC-100, and the like.
前記、芳香環を有するポリエステルポリオールは一般的に二塩基酸と二価アルコールを縮合反応することにより得ることが出来る。前記二塩基酸としては特に限定されないが具体的には、フタル酸、イソフタル酸、テレフタル酸、1,4−ナフタレンジカルボン酸、2,6−ナフタレンジカルボン酸のような芳香族二塩基酸が挙げられる。前記二価アルコールとしては特に限定されないが具体的には、エチレングルコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、1,4−ブタンジオール、1,5−ペンタンジオール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、などのような脂肪族グリコール及びシクロヘキサンジオール等の脂環式グリコールやビスフェノールAのアルキレンオキサイド付加物のような芳香族グリコール等が挙げられる。 The polyester polyol having an aromatic ring can be generally obtained by condensation reaction of a dibasic acid and a dihydric alcohol. Specific examples of the dibasic acid include, but are not limited to, aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. . Specific examples of the dihydric alcohol include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3 -Aliphatic glycols such as methyl-1,5-pentanediol, alicyclic glycols such as cyclohexanediol, and aromatic glycols such as alkylene oxide adducts of bisphenol A.
前記芳香環を有するポリエーテルポリオールとしては、具体的にはビスフェノールAのアルキレンオキサイド付加物(エチレンオキサイド付加物、プロピレンオキサイド付加物)などが挙げられる。 Specific examples of the polyether polyol having an aromatic ring include alkylene oxide adducts of bisphenol A (ethylene oxide adducts, propylene oxide adducts) and the like.
また前記(B成分)はポリウレタン内でウレタン結合を局在化させるために、エチレングリコール、1,4―ブタンジオール、1,4―シクロヘキサンジメタノールなどの単鎖の低分子量ジオールを添加してもよい。 In addition, the (component B) may be added with a single-chain low molecular weight diol such as ethylene glycol, 1,4-butanediol, or 1,4-cyclohexanedimethanol in order to localize the urethane bond in the polyurethane. Good.
上記ポリカーボネートポリオール、芳香環を有するポリエステルポリオール及び/又は芳香環を有するポリエーテルポリオールは、数平均分子量300以上3,000以下であることが好ましい。数平均分子量が300未満であると結着性が低下し、数平均分子量3000を超える場合は耐電解液性が低下する傾向が生じる。 The polycarbonate polyol, the polyester polyol having an aromatic ring, and / or the polyether polyol having an aromatic ring preferably have a number average molecular weight of 300 to 3,000. When the number average molecular weight is less than 300, the binding property decreases, and when the number average molecular weight exceeds 3000, the electrolytic solution resistance tends to decrease.
また、前記(B成分)として、分子内に分岐構造を導入するために、多価アルコール及び/又は多価アルコールのオキシアルキレン誘導体を使用することができる。該化合物として具体的にはトリメチロールプロパン、グリセリン、ペンタエリスリトール等の多価アルコール、それらのオキシアルキレン誘導体又はそれらの多価アルコール及びオキシアルキレン誘導体と多価カルボン酸、多価カルボン酸無水物、若しくは多価カルボン酸エステルからのエステル化合物を挙げることができる。前述のようにポリウレタンに分岐構造を導入しウレタン結合の局在化により該ウレタン水分散体を含有する結着剤を使用した電極の耐電解液性が向上するという効果が得られるので好ましい。また、前記化合物の数平均分子量は特に制限されないが、50以上5000以下である事が好ましい。前記(B成分)のポリウレタン水分散体に含有されるポリウレタン中の含有量は特に制限されないが、結着性及び耐電解液性の両立の点からポリウレタン中30〜75重量%が好ましい。 Moreover, in order to introduce | transduce a branched structure into a molecule | numerator as said (B component), the oxyalkylene derivative of a polyhydric alcohol and / or a polyhydric alcohol can be used. Specific examples of the compound include polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol, oxyalkylene derivatives thereof, polyhydric alcohols and oxyalkylene derivatives and polycarboxylic acids, polyhydric carboxylic acid anhydrides, or Mention may be made of ester compounds from polyvalent carboxylic acid esters. As described above, a branched structure is introduced into the polyurethane, and localization of the urethane bond is preferable because an effect of improving the electrolytic solution resistance of the electrode using the binder containing the urethane water dispersion can be obtained. The number average molecular weight of the compound is not particularly limited, but is preferably 50 or more and 5000 or less. The content in the polyurethane contained in the polyurethane water dispersion of the (B component) is not particularly limited, but is preferably 30 to 75% by weight in the polyurethane from the viewpoint of compatibility between binding properties and electrolytic solution resistance.
本発明の(C成分)は1以上の親水性基と1以上の活性水素基を有する化合物である。
親水性基としては、アニオン性親水基、カチオン性親水基、ノニオン性親水基が挙げられ、具体的にはアニオン性親水基としては、カルボキシル基及びその塩、スルホン酸基及びその塩が、カチオン性親水基としては、第三級アンモニウム塩、第四級アンモニウム塩が、ノニオン性親水基としては、エチレンオキシドの繰り返し単位からなる基、エチレンオキシドの繰り返し単位とその他のアルキレンオキシドの繰り返し単位からなる基等が挙げられる。
(C component) of the present invention is a compound having one or more hydrophilic groups and one or more active hydrogen groups.
Examples of the hydrophilic group include an anionic hydrophilic group, a cationic hydrophilic group, and a nonionic hydrophilic group. Specifically, as the anionic hydrophilic group, a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof are cationic. Examples of the hydrophilic hydrophilic group include tertiary ammonium salts and quaternary ammonium salts, and the nonionic hydrophilic group includes a group consisting of ethylene oxide repeating units, a group consisting of ethylene oxide repeating units and other alkylene oxide repeating units, etc. Is mentioned.
1個以上の活性水素基とカルボキシル基を含有する化合物としては、例えば、2,2−ジメチロールプロピオン酸、2,2−ジメチロール酪酸、2,2−ジメチロール吉草酸、ジオキシマレイン酸、2,6−ジオキシ安息香酸、3,4−ジアミノ安息香酸等のカルボン酸含有化合物及びこれらの誘導体並びにそれらの塩に加え、これらを使用して得られるポリエステルポリオールが挙げられる。更に、アラニン、アミノ酪酸、アミノカプロン酸、グリシン、グルタミン酸、アスパラギン酸、ヒスチジン等のアミノ酸類、コハク酸、アジピン酸、無水マレイン酸、フタル酸、無水トリメリット酸等のカルボン酸類も挙げられる。 Examples of the compound containing one or more active hydrogen groups and a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, dioxymaleic acid, 2, In addition to carboxylic acid-containing compounds such as 6-dioxybenzoic acid and 3,4-diaminobenzoic acid, derivatives thereof, and salts thereof, polyester polyols obtained using these are included. Further examples include amino acids such as alanine, aminobutyric acid, aminocaproic acid, glycine, glutamic acid, aspartic acid, and histidine, and carboxylic acids such as succinic acid, adipic acid, maleic anhydride, phthalic acid, and trimellitic anhydride.
1個以上の活性水素基とスルホン酸基及びその塩を有する化合物としては、例えば、2−オキシエタンスルホン酸、フェノールスルホン酸、スルホ安息香酸、スルホコハク酸、5−スルホイソフタル酸、スルファニル酸、1,3−フェニレンジアミン−4,6−ジスルホン酸、2,4−ジアミノトルエン−5−スルホン酸等のスルホン酸含有化合物及びこれらの誘導体、並びにこれらを共重合して得られるポリエステルポリオール、ポリアミドポリオール、ポリアミドポリエステルポリオール等が挙げられる。これらのカルボキシル基又はスルホン酸基は、中和して塩にすることにより、最終的に得られるポリウレタンを水分散性にすることができる。この場合の中和剤としては、例えば、水酸化ナトリウム、水酸化カリウム等の不揮発性塩基、トリメチルアミン、トリエチルアミン、ジメチルエタノールアミン、メチルジエタノールアミン、トリエタノールアミン等の三級アミン類、アンモニア等の揮発性塩基等が挙げられる。中和は、ウレタン化反応前、反応中、又は反応後の何れにおいても行うことができる。 Examples of the compound having one or more active hydrogen groups and sulfonic acid groups and salts thereof include, for example, 2-oxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, sulfanilic acid, 1 , 3-phenylenediamine-4,6-disulfonic acid, sulfonic acid-containing compounds such as 2,4-diaminotoluene-5-sulfonic acid and their derivatives, and polyester polyols, polyamide polyols obtained by copolymerizing these, Examples thereof include polyamide polyester polyol. By neutralizing these carboxyl groups or sulfonic acid groups into salts, the finally obtained polyurethane can be made water-dispersible. Examples of the neutralizing agent in this case include non-volatile bases such as sodium hydroxide and potassium hydroxide, tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine and triethanolamine, and volatile properties such as ammonia. Examples include bases. Neutralization can be performed before, during or after the urethanization reaction.
1以上の活性水素基と第3級アンモニウム塩を含有する化合物は、メチルアミノエタノール、メチルジエタノールアミン等のアルカノールアミンが挙げられる。これらをギ酸、酢酸などの有機カルボン酸、塩酸、硫酸などの無機酸で中和して塩にすることによりポリウレタンを水分散性にすることができる。中和は、ウレタン化反応前、反応中、又は反応後の何れにおいても行うことができる。これらの内、乳化の容易性の観点からメチルジエタノールアミンを有機カルボン酸で中和したものが好ましい。 Examples of the compound containing one or more active hydrogen groups and a tertiary ammonium salt include alkanolamines such as methylaminoethanol and methyldiethanolamine. By neutralizing these with organic carboxylic acids such as formic acid and acetic acid and inorganic acids such as hydrochloric acid and sulfuric acid to form salts, the polyurethane can be made water-dispersible. Neutralization can be performed before, during or after the urethanization reaction. Of these, those obtained by neutralizing methyldiethanolamine with an organic carboxylic acid are preferred from the viewpoint of ease of emulsification.
1以上の活性水素基と第4級アンモニウム塩を有する化合物は、前述のメチルアミノエタノール、メチルジエタノールアミン等のアルカノールアミンを塩化メチル、臭化メチルなどのハロゲン化アルキル、ジメチル硫酸などのジアルキル硫酸により4級化した化合物である。これらの内、乳化の容易性の観点から、メチルジエタノールアミンをジメチル硫酸で4級化した化合物である。 A compound having one or more active hydrogen groups and a quaternary ammonium salt is obtained by reacting alkanolamines such as methylaminoethanol and methyldiethanolamine with dialkyl sulfates such as methyl chloride and methyl bromide, and dimethyl sulfate. It is a graded compound. Among these compounds, methyldiethanolamine is quaternized with dimethylsulfate from the viewpoint of ease of emulsification.
1以上の活性水素基とノニオン性親水基を有する化合物は、特に制限されないが、エチレンオキシドの繰り返し単位を少なくとも30重量%以上含有し、数平均分子量300〜20,000の化合物が好ましく、例えば、ポリオキシエチレングリコール又はポリオキシエチレン−ポリオキシプロピレン共重合体グリコール、ポリオキシエチレン−ポリオキシブチレン共重合体グリコール、ポリオキシエチレン−ポリオキシアルキレン共重合体グリコール又はそのモノアルキルエーテル等のノニオン性基含有化合物又はこれらを共重合して得られるポリエステルポリエーテルポリオールが挙げられる。 The compound having one or more active hydrogen groups and a nonionic hydrophilic group is not particularly limited, but is preferably a compound containing at least 30% by weight of ethylene oxide repeating units and having a number average molecular weight of 300 to 20,000. Nonionic group content such as oxyethylene glycol or polyoxyethylene-polyoxypropylene copolymer glycol, polyoxyethylene-polyoxybutylene copolymer glycol, polyoxyethylene-polyoxyalkylene copolymer glycol or monoalkyl ether thereof The polyester polyether polyol obtained by copolymerizing a compound or these is mentioned.
