JPH08124560A - Manufacture of plate for nonaqueous electrolytic secondary battery - Google Patents
Manufacture of plate for nonaqueous electrolytic secondary batteryInfo
- Publication number
- JPH08124560A JPH08124560A JP6257030A JP25703094A JPH08124560A JP H08124560 A JPH08124560 A JP H08124560A JP 6257030 A JP6257030 A JP 6257030A JP 25703094 A JP25703094 A JP 25703094A JP H08124560 A JPH08124560 A JP H08124560A
- Authority
- JP
- Japan
- Prior art keywords
- binder
- active material
- electron beam
- current collector
- secondary battery
- 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.)
- Pending
Links
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非水電解液２次電池用
電極板の製造方法に関し、特に２次電池を構成した際経
時的に安定な電極板を付与することができる非水電解液
２次電池用電極板の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an electrode plate for a non-aqueous electrolyte secondary battery, and more particularly to a non-aqueous electrolysis device capable of imparting a stable electrode plate with time when a secondary battery is constructed. The present invention relates to a method for manufacturing an electrode plate for a liquid secondary battery.
【０００２】[0002]
【従来の技術】近年、電子機器、通信機器の小型化、軽
量化が急速に進んでおり、これらの駆動用電源として用
いられる２次電池も同様な要求が強く、高エネルギー密
度、高電圧を有するリチウムイオン２次電池を代表とさ
れる非水電解液２次電池が、アルカリ蓄電池に代わり提
案されている。また、２次電池の性能に大きく影響を及
ぼす電極板に関しては、充放電サイクル寿命延長のた
め、また高エネルギー密度化のため薄膜大面積化を図る
ことが提案されている。例えば、特開昭６３−１０４５
６号公報、特開平３−２８５２６２号公報等には、金属
酸化物、硫化物、ハロゲン化物等の正極活物質粉末に、
導電剤及び結着剤（バインダー）を適当な湿潤剤（溶
媒）に溶解させたものを加えて、ペースト状の活物質塗
布液を調製し、金属箔集電体へ塗布して得られる正極電
極板が開示されている。このバインダーとしては、例え
ばポリフッ化ビニリデン等のフッ素系樹脂またはシリコ
ーン＝アクリル共重合体が用いられている。一般に、こ
の活物質塗布液に含まれるバインダーは、非水電解液に
対して電気化学的に安定であること、非水電解液へ溶出
しないこと、および金属箔集電体に対する高い密着性を
有することが必要とされていた。2. Description of the Related Art In recent years, electronic devices and communication devices have been rapidly reduced in size and weight. Secondary batteries used as power sources for driving these devices are also strongly required to have high energy density and high voltage. A non-aqueous electrolyte secondary battery represented by a lithium-ion secondary battery has been proposed instead of an alkaline storage battery. In addition, regarding the electrode plate that greatly affects the performance of the secondary battery, it has been proposed to increase the area of the thin film in order to extend the charge / discharge cycle life and increase the energy density. For example, Japanese Patent Laid-Open No. 63-1045
No. 6, JP-A-3-285262, etc. describe positive electrode active material powders such as metal oxides, sulfides, and halides.
A positive electrode obtained by adding a solution of a conductive agent and a binder (binder) dissolved in an appropriate wetting agent (solvent) to prepare a paste-like active material coating solution, and coating the solution on a metal foil current collector. A board is disclosed. As the binder, for example, a fluororesin such as polyvinylidene fluoride or a silicone = acrylic copolymer is used. In general, the binder contained in the active material coating solution is electrochemically stable with respect to the non-aqueous electrolyte, does not elute into the non-aqueous electrolyte, and has high adhesion to the metal foil current collector. Was needed.
【０００３】一方、電解液としては、リチウムイオンが
移動できるように一般的に極性の大きな溶媒が用いられ
る。On the other hand, as the electrolytic solution, a solvent having a large polarity is generally used so that lithium ions can move.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、バイン
ダーとして用いられる高分子材料に対して特定の極性溶
媒が組み合わされる場合、例えば、ポリエステル、ポリ
アクリルニトリル−ブタジエン等に対して非水電解液と
してプロピレンカーボネート等の極性溶媒が組み合わさ
れた場合には、これらの高分子材料をバインダーとして
用いた電極板では電解液への耐溶解性に問題（経時的に
バインダーが溶出する傾向がある）が生じていた。However, when a specific polar solvent is combined with the polymer material used as the binder, for example, polyester, polyacrylonitrile-butadiene, etc. are used as the non-aqueous electrolyte in propylene carbonate. When a polar solvent such as the above was combined, there was a problem in the resistance to dissolution in the electrolyte solution (the binder tends to elute with time) in the electrode plate using these polymer materials as the binder. .
【０００５】また、非水電解液への耐溶解性を有する高
分子材料であってその分子中に極性基をあまり持たない
もの、例えば、ポリスチレン−ブタジエンゴム等におい
ては、ポリエステル等の極性基を有するバインダーに比
べて金属箔集電体への密着性が劣るという課題を有して
いた。Further, a polymer material having resistance to dissolution in a non-aqueous electrolytic solution and having few polar groups in its molecule, for example, in polystyrene-butadiene rubber, a polar group such as polyester is used. There was a problem that the adhesiveness to the metal foil current collector was inferior to the binder that it had.
【０００６】したがって、かかる耐溶解性、密着性を満
足しない高分子材料をバインダーとした電極板を用いて
２次電池を構成したときには経時的に安定しないことか
ら、必然的に電極板塗膜形成用のバインダーとして使用
できる高分子材料の種類が限定されてしまうという課題
を有していた。Therefore, when a secondary battery is constructed using an electrode plate using a polymer material as a binder, which does not satisfy such dissolution resistance and adhesiveness, it is not stable over time, and therefore an electrode plate coating film is inevitably formed. However, there is a problem in that the types of polymer materials that can be used as a binder for a glass are limited.
