JPH09320607A - Binder for electrode formation, electrode mix and electrode structure for non-aqueous battery and the battery - Google Patents
Binder for electrode formation, electrode mix and electrode structure for non-aqueous battery and the batteryInfo
- Publication number
- JPH09320607A JPH09320607A JP8152944A JP15294496A JPH09320607A JP H09320607 A JPH09320607 A JP H09320607A JP 8152944 A JP8152944 A JP 8152944A JP 15294496 A JP15294496 A JP 15294496A JP H09320607 A JPH09320607 A JP H09320607A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- polymer
- vinylidene fluoride
- binder
- fluoride polymer
- 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
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]
【発明の属する技術分野】本発明は、非水電解液に対し
て安定で且つ集電基体に対する良好な接着力を有する電
極を形成するに適した非水系電池電極形成用のフッ化ビ
ニリデン系重合体バインダー、ならびに該バインダーを
用いて形成される電極合剤、電極構造体および非水系電
池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinylidene fluoride-based heavy metal for forming a non-aqueous battery electrode, which is suitable for forming an electrode that is stable to a non-aqueous electrolyte and has good adhesion to a current collector. The present invention relates to a combined binder, an electrode mixture formed using the binder, an electrode structure and a non-aqueous battery.
【０００２】[0002]
【従来の技術】非水系電池の電極活物質のバインダーと
して、フッ化ビニリデン系重合体が使用されているが、
従来のフッ化ビニリデン系重合体は活物質との結着力や
集電体との接着力が比較的に弱いため、使用中に活物質
の脱落や合剤層の集電体からの剥離などの現象が見られ
た。このため、電池を長期間使用中にその放電容量の低
下が大きくなる場合があり、実用上問題であった。2. Description of the Related Art A vinylidene fluoride polymer is used as a binder for an electrode active material of a non-aqueous battery.
Since conventional vinylidene fluoride-based polymers have a relatively weak binding force with the active material and adhesiveness with the current collector, the active material may fall off during use, or the mixture layer may peel off from the current collector. A phenomenon was seen. For this reason, the discharge capacity may be greatly reduced during long-term use of the battery, which is a practical problem.
【０００３】この問題を解決するために、シラン変性し
たフッ化ビニリデン系重合体（特開平６−９３０２５号
公報）、カルボキシル基またはカーボネート基を含有す
るフッ化ビニリデン系重合体（特開平６−１７２４５２
号公報）などが提案されているが、若干の問題点があ
り、また材料の安定性や生産性において、いずれも接着
力が未だ満足とはいえず、他方従来のフッ化ビニリデン
系重合体に比べて電解液に対する初期膨潤度が増大する
という欠点も認められた。In order to solve this problem, a silane-modified vinylidene fluoride polymer (JP-A-6-93025) and a vinylidene fluoride polymer containing a carboxyl group or a carbonate group (JP-A-6-172452).
However, there are some problems, and in terms of stability and productivity of the material, the adhesive strength is not yet satisfactory. On the other hand, the conventional vinylidene fluoride-based polymer has In comparison, a drawback that the initial swelling degree with respect to the electrolytic solution was increased was also recognized.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明の主た
る目的は、非水電解液に対して安定で且つ集電基体に対
する良好な接着力を有する電極を形成するに適したフッ
化ビニリデン系重合体バインダーを提供することにあ
る。Therefore, the main object of the present invention is to provide a vinylidene fluoride-based heavy metal suitable for forming an electrode which is stable to a non-aqueous electrolyte and has good adhesion to a current collecting substrate. To provide a coalescing binder.
【０００５】本発明の別の目的は、上記バインダーを用
いて良好な特性を有する電極合剤、電極構造体および非
水系電池を提供することにある。Another object of the present invention is to provide an electrode mixture, an electrode structure and a non-aqueous battery which have good characteristics by using the above binder.
【０００６】[0006]
【課題を解決するための手段】本発明者らの研究によ
り、上述の目的の達成のためには、比較的大なる固有粘
度（従って大なる重合度）を有するフッ化ビニリデン系
重合体と、カルボキシル基又はエポキシ基を導入したフ
ッ化ビニリデン系重合体とを併用することが極めて効果
的であることが見出された。According to the studies by the present inventors, in order to achieve the above-mentioned object, a vinylidene fluoride-based polymer having a relatively large intrinsic viscosity (and thus a large polymerization degree), It has been found that the combined use with a vinylidene fluoride polymer having a carboxyl group or an epoxy group introduced is extremely effective.