(C成分)は上記化合物をそれぞれ単独で用いてもよく、組み合わせて使用してもよい。(C成分)の含有量は、アニオン性親水基含有化合物の場合は、そのアニオン性親水基含有量を表す酸価が5〜50mgKOH/gであることが好ましく、5〜45mgKOH/gであることがより好ましい。酸価が5mgKOH/g未満の場合には、水への分散性が困難になるという問題がある。また、酸価が50mgKOH/gを超える場合には、耐電解液性が低下するという問題がある。酸価は、JISK0070−1992に準拠して、ポリウレタン水分散体の固形分1g中に含まれる遊離カルボキシル基を中和するのに要するKOHのmg数より求めた。ノニオン性基含有化合物を使用する場合は、1〜30重量部とし、特に5〜20重量部使用したものであることが好ましい。この中で、(C成分)としては、集電体との密着性の面から分子中に1個以上の活性水素基とカルボキシル基を含有する化合物が好ましい。 As the component (C), the above compounds may be used alone or in combination. In the case of an anionic hydrophilic group-containing compound, the content of (C component) is preferably 5 to 50 mgKOH / g, and more preferably 5 to 45 mgKOH / g, indicating the anionic hydrophilic group content. Is more preferable. When the acid value is less than 5 mgKOH / g, there is a problem that dispersibility in water becomes difficult. Moreover, when an acid value exceeds 50 mgKOH / g, there exists a problem that electrolyte solution resistance falls. The acid value was determined from the mg number of KOH required to neutralize free carboxyl groups contained in 1 g of the solid content of the polyurethane water dispersion in accordance with JIS K0070-1992. When using a nonionic group containing compound, it is 1-30 weight part, It is preferable to use especially 5-20 weight part. Among these, (C component) is preferably a compound containing one or more active hydrogen groups and a carboxyl group in the molecule from the viewpoint of adhesion to the current collector.
前記(D成分)のアルコキシシラン誘導体は、シランカップリング剤であることが好ましい。本発明におけるシランカップリング剤としては、本発明の属する技術分野で一般的に使用されているシランカップリング剤を使用することが出来、特に制限されないが具体的には、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルメチルジメトキシシラン、3- アミノプロピルメチルジエトキシシラン、N-2(アミノエチル)3-アミノプロピルメチルジメトキシシラン、N-2(アミノエチル) 3- アミノプロピルトリメトキシシラン、N-2(アミノエチル)3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン、N-フェニル-3-アミノプロピルトリメトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3- イソシアネートプロピルトリエトキシシラン等を例示することができる。これらのうち、ポリウレタン水分散体の安定性及び耐電解液性の観点から、N-2 ( アミノエチル) 3-アミノプロピルトリメトキシシランが好ましい。これらのシランカップリング剤は2種以上混合して使用することができる。 The alkoxysilane derivative (component D) is preferably a silane coupling agent. As the silane coupling agent in the present invention, a silane coupling agent generally used in the technical field to which the present invention belongs can be used, and although not particularly limited, specifically, 3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3 -Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyl Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercap Trimethoxysilane can be exemplified 3-isocyanate propyl triethoxysilane. Among these, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane is preferable from the viewpoint of stability of the polyurethane water dispersion and resistance to electrolytic solution. These silane coupling agents can be used in combination of two or more.
また、前記(D成分)には、当該技術分野で一般的に使用される鎖伸長剤をアルコキシシラン誘導体と併用して用いることができる。特に制限はされないが具体的にはジアミンやポリアミンが使用できる。ジアミンとしては、エチレンジアミン、トリメチレンジアミン、ピペラジン、イソホロンジアミンなどを例示することができ、ポリアミンとしては、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン等を例示することができる。 In addition, as the component (D), a chain extender generally used in the technical field can be used in combination with an alkoxysilane derivative. Although not particularly limited, specifically, diamine or polyamine can be used. Examples of the diamine include ethylene diamine, trimethylene diamine, piperazine, and isophorone diamine, and examples of the polyamine include diethylene triamine, dipropylene triamine, and triethylene tetramine.
本発明のポリウレタン水分散体の製造方法は、特に限定されるものではないが、一般的には、(B成分)2以上の活性水素基を有する化合物(C成分)1以上の親水性基並びに1以上の活性水素基含有化合物及び(D成分)鎖伸長剤に含まれる活性水素基の合計より、化学量論的に過剰の(A成分)ポリイソシアネート(イソシアネート基と反応性官能基との当量比1:0.85〜1.1)を溶剤なしに、又は活性水素基を有しない有機溶媒中で反応させてイソシアネート末端のウレタンプレポリマーを合成した後、必要に応じて(C成分)のアニオン性親水基、カチオン性親水基の中和、又は4級化を行ってから、水中に分散乳化を行う。その後、残存するイソアネート基より少ない当量の(D成分)鎖伸長剤(イソシアネート基と鎖伸長剤中のアミノ基との当量比1:0.5〜0.9)を加えて乳化ミセル中のイソシアシネート基と(D成分)鎖伸長剤を界面重合反応させてウレア結合を生成させる。これにより乳化ミセル内の高分子量化または架橋密度向上が図られ、優れた耐電解液性を示すポリウレタン水分散体が得られる。その後、必要に応じて使用した溶剤を除去することにより、ポリウレタン水分散体を得ることができる。 The method for producing the polyurethane water dispersion of the present invention is not particularly limited. In general, (B component) a compound having two or more active hydrogen groups (C component) one or more hydrophilic groups and A stoichiometric excess of (component A) polyisocyanate (equivalent of isocyanate group and reactive functional group) from the sum of active hydrogen groups contained in one or more active hydrogen group-containing compounds and (component D) chain extender After the synthesis of an isocyanate-terminated urethane prepolymer by reacting the ratio 1: 0.85 to 1.1) without a solvent or in an organic solvent having no active hydrogen group, An anionic hydrophilic group and a cationic hydrophilic group are neutralized or quaternized, and then dispersed and emulsified in water. Thereafter, an equivalent (D component) chain extender (equivalent ratio of isocyanate group to amino group in the chain extender 1: 0.5 to 0.9) less than the remaining isocyanate group was added to add isocyanate in the emulsion micelle. A urea bond is formed by interfacial polymerization reaction between a cinto group and a (D component) chain extender. Thereby, the high molecular weight in the emulsified micelle or the crosslinking density is improved, and a polyurethane water dispersion exhibiting excellent electrolytic solution resistance is obtained. Then, the polyurethane water dispersion can be obtained by removing the solvent used as needed.
前記活性水素基を有しない有機溶媒としては特に制限されないが具体的には、ジオキサン、メチルエチルケトン、ジメチルホルムアミド、テトラヒドロフラン、N−メチル−2−ピロリドン、トルエン、プロピレングリコールモノメチルエーテルアセテートなどが挙げられる。反応で使用したこれら親水性有機溶剤は、最終的に除去するのが好ましい。 The organic solvent having no active hydrogen group is not particularly limited, and specific examples include dioxane, methyl ethyl ketone, dimethylformamide, tetrahydrofuran, N-methyl-2-pyrrolidone, toluene, propylene glycol monomethyl ether acetate and the like. These hydrophilic organic solvents used in the reaction are preferably finally removed.
本発明におけるポリウレタン水分散体のポリウレタンの数平均分子量は、分岐構造や内部架橋構造を導入して可能な限り大きくすることが好ましく、50,000以上であることが好ましい。分子量を大きくして溶剤に不溶とした方が、耐電解液性に優れた塗膜が得られるためである。 The number average molecular weight of the polyurethane in the polyurethane water dispersion in the present invention is preferably as large as possible by introducing a branched structure or an internal cross-linked structure, and is preferably 50,000 or more. This is because when the molecular weight is increased to make it insoluble in a solvent, a coating film excellent in electrolytic solution resistance can be obtained.
本発明において使用されるポリウレタン樹脂水分散体のポリウレタン樹脂は、架橋密度が、このポリウレタン樹脂の1000原子量あたり、0.01〜0.50であることが好ましい。ここでいう架橋密度とは、次の数1に示す式に基づき計算することにより求められる数値である。すなわち、分子量MWA1及び官能基数F A1のポリイソシアネート(A)をW A1gと、分子量MWA2及び官能基数FA2 のポリイソシアネート(A)をWA2gと、分子量MWAJ及び官能基数FAJのポリイソシアネート(A)をWAjg(jは1以上の整数)と、分子量MWB1、官能基数FB1の活性水素基含有化合物(B)をW B1gと、分子量MWB2及び官能基数FB2 の活性水素基含有化合物(B)をWB2gと、分子量MWBk及び官能基数FBkの活性水素基含有化合物(B)をWBkg(kは1以上の整数)と、分子量MWC1、官能基数FC1の1以上の活性水素基と親水性基を有する化合物(C)をWC1gと、分子量MWCm、官能基数FCmの1以上の活性水素基と親水性基を有する化合物(C)をWCmg(mは1以上の整数)と、分子量MWD1、官能基数FD1の鎖伸長剤(D)をWD1gと、分子量MWDn、官能基数FDnの鎖長剤(D)をWDng(nは1以上の整数)とを反応せしめて得られたポリウレタン水分散体に含まれる樹脂固形分の1000分子量あたりの架橋密度は、下記の式により計算で求めることができる。 The polyurethane resin of the polyurethane resin aqueous dispersion used in the present invention preferably has a crosslinking density of 0.01 to 0.50 per 1000 atomic weight of the polyurethane resin. The crosslinking density here is a numerical value obtained by calculation based on the following equation (1). That is, the polyisocyanate (A) having a molecular weight MW A1 and the functional group number F A1 is WA 1 g, the polyisocyanate (A) having a molecular weight MW A2 and the functional group number F A2 is WA 2 g, the molecular weight MW AJ and the functional group number F AJ polyisocyanate (a) and W Aj g (j is an integer of 1 or more) of a molecular weight MW B1, the active hydrogen group-containing compound functional groups F B1 and (B) and W B1 g, molecular weight MW B2 and functionality F B2 active hydrogen group-containing compound of the (B) and W B2 g, the active hydrogen group-containing compound having a molecular weight MW Bk and functional groups F Bk (B) and W Bk g (k is an integer of 1 or more), the molecular weight MW C1 A compound (C) having one or more active hydrogen groups having a functional group number F C1 and a hydrophilic group W C1 g, a compound having one or more active hydrogen groups and a hydrophilic group having a molecular weight MW Cm and a functional group number F Cm the (C) and W Cm g (m is an integer of 1 or more), the molecular weight MW D1, a functionality F D1 of chain extender and (D) W D1 g, min The amount MW Dn, chain length agent functionality F Dn (D) a W Dn g (n is an integer of 1 or more) and per 1000 molecular weight of the resin solids contained in the aqueous polyurethane dispersion obtained by reacting the The crosslinking density can be calculated by the following formula.
架橋密度が0.01未満では耐電解液性や耐熱性に劣る傾向が生じ、0.50を超えるとウレタン樹脂の柔軟性が低下し、結着性も低下する傾向が生じる。 When the crosslink density is less than 0.01, the electrolytic solution resistance and the heat resistance tend to be inferior, and when it exceeds 0.50, the flexibility of the urethane resin is lowered and the binding property is also lowered.