【０００７】[0007]
【課題を解決するための手段】本発明は上記の課題に鑑
みてなされたものであり、２次電池を構成した際経時的
に安定な電極板を付与するとともにバインダーとして適
用可能な高分子材料の範囲を拡大するため、粉末状の活
物質、粉末状の導電材およびバインダーを所定の溶媒に
混合したスラリー状の活物質塗布液を調製し、該塗布液
を集電体の表面に塗布し、次いで溶媒を除去して集電体
上に塗膜を形成する非水電解液２次電池用電極板の製造
方法であって、前記バインダーとして高分子材料と電子
線硬化型モノマーとの混合物を用い、塗膜を形成する際
に電子線照射して前記高分子材料を架橋反応させること
を特徴とする非水電解液２次電池用電極板の製造方法を
提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and is a polymer material that can be applied as a binder while providing a stable electrode plate with time when a secondary battery is constructed. In order to expand the range of, a slurry-like active material coating liquid prepared by mixing a powdery active material, a powdery conductive material and a binder into a predetermined solvent is prepared, and the coating liquid is applied to the surface of the current collector. A method of manufacturing an electrode plate for a non-aqueous electrolyte secondary battery, in which a solvent is then removed to form a coating film on a current collector, wherein a mixture of a polymer material and an electron beam curable monomer is used as the binder. The present invention provides a method for producing an electrode plate for a non-aqueous electrolyte secondary battery, which comprises subjecting the polymer material to a crosslinking reaction by irradiating it with an electron beam when forming a coating film.
【０００８】[0008]
【作用】本発明の方法によれば、非水電解液に対する耐
溶解性が低いか、または金属箔集電体に対する密着性が
低いためバインダー材料としては適当ではなかった高分
子材料に電子線硬化型モノマーを混合し、かつ該混合物
からなる塗膜の形成時に電子線照射して高分子材料内に
架橋構造を形成させることにより、非水電解液に対する
電極板塗膜（バインダー）の耐溶解性が向上するととも
に、金属箔集電体に対する塗膜（バインダー）の密着性
が高められる。According to the method of the present invention, a polymer material which is not suitable as a binder material due to its low resistance to dissolution in a non-aqueous electrolyte or its low adhesion to a metal foil current collector is cured by electron beam. Dissolution resistance of electrode plate coating film (binder) to non-aqueous electrolyte by mixing type monomers and forming a cross-linked structure in the polymer material by electron beam irradiation when forming a coating film composed of the mixture And the adhesion of the coating film (binder) to the metal foil current collector is improved.
【０００９】前記バインダーとして、非水電解液に溶解
してしまう様なバインダーでも、集電体である銅箔との
密着性が乏しいものでも、また逆に電解液に全く解けな
いようなポリマーであって銅箔との密着性が乏しいとい
ったポリマーであっても電子線硬化型モノマーとの混合
物により非水電解液２次電池用バインダーとして用いる
ことが可能となる。As the binder, a binder that is soluble in a non-aqueous electrolyte, a binder that has poor adhesion to a copper foil as a current collector, or a polymer that cannot be dissolved in the electrolyte at all is used. Therefore, even a polymer having poor adhesion to a copper foil can be used as a binder for a non-aqueous electrolyte secondary battery by mixing it with an electron beam curable monomer.
【００１０】一般的には、電解液はイオンの移動が容易
となるような有機溶媒が用いられており、たとえば環状
エステル類、鎖状エステル類、環状エステル類、鎖状エ
ーテル類などがあり、例えば、環状エステル類として
は、プロピレンカーボネート、ブチレンカーボネート、
アセチル−γ−ブチロラクトン、γ−バレロラクトンな
どがあり、また、鎖状エステル類としては、ジメチルカ
ーボネート、ジエチルカーボネート、ジブチルカーボネ
ート、ジプロピルカーボネート、メチルエチルカーボネ
ート、メチルブチルカーボネート、メチルプロピルカー
ボネート、エチルブチルカーボネート、エチルプロピル
カーボネート、ブチルプロピルカーボネート、プロピオ
ン酸アルキルエステル、マロン酸ジアルキルエステル、
酢酸アルキルエステルなどがあり、また、環状エーテル
類としては、テトラヒドロフラン、アルキルテトラヒド
ロフラン、ジアルキルテトラヒドロフラン、アルコキシ
テトラヒドロフラン、ジアルコキシテトラヒドロフラ
ン、１，３−ジオキソラン、アルキル−１，３−ジオキ
ソラン、１，４−ジオキソランなどがあり、また、鎖状
エーテル類としては、１，２−ジメトキシエタン、１，
２−ジエトキシエタン、ジエチルエーテル、エチレング
リコールジアルキルエーテル、ジエチレングリコールジ
アルキルエーテル、トリエチレングリコールジアルキル
エーテル、テトラエチレングリコールジアルキルエーテ
ルなどがある。In general, the electrolytic solution uses an organic solvent that facilitates the movement of ions, such as cyclic esters, chain esters, cyclic esters and chain ethers. For example, as cyclic esters, propylene carbonate, butylene carbonate,
Acetyl-γ-butyrolactone, γ-valerolactone and the like, and as chain esters, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl butyl carbonate, methyl propyl carbonate, ethyl butyl. Carbonate, ethyl propyl carbonate, butyl propyl carbonate, propionic acid alkyl ester, malonic acid dialkyl ester,
There are alkyl acetates and the like, and as cyclic ethers, tetrahydrofuran, alkyltetrahydrofuran, dialkyltetrahydrofuran, alkoxytetrahydrofuran, dialkoxytetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, 1,4-dioxolane and the like. And the chain ethers include 1,2-dimethoxyethane, 1,
2-diethoxyethane, diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether, tetraethylene glycol dialkyl ether and the like.
【００１１】上記の電解液はリチウムイオンの移動が必
要なため、一般的には極性の大きな溶媒を用いる。ポリ
マーハンドブックに記載されている電解液の溶解性パラ
メーターは、たとえば、ジエチルカーボネートは１８．
０、プロピレンカーボネートは１３．３、エチレンカー
ボネートは１４．７、カプロラクトンは１０．１、テト
ラヒドロフランは９．１である。Since the above-mentioned electrolytic solution requires the movement of lithium ions, a solvent having a large polarity is generally used. The solubility parameter of the electrolyte described in the Polymer Handbook is, for example, diethyl carbonate 18.
0, propylene carbonate is 13.3, ethylene carbonate is 14.7, caprolactone is 10.1, and tetrahydrofuran is 9.1.