【０００７】すなわち、本発明の非水系電池形成用バイ
ンダーは、固有粘度が１．２ｄｌ／ｇ以上であるフッ化
ビニリデン系重合体（Ａ）と、カルボキシル基またはエ
ポキシ基を有するフッ化ビニリデン系重合体（Ｂ）とか
らなり、重合体（Ａ）と（Ｂ）との合計量に対する重合
体（Ａ）の割合が５〜７５重量％の範囲にあることを特
徴とするものである。That is, the non-aqueous battery-forming binder of the present invention comprises a vinylidene fluoride polymer (A) having an intrinsic viscosity of 1.2 dl / g or more and a vinylidene fluoride-based polymer having a carboxyl group or an epoxy group. The polymer (A) is composed of the polymer (B), and the ratio of the polymer (A) to the total amount of the polymers (A) and (B) is in the range of 5 to 75% by weight.
【０００８】また本発明のバインダーは、好ましくは上
記重合体（Ａ）および（Ｂ）を有機溶媒に溶解した状態
で使用に供せられ、これに、電極活物質および必要に応
じて加えられるカーボンブラック等の導電助剤等からな
る粉末電極材料を分散させることにより、電極合剤が得
られる。この電極合剤を集電基体の少なくとも一面に塗
布し電極合剤層（電極層）を形成することにより電極構
造体が得られ、更にこの電極構造体により正極および負
極の少なくとも一方を形成し、正極−負極間に非水電解
液を配置することにより非水系電池が形成される。The binder of the present invention is preferably used in a state in which the above polymers (A) and (B) are dissolved in an organic solvent, to which an electrode active material and carbon added as necessary are added. An electrode mixture is obtained by dispersing a powder electrode material such as a conductive auxiliary agent such as black. An electrode structure is obtained by applying this electrode mixture to at least one surface of a current collecting substrate to form an electrode mixture layer (electrode layer), and further forming at least one of a positive electrode and a negative electrode with this electrode structure, A non-aqueous battery is formed by disposing a non-aqueous electrolytic solution between the positive electrode and the negative electrode.
【０００９】本発明のフッ化ビニリデン系重合体（Ａ）
（非（接着）改質重合体）とフッ化ビニリデン系重合体
（Ｂ）（（接着）改質重合体）との併用にかかるバイン
ダーは、重合体（Ａ）単独にほぼ匹敵する非水電解液に
対する耐膨潤性を示す（後記表１参照）のみならず、形
成された電極合剤層の集電基体に対する接着性が、カル
ボキシル基またはエポキシ基を導入して接着性を改質し
た重合体（Ｂ）単独の場合に比べても著しく改善された
接着強度を示す（後記表２参照）。この結果は、本発明
者らにとっても極めて意外であり、その理由は必ずしも
明らかでないが、以下の（イ）〜（ロ）のような効果が
総合して発現したものと解される。The vinylidene fluoride polymer (A) of the present invention
The binder used in combination with the (non- (adhesive) modified polymer) and the vinylidene fluoride-based polymer (B) ((adhesive) modified polymer) is a non-aqueous electrolyte that is almost comparable to the polymer (A) alone. A polymer not only showing swelling resistance to a liquid (see Table 1 below), but also having improved adhesiveness of the formed electrode mixture layer to a current collecting substrate by introducing a carboxyl group or an epoxy group. (B) shows significantly improved adhesive strength as compared with the case of using alone (see Table 2 below). This result is extremely surprising to the present inventors, and although the reason is not always clear, it is understood that the following effects (a) to (b) are comprehensively expressed.
【００１０】（イ）電極合剤層中の改質重合体（Ｂ）の
カルボキシル基またはエポキシ基が集電基体である金属
との界面で形成する水素結合が、電極合剤層−集電基体
界面強度を向上する。(A) The hydrogen bond formed at the interface between the carboxyl group or the epoxy group of the modified polymer (B) in the electrode mixture layer and the metal which is the current collecting substrate is the electrode mixture layer-current collecting substrate. Improve the interface strength.
【００１１】（ロ）高分子量化した重合体（Ａ）の配合
により、フッ化ビニリデン系重合体分子相互間での分子
の絡み合い、フッ化ビニリデン系重合体分子と粉末電極
材料との絡み合いが増大し、電極合剤層のマトリクス強
度が増大し、集電基体表面へのアンカー強度の向上にも
寄与する。改質重合体（Ｂ）単独を高分子量化した際
の、低結晶性による電解液に対する膨潤度の増大も防止
される。(B) By blending the polymer (A) having a high molecular weight, the entanglement of molecules between vinylidene fluoride polymer molecules and the entanglement of vinylidene fluoride polymer molecules with the powder electrode material are increased. However, the matrix strength of the electrode mixture layer is increased, which also contributes to the improvement of the anchor strength to the surface of the current collecting substrate. When the modified polymer (B) alone has a high molecular weight, it is also possible to prevent an increase in the degree of swelling in the electrolytic solution due to low crystallinity.