本発明のポリウレタン水分散体は、該ウレタン樹脂中のウレタン結合量が150〜2000g/eqであることが好ましく、200〜1000g/eqであることがより好ましい。ウレタン結合量が150g/eq未満ではウレタン結合量が多すぎるためポリウレタン樹脂の柔軟性が低下し、結着性に劣り、2000g/eqを超えると耐電解液性や耐熱性に劣ってしまう。 In the polyurethane water dispersion of the present invention, the urethane bond amount in the urethane resin is preferably 150 to 2000 g / eq, and more preferably 200 to 1000 g / eq. If the urethane bond amount is less than 150 g / eq, the polyurethane bond amount is too large, so the flexibility of the polyurethane resin is lowered and the binding property is inferior. If it exceeds 2000 g / eq, the electrolytic solution resistance and heat resistance are inferior.
本発明のポリウレタン水分散体は、該ウレタン樹脂中のウレア結合量が300〜20000g/eqであることが好ましく、400〜10000g/eqであることがより好ましい。ウレア結合量が300g/eq未満ではウレア結合量が多すぎるためポリウレタン樹脂の柔軟性が低下し、結着性に劣り、20000g/eqを超えると合成時の作業性の悪化を招く場合があること、および耐電解液性や耐熱性に劣ってしまうため好ましくない。 In the polyurethane water dispersion of the present invention, the urea bond amount in the urethane resin is preferably 300 to 20000 g / eq, and more preferably 400 to 10000 g / eq. When the amount of urea bonds is less than 300 g / eq, the amount of urea bonds is too large, so the flexibility of the polyurethane resin is lowered and the binding property is inferior, and when it exceeds 20000 g / eq, workability during synthesis may be deteriorated. , And the electrolyte solution resistance and heat resistance are inferior.
本発明において使用されるポリウレタン水分散体の平均粒子径は、添加量、塗工性及び結着性の面から0.005〜0.5μmの範囲であることが好ましい。 The average particle size of the polyurethane water dispersion used in the present invention is preferably in the range of 0.005 to 0.5 μm from the viewpoint of the amount added, coating properties, and binding properties.
本発明のリチウム二次電池は、正極と負極、この正極と負極との間に設けられ両者を隔離するセパレータと、リチウムイオンを伝導するための溶媒に支持電解質としてリチウム塩を溶解した非水電解液やポリマーまたは高分子ゲル電解質を含む電解質層とで構成される。 The lithium secondary battery of the present invention includes a positive electrode and a negative electrode, a separator provided between the positive electrode and the negative electrode and isolating both, and a non-aqueous electrolysis in which a lithium salt is dissolved as a supporting electrolyte in a solvent for conducting lithium ions It is comprised with the electrolyte layer containing a liquid, a polymer, or a polymer gel electrolyte.
本発明のリチウム二次電池に用いられる正極及び負極は、電極活物質、導電剤、電極活物質の集電体、及び電極活物質並びに導電剤を集電体に結着させる結着剤等から構成される。 The positive electrode and the negative electrode used in the lithium secondary battery of the present invention include an electrode active material, a conductive agent, a current collector of the electrode active material, and a binder that binds the electrode active material and the conductive agent to the current collector. Composed.
本発明のリチウム二次電池は、前記ポリウレタン水分散体を含有する結着剤を使用して製造された電極から構成されるものである。 The lithium secondary battery of this invention is comprised from the electrode manufactured using the binder containing the said polyurethane water dispersion.
本発明のリチウム二次電池において、前記ポリウレタン水分散体を使用しない方の電極用結着剤としては、ポリフッ化ビニリデン(PVDF)、PVDFとヘキサフルオロプロピレン(HFP)やパーフルオロメチルビニルエーテル(PFMV)及びテトラフルオロエチレン(TFE)との共重合体などのPVDF共重合体樹脂、ポリテトラフルオロエチレン(PTFE)、フッ素ゴムなどのフッ素系樹脂や、スチレン−ブタジエンゴム(SBR)、エチレン−プロピレンゴム(EPDM)スチレン−アクリロニトリル共重合体などのポリマーが使用可能であるが、これに限定されるものではない。 In the lithium secondary battery of the present invention, the binder for the electrode not using the polyurethane water dispersion may be polyvinylidene fluoride (PVDF), PVDF and hexafluoropropylene (HFP), or perfluoromethyl vinyl ether (PFMV). And PVDF copolymer resins such as copolymers with tetrafluoroethylene (TFE), fluorine resins such as polytetrafluoroethylene (PTFE) and fluorine rubber, styrene-butadiene rubber (SBR), ethylene-propylene rubber ( EPDM) polymers such as styrene-acrylonitrile copolymers can be used, but are not limited thereto.
本発明のリチウム二次電池の正極に使用する正極活物質としては、リチウムイオンの挿入、脱離が可能であるものであれば、特に制限されることはない。例としては、CuO、Cu2O、MnO2、MoO3、V2O5、CrO3、MoO3、Fe2O3、Ni2O3、CoO3等の金属酸化物、LixCoO2、LixNiO2、LixMn2O4、LiFePO4等のリチウムと遷移金属との複合酸化物や、TiS2、MoS2、NASe3等の金属カルコゲン化物、ポリアセン、ポリパラフェニレン、ポリピロール、ポリアニリン等の導電性高分子化合物等が挙げられる。 The positive electrode active material used for the positive electrode of the lithium secondary battery of the present invention is not particularly limited as long as it can insert and desorb lithium ions. Examples include metal oxides such as CuO, Cu 2 O, MnO 2 , MoO 3 , V 2 O 5 , CrO 3 , MoO 3 , Fe 2 O 3 , Ni 2 O 3 , CoO 3 , LixCoO 2 , LixNiO 2. , LixMn 2 O 4 , LiFePO 4 and other complex oxides of lithium and transition metals, metal chalcogenides such as TiS 2 , MoS 2 and NASe 3 , conductive polymers such as polyacene, polyparaphenylene, polypyrrole and polyaniline Compounds and the like.
上記の中でも、一般に高電圧系と呼ばれる、コバルト、ニッケル、マンガン等の遷移金属から選ばれる1種以上とリチウムとの複合酸化物がリチウムイオンの放出性や、高電圧が得られやすい点で好ましい。コバルト、ニッケル、マンガンとリチウムとの複合酸化物の具体例としては、LiCoO2、LiMnO2、LiMn2O4、LiNiO2、LiNixCo(1−x)O2、LiMnaNibCoc(a+b+c=1)などが挙げられる。 Among these, a composite oxide of lithium and one or more selected from transition metals such as cobalt, nickel, and manganese, which is generally called a high voltage system, is preferable in terms of lithium ion release properties and high voltage. . Specific examples of the composite oxide of cobalt, nickel, manganese and lithium include LiCoO 2 , LiMnO 2 , LiMn 2 O 4 , LiNiO 2 , LiNixCo (1-x) O 2 , LiMnaNibCoc (a + b + c = 1) and the like. It is done.
また、これらのリチウム複合酸化物に、少量のフッ素、ホウ素、アルミニウム、クロム、ジルコニウム、モリブデン、鉄などの元素をドーブしたものや、リチウム複合酸化物の粒子表面を、炭素、MgO、Al2O3、SiO2等で表面処理したものも使用できる。上記正極活物質は2種類以上を併用することも可能である。 In addition, these lithium composite oxides doped with a small amount of elements such as fluorine, boron, aluminum, chromium, zirconium, molybdenum, iron, etc., or the surface of lithium composite oxide particles are made of carbon, MgO, Al 2 O 3 , those treated with SiO 2 or the like can also be used. Two or more kinds of the positive electrode active materials can be used in combination.
本発明の負極に使用する負極活物質としては、金属リチウム又はリチウムイオンを挿入/脱離することができるものであれば公知の活物質を特に限定なく用いることができる。たとえば、天然黒鉛、人造黒鉛、難黒鉛化炭素、易黒鉛化炭素などの炭素材料を用いることができる。また、金属リチウムや合金、スズ化合物などの金属材料、リチウム遷移金属窒化物、結晶性金属酸化物、非晶質金属酸化物、ケイ素化合物、導電性ポリマー等を用いることもでき、具体例としては、Li4Ti5O12、NiSi5C6等が挙げられる。 As the negative electrode active material used for the negative electrode of the present invention, any known active material can be used without particular limitation as long as it can insert / extract metallic lithium or lithium ions. For example, carbon materials such as natural graphite, artificial graphite, non-graphitizable carbon, and graphitizable carbon can be used. In addition, metallic materials such as metallic lithium, alloys, tin compounds, lithium transition metal nitrides, crystalline metal oxides, amorphous metal oxides, silicon compounds, conductive polymers, etc. can be used. , Li 4 Ti 5 O 12 , NiSi 5 C 6 and the like.
本発明のリチウム二次電池の正極及び負極には導電剤が用いられる。該導電剤としては、電池性能に悪影響を及ぼさない電子伝導性材料であれば使用することができる。通常、アセチレンブラックやケッチンブラック等のカーボンブラックが使用されるが、天然黒鉛(鱗状黒鉛、鱗片状黒鉛、土状黒鉛など)、人造黒鉛、カーボンウイスカー、炭素繊維や金属(銅、ニッケル、アルミニウム、銀、金等)粉末、金属繊維、導電性セラミックス材料等の導電性材料でもよい。これらは2種類以上の混合物として含ませることができる。その添加量は活物質量に対して0.1〜30重量%が好ましく、特に0.2〜20重量%が好ましい。 A conductive agent is used for the positive electrode and the negative electrode of the lithium secondary battery of the present invention. Any electrically conductive material that does not adversely affect battery performance can be used as the conductive agent. Usually, carbon black such as acetylene black and kettin black is used. A conductive material such as silver, gold, etc.) powder, metal fiber, or conductive ceramic material may be used. These can be included as a mixture of two or more. The addition amount is preferably 0.1 to 30% by weight, particularly preferably 0.2 to 20% by weight, based on the amount of the active material.
本発明のリチウム二次電池の電極活物質の集電体としては、構成された電池において悪影響を及ぼさない電子伝導体であれば何でも使用可能である。例えば、正極用集電体としては、アルミニウム、チタン、ステンレス鋼、ニッケル、焼成炭素、導電性高分子、導電性ガラス等の他に、接着性、導電性、耐酸化性向上の目的で、アルミニウムや銅等の表面を、カーボン、ニッケル、チタンや銀等で処理した物を用いることができる。また、負極用集電体としては、銅、ステンレス鋼、ニッケル、アルミニウム、チタン、焼成炭素、導電性高分子、導電性ガラス、Al−CD合金等の他に、接着性、導電性、耐酸化性向上の目的で、銅等の表面をカーボン、ニッケル、チタンや銀等で処理したものを用いることができる。これらの集電体材料は表面を酸化処理することも可能である。また、その形状については、フォイル状の他、フィルム状、シート状、ネット状、パンチ又はエキスパンドされた物、ラス体、多孔質体、発泡体等の成形体も用いられる。厚みは特に限定はないが、1〜100μmのものが通常用いられる。 As the current collector for the electrode active material of the lithium secondary battery of the present invention, any electronic conductor can be used as long as it does not adversely affect the constructed battery. For example, as a positive electrode current collector, aluminum, titanium, stainless steel, nickel, calcined carbon, conductive polymer, conductive glass, etc., in addition to aluminum for the purpose of improving adhesiveness, conductivity, and oxidation resistance. A material obtained by treating the surface of copper or copper with carbon, nickel, titanium, silver or the like can be used. In addition to negative electrode current collectors, copper, stainless steel, nickel, aluminum, titanium, calcined carbon, conductive polymer, conductive glass, Al-CD alloy, etc., adhesion, conductivity, oxidation resistance For the purpose of improving the properties, it is possible to use a surface of copper or the like treated with carbon, nickel, titanium, silver or the like. The surface of these current collector materials can be oxidized. Moreover, about the shape, molded bodies, such as a film form, a sheet form, a net form, the punched or expanded thing, a lath body, a porous body, and a foam other than foil shape, are also used. The thickness is not particularly limited, but a thickness of 1 to 100 μm is usually used.