【００１２】このような電解液に不溶のポリマーとして
は極性の小さいものを用いれば良く、たとえばポリブタ
ジエン（７．２〜８．４）、ポリエチレン（７．７）、
ポリイソブテン（７．１）などが挙げられる。また共重
合ポリマーとしてはポリ（ブタジエン−スチレン）の共
重合体（９０／１０の共重合体比）（８．４）などがあ
る。しかしながら、これらのような極性の小さなポリマ
ーは接着性に乏しいことが知られている。一般的には極
性基、たとえばカルボキシル基、エステル結合基、水酸
基などが接着性に関与していることが知られている。As the polymer insoluble in the electrolytic solution, a polymer having a small polarity may be used. For example, polybutadiene (7.2 to 8.4), polyethylene (7.7),
Examples thereof include polyisobutene (7.1). As the copolymer, there is a poly (butadiene-styrene) copolymer (copolymer ratio of 90/10) (8.4). However, it is known that polymers with small polarities such as these have poor adhesiveness. It is generally known that a polar group such as a carboxyl group, an ester bond group and a hydroxyl group is involved in the adhesiveness.
【００１３】電解液に不溶で集電体に密着するポリマー
は少なく、用いるバインダーが制限される。しかしなが
ら、電子硬化可能なモノマーは極性基であるアクリロイ
ル基を含むため、密着性を上昇させる効果がある。ま
た、電解液に可溶なポリマー、たとえば、ポリエステ
ル、ポリアクリロニトリル、ポリウレタン等は極性基を
持っているため、集電体との密着性が良好である。しか
しながら、電解液に溶解してしまうといった問題があ
る。そこで電子線硬化型モノマーを添加し、電子線照射
することにより、架橋構造を持たせることが可能となる
ため、電解液に溶解しないようになる。There are few polymers that are insoluble in the electrolytic solution and adhere to the current collector, and the binder to be used is limited. However, since the electron-curable monomer contains an acryloyl group which is a polar group, it has an effect of increasing the adhesiveness. Further, since polymers soluble in the electrolytic solution, such as polyester, polyacrylonitrile, and polyurethane, have polar groups, they have good adhesion to the current collector. However, there is a problem that it is dissolved in the electrolytic solution. Therefore, by adding an electron beam-curable monomer and irradiating it with an electron beam, it becomes possible to have a crosslinked structure, so that it will not dissolve in the electrolytic solution.
【００１４】このようなことから、電子線硬化型モノマ
ーの添加により、今までバインダーとして用いることが
不可能であったポリマーも利用することが可能となる。From the above, by adding the electron beam curable monomer, it becomes possible to utilize a polymer which has been impossible to use as a binder until now.
【００１５】ここで、電子線硬化モノマーの添加量は、
多すぎるとそのもの自体が粒子（カーボン）の分散性が
劣るため、あまり多くは添加できない。その適当な配合
比は、用いるモノマー及びバインダーによって異なる
が、０．０５〜２、好ましくは０．０５〜１（重量比）
である。Here, the addition amount of the electron beam curing monomer is
If the amount is too large, the particles themselves have poor dispersibility of the particles (carbon), so too much cannot be added. The suitable compounding ratio varies depending on the monomer and binder used, but is 0.05 to 2, preferably 0.05 to 1 (weight ratio).
Is.
【００１６】本発明において、非水電解液２次電池と
は、リチウム系２次電池で代表される。即ち、その正極
活物質として、例えばＬｉＣｏＯ2 、ＬｉＭｎ2 Ｏ4 等
のリチウム酸化物、ＴｉＳ2 、ＭｎＯ2 、ＭｏＯ3 、Ｖ
2 Ｏ5 等のカルコゲン化合物のうち、一種或いは複数種
を組み合わせて用いると共に、負極活物質として、リチ
ウム、リチウム合金或いは、グラファイト、カーボンブ
ラック、アセチレンブラック等の炭素質材料が好んで用
いられる。特に、ＬｉＣｏＯ2 を正極活物質、炭素質材
料を負極活物質として用いることにより、４ボルト程度
の高い放電電圧が得られる。In the present invention, the non-aqueous electrolyte secondary battery is represented by a lithium secondary battery. That is, examples of the positive electrode active material include lithium oxides such as LiCoO 2 and LiMn 2 O 4 , TiS 2 , MnO 2 , MoO 3 , and V.
Among chalcogen compounds such as 2 O 5 and the like, one kind or a plurality of kinds are used in combination, and as a negative electrode active material, lithium, a lithium alloy, or a carbonaceous material such as graphite, carbon black or acetylene black is preferably used. Particularly, by using LiCoO 2 as the positive electrode active material and the carbonaceous material as the negative electrode active material, a high discharge voltage of about 4 V can be obtained.
【００１７】本発明における電極板は、上記の粉末状活
物質と、バインダー（結着剤）及び適当な分散媒を用い
て混練或いは分散し、活物質塗液を調製し、それを、ア
ルミニウム、銅、ステンレス等の金属箔集電体に塗布し
て得られる。この活物質塗液に、導電剤としてグラファ
イト、カーボンブラック、アセチレンブラック及び金属
粉等を混合することが好ましい。The electrode plate in the present invention is kneaded or dispersed with the above powdery active material using a binder (binder) and an appropriate dispersion medium to prepare an active material coating liquid, which is made of aluminum, It is obtained by coating a metal foil current collector such as copper or stainless steel. It is preferable to mix graphite, carbon black, acetylene black, metal powder and the like as a conductive agent with the active material coating liquid.
【００１８】そのバインダーとして、例えば、熱可塑性
樹脂、即ち、ポリエステル樹脂、ポリアミド樹脂、ポリ
アクリル酸エステル樹脂、ポリカーボネート樹脂、ポリ
ウレタン樹脂、セルロース樹脂、ポリオレフィン樹脂、
ポリビニル樹脂、フッ素系樹脂、ポリイミド樹脂等の中
から任意選択できる。As the binder, for example, thermoplastic resin, that is, polyester resin, polyamide resin, polyacrylic ester resin, polycarbonate resin, polyurethane resin, cellulose resin, polyolefin resin,
It can be arbitrarily selected from polyvinyl resin, fluorine resin, polyimide resin and the like.
【００１９】一方、２次電池を作成するのに用いる電解
液としては、溶質のリチウム塩を前述した有機溶媒に溶
かした非水電解液が用いられる。On the other hand, as the electrolytic solution used for producing the secondary battery, a non-aqueous electrolytic solution prepared by dissolving a solute lithium salt in the above-mentioned organic solvent is used.