【００１２】[0012]
【発明の実施の形態】本発明の非水系電池電極形成用バ
インダーの第一の成分としてのフッ化ビニリデン系重合
体（Ａ）には、フッ化ビニリデンの単独重合体および、
フッ化ビニリデンと、これと共重合可能な他の単量体、
例えばエチレン、プロピレン等の炭化水素系単量体、ま
たはフッ化ビニル・トリフルオロエチレン、トリフルオ
ロクロロエチレン、テトラフルオロエチレン、ヘキサフ
ルオロプロピレン、フルオロアルキルビニルエーテル等
のフッ化ビニリデン以外の含フッ素単量体との共重合体
が含まれるが、共重合体の場合、フッ化ビニリデン単位
を９０モル％以上、特に９５モル％以上の範囲で維持す
ることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION A vinylidene fluoride polymer (A) as a first component of a binder for forming a non-aqueous battery electrode of the present invention includes a vinylidene fluoride homopolymer and
Vinylidene fluoride and other monomers copolymerizable with it,
For example, hydrocarbon-based monomers such as ethylene and propylene, or fluorine-containing monomers other than vinylidene fluoride such as vinyl fluoride / trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, and fluoroalkyl vinyl ethers. In the case of the copolymer, it is preferable to maintain the vinylidene fluoride unit in the range of 90 mol% or more, particularly 95 mol% or more.
【００１３】本発明に従いフッ化ビニリデン系重合体
（Ａ）としては、固有粘度（本書においては、樹脂４ｇ
を１リットルのＮ，Ｎ−ジメチルホルムアミドに溶解し
た溶液の３０℃における対数粘度をいう）が、１．２ｄ
ｌ／ｇ以上、好ましくは１．６ｄｌ／ｇ以上、のものが
用いられる。１．２ｄｌ／ｇ未満では、重合体（Ａ）の
高分子量化による本発明の所定の効果を得ることが困難
である。フッ化ビニリデン系重合体（Ａ）の固有粘度
は、２０ｄｌ／ｇ以下、特に１５ｄｌ／ｇ以下であるこ
とが好ましい。２０ｄｌ／ｇを超えると、有機溶媒への
溶解によりバインダー溶液ならびに電極合剤を形成する
際の溶解が困難になり、またバインダー溶液のゲル化の
制御が困難となり、電極合剤の塗布による電極合剤層の
形成が困難となる。The vinylidene fluoride polymer (A) according to the present invention has an intrinsic viscosity (in this specification, 4 g of resin).
Is a solution of 1 liter of N, N-dimethylformamide in 30 ° C.) of 1.2d
Those having a l / g or more, preferably 1.6 dl / g or more are used. When it is less than 1.2 dl / g, it is difficult to obtain the predetermined effect of the present invention by increasing the molecular weight of the polymer (A). The intrinsic viscosity of the vinylidene fluoride polymer (A) is preferably 20 dl / g or less, and particularly preferably 15 dl / g or less. When it exceeds 20 dl / g, it becomes difficult to dissolve the binder solution and the electrode mixture when forming the binder solution due to the dissolution in the organic solvent, and it becomes difficult to control the gelation of the binder solution, and the electrode mixture by the application of the electrode mixture is difficult. It becomes difficult to form the agent layer.
【００１４】フッ化ビニリデン系重合体（Ａ）は、上記
モノマーの懸濁重合、乳化重合、溶液重合等により得ら
れるが、分子量制御および高分子量化の容易な懸濁重合
あるいは乳化重合により製造することが好ましい。The vinylidene fluoride polymer (A) can be obtained by suspension polymerization, emulsion polymerization, solution polymerization or the like of the above-mentioned monomers, but it is produced by suspension polymerization or emulsion polymerization which facilitates molecular weight control and high molecular weight. It is preferable.