本発明のリチウム二次電池の電極は、電極活物質、導電剤、電極活物質の集電体、及び電極活物質並びに導電剤を集電体に結着させる結着剤等を混合してスラリーじょうの電極材料を調製し、集電体となるアルミ箔或いは銅箔等に塗布して分散媒を揮発させることにより製造することができる。 The electrode of the lithium secondary battery of the present invention is a slurry obtained by mixing an electrode active material, a conductive agent, a current collector of the electrode active material, and a binder that binds the electrode active material and the conductive agent to the current collector. It can be produced by preparing an electrode material and applying it to an aluminum foil or copper foil as a current collector and volatilizing the dispersion medium.
本発明の電極材料にはスラリー化の粘性調整剤として、水溶性高分子などの増粘剤を使用できる。具体的には、カルボキシメチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシメチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルメチルセルロースなどのセルロース類; ポリアクリル酸、ポリアクリル酸ソーダなどのポリカルボン酸系化合物; ポリビニルピロリドンなどのビニルピロリドン構造を有する化合物; ポリアクリルアマイド、ポリエチレンオキシド、ポリビニルアルコール、アルギン酸ソーダ、キサンタンガム、カラギーナン、グアーガム、カンテン、デンプンなどから選択された1 種又は2 種以上が使用可能であり、中でもカルボキシメチルセルロース塩が好ましい。 In the electrode material of the present invention, a thickener such as a water-soluble polymer can be used as a slurry viscosity adjusting agent. Specifically, celluloses such as carboxymethylcellulose, methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose; polycarboxylic acid compounds such as polyacrylic acid and sodium polyacrylate; vinylpyrrolidone structures such as polyvinylpyrrolidone 1 type or 2 or more types selected from polyacrylamide, polyethylene oxide, polyvinyl alcohol, sodium alginate, xanthan gum, carrageenan, guar gum, agar, starch and the like can be used, and among them, carboxymethyl cellulose salt is preferable.
上記電極材料の混合の方法・順序等は特に限定されず、例えば、活物質と導電剤は予め混合して用いることが可能であり、その場合の混合には、乳鉢、ミルミキサー、遊星型ボールミル又はシェイカー型ボールミルなどのボールミル、メカノフュージョン等を用いることができる。 The method and order of mixing the electrode materials are not particularly limited. For example, the active material and the conductive agent can be mixed and used in advance. For mixing in this case, a mortar, a mill mixer, a planetary ball mill is used. Alternatively, a ball mill such as a shaker type ball mill, a mechano-fusion, or the like can be used.
本発明のリチウム二次電池に使用するセパレータは、通常のリチウム二次電池に用いられるセパレータを特に限定なしに使用でき、その例としては、ポリエチレン、ポリプロピレン、ポリオレフィン、ポリテトラフルオロエチレン等よりなる多孔質樹脂、セラミック、不織布などが挙げられる。 As the separator used in the lithium secondary battery of the present invention, a separator used in a normal lithium secondary battery can be used without particular limitation, and examples thereof include porous materials made of polyethylene, polypropylene, polyolefin, polytetrafluoroethylene, and the like. Resin, ceramic, non-woven fabric and the like.
本発明のリチウム二次電池に使用する電解液は通常のリチウム二次電池に用いられる電解液であればよく、有機電解液およびイオン液体等の一般的なものを使用することができる。 The electrolytic solution used in the lithium secondary battery of the present invention may be an electrolytic solution used in a normal lithium secondary battery, and common ones such as an organic electrolytic solution and an ionic liquid can be used.
本発明のリチウム二次電池に使用する電解質塩としては、例えば、LiPF6、LiBF4、LiClO4、LiAsF6、LiCl、LiAr、LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3、LiI、LiAlCl4、NaClO4、NaAF4、NaI等を挙げることができ、特に、LiPF6、LiBF4、LiClO4、LiAsF6などの無機リチウム塩、LiN(SO2CxF2x+1)(SO2CyF2y+1)で表される有機リチウム塩を挙げることができる。ここで、xおよびyは0又は1〜4の整数を表し、また、x+yは2〜8である。有機リチウム塩としては、具体的には、LiN(SO2F)2、LiN(SO2CF3)(SO2C2F5)、LiN(SO2CF3)(SO2C3F7)、LiN(SO2CF3)(SO2C4F9)、LiN(SO2C2F5)2、LiN(SO2C2F5)(SO2C3F7)、LiN(SO2C2F5)(SO2C4F9)等が挙げられる。中でも、LiPF6、LiAF4、LiN(CF3SO2)2、LiN(SO2F)2、LiN(SO2C2F5)2などを電解質に使用すると、電気特性に優れるので好ましい。上記電解質塩は1種類用いても2種類以上用いても良い。このようなリチウム塩は、通常、0.1〜2.0モル/リットル、好ましくは0.3〜1.5モル/リットルの濃度で、電解液に含まれていることが望ましい。 Examples of the electrolyte salt used in the lithium secondary battery of the present invention include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCl, LiAr, LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiI, LiAlCl 4 , NaClO 4 , NaAF 4 , NaI, and the like. In particular, inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiN (SO 2 CxF2x + 1) An organic lithium salt represented by (SO 2 CyF2y + 1) can be given. Here, x and y represent 0 or an integer of 1 to 4, and x + y is 2 to 8. Specifically, as the organic lithium salt, LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) (SO 2 C 2 F 5 ), LiN (SO 2 CF 3 ) (SO 2 C 3 F 7 ) LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 C 2 F 5 ) (SO 2 C 3 F 7 ), LiN (SO 2 C 2 F 5 ) (SO 2 C 4 F 9 ) and the like. Among them, it is preferable to use LiPF 6 , LiAF 4 , LiN (CF 3 SO 2 ) 2 , LiN (SO 2 F) 2 , LiN (SO 2 C 2 F 5 ) 2, etc. because of excellent electrical characteristics. The above electrolyte salt may be used alone or in combination of two or more. Such a lithium salt is usually contained in the electrolytic solution at a concentration of 0.1 to 2.0 mol / liter, preferably 0.3 to 1.5 mol / liter.
本発明のリチウム二次電池の電解質塩を溶解させる有機溶媒としては、通常のリチウム二次電池の非水電解液に用いられる有機溶媒であれば特に限定されず、例えば、カーボネート化合物、ラクトン化合物、エーテル化合物、スルホラン化合物、ジオキソラン化合物、ケトン化合物、ニトリル化合物、ハロゲン化炭化水素化合物等を挙げることができる。詳しくは、ジメチルカーボネート、メチルエチルカーボネート、ジエチルカーボネート、エチレンカーボネート、プロピレンカーボネート、エチレングリコールジメチルカーボネート、プロピレングリコールジメチルカーボネート、エチレングリコールジエチルカーボネート、ビニレンカーボネート等のカーボネート類、γ−ブチルラクトン等のラクトン類、ジメトキシエタン、テトラヒドロフラン、2−メチルテトラヒドロフラン、テトラヒドロピラン、1,4−ジオキサンなどのエーテル類、スルホラン、3−メチルスルホラン等のスルホラン類、1,3−ジオキソラン等のジオキソラン類、4−メチル−2−ペンタノン等のケトン類、アセトニトリル、ピロピオニトリル、バレロニトリル、ベンソニトリル等のニトリル類、1,2−ジクロロエタン等のハロゲン化炭化水素類、その他のメチルフォルメート、ジメチルホルムアミド、ジエチルホルムアミド、ジメチルスルホキシド、イミダゾリウム塩、4級アンモニウム塩などのイオン性液体等を挙げることができる。さらに、これらの混合物であってもよい。 The organic solvent for dissolving the electrolyte salt of the lithium secondary battery of the present invention is not particularly limited as long as it is an organic solvent used for a non-aqueous electrolyte solution of a normal lithium secondary battery. For example, a carbonate compound, a lactone compound, Examples include ether compounds, sulfolane compounds, dioxolane compounds, ketone compounds, nitrile compounds, and halogenated hydrocarbon compounds. Specifically, carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylene glycol dimethyl carbonate, propylene glycol dimethyl carbonate, ethylene glycol diethyl carbonate, vinylene carbonate, lactones such as γ-butyl lactone, Ethers such as dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, sulfolanes such as sulfolane and 3-methylsulfolane, dioxolanes such as 1,3-dioxolane, 4-methyl-2- Ketones such as pentanone, nitriles such as acetonitrile, pyropionitrile, valeronitrile, benzonitrile, 1,2-di Halogenated hydrocarbons such as Roroetan, other methyl formate, dimethyl formamide, diethyl formamide, dimethyl sulfoxide, imidazolium salts, and ionic liquids such as such as quaternary ammonium salts. Furthermore, a mixture thereof may be used.
これらの有機溶媒のうち、特に、カーボネート類からなる群より選ばれた非水溶媒を一種類以上含有することが、電解質の溶解性、誘電率および粘度において優れているので好ましい。 Among these organic solvents, it is particularly preferable to contain one or more types of non-aqueous solvents selected from the group consisting of carbonates because they are excellent in electrolyte solubility, dielectric constant and viscosity.
本発明のリチウム二次電池において、ポリマー電解質または高分子ゲル電解質に用いる場合は、高分子化合物であるエーテル、エステル、シロキサン、アクリロニトリル、ビニリデンフロライド、ヘキサフルオロプロピレン、アクリレート、メタクリレート、スチレン、酢酸ビニル、塩化ビニル、オキセタンなどの重合体またはその共重合体構造を有する高分子またはその架橋体などが挙げられ、高分子は一種類でも二種類以上でもよい。高分子構造は特に限定されるものではないが、ポリエチレンオキサイドなどのエーテル構造を有する高分子が特に好ましい。 In the lithium secondary battery of the present invention, when used as a polymer electrolyte or a polymer gel electrolyte, the polymer compounds such as ether, ester, siloxane, acrylonitrile, vinylidene fluoride, hexafluoropropylene, acrylate, methacrylate, styrene, vinyl acetate , Polymers such as vinyl chloride and oxetane, polymers having a copolymer structure thereof, or cross-linked products thereof, and the like may be one kind or two or more kinds. The polymer structure is not particularly limited, but a polymer having an ether structure such as polyethylene oxide is particularly preferable.
本発明のリチウム二次電池において、液系の電池は電解液、ゲル系の電池はポリマーを電解液に溶解したプレカーサー溶液、固体電解質電池は電解質塩を溶解した架橋前のポリマーを電池容器内に収容する。 In the lithium secondary battery of the present invention, a liquid battery is an electrolyte solution, a gel battery is a precursor solution in which a polymer is dissolved in an electrolyte solution, and a solid electrolyte battery is a polymer before crosslinking in which an electrolyte salt is dissolved in a battery container. Accommodate.