【００２０】上記溶質のリチウム塩にはＬｉＣｌＯ4 、
ＬｉＢＦ4 、ＬｉＰＦ6 、ＬｉＡｓＦ6 、ＬｉＣｌ、Ｌ
ｉＢｒ等の無機リチウム塩、およびＬｉＢ（Ｃ6 Ｈ5 ）
4 、ＬｉＮ（ＳＯ2 ＣＦ3 ）2 、ＬｉＣ（ＳＯ2 Ｃ
Ｆ3 ）3 、ＬｉＯＳＯ2 ＣＦ3 、ＬｉＯＳＯ2 Ｃ
2 Ｆ5 、ＬｉＯＳＯ2 Ｃ3 Ｆ7 、ＬｉＯＳＯ2 Ｃ
4 Ｆ9 、ＬｉＯＳＯ2 Ｃ5 Ｆ11、ＬｉＯＳＯ2 Ｃ
6 Ｆ13、ＬｉＯＳＯ2 Ｃ7 Ｆ15等の有機リチウム塩があ
る。The lithium salt of the solute includes LiClO 4 ,
LiBF 4 , LiPF 6 , LiAsF 6 , LiCl, L
Inorganic lithium salt such as iBr, and LiB (C 6 H 5 ).
4 , LiN (SO 2 CF 3 ) 2 , LiC (SO 2 C
F 3) 3, LiOSO 2 CF 3, LiOSO 2 C
2 F 5 , LiOSO 2 C 3 F 7 , LiOSO 2 C
4 F 9 , LiOSO 2 C 5 F 11 , LiOSO 2 C
There are organic lithium salts such as 6 F 13 and LiOSO 2 C 7 F 15 .
【００２１】ここで、バインダーに用いる高分子樹脂
は、塗工溶液の分散性や、コーティング時の塗工性など
を考えると、例えばポリエステル、ポリ（アクリロニト
リル−ブタジエン）ゴム、アルキド樹脂、ポリ（スチレ
ン−ブタジエン）ゴム、水添ポリ（スチレン−ブタジエ
ン）ゴム、ゴムブタジエンゴム等がよい。しかしなが
ら、これらの樹脂の多くは、前述の非水電解液に対して
耐性がなく、これらの樹脂をバインダーとして用いた電
極は非水電解液に溶出してしまう。また、ポリ（スチレ
ン−ブタジエン）ゴムや水添ポリ（スチレン−ブタジエ
ン）ゴム等のバインダーは非水電解液に対しての耐性は
あるが、塗工性においてポリ（スチレン−ブタジエン）
ゴムより優れる水添ポリ（スチレン−ブタジエン）ゴム
は、集電体金属箔への密着性においてポリ（スチレン−
ブタジエン）ゴムに劣る。Here, the polymer resin used as the binder is, for example, polyester, poly (acrylonitrile-butadiene) rubber, alkyd resin, poly (styrene) in view of the dispersibility of the coating solution and the coating property at the time of coating. -Butadiene) rubber, hydrogenated poly (styrene-butadiene) rubber, rubber butadiene rubber and the like are preferable. However, many of these resins do not have resistance to the above-mentioned non-aqueous electrolytic solution, and the electrodes using these resins as binders are eluted in the non-aqueous electrolytic solution. In addition, although binders such as poly (styrene-butadiene) rubber and hydrogenated poly (styrene-butadiene) rubber have resistance to non-aqueous electrolytes, they are poly (styrene-butadiene) in terms of coatability.
Hydrogenated poly (styrene-butadiene) rubber, which is superior to rubber, has good adhesion to the current collector metal foil.
Butadiene) is inferior to rubber.
【００２２】しかし、これらの樹脂に電子線硬化型のモ
ノマーを加えバインダーとし、このバインダーを活物質
及び分散媒と混練したインクを集電体金属箔上に塗布後
乾燥し作成した電極は、電子線を照射して電子線硬化型
モノマーを架橋させる事によって、非水電解液に対する
耐性の付与、および集電体金属箔への密着性向上が可能
である。However, an electrode prepared by adding an electron beam curing type monomer to these resins as a binder, coating the ink on which the binder is kneaded with the active material and the dispersion medium on the current collector metal foil, and drying it is By irradiating with a beam to crosslink the electron beam curable monomer, it is possible to impart resistance to the non-aqueous electrolyte and improve the adhesion to the current collector metal foil.
【００２３】電子線硬化型モノマーと前述樹脂との重量
比は０．０５〜２、好ましくは０．０５〜１の範囲であ
り、用いる電子線硬化型モノマーとしては、１価〜多価
アクリレートモノマー（オリゴマー）、１価〜多価メタ
クリレートモノマー（オリゴマー）、１価〜多価ウレタ
ンアクリレートモノマー（オリゴマー）、１価〜多価エ
ポキシアクリレートモノマー（オリゴマー）、１価〜多
価（メタ）アクリル系含燐モノマー（オリゴマー）、ポ
リエチレングリコールジメタクリレート等がある。The weight ratio of the electron beam curable monomer to the above resin is in the range of 0.05 to 2, preferably 0.05 to 1, and the electron beam curable monomer used is a monovalent to polyvalent acrylate monomer. (Oligomer), monovalent to polyvalent methacrylate monomer (oligomer), monovalent to polyvalent urethane acrylate monomer (oligomer), monovalent to polyvalent epoxy acrylate monomer (oligomer), monovalent to polyvalent (meth) acrylic Examples include phosphorus monomers (oligomers) and polyethylene glycol dimethacrylate.
【００２４】[0024]
実施例１ 負極活物質として、グラファイト粉末（ロンザジャパン
（株）製、ＳＦＧ６）８０重量部、結着剤として水添Ｓ
ＢＲ（日本合成ゴム（株）製、ＤＹＮＡＲＯＮ０９００
Ｐ）１８重量部、電子線硬化型モノマーとしてアクリル
系含燐モノマー（日本化薬（株）製、ＫＡＹＡＭＥＲ
ＰＭ−２、）２．０重量部、及びトルエン１６１．１重
量部を用い、あらかじめトンエルに結着剤を溶解した
後、グラファイト粉末とモノマーをホモジナイザー
（（株）日本精機製作所製、エクセルホモジナイザー）
にて回転数７０００回転で３分間撹拌混合することによ
り、スラリー状の負極活物質合剤を得た。次いで、厚さ
１０μｍの圧延銅箔からなる集電体に前述の負極活物質
合剤をブレードコーターを用い片面に塗布した後、１０
０℃オーブンで乾燥し、溶媒を除去することにより、集
電体に厚さ１００μｍ活物質合剤塗膜を得た。その後、
同様に反対面に塗布し、両面塗布された塗膜を得た。Example 1 80 parts by weight of graphite powder (SFG6 manufactured by Lonza Japan Co., Ltd.) as a negative electrode active material, and hydrogenated S as a binder
BR (manufactured by Japan Synthetic Rubber Co., Ltd., DYNARON 0900)
P) 18 parts by weight, as an electron beam curable monomer, an acrylic phosphorus-containing monomer (manufactured by Nippon Kayaku Co., Ltd., KAYAMER)
PM-2,) 2.0 parts by weight, and toluene 161.1 parts by weight were used to dissolve the binder in the toner beforehand, and then the graphite powder and the monomer were homogenized (excell homogenizer manufactured by Nippon Seiki Co., Ltd.).
The mixture was stirred and mixed at 7,000 rpm for 3 minutes to obtain a slurry-like negative electrode active material mixture. Then, the above negative electrode active material mixture was applied to one surface of a current collector made of rolled copper foil having a thickness of 10 μm using a blade coater, and then 10
By drying in a 0 ° C. oven and removing the solvent, a 100 μm-thick active material mixture coating film was obtained on the current collector. afterwards,
Similarly, the opposite surface was coated to obtain a coating film coated on both sides.
【００２５】得られた活物質塗膜に、電子線照射装置
（日新ハイボルテージ社製、ＥＢＣ−２００−ＡＡ２）
を用いて１０Ｍｒａｄの電子線を照射し、モノマーの重
合を行った。An electron beam irradiator (manufactured by Nisshin High Voltage, EBC-200-AA2) was applied to the obtained active material coating film.
Was irradiated with an electron beam of 10 Mrad to polymerize the monomer.
【００２６】続いて、前記塗膜を有する各集電体を１２
０℃、７２時間のエージング処理に付した。Subsequently, each current collector having the above coating film
It was subjected to an aging treatment at 0 ° C. for 72 hours.
【００２７】さらに、前記活物質合剤塗膜を有する各集
電体の活物質塗膜面を２００℃の加熱ローラプレス機に
よって圧縮処理し、活物質塗膜の均一化を行うことによ
り、目的とする非水電解液２次電池用負極板を得た。Further, the active material coating film surface of each current collector having the active material mixture coating film is compressed by a heating roller press machine at 200 ° C. to homogenize the active material coating film. A negative electrode plate for a non-aqueous electrolyte secondary battery was obtained.
【００２８】得られた極板を２５０℃の熱処理に付して
水分を除去し負極板とした。 実施例２ 負極活物質として、グラファイト粉末（ロンザジャパン
（株）製、ＳＦＧ６）８０重量部、結着剤としてポリエ
ステル樹脂（バイロン３００、東洋防（株）製）２０重
量部、電子線硬化型モノマーとしてエポキシアクリレー
トモノマー（ダイセルユーシービー（株）製、ＥＢ−３
５００）１０重量部、及びトルエン１６４．３重量部を
用い、実施例１と同様の方法で負極活物質合剤を得た。The obtained electrode plate was subjected to heat treatment at 250 ° C. to remove water, thereby obtaining a negative electrode plate. Example 2 80 parts by weight of graphite powder (SFG6, manufactured by Lonza Japan Co., Ltd.) as a negative electrode active material, 20 parts by weight of polyester resin (Vylon 300, manufactured by Toyo Co., Ltd.) as a binder, electron beam curable monomer As an epoxy acrylate monomer (manufactured by Daicel UCB Ltd., EB-3)
500) 10 parts by weight and 164.3 parts by weight of toluene were used to obtain a negative electrode active material mixture in the same manner as in Example 1.
【００２９】ついで、厚さ１０μｍの圧延銅箔からなる
集電体の前述の負極活物質合剤をブレードコーターを用
い両面に塗布した後、１００℃オーブンで乾燥し、溶媒
を除去することにより、集電体に厚さ１００μｍの活物
質合剤塗膜を形成した。以下、実施例１と同様に水分の
除去及びエージングを行った。 比較例１ 負極活物質として、グラファイト粉末（ロンザジャパン
（株）製、ＳＦＧ６）８０重量部、結着剤として水添Ｓ
ＢＲ（日本合成ゴム（株）製、ＤＹＮＡＲＯＮ０９００
Ｐ）２０重量部、及びトルエン１６１．１重量部を用
い、実施例１と同様に負極活物質合剤を得た。さらに、
実施例１と同様にして、この合剤を圧延銅箔に塗布し、
乾燥した（但し、電子線照射は行わなかった）。 比較例２ 負極活物質として、グラファイト粉末（ロンザジャパン
（株）製、ＳＦＧ６）８０重量部、結着剤としてポリエ
ステル樹脂（バイロン３００、東洋紡（株）製）２０重
量部、及びトルエン２３２．０重量部を用い、実施例１
と同様の方法で負極活物質合剤を得た。さらに、実施例
１と同様にこの合剤を圧延銅箔上に塗布し、乾燥及びエ
ージングを行った。Then, the above-mentioned negative electrode active material mixture of a current collector made of rolled copper foil having a thickness of 10 μm was applied on both sides using a blade coater, and then dried in an oven at 100 ° C. to remove the solvent. An active material mixture coating film having a thickness of 100 μm was formed on the current collector. Thereafter, water removal and aging were performed in the same manner as in Example 1. Comparative Example 1 80 parts by weight of graphite powder (SFG6 manufactured by Lonza Japan Co., Ltd.) as a negative electrode active material, and hydrogenated S as a binder.
BR (manufactured by Japan Synthetic Rubber Co., Ltd., DYNARON 0900)
Using 20 parts by weight of P) and 161.1 parts by weight of toluene, a negative electrode active material mixture was obtained in the same manner as in Example 1. further,
This mixture was applied to rolled copper foil in the same manner as in Example 1,
It was dried (however, electron beam irradiation was not performed). Comparative Example 2 80 parts by weight of graphite powder (SFG6 manufactured by Lonza Japan Co., Ltd.) as a negative electrode active material, 20 parts by weight of polyester resin (Byron 300, manufactured by Toyobo Co., Ltd.) as a binder, and 232.0 parts by weight of toluene. Example 1
A negative electrode active material mixture was obtained in the same manner as in. Further, this mixture was applied onto a rolled copper foil in the same manner as in Example 1, dried and aged.
【００３０】まず、集電体である銅箔との密着性及び耐
電解液性を評価するため、以下の実験を行った。First, the following experiments were carried out in order to evaluate the adhesion to a copper foil which is a current collector and the electrolytic solution resistance.