本発明に係るリチウム二次電池は、円筒型、コイン型、角型、その他任意の形状に形成することができ、電池の基本構成は形状によらず同じであり、目的に応じて設計変更して実施することができる。例えば、円筒型では、負極集電体に負極活物質を塗布してなる負極と、正極集電体に正極活物質を塗布してなる正極とを、セパレータを介して捲回した捲回体を電池缶に収納し、非水電解液を注入し上下に絶縁板を載置した状態で密封して得られる。また、コイン型リチウム二次電池に適用する場合では、円盤状負極、セパレータ、円盤状正極、およびステンレスの板が積層された状態でコイン型電池缶に収納され、非水電解液が注入され、密封される。 The lithium secondary battery according to the present invention can be formed into a cylindrical shape, a coin shape, a square shape, or any other shape, and the basic configuration of the battery is the same regardless of the shape, and the design is changed according to the purpose. Can be implemented. For example, in a cylindrical type, a wound body in which a negative electrode formed by applying a negative electrode active material to a negative electrode current collector and a positive electrode formed by applying a positive electrode active material to a positive electrode current collector are wound through a separator. It is housed in a battery can, sealed with a non-aqueous electrolyte injected, and insulating plates placed on top and bottom. When applied to a coin-type lithium secondary battery, a disc-shaped negative electrode, a separator, a disc-shaped positive electrode, and a stainless steel plate are stacked and stored in a coin-type battery can, and a non-aqueous electrolyte is injected. Sealed.
つぎに、実施例について比較例とあわせて説明する。ただし、本発明はこれらの実施例に限定されるものではない。
[ポリウレタン水分散体の合成]
(合成例1)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにニューポールBPE−20NK(三洋化成社製、ビスフェノールAのエチレンオキサイド付加物、平均水酸基価360mgKOH/g、活性水素基数2)100質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート174.2質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量4.2%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素基数2)6.1質量部,及びN-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Aを得た。
(合成例2)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにニューポールBPE−20NK(三洋化成社製、ビスフェノールAのエチレンオキサイド付加物、平均水酸基価360mgKOH/g、活性水素基数2)100質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート174.2質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量4.2%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素基数3)7.0質量部,及び3-アミノプロピルトリメトキシシラン(信越シリコーン株式会社製、製品名:KBM−903)14.7質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Bを得た。
(合成例3)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにニューポールBPE−20NK(三洋化成社製、ビスフェノールAのエチレンオキサイド付加物、平均水酸基価360mgKOH/g、活性水素基数2)100質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート144.2質量部、ジフェニルメタンジイソシアネート30.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量4.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素基数3)7.0質量部,及び3-アミノプロピルトリメトキシシラン(信越シリコーン株式会社製、製品名:KBM−903)14.7質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Cを得た。
(合成例4)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP−1020(クラレ社製、3−メチル−1,5−ペンタンジオールとテレフタル酸からなるポリエステルポリオール、平均水酸基価110mgKOH/g、活性水素基数2)145.2質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート129.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素基数2)4.2質量部,及びN-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Dを得た。
(合成例5)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにPCDL T−4671(旭化成ケミカルズ社製、1,4−ブタンジオールと1,6−ヘキサンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)145.2質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート129.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素基数2)4.2質量部,及びN-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Eを得た。
(合成例6)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにPCDL T−4671(旭化成ケミカルズ社製、1,4−ブタンジオールと1,6−ヘキサンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)145.2質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート129.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素基数3)4.8質量部,及びN-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Fを得た。
(合成例7)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにPCDL T−4671(旭化成ケミカルズ社製、1,4−ブタンジオールと1,6−ヘキサンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)145.2質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート129.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素基数3)4.8質量部,及び3-メルカプトプロピルトリメトキシシラン(信越シリコーン株式会社製、製品名:KBM−803)13.0質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Gを得た。
(合成例8)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにPCDL T−4671(旭化成ケミカルズ社製、1,4−ブタンジオールと1,6−ヘキサンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)161.7質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、イソホロンジイソシアネート112.5質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.2%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、4,4’―ジアミノ―ジフェニルメタン(活性水素基数2)13.7質量部,及びN-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.40質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Hを得た。
(合成例9)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにETERNACOLL UM−90 (1/3)(宇部興産社製、1,6−ヘキサンジオールと1,4−シクロヘキサンジメタノールを構成成分とするポリカーボネートポリオール、平均水酸基価125mgKOH/g、活性水素基数2)141.9質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート132.3質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素基数2)4.2質量部,及びN―2―(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Iを得た。
(合成例10)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールC−1065N(クラレ社製、1,9−ノナンジオールと2−メチル−1,8−オクタンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)145.2質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート129.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、エチレンジアミン(活性水素基数2)4.2質量部,及びN―2―(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Jを得た。
(合成例11)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールC−1065N(クラレ社製、1,9−ノナンジオールと2−メチル−1,8−オクタンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)145.2質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ジシクロヘキシルメタンジイソシアネート129.0質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.3%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3質量部加え中和後、水900質量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素基数3)9.5質量部,及び3-イソシアネートプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBE−9007)15.0質量部を水100重量部で希釈した水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Kを得た。
(合成例12)
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4つ口フラスコに、クラレポリオールP−1020(クラレ社製、3−メチル−1,5−ペンタンジオールとテレフタル酸からなるポリエステルポリオール、平均水酸基価110mgKOH/g、活性水素基数2)147.0重量部、トリメチロールプロパン(活性水素基数3)9.5重量部、N−メチルジエタノールアミン(活性水素基数2)14.5重量部、ジシクロヘキシルメタンジイソシアネート 129.0重量部、およびメチルエチルケトン200重量部を加え、75℃で4時間反応させて不揮発分に対する遊離のイソシアネート基含有量3.2%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。次に、この溶液を45℃まで冷却し、ジメチル硫酸15.3重量部を加えて四級化した後、水900重量部を徐々に加えながらホモジナイザーを使用して乳化分散させ、N―2―(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え鎖伸長反応を1時間行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Lを得た。
(合成例13)
撹拌機、還流冷却管、温度計及び窒素吹き込み管を備えた4つ口フラスコに、PCDL T−4671(旭化成ケミカルズ社製、1,4−ブタンジオールと1,6−ヘキサンジオールを構成成分とするポリカーボネートポリオール、平均水酸基価110mgKOH/g、活性水素基数2)147.0重量部、トリメチロールプロパン(活性水素基数3)9.5重量部、N−メチルジエタノールアミン(活性水素基数2)14.5重量部、ジシクロヘキシルメタンジイソシアネート 129.0重量部、およびメチルエチルケトン200重量部を加え、75℃で4時間反応させて不揮発分に対する遊離のイソシアネート基含有量3.2%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。次に、この溶液を45℃まで冷却し、ジメチル硫酸15.3重量部を加えて四級化した後、水900重量部を徐々に加えながらホモジナイザーを使用して乳化分散させ、エチレンジアミン(活性水素基数2)4.2質量部、及びN―2―(アミノエチル)-3-アミノプロピルトリエトキシシラン(信越シリコーン株式会社製、製品名:KBM−603)7.4質量部を水100重量部で希釈した水溶液を加え鎖伸長反応を1時間行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Mを得た。
(合成例14)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにPolyTHF1000(BASF社製、ポリテトラメチレンエーテルグリコール、平均水酸基価110mgKOH/g、活性水素基数2)181.7質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ヘキサメチレンジイソシアネート92.5質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.8%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3重量部加え中和後、水900重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、水(活性水素基数2)により、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Nを得た。
(合成例15)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP―1010(商品名、クラレ社製、3−メチル−1,5−ペンタンジオールとアジピン酸からなるポリエステルポリオール、平均水酸基価110mgKOH/g、活性水素基数2)181.7質量部、トリメチロールプロパン(活性水素基数3)9.5質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ヘキサメチレンジイソシアネート92.5質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量3.8%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3重量部加え中和後、水900重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。続いて、ジエチレントリアミン(活性水素基数3)7.8質量部を水100重量部で希釈したアミン水溶液を加え、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Oを得た。
(合成例16)
攪拌機、還流冷却管、温度計および窒素吹き込み管を備えた4つ口フラスコにクラレポリオールP―1010(商品名、クラレ社製、3−メチル−1,5−ペンタンジオールとアジピン酸からなるポリエステルポリオール、平均水酸基価110mgKOH/g、活性水素基数2)212.9質量部、トリメチロールプロパン(活性水素基数3)0.3質量部、ジメチロールプロピオン酸(活性水素基数2)16.3質量部、ヘキサメチレンジイソシアネート70.5質量部、メチルエチルケトン200質量部を加え、75℃で4時間反応させ、不揮発分に対する遊離のイソシアネート基含有量2.2%であるウレタンプレポリマーのメチルエチルケトン溶液を得た。この溶液を45℃まで冷却し、トリエチルアミンを12.3重量部加え中和後、水900重量部を徐々に加えてホモジナイザーを使用し乳化分散させた。水(活性水素基数2)により、1時間鎖伸長反応を行った。これを減圧、50℃下、脱溶剤を行い、不揮発分約30%のポリウレタン水分散体Pを得た。
[ポリウレタン水分散体の評価]
得られたポリウレタン水分散体に関する各測定に際しては、下記方法を用いた。また、その結果を表1に示す。
(ポリウレタン水分散体の不揮発分の重量)
JIS K 6828に準じて測定した。
(ポリウレタン樹脂の酸価、ウレタン結合量、ウレア結合量)
ウレタン樹脂の合成時の仕込量および反応後の不揮発分に対する遊離のイソシアネート基含有量から算出した。
Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
[Synthesis of polyurethane water dispersion]
(Synthesis Example 1)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to Newpole BPE-20NK (manufactured by Sanyo Chemical Co., Ltd., bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, number of active hydrogen groups 2 ) 100 parts by mass, 9.5 parts by mass of trimethylolpropane (number of active hydrogen groups 3), 16.3 parts by mass of dimethylolpropionic acid (number of active hydrogen groups 2), 174.2 parts by mass of dicyclohexylmethane diisocyanate, 200 parts by mass of methyl ethyl ketone In addition, the reaction was carried out at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 4.2% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 6.1 parts by mass of ethylenediamine (number of active hydrogen groups 2) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 An aqueous solution obtained by diluting a part by mass with 100 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion A having a nonvolatile content of about 30%.
(Synthesis Example 2)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to Newpole BPE-20NK (manufactured by Sanyo Chemical Co., Ltd., bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, number of active hydrogen groups 2 ) 100 parts by mass, 9.5 parts by mass of trimethylolpropane (number of active hydrogen groups 3), 16.3 parts by mass of dimethylolpropionic acid (number of active hydrogen groups 2), 174.2 parts by mass of dicyclohexylmethane diisocyanate, 200 parts by mass of methyl ethyl ketone In addition, the reaction was carried out at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 4.2% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 7.0 parts by mass of diethylenetriamine (3 active hydrogen groups) and 14.7 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-903) are diluted with 100 parts by weight of water. The resulting aqueous solution was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion B having a nonvolatile content of about 30%.
(Synthesis Example 3)
A four-necked flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen blowing tube was added to Newpole BPE-20NK (manufactured by Sanyo Chemical Co., Ltd., bisphenol A ethylene oxide adduct, average hydroxyl value 360 mgKOH / g, number of active hydrogen groups 2 ) 100 parts by mass, 9.5 parts by mass of trimethylolpropane (number of active hydrogen groups 3), 16.3 parts by mass of dimethylolpropionic acid (number of active hydrogen groups 2), 144.2 parts by mass of dicyclohexylmethane diisocyanate, 30.0 diphenylmethane diisocyanate Part by mass and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 4.3% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 7.0 parts by mass of diethylenetriamine (3 active hydrogen groups) and 14.7 parts by mass of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-903) are diluted with 100 parts by weight of water. The resulting aqueous solution was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion C having a nonvolatile content of about 30%.