【００３１】実施例、比較例で得られた負極板を非水電
解質液の一種であるプロピレンカーボネート（ＰＣ）に
室温で浸漬したところ、比較例２の電極板においては塗
布活物質が集電体銅箔から速やかに剥離し、または溶出
するのが確認された。（確認は目視及びゲルパーミエシ
ョンクロマトグラフィーにて樹脂の溶出のを確認し
た。）しかしながら、実施例１，２及び比較例１におい
ては１週間の浸漬では変化が確認されなかった。When the negative electrode plates obtained in Examples and Comparative Examples were immersed in propylene carbonate (PC), which is a type of non-aqueous electrolyte solution, at room temperature, in the electrode plates of Comparative Example 2, the coating active material was the current collector. It was confirmed that the copper foil was quickly peeled off or eluted. (Confirmation was made by visual observation and gel permeation chromatography to confirm the elution of the resin.) However, in Examples 1 and 2 and Comparative Example 1, no change was confirmed by immersion for 1 week.
【００３２】また、実施例１，２及び比較例１で作成し
た各電極板の集電体と活物質塗膜との密着性を基盤目テ
スト（ＪＩＳ Ｋ ５４００）にて評価したところ、比
較例１の電極板においては評価２であったが、実施例１
及び２ではいずれも評価１０であった。Further, the adhesion between the current collector of each electrode plate prepared in Examples 1 and 2 and Comparative Example 1 and the coating film of the active material was evaluated by the basic test (JIS K 5400). The evaluation was 2 for the electrode plate of Example 1, but Example 1
In both cases 2 and 2, the evaluation was 10.
【００３３】次に、実施例及び比較例にて得られた極板
を負極として、これを以下に示す正極板と組み合わせ非
水電解液２次電池とした。Next, the electrode plates obtained in Examples and Comparative Examples were used as a negative electrode, and this was combined with the following positive electrode plate to form a non-aqueous electrolyte secondary battery.
【００３４】正極板は、ＬｉＣｏＯ2 粉末９０重量部、
導電剤としてグラファイト粉末５．０重量部、結着剤と
してポリフッ化ビニリデン樹脂（ダイキン工業（株）
製、ネオフロンＶＤＦ ＶＰ−８５０）５．０重量部及
びＮ−メチルピロリドン２０重量部を用い、先にＮ−メ
チルピロリドンに溶解したポリフッ化ビニリデン樹脂
と、すべての添加物を混合し、撹拌機（（株）小平製作
所製、プラネタリーミキサー ＡＣＭ−２ＬＶＴ）にて
２０分間撹拌し、正極活物質合剤を得た。The positive electrode plate was composed of 90 parts by weight of LiCoO 2 powder,
5.0 parts by weight of graphite powder as a conductive agent, polyvinylidene fluoride resin as a binder (Daikin Industries, Ltd.)
(Manufactured by NEOFLON VDF VP-850) 5.0 parts by weight and N-methylpyrrolidone 20 parts by weight, the polyvinylidene fluoride resin previously dissolved in N-methylpyrrolidone and all the additives were mixed, and a stirrer ( The mixture was stirred for 20 minutes with a planetary mixer ACM-2LVT manufactured by Kodaira Manufacturing Co., Ltd. to obtain a positive electrode active material mixture.
【００３５】次いで、厚さ２０μｍのアルミ箔からなる
集電体にこの正極活物質合剤をブレードコーターを用い
て片面塗布した後、１００℃のオーブンで乾燥し溶媒を
除去することにより、集電体上に厚さ９０μｍの活物質
塗膜を形成した。その後、反対面にも同様にして塗布、
乾燥後、両面に塗膜が形成された正極板を得た。Then, the positive electrode active material mixture was applied to one side of a current collector made of an aluminum foil having a thickness of 20 μm by using a blade coater and then dried in an oven at 100 ° C. to remove the solvent to collect the current. A 90 μm-thick active material coating film was formed on the body. After that, apply it to the other side in the same way,
After drying, a positive electrode plate having coating films formed on both surfaces was obtained.
【００３６】さらに、前記集電体の活物質塗膜をローラ
プレス機によって圧延処理し、目的とした非水電解液２
次電池用正極板を得た。得られた正極板は水分除去のた
め、８０℃真空オーブン中にて４８時間エージング処理
した。圧延処理は５０００ｋｇｆ／ｃｍ2 の圧力で行っ
た。Further, the active material coating film of the current collector is rolled by a roller press to obtain the desired non-aqueous electrolyte solution 2.
A positive electrode plate for a secondary battery was obtained. The obtained positive electrode plate was aged in a vacuum oven at 80 ° C. for 48 hours to remove water. The rolling treatment was performed at a pressure of 5000 kgf / cm 2 .
【００３７】実施例１、２および比較例１、２で作製し
たそれぞれの正負極板間に、正負極板より幅広の三次元
空孔構造（海綿状）を有するポリオレフィン系（ポリプ
ロピレン、ポリエチレンまたはそれらの共重合体）の微
多孔性フィルムから成るセパレータを介して、渦巻き状
に捲回して、まず電極体を構成した。次に、この電極体
を、負極端子を兼ねる有底円筒状のステンレス容器内に
挿入し、Ａ４サイズで定格容量５００ｍＡｈの電池を組
み立てた。Between the positive and negative electrode plates produced in Examples 1 and 2 and Comparative Examples 1 and 2, a polyolefin-based (polypropylene, polyethylene or the like) having a three-dimensional pore structure (sponge-like structure) wider than the positive and negative electrode plates. First, an electrode body was constructed by spirally winding the same through a separator made of a microporous film of (copolymer). Next, this electrode body was inserted into a cylindrical stainless steel container having a bottom and also serving as a negative electrode terminal, and a battery of A4 size and rated capacity of 500 mAh was assembled.
【００３８】この電池に、ＥＣ（エチレンカーボネー
ト）：ＰＣ（プロピレンカーボネート）：ＤＭＥ（ジメ
トキシエタン）を体積比１：１：２で全量１リットルに
なるように調製した混合溶媒に、支持塩として１モルの
ＬｉＰＦ6 を溶解したものを電解液とし、注液した。In this battery, a mixed solvent of EC (ethylene carbonate): PC (propylene carbonate): DME (dimethoxyethane) prepared in a volume ratio of 1: 1: 2 to a total volume of 1 liter was used as a supporting salt. A solution obtained by dissolving moles of LiPF 6 was used as an electrolytic solution and injected.
【００３９】電池特性の測定には、２５℃の温度で、各
２０セルずつ、充放電測定装置を用い、最大充電々流
０．２ＣｍＡの電流値で、まず充電方向から、電池電圧
が４．１Ｖになるまで充電し、１０分間の休止の後、同
一電流で、２．７５Ｖになるまで放電し、１０分間の休
止の後、以下、同一条件で、１００サイクル充放電を繰
り返し、充放電特性を測定した。To measure the battery characteristics, at a temperature of 25 ° C., 20 cells each, using a charge / discharge measuring device, and a maximum charge current of 0.2 CmA, a battery voltage of 4. Charge to 1V, rest for 10 minutes, discharge at the same current until 2.75V, rest for 10 minutes, and then repeat 100 cycles of charging and discharging under the same conditions. Was measured.
【００４０】測定結果を表１に示す。The measurement results are shown in Table 1.
【００４１】 ＜表 １＞ １サイクル容量 １００サイクル容量 容量維持率（％） 実施例１ １００ ９４ ９４．０ 実施例２ ９６ ９０ ９３．８ 比較例１ ７２ ５４ ７５．０ 比較例２ ６３ ４８ ７６．２ 実施例１の１サイクル目放電容量を１００とした。実施
例１および実施例２の電池においては、１サイクル目の
初期容量は、比較例１、比較例２と比較しても大きく、
また、１００サイクル経過後の放電容量も比較的大きな
容量を示し、高い容量維持率を示した。<Table 1> 1 cycle capacity 100 cycle capacity Capacity retention rate (%) Example 1 100 94 94.0 Example 2 96 90 93.8 Comparative Example 1 72 54 75.0 Comparative Example 2 63 48 76. The discharge capacity in the first cycle of Example 2 was set to 100. In the batteries of Example 1 and Example 2, the initial capacity in the first cycle was large compared with Comparative Examples 1 and 2,
The discharge capacity after 100 cycles also showed a relatively large capacity and a high capacity retention rate.
【００４２】一方、比較例１及び比較例２の電池におい
ては実施例１および実施例２の電池と比較し１サイクル
目の放電容量も小さく、しかも、１００サイクル経過後
の容量維持率も劣った。On the other hand, in the batteries of Comparative Examples 1 and 2, the discharge capacity at the first cycle was smaller than that of the batteries of Examples 1 and 2, and the capacity retention ratio after 100 cycles was inferior. .
【００４３】このように、実施例１および実施例２で作
製した電池においては高容量、高容量維持率といった優
れた特徴を有することにより、二次電池として十分使用
できるものである。As described above, the batteries produced in Examples 1 and 2 have excellent characteristics such as high capacity and high capacity retention rate, and thus can be sufficiently used as a secondary battery.
【００４４】一方、実施例１、２および比較例１、２で
作製した各電極板を、非水電解液であるプロピレンカー
ボネート（ＰＣ）に浸漬したところ、比較例２の電極板
においては塗布活物質が集電体銅箔上から速やかに剥
離、または溶出したが、実施例１、２及び比較例１の電
極板は浸漬後１週間以上経過しても変化が認められなか
った。On the other hand, when the electrode plates prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were immersed in propylene carbonate (PC) which is a non-aqueous electrolyte solution, the electrode plates of Comparative Example 2 were coated with active material. The substance was quickly peeled off or eluted from the collector copper foil, but no change was observed in the electrode plates of Examples 1 and 2 and Comparative Example 1 even after 1 week or more after immersion.
【００４５】また、実施例１、２および比較例１、２で
作成した各電極板の密着性を碁盤目試験（ＪＩＳ Ｋ
５４００）にて評価したところ、比較例１の電極板にお
いては評価２であったが、実施例１、２および比較例２
の電極板はいずれも評価１０であった。Further, the adhesion of the electrode plates prepared in Examples 1 and 2 and Comparative Examples 1 and 2 was checked by a cross-cut test (JIS K).
5400), the electrode plate of Comparative Example 1 had an evaluation of 2, but Examples 1 and 2 and Comparative Example 2
All of the electrode plates had a rating of 10.
【００４６】[0046]
【発明の効果】以上詳述した通り、本発明の非水電解液
２次電池用電極板の製造方法によれば、粉末状の活物
質、粉末状の導電材およびバインダーを所定の溶媒に混
合したスラリー状の活物質塗布液を調製し、該塗布液を
集電体の表面に塗布し、次いで溶媒を除去して集電体上
に塗膜を形成する非水電解液２次電池用電極板の製造方
法であって、前記バインダーとして高分子材料と電子線
硬化型モノマーとの混合物を用い、塗膜を形成する際に
電子線照射して前記高分子材料を架橋反応させるように
したため、２次電池を構成した際経時的に安定な電極板
を付与するとともにバインダーとして適用可能な高分子
材料の範囲を拡大することができる。As described in detail above, according to the method for producing an electrode plate for a non-aqueous electrolyte secondary battery of the present invention, a powdery active material, a powdery conductive material and a binder are mixed in a predetermined solvent. A non-aqueous electrolyte secondary battery electrode for preparing a slurry-like active material coating solution, applying the coating solution on the surface of a current collector, and then removing the solvent to form a coating film on the current collector A method for producing a plate, wherein a mixture of a polymer material and an electron beam curable monomer is used as the binder, and the polymer material is irradiated with an electron beam to cause a cross-linking reaction when forming a coating film. When a secondary battery is constructed, it is possible to provide a stable electrode plate with time and expand the range of polymer materials applicable as a binder.