(Synthesis Example 4)
Kuraray polyol P-1020 (manufactured by Kuraray Co., Ltd., polyester polyol composed of 3-methyl-1,5-pentanediol and terephthalic acid, average hydroxyl group) 110 mg KOH / g, number of active hydrogen groups 2) 145.2 parts by mass, trimethylolpropane (number of active hydrogen groups 3) 9.5 parts by mass, dimethylolpropionic acid (number of active hydrogen groups 2) 16.3 parts by mass, dicyclohexylmethane diisocyanate 129.0 parts by mass and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Then, 4.2 parts by mass of ethylenediamine (number of active hydrogen groups 2) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 An aqueous solution obtained by diluting a part by mass with 100 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion D having a nonvolatile content of about 30%.
(Synthesis Example 5)
PCDL T-4671 (manufactured by Asahi Kasei Chemicals Corporation, polycarbonate polyol containing 1,4-butanediol and 1,6-hexanediol as constituents) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Average hydroxyl value 110 mg KOH / g, active hydrogen group number 2) 145.2 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16.3 parts by mass, 129.0 parts by mass of dicyclohexylmethane diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Then, 4.2 parts by mass of ethylenediamine (number of active hydrogen groups 2) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 An aqueous solution obtained by diluting a part by mass with 100 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion E having a nonvolatile content of about 30%.
(Synthesis Example 6)
PCDL T-4671 (manufactured by Asahi Kasei Chemicals Corporation, polycarbonate polyol containing 1,4-butanediol and 1,6-hexanediol as constituents) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Average hydroxyl value 110 mg KOH / g, active hydrogen group number 2) 145.2 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16.3 parts by mass, 129.0 parts by mass of dicyclohexylmethane diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 4.8 parts by mass of diethylenetriamine (number of active hydrogen groups 3) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 An aqueous solution obtained by diluting a part by mass with 100 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion F having a nonvolatile content of about 30%.
(Synthesis Example 7)
PCDL T-4671 (manufactured by Asahi Kasei Chemicals Corporation, polycarbonate polyol containing 1,4-butanediol and 1,6-hexanediol as constituents) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Average hydroxyl value 110 mg KOH / g, active hydrogen group number 2) 145.2 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16.3 parts by mass, 129.0 parts by mass of dicyclohexylmethane diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 4.8 parts by mass of diethylenetriamine (3 active hydrogen groups) and 13.0 parts by mass of 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-803) are diluted with 100 parts by weight of water. The resulting aqueous solution was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion G having a nonvolatile content of about 30%.
(Synthesis Example 8)
PCDL T-4671 (manufactured by Asahi Kasei Chemicals Corporation, polycarbonate polyol containing 1,4-butanediol and 1,6-hexanediol as constituents) in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube Average hydroxyl value 110 mg KOH / g, active hydrogen group number 2) 161.7 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16.3 parts by mass, 112.5 parts by mass of isophorone diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.2% based on the nonvolatile content. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 13.7 parts by mass of 4,4′-diamino-diphenylmethane (number of active hydrogen groups 2) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: (KBM-603) An aqueous solution obtained by diluting 7.40 parts by mass with 100 parts by weight of water was added, and chain extension reaction was performed for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion H having a nonvolatile content of about 30%.
(Synthesis Example 9)
ETERNACOLL UM-90 (1/3) (manufactured by Ube Industries, Ltd., 1,6-hexanediol and 1,4-cyclohexanedimethanol was added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube. Polycarbonate polyol as constituent components, average hydroxyl value 125 mgKOH / g, number of active hydrogen groups 2) 141.9 parts by mass, trimethylolpropane (number of active hydrogen groups 3) 9.5 parts by mass, dimethylolpropionic acid (number of active hydrogen groups 2) 16.3 parts by mass, 132.3 parts by mass of dicyclohexylmethane diisocyanate, and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours, and methyl ethyl ketone of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. A solution was obtained. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 4.2 parts by mass of ethylenediamine (number of active hydrogen groups 2) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 An aqueous solution obtained by diluting a part by mass with 100 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion I having a nonvolatile content of about 30%.
(Synthesis Example 10)
Kuraray polyol C-1065N (manufactured by Kuraray Co., Ltd., 1,9-nonanediol and 2-methyl-1,8-octanediol) was added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube. Polycarbonate polyol, average hydroxyl value 110 mgKOH / g, active hydrogen group number 2) 145.2 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16. 3 parts by mass, 129.0 parts by mass of dicyclohexylmethane diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. Obtained. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 4.2 parts by mass of ethylenediamine (number of active hydrogen groups 2) and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 An amine aqueous solution diluted with 100 parts by weight of water was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion J having a nonvolatile content of about 30%.
(Synthesis Example 11)
Kuraray polyol C-1065N (manufactured by Kuraray Co., Ltd., 1,9-nonanediol and 2-methyl-1,8-octanediol) was added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube. Polycarbonate polyol, average hydroxyl value 110 mgKOH / g, active hydrogen group number 2) 145.2 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16. 3 parts by mass, 129.0 parts by mass of dicyclohexylmethane diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.3% based on the nonvolatile content. Obtained. The solution was cooled to 45 ° C., 12.3 parts by mass of triethylamine was added to neutralize, 900 parts by mass of water was gradually added, and the mixture was emulsified and dispersed using a homogenizer. Subsequently, 9.5 parts by mass of diethylenetriamine (number of active hydrogen groups 3) and 15.0 parts by mass of 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBE-9007) are diluted with 100 parts by weight of water. The resulting aqueous solution was added to carry out a chain extension reaction for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion K having a nonvolatile content of about 30%.
(Synthesis Example 12)
To a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, Kuraray polyol P-1020 (manufactured by Kuraray Co., Ltd., polyester polyol composed of 3-methyl-1,5-pentanediol and terephthalic acid, Average hydroxyl value 110 mgKOH / g, number of active hydrogen groups 2) 147.0 parts by weight, trimethylolpropane (number of active hydrogen groups 3) 9.5 parts by weight, N-methyldiethanolamine (number of active hydrogen groups 2) 14.5 parts by weight, dicyclohexyl 129.0 parts by weight of methane diisocyanate and 200 parts by weight of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.2% based on the nonvolatile content. Next, this solution was cooled to 45 ° C., quaternized by adding 15.3 parts by weight of dimethyl sulfuric acid, and then emulsified and dispersed using a homogenizer while gradually adding 900 parts by weight of water, and N-2- (Aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) was added with an aqueous solution obtained by diluting 7.4 parts by mass with 100 parts by weight of water, and chain extension reaction was performed for 1 hour. . The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion L having a nonvolatile content of about 30%.
(Synthesis Example 13)
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, PCDL T-4671 (manufactured by Asahi Kasei Chemicals Corporation, 1,4-butanediol and 1,6-hexanediol as constituent components) Polycarbonate polyol, average hydroxyl value 110 mgKOH / g, active hydrogen group number 2) 147.0 parts by weight, trimethylolpropane (active hydrogen group number 3) 9.5 parts by weight, N-methyldiethanolamine (active hydrogen group number 2) 14.5 parts by weight Part, dicyclohexylmethane diisocyanate 129.0 parts by weight, and methyl ethyl ketone 200 parts by weight were reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.2% based on the nonvolatile content. It was. Next, the solution was cooled to 45 ° C., quaternized by adding 15.3 parts by weight of dimethyl sulfate, and then emulsified and dispersed using a homogenizer while gradually adding 900 parts by weight of water, and ethylenediamine (active hydrogen Radical number 2) 4.2 parts by mass and N-2- (aminoethyl) -3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM-603) 7.4 parts by mass of water 100 parts by weight A chain extension reaction was performed for 1 hour by adding an aqueous solution diluted with 1. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion M having a nonvolatile content of about 30%.
(Synthesis Example 14)
PolyTHF1000 (manufactured by BASF, polytetramethylene ether glycol, average hydroxyl value 110 mg KOH / g, number of active hydrogen groups 2) 181.7 parts by mass in a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube, Add 9.5 parts by mass of trimethylolpropane (number of active hydrogen groups 3), 16.3 parts by mass of dimethylolpropionic acid (number of active hydrogen groups 2), 92.5 parts by mass of hexamethylene diisocyanate, 200 parts by mass of methyl ethyl ketone at 75 ° C. The reaction was performed for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.8% based on the nonvolatile content. The solution was cooled to 45 ° C., neutralized by adding 12.3 parts by weight of triethylamine, and then 900 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. Subsequently, a chain extension reaction was performed with water (2 active hydrogen groups) for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion N having a nonvolatile content of about 30%.
(Synthesis Example 15)
Kuraray polyol P-1010 (trade name, manufactured by Kuraray Co., Ltd., polyester polyol consisting of 3-methyl-1,5-pentanediol and adipic acid) was added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube. Average hydroxyl value 110 mg KOH / g, active hydrogen group number 2) 181.7 parts by mass, trimethylolpropane (active hydrogen group number 3) 9.5 parts by mass, dimethylolpropionic acid (active hydrogen group number 2) 16.3 parts by mass, 92.5 parts by mass of hexamethylene diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.8% based on the nonvolatile content. The solution was cooled to 45 ° C., neutralized by adding 12.3 parts by weight of triethylamine, and then 900 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. Subsequently, an aqueous amine solution in which 7.8 parts by mass of diethylenetriamine (number of active hydrogen groups 3) was diluted with 100 parts by weight of water was added, and a chain extension reaction was performed for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion O having a nonvolatile content of about 30%.
(Synthesis Example 16)
Kuraray polyol P-1010 (trade name, manufactured by Kuraray Co., Ltd., polyester polyol consisting of 3-methyl-1,5-pentanediol and adipic acid) was added to a four-necked flask equipped with a stirrer, reflux condenser, thermometer and nitrogen blowing tube. Average hydroxyl value 110 mg KOH / g, active hydrogen group number 2) 212.9 parts by mass, trimethylolpropane (active hydrogen group number 3) 0.3 part by mass, dimethylolpropionic acid (active hydrogen group number 2) 16.3 parts by mass, 70.5 parts by mass of hexamethylene diisocyanate and 200 parts by mass of methyl ethyl ketone were added and reacted at 75 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 2.2% based on the nonvolatile content. The solution was cooled to 45 ° C., neutralized by adding 12.3 parts by weight of triethylamine, and then 900 parts by weight of water was gradually added and emulsified and dispersed using a homogenizer. A chain extension reaction was carried out with water (2 active hydrogen groups) for 1 hour. The solvent was removed under reduced pressure at 50 ° C. to obtain a polyurethane water dispersion P having a nonvolatile content of about 30%.
[Evaluation of polyurethane water dispersion]
The following methods were used for each measurement regarding the obtained polyurethane water dispersion. The results are shown in Table 1.
(Nonvolatile content of polyurethane water dispersion)
It measured according to JIS K 6828.
(Acid value of polyurethane resin, urethane bond amount, urea bond amount)
It calculated from the charged amount at the time of the synthesis | combination of a urethane resin, and the free isocyanate group content with respect to the non volatile matter after reaction.
[電極の作製]
[負極の作製]
(負極1)
負極活物質として、天然黒鉛100g、導電剤としてカーボンブラック0.5g(Timcal社製、Super−P)と増粘剤としてカルボキシメチルセルロース(CMC)(第一工業製薬製、品名:セロゲンWS―C)2重量%水溶液100g、結着剤としてポリウレタン水分散体Aの30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように負極スラリーを調製した。この負極スラリーを塗工機で厚み10μmの電解銅箔上にコーティングを行い、120℃で乾燥後、ロールプレス処理を行い、負極活物質7mg/cm2の負極1を得た。
(負極2〜11、負極14〜17)
前記ポリウレタン水分散体Aを下記表2に記載のポリウレタン水分散体、SBRに変更した以外は負極1と同様の方法で作成した。
(負極12〜13)
負極活物質として、天然黒鉛100g、導電剤としてカーボンブラック0.5g(Timcal社製、Super−P)と増粘剤としてヒドロキシエチルセルロース(HEC)(ダイセル化学、品名:HECダイセル SP900)1重量%水溶液100g、結着剤として表2に記載のポリウレタン水分散体の30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように負極スラリーを調製した。この負極スラリーを塗工機で厚み10μmの電解銅箔上にコーティングを行い、120℃で乾燥後、ロールプレス処理を行い、負極活物質7mg/cm2の負極を得た。
(負極18)
負極活物質として、SiO(平均粒径4.5μm、比表面積5.5m2/g)100g、導電剤としてカーボンブラック5g(Timcal社製、Super−P)と増粘剤としてカルボキシメチルセルロース(CMC)(第一工業製薬製、品名:セロゲンWS―C)2重量%水溶液100g、結着剤としてポリウレタン水分散体Aの30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように負極スラリーを調製した。この負極スラリーを塗工機で厚み10μmの電解銅箔上にコーティングを行い、120℃で乾燥後、ロールプレス処理を行い、負極活物質2.5mg/cm2の負極を得た。
(負極19)
前記ポリウレタン水分散体AをSBRに変更した以外は負極18と同様の方法で作成した。
(負極20)
負極活物質として、Li4Ti5O12100g、導電剤としてカーボンブラック5g(Timcal社製、Super−P)と増粘剤としてカルボキシメチルセルロース(CMC)(第一工業製薬製、品名:セロゲンWS―C)2重量%水溶液100g、結着剤としてポリウレタン水分散体Eの30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように負極スラリーを調製した。この負極スラリーを塗工機で厚み10μmの電解銅箔上にコーティングを行い、120℃で乾燥後、ロールプレス処理を行い、負極活物質9.7mg/cm2の負極を得た。
(負極21)
前記ポリウレタン水分散体AをSBRに変更した以外は負極20と同様の方法で作成した。
[正極の作製]
(正極1)
正極活物質であるLiNi1/3Co1/3Mn1/3O2100g、導電剤としてカーボンブラック(Timcal社製、Super−P)を7.8g、結着剤としてポリフッ化ビニリデン6g、分散媒としてN−メチル−2−ピロリドン61.3gを遊星型ミキサーで混合し、固形分65%になるように正極スラリーを調製した。この正極スラリーを塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後、ロールプレス処理を行い、正極活物質13.8mg/cm2の正極を得た。
(正極2〜3)
正極活物質であるLiNi1/3Co1/3Mn1/3O2100g、導電剤としてカーボンブラック(Timcal社製、Super−P)を7.8g、増粘剤としてカルボキシメチルセルロース(第一工業製薬製、品名:セロゲンWS―C)2重量%水溶液100g、結着剤として表2に記載のポリウレタン水分散体の30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように正極スラリーを調製した。この正極スラリーを塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後、ロールプレス処理を行い、正極活物質13.8mg/cm2の正極を得た。
(正極4)
正極活物質であるLiMn2O4100g、導電剤としてカーボンブラック(Timcal社製、Super−P)を5g、結着剤としてポリフッ化ビニリデン6g、分散媒としてN−メチル−2−ピロリドン59.8gを遊星型ミキサーで混合し、固形分65%になるように正極スラリーを調製した。この正極スラリーを塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後、ロールプレス処理を行い、正極活物質22mg/cm2の正極を得た。
(正極5)
正極活物質であるLiMn2O4100g、導電剤としてカーボンブラック(Timcal社製、Super−P)を5g、増粘剤としてカルボキシメチルセルロース(第一工業製薬製、品名:セロゲンWS―C)2重量%水溶液100g、結着剤としてポリウレタンン水分散体Jの30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように正極スラリーを調製した。この正極スラリーを塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後、ロールプレス処理を行い、正極活物質22mg/cm2の正極を得た。
(正極6)
正極活物質であるLiFePO4100g、導電剤としてカーボンブラック(Timcal社製、Super−P)を5g、結着剤としてポリフッ化ビニリデン6g、分散媒としてN−メチル−2−ピロリドン135.7gを遊星型ミキサーで混合し、固形分45%になるように正極スラリーを調製した。この正極スラリーを塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後、ロールプレス処理を行い、正極活物質14.5mg/cm2の正極を得た。
(正極7)
正極活物質であるLiFePO4100g、導電剤としてカーボンブラック(Timcal社製、Super−P)を5g、増粘剤としてカルボキシメチルセルロース(第一工業製薬製、品名:セロゲンWS―C)2重量%水溶液100g、結着剤としてポリウレタン水分散体Cの30重量%溶液6.7gを遊星型ミキサーで混合し、固形分50%になるように正極スラリーを調製した。この正極スラリーを塗工機で厚み20μmのアルミニウム箔上にコーティングを行い、130℃で乾燥後、ロールプレス処理を行い、正極活物質14.5mg/cm2の正極を得た。
[Production of electrodes]
[Preparation of negative electrode]
(Negative electrode 1)
100 g of natural graphite as a negative electrode active material, 0.5 g of carbon black as a conductive agent (Supercal-P, manufactured by Timcal) and carboxymethyl cellulose (CMC) as a thickener (Daiichi Kogyo Seiyaku, product name: Cellogen WS-C) 100 g of a 2 wt% aqueous solution and 6.7 g of a 30 wt% solution of polyurethane water dispersion A as a binder were mixed with a planetary mixer to prepare a negative electrode slurry so that the solid content was 50%. This negative electrode slurry was coated on an electrolytic copper foil having a thickness of 10 μm with a coating machine, dried at 120 ° C., and then subjected to a roll press treatment, to obtain a negative electrode 1 having a negative electrode active material of 7 mg / cm 2 .
(Negative electrodes 2-11, negative electrodes 14-17)
The polyurethane water dispersion A was prepared in the same manner as the negative electrode 1 except that the polyurethane water dispersion A described in Table 2 was changed to SBR.
(Negative electrodes 12-13)
100 g of natural graphite as a negative electrode active material, 0.5 g of carbon black as a conductive agent (Super-P, manufactured by Timcal) and hydroxyethyl cellulose (HEC) as a thickener (Daicel Chemical, product name: HEC Daicel SP900) 1 wt% aqueous solution 100 g and 6.7 g of a 30% by weight polyurethane water dispersion listed in Table 2 as a binder were mixed with a planetary mixer to prepare a negative electrode slurry so that the solid content was 50%. This negative electrode slurry was coated on an electrolytic copper foil having a thickness of 10 μm with a coating machine, dried at 120 ° C., and then subjected to a roll press treatment, to obtain a negative electrode having a negative electrode active material of 7 mg / cm 2 .
(Negative electrode 18)
As a negative electrode active material, SiO (average particle size 4.5 μm, specific surface area 5.5 m 2 / g) 100 g, as a conductive agent 5 g of carbon black (manufactured by Timcal, Super-P) and as a thickener carboxymethyl cellulose (CMC) (Daiichi Kogyo Seiyaku Co., Ltd., product name: Serogen WS-C) 2% by weight aqueous solution 100g, 30% by weight polyurethane aqueous dispersion A solution 6.7g as a binder was mixed with a planetary mixer to a solid content of 50%. A negative electrode slurry was prepared so as to be. The negative electrode slurry perform a coating on an electrolytic copper foil having a thickness of 10μm with a coater, dried at 120 ° C., followed by conducting roll press treatment, to obtain a negative electrode of the negative electrode active material 2.5mg / c m 2.
(Negative electrode 19)
It was prepared in the same manner as the negative electrode 18 except that the polyurethane water dispersion A was changed to SBR.
(Negative electrode 20)
As a negative electrode active material, Li 4 Ti 5 O 12 100 g, as a conductive agent 5 g of carbon black (manufactured by Timcal, Super-P) and as a thickener carboxymethylcellulose (CMC) (Daiichi Kogyo Seiyaku, product name: Serogen WS— C) 100 g of a 2 wt% aqueous solution and 6.7 g of a 30 wt% solution of polyurethane water dispersion E as a binder were mixed with a planetary mixer to prepare a negative electrode slurry so as to have a solid content of 50%. This negative electrode slurry was coated on an electrolytic copper foil having a thickness of 10 μm with a coating machine, dried at 120 ° C., and then subjected to a roll press treatment to obtain a negative electrode having a negative electrode active material of 9.7 mg / cm 2 .
(Negative electrode 21)
It was prepared in the same manner as the negative electrode 20 except that the polyurethane water dispersion A was changed to SBR.
[Preparation of positive electrode]
(Positive electrode 1)
LiNi 1/3 Co 1/3 Mn 1/3 O 2 100 g as a positive electrode active material, 7.8 g of carbon black (Super-P, manufactured by Timcal) as a conductive agent, 6 g of polyvinylidene fluoride as a binder, dispersion As a medium, 61.3 g of N-methyl-2-pyrrolidone was mixed with a planetary mixer to prepare a positive electrode slurry so as to have a solid content of 65%. This positive electrode slurry was coated on an aluminum foil having a thickness of 20 μm with a coating machine, dried at 130 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material of 13.8 mg / cm 2 .
(Positive electrode 2-3)
LiNi 1/3 Co 1/3 Mn 1/3 O 2 100 g as a positive electrode active material, 7.8 g of carbon black (manufactured by Timcal, Super-P) as a conductive agent, carboxymethyl cellulose (Daiichi Kogyo) as a thickener 100 g of 2 wt% aqueous solution manufactured by Pharmaceutical, product name: Serogen WS-C) and 6.7 g of a 30 wt% solution of polyurethane water dispersion listed in Table 2 as a binder were mixed with a planetary mixer to obtain a solid content of 50%. A positive electrode slurry was prepared as described above. This positive electrode slurry was coated on an aluminum foil having a thickness of 20 μm with a coating machine, dried at 130 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material of 13.8 mg / cm 2 .
(Positive electrode 4)
100 g of LiMn 2 O 4 as a positive electrode active material, 5 g of carbon black (manufactured by Timcal, Super-P) as a conductive agent, 6 g of polyvinylidene fluoride as a binder, and 59.8 g of N-methyl-2-pyrrolidone as a dispersion medium Were mixed with a planetary mixer to prepare a positive electrode slurry to a solid content of 65%. This positive electrode slurry was coated on an aluminum foil having a thickness of 20 μm with a coating machine, dried at 130 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material of 22 mg / cm 2 .
(Positive electrode 5)
LiMn 2 O 4 100 g as a positive electrode active material, carbon black (manufactured by Timcal, Super-P) as a conductive agent, 5 g, carboxymethyl cellulose (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Serogen WS-C) as a thickener A positive electrode slurry was prepared so as to have a solid content of 50% by mixing 100 g of a 100% aqueous solution and 6.7 g of a 30 wt% solution of polyurethane aqueous dispersion J as a binder. This positive electrode slurry was coated on an aluminum foil having a thickness of 20 μm with a coating machine, dried at 130 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material of 22 mg / cm 2 .
(Positive electrode 6)
100 g LiFePO 4 as a positive electrode active material, 5 g carbon black (manufactured by Timcal, Super-P) as a conductive agent, 6 g polyvinylidene fluoride as a binder, and 135.7 g N-methyl-2-pyrrolidone as a dispersion medium A positive electrode slurry was prepared so as to have a solid content of 45% by mixing with a mold mixer. This positive electrode slurry was coated on an aluminum foil having a thickness of 20 μm with a coating machine, dried at 130 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material of 14.5 mg / cm 2 .