フロントページの続き (72)発明者 宮 崎 祐 一 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 梅 田 和 夫 東京都新宿区市谷加賀町一丁目１番１号 大日本印刷株式会社内 (72)発明者 中 野 憲 二 福島県いわき市常磐下船尾町杭出作23−６ 古河電池株式会社いわき事業所内 (72)発明者 萬ヶ原 徹 福島県いわき市常磐下船尾町杭出作23−６ 古河電池株式会社いわき事業所内Front Page Continuation (72) Inventor Yuichi Miyazaki 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Within Dai Nippon Printing Co., Ltd. (72) Inventor Kazuo Umeda, Ichigaya-Kagacho, Shinjuku-ku, Tokyo 1st-1 Dai Nippon Printing Co., Ltd. (72) Inventor Kenji Nakano 23-6 Joban Shimofunao-cho, Iwaki City, Fukushima Prefecture Furukawa Battery Co., Ltd. Iwaki Plant (72) Inventor Toru Mangahara Fukushima 23-6 Fukukawa Battery Co., Ltd., Iwaki Works, Joban Shimo-Funao, Iwaki, Japan
Claims (2)
インダーを所定の溶媒に混合したスラリー状の活物質塗
布液を調製し、該塗布液を集電体の表面に塗布し、次い
で溶媒を除去して集電体上に塗膜を形成する非水電解液
２次電池用電極板の製造方法であって、 前記バインダーとして高分子材料と電子線硬化型モノマ
ーとの混合物を用い、塗膜を形成する際に電子線照射し
て前記高分子材料を架橋反応させることを特徴とする非
水電解液２次電池用電極板の製造方法。1. A powdery active material, a powdery conductive material, and a binder are mixed with a predetermined solvent to prepare a slurry-form active material coating solution, which is applied to the surface of a current collector, and A method for producing an electrode plate for a non-aqueous electrolyte secondary battery, which comprises removing a solvent to form a coating film on a current collector, wherein a mixture of a polymer material and an electron beam curable monomer is used as the binder, A method for producing an electrode plate for a non-aqueous electrolyte secondary battery, which comprises irradiating an electron beam to cross-link the polymer material when forming a coating film.
線硬化型モノマーとの混合物であって、前記高分子材料
に対する前記電子線硬化型モノマーの重量比が０．０５
〜２の範囲にあるものを用いる、請求項１に記載の方
法。2. The binder is a mixture of a polymer material and an electron beam curable monomer, and the weight ratio of the electron beam curable monomer to the polymer material is 0.05.
The method according to claim 1, wherein one in the range of ~ 2 is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6257030A JPH08124560A (en) | 1994-10-21 | 1994-10-21 | Manufacture of plate for nonaqueous electrolytic secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6257030A JPH08124560A (en) | 1994-10-21 | 1994-10-21 | Manufacture of plate for nonaqueous electrolytic secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08124560A true JPH08124560A (en) | 1996-05-17 |
Family
ID=17300773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6257030A Pending JPH08124560A (en) | 1994-10-21 | 1994-10-21 | Manufacture of plate for nonaqueous electrolytic secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08124560A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11283614A (en) * | 1998-03-26 | 1999-10-15 | Tdk Corp | Manufacture of electrode for nonaqueous electrolyte battery |
| JP2006040800A (en) * | 2004-07-29 | 2006-02-09 | Hitachi Chem Co Ltd | Electrode and battery manufactured from binder resin solution for lithium cell electrode, and the solution and active material |
| WO2011044310A1 (en) * | 2009-10-07 | 2011-04-14 | Miltec Corporation | Actinic and electron beam radiation curable electrode binders and electrodes incorporating same |
| JP2018505517A (en) * | 2014-12-08 | 2018-02-22 | 東莞新能源科技有限公司Ｄｏｎｇｇｕａｎ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ | Electrochemical energy storage device |
| US10102979B2 (en) | 2013-05-17 | 2018-10-16 | Miltec Corporation | Actinic and electron beam radiation curable water based electrode binders and electrodes incorporating same |
| US11380884B2 (en) | 2019-01-08 | 2022-07-05 | Ricoh Company, Ltd. | Liquid composition for producing electrode composite material, method for producing electrode, and method for producing electrochemical element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02602A (en) * | 1987-10-30 | 1990-01-05 | Devars Ms Co | Radiation-curable solid electrolyte and equipment for electrolysis by using it |
| JPH06243896A (en) * | 1992-12-25 | 1994-09-02 | Tdk Corp | Lithium secondary battery |
-
1994
- 1994-10-21 JP JP6257030A patent/JPH08124560A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02602A (en) * | 1987-10-30 | 1990-01-05 | Devars Ms Co | Radiation-curable solid electrolyte and equipment for electrolysis by using it |
| JPH06243896A (en) * | 1992-12-25 | 1994-09-02 | Tdk Corp | Lithium secondary battery |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11283614A (en) * | 1998-03-26 | 1999-10-15 | Tdk Corp | Manufacture of electrode for nonaqueous electrolyte battery |
| US6475554B1 (en) | 1998-03-26 | 2002-11-05 | Tdk Corporation | Method of producing electrode of non-aqueous electrolyte battery |
| KR100577907B1 (en) * | 1998-03-26 | 2006-05-09 | 티디케이가부시기가이샤 | Method of manufacturing electrode of electrochemical elements |
| JP2006040800A (en) * | 2004-07-29 | 2006-02-09 | Hitachi Chem Co Ltd | Electrode and battery manufactured from binder resin solution for lithium cell electrode, and the solution and active material |
| JP2013507738A (en) * | 2009-10-07 | 2013-03-04 | ミルテック・コーポレーション | Actinic or electron beam curable electrode binder and electrode comprising the same |
| CN102742047A (en) * | 2009-10-07 | 2012-10-17 | 美奥泰科公司 | Actinic and electron beam radiation curable electrode binders and electrodes incorporating same |
| WO2011044310A1 (en) * | 2009-10-07 | 2011-04-14 | Miltec Corporation | Actinic and electron beam radiation curable electrode binders and electrodes incorporating same |
| US8906548B2 (en) | 2009-10-07 | 2014-12-09 | Miltec Corporation | Actinic and electron beam radiation curable electrode binders and electrodes incorporating same |
| US9543565B2 (en) | 2009-10-07 | 2017-01-10 | Miltec Corporation | Actinic and electron beam radiation curable electrode binders and electrodes incorporating same |
| US10102979B2 (en) | 2013-05-17 | 2018-10-16 | Miltec Corporation | Actinic and electron beam radiation curable water based electrode binders and electrodes incorporating same |
| US11043336B2 (en) | 2013-05-17 | 2021-06-22 | Miltec Corporation | Actinic and electron beam radiation curable water based electrode binders and electrodes incorporating same |
| JP2018505517A (en) * | 2014-12-08 | 2018-02-22 | 東莞新能源科技有限公司Ｄｏｎｇｇｕａｎ Ａｍｐｅｒｅｘ Ｔｅｃｈｎｏｌｏｇｙ Ｌｉｍｉｔｅｄ | Electrochemical energy storage device |
| US11380884B2 (en) | 2019-01-08 | 2022-07-05 | Ricoh Company, Ltd. | Liquid composition for producing electrode composite material, method for producing electrode, and method for producing electrochemical element |
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