(Positive electrode 7)
LiFePO 4 100 g as a positive electrode active material, carbon black (manufactured by Timcal, Super-P) as a conductive agent, 5 g, carboxymethyl cellulose (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product name: Cellogen WS-C) as a 2 wt% aqueous solution 100 g and 6.7 g of a 30 wt% solution of polyurethane water dispersion C as a binder were mixed with a planetary mixer to prepare a positive electrode slurry so as to have a solid content of 50%. This positive electrode slurry was coated on an aluminum foil having a thickness of 20 μm with a coating machine, dried at 130 ° C., and then subjected to a roll press treatment to obtain a positive electrode having a positive electrode active material of 14.5 mg / cm 2 .
[電極の評価]
得られた電極について以下の項目について評価を実施した。評価結果を下記表3に示す。
(結着性評価)
上記で得られた電極の塗工面を外側に180度折り曲げて戻した後に、塗工面の活物質の脱落程度(脱落部分の面積が全体に占める割合)を目視で判断した。
評価基準:
5点:0%脱落
4点:25%脱落
3点:50%脱落
2点:75%脱落
1点:100%脱落
(耐電解液性評価)
上記で得られた電極をEC(エチレンカーボネート)/PC(プロピレンカーボネート)/DMC(ジメチルカーボネート)/EMC(エチルメチルカーボネート)/DEC(ジエチルカーボネート)=1/1/1/1/1(vol)の混合溶剤に60℃、7日後浸漬後の塗膜外観を目視で判断した。
評価基準
○ :塗膜に変化無し
△ :塗膜に膨れ数点発生
× :塗膜が剥がれる。
[Electrode evaluation]
The obtained electrode was evaluated for the following items. The evaluation results are shown in Table 3 below.
(Evaluation of binding properties)
After the coated surface of the electrode obtained above was bent 180 degrees outward and returned, the extent of falling off of the active material on the coated surface (the ratio of the area of the dropped portion to the whole) was visually judged.
Evaluation criteria:
5 points: 0% dropout 4 points: 25% dropout 3 points: 50% dropout 2 points: 75% dropout 1 point: 100% dropout (electrolytic solution resistance evaluation)
The electrode obtained above was EC (ethylene carbonate) / PC (propylene carbonate) / DMC (dimethyl carbonate) / EMC (ethyl methyl carbonate) / DEC (diethyl carbonate) = 1/1/1/1/1 (vol). The appearance of the coating film after being immersed in the mixed solvent at 60 ° C. for 7 days was visually judged.
Evaluation criteria ○: No change in the coating film △: Several points of swelling occur in the coating film ×: The coating film peels off.
[リチウム二次電池の作製]
上記で得られた正極、負極を下記表4のように組み合わせて、電極間にセパレータとしてポリオレフィン系(PE/PP)セパレータを挟んで積層し、各正負極に正極端子と負極端子を超音波溶接した。この積層体をアルミラミネート包材に入れ、注液用の開口部を残しヒートシールした。正極面積18cm2、負極面積19.8cm2とした注液前電池を作製した。次にエチレンカーボネートとジエチルカーボネート(30/70vol比)とを混合した溶媒にLiPF6(1.0mol/L)を溶解させた電解液を注液し、開口部をヒートシールし、評価用電池を得た。
[Production of lithium secondary battery]
The positive electrode and negative electrode obtained above are combined as shown in Table 4 below, and a polyolefin (PE / PP) separator is sandwiched between the electrodes as a separator, and a positive electrode terminal and a negative electrode terminal are ultrasonically welded to each positive and negative electrode. did. This laminate was put in an aluminum laminate packaging material, and heat sealed, leaving an opening for injection. The positive electrode area of 18cm 2, to prepare a liquid injection before batteries with anode area 19.8cm 2. Next, an electrolytic solution in which LiPF 6 (1.0 mol / L) was dissolved in a solvent in which ethylene carbonate and diethyl carbonate (30/70 vol ratio) were mixed was poured, the opening was heat sealed, and an evaluation battery was prepared. Obtained.
[電池性能の評価]
作製したリチウム二次電池について、20℃における性能試験を行った。試験方法は下記の通りである。試験結果を表5に示す。
(セルインピーダンス)
セルインピーダンスは、インピーダンスアナライザー(ZAHNER社製)を用いて、周波数1kHzでの抵抗値を測定した。
(充放電サイクル特性)
充放電サイクル特性は、以下の条件で測定した。
正極活物質としてLiNi1/3Co1/3Mn1/3O2或いはLiMn2O4、負極活物質として天然黒鉛を使用した場合は、1C相当の電流密度で4.2VまでCC(定電流)充電を行い、続いて4.2VでCV(定電圧)充電に切り替え、1.5時間充電したのち、1C相当の電流密度で2.7VまでCC放電するサイクルを20℃で300サイクル行い、このときの初回1C放電容量に対する300サイクル後1C放電容量比を1C充放電サイクル保持率とした。
正極活物質としてLiFePO4、負極活物質として天然黒鉛を使用した場合は、1C相当の電流密度で4.0VまでCC(定電流)充電を行い、続いて4.0VでCV(定電圧)充電に切り替え、1.5時間充電したのち、1C相当の電流密度で2.0VまでCC放電するサイクルを20℃で300サイクル行い、このときの初回1C放電容量に対する300サイクル後1C放電容量比を1C充放電サイクル保持率とした。
正極活物質としてLiNi1/3Co1/3Mn1/3O2、負極活物質としてLi4Ti5O12を使用した場合は、1C相当の電流密度で2.9VまでCC(定電流)充電を行い、続いて2.9VでCV(定電圧)充電に切り替え、1.5時間充電したのち、1C相当の電流密度で1.0VまでCC放電するサイクルを20℃で300サイクル行い、このときの初回1C放電容量に対する300サイクル後1C放電容量比を1C充放電サイクル保持率とした。
正極活物質としてLiNi1/3Co1/3Mn1/3O2、負極活物質としてSiOを使用した場合は、1C相当の電流密度で4.2VまでCC(定電流)充電を行い、続いて4.2VでCV(定電圧)充電に切り替え、1.5時間充電したのち、1C相当の電流密度で2.7VまでCC放電するサイクルを20℃で50サイクル行い、このときの初回1C放電容量に対する50サイクル後1C放電容量比を1C充放電サイクル保持率とした。
[Evaluation of battery performance]
About the produced lithium secondary battery, the performance test in 20 degreeC was done. The test method is as follows. The test results are shown in Table 5.
(Cell impedance)
For the cell impedance, an impedance analyzer (manufactured by ZAHNER) was used to measure the resistance value at a frequency of 1 kHz.
(Charge / discharge cycle characteristics)
The charge / discharge cycle characteristics were measured under the following conditions.
When LiNi 1/3 Co 1/3 Mn 1/3 O 2 or LiMn 2 O 4 is used as the positive electrode active material and natural graphite is used as the negative electrode active material, CC (constant current) up to 4.2 V at a current density equivalent to 1C. ) Charging, followed by switching to CV (constant voltage) charging at 4.2V, charging for 1.5 hours, and then performing a CC discharge to 2.7V at a current density equivalent to 1C for 300 cycles at 20 ° C. The 1C discharge capacity ratio after 300 cycles to the initial 1C discharge capacity at this time was defined as the 1C charge / discharge cycle retention rate.
When LiFePO 4 is used as the positive electrode active material and natural graphite is used as the negative electrode active material, CC (constant current) charging is performed up to 4.0 V at a current density equivalent to 1 C, followed by CV (constant voltage) charging at 4.0 V. After charging for 1.5 hours, a cycle of CC discharge to 2.0 V at a current density equivalent to 1 C is performed 300 cycles at 20 ° C., and the 1 C discharge capacity ratio after 300 cycles to the initial 1 C discharge capacity at this time is 1 C The charge / discharge cycle retention rate was used.
When LiNi 1/3 Co 1/3 Mn 1/3 O 2 is used as the positive electrode active material and Li 4 Ti 5 O 12 is used as the negative electrode active material, CC (constant current) up to 2.9 V at a current density equivalent to 1C. Charge, then switch to CV (constant voltage) charge at 2.9V, charge for 1.5 hours, and then perform a cycle of CC discharge to 1.0V at a current density equivalent to 1C, 300 cycles at 20 ° C The 1C discharge capacity ratio after 300 cycles with respect to the initial 1C discharge capacity was defined as the 1C charge / discharge cycle retention rate.
When LiNi 1/3 Co 1/3 Mn 1/3 O 2 is used as the positive electrode active material and SiO is used as the negative electrode active material, CC (constant current) charging is performed up to 4.2 V at a current density equivalent to 1 C, and then After switching to CV (constant voltage) charging at 4.2V and charging for 1.5 hours, 50 cycles of CC discharge to 2.7V at a current density equivalent to 1C were performed at 20 ° C, and the initial 1C discharge at this time The 1C discharge capacity ratio after 50 cycles with respect to the capacity was defined as the 1C charge / discharge cycle retention rate.
表5より、従来から使用されてきたスチレンブタジエンゴム或いはポリフッ化ビニリデンを使用した場合より、本発明のポリウレタン水分散体を使用した場合の方が、結着性に優れ、セルインピーダンスが低く、サイクル特性後の容量保持率が高く保持されることがわかる。 From Table 5, the case where the polyurethane water dispersion of the present invention is used is superior to the case where the conventionally used styrene butadiene rubber or polyvinylidene fluoride is used. It can be seen that the capacity retention after the characteristics is kept high.
本発明の結着剤は、リチウム二次電池用電極の結着剤として利用でき、それから製造された電極は各種リチウム二次電池の製造に用いられる。得られたリチウム二次電池は、携帯電話、ノートパソコン、携帯情報端末(PDA)、ビデオカメラ、デジタルカメラなどの各種携帯型機器や、更には電動自転車、電気自動車などに搭載する中型又は大型リチウム二次電池に使用することが出来る。
The binder of this invention can be utilized as a binder of the electrode for lithium secondary batteries, and the electrode manufactured from it is used for manufacture of various lithium secondary batteries. The obtained lithium secondary battery is a medium- or large-sized lithium battery mounted on various portable devices such as mobile phones, notebook computers, personal digital assistants (PDAs), video cameras, and digital cameras, as well as electric bicycles and electric vehicles. Can be used for secondary batteries.
Claims (4)
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WO2016132589A1 (en) * | 2015-02-20 | 2016-08-25 | 第一工業製薬株式会社 | Binder for electrodes of lithium secondary batteries, electrode produced using said binder, and lithium secondary battery using said electrode |
JP2018053109A (en) * | 2016-09-29 | 2018-04-05 | 第一工業製薬株式会社 | Water dispersion |
JP2018053108A (en) * | 2016-09-29 | 2018-04-05 | 第一工業製薬株式会社 | Water dispersion |
WO2023216095A1 (en) * | 2022-05-10 | 2023-11-16 | 宁德时代新能源科技股份有限公司 | Positive electrode slurry, positive electrode plate, and secondary battery comprising positive electrode plate |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016132589A1 (en) * | 2015-02-20 | 2016-08-25 | 第一工業製薬株式会社 | Binder for electrodes of lithium secondary batteries, electrode produced using said binder, and lithium secondary battery using said electrode |
JPWO2016132589A1 (en) * | 2015-02-20 | 2017-11-30 | 第一工業製薬株式会社 | Binder for electrode of lithium secondary battery, electrode manufactured using the binder, and lithium secondary battery using the electrode |
JP2018053109A (en) * | 2016-09-29 | 2018-04-05 | 第一工業製薬株式会社 | Water dispersion |
JP2018053108A (en) * | 2016-09-29 | 2018-04-05 | 第一工業製薬株式会社 | Water dispersion |
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US11990624B2 (en) | 2022-05-10 | 2024-05-21 | Contemporary Amperex Technology Co., Limited | Positive electrode slurry, positive electrode plate, and secondary battery including such positive electrode plate |
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