【００１５】他方、改質フッ化ビニリデン系重合体
（Ｂ）としては、カルボキシル基またはエポキシ基を有
するものが用いられる。カルボキシル基を有するフッ化
ビニリデン系重合体（Ｂ）としては、上記したフッ化ビ
ニリデン系重合体（Ａ）を構成するフッ化ビニリデンモ
ノマー１００重量部に対して、０．１〜３重量部のアク
リル酸、クロトン酸などの不飽和一塩基酸、またはマレ
イン酸、シトラコン酸などの不飽和二塩基酸もしくはそ
のモノアルキルエステルを共重合させて得られるカルボ
キシル基含有フッ化ビニリデン系共重合体（例えば特開
平６−１７２４５２号公報に開示されるように後述の方
法で測定されたカルボニル基含有量が１×１０-5〜５×
１０-4モル／ｇを有するもの）などが好ましく用いられ
る。またエポキシ基を有するフッ化ビニリデン系重合体
（Ｂ）の好ましい具体例としては、特願平７−１８４９
６１号の明細書に開示されるエポキシ基含有フッ化ビニ
リデン系共重合体が挙げられる。より具体的には、該エ
ポキシ基含有フッ化ビニリデン系共重合体は、上記した
フッ化ビニリデン系重合体を構成するモノマー（特にフ
ッ化ビニリデン）１００モルに対して、０．２−５．０
モルのアリルグリシジルエーテル、メタアリルグリシジ
ルエーテル、クロトン酸グリシジルエステル、アリル酢
酸グリシジルエステル等のエポキシ基含有ビニル単量体
（好ましくはアリルグリシジルエーテル）および０−
５．０モルの第３の単量体（好ましくは上記したような
不飽和二塩基酸のモノエステル）を共重合することによ
り得られるものである。On the other hand, as the modified vinylidene fluoride polymer (B), one having a carboxyl group or an epoxy group is used. As the vinylidene fluoride polymer (B) having a carboxyl group, 0.1 to 3 parts by weight of acrylic is used with respect to 100 parts by weight of the vinylidene fluoride monomer constituting the above-mentioned vinylidene fluoride polymer (A). An unsaturated monobasic acid such as an acid or crotonic acid, or an unsaturated dibasic acid such as maleic acid or citraconic acid, or a monoalkyl ester thereof is used to obtain a carboxyl group-containing vinylidene fluoride-based copolymer (for example, As disclosed in Kaihei 6-172452, the carbonyl group content measured by the method described later is from 1 × 10 −5 to 5 ×.
Those having a concentration of 10 −4 mol / g) are preferably used. Further, as a preferred specific example of the vinylidene fluoride polymer (B) having an epoxy group, Japanese Patent Application No. 7-1849
Epoxy group-containing vinylidene fluoride copolymers disclosed in the specification of No. 61 are mentioned. More specifically, the epoxy group-containing vinylidene fluoride copolymer is 0.2-5.0 with respect to 100 mol of the monomer (particularly vinylidene fluoride) constituting the above-mentioned vinylidene fluoride polymer.
Moles of allyl glycidyl ether, methallyl glycidyl ether, crotonic acid glycidyl ester, allyl acetic acid glycidyl ester, and other epoxy group-containing vinyl monomers (preferably allyl glycidyl ether) and 0-
It is obtained by copolymerizing 5.0 mol of a third monomer (preferably a monoester of unsaturated dibasic acid as described above).
【００１６】これらカルボキシル基またはエポキシ基を
有する改質フッ化ビニリデン系重合体（Ｂ）は、懸濁重
合、乳化重合、溶液重合等により、固有粘度が、好まし
くは０．２−５．０ｄｌ／ｇ、より好ましくは０．５−
２．０ｄｌ／ｇのものとして調製される。フッ化ビニリ
デン系重合体（Ｂ）は、重合体（Ａ）よりも小なる固有
粘度を有することが好ましく、特に重合体（Ｂ）の固有
粘度をηB 、重合体（Ａ）の固有粘度をηA としたとき
にηB ／ηA が０．９以下、より好ましくは０．８以
下、更に好ましくは０．７以下となるような固有粘度を
有することが好ましい。これは、改質フッ化ビニリデン
系重合体（Ｂ）を、フッ化ビニリデン系重合体（Ａ）と
同様なレベルまで高分子量化するのは、重合性の低下に
より極めて長時間を要するのみでなく、改質フッ化ビニ
リデン系重合体（Ｂ）の熱安定性が低下しがちであると
いう消極的理由に加えて、改質重合体（Ｂ）の分子量を
相対的に低分子量化し、高分子量重合体（Ａ）と組み合
わせることにより得られる比較的ブロードな分子量分布
特性が、特にバインダー溶液ならびに電極合剤スラリー
ないしペーストを形成して、その塗布乾燥により集電基
体上に電極合剤層を形成する際に、粘度調整が容易であ
り、改善された塗布適性を通じて、均質な電極合剤層を
与え、ひいては集電基体との良好な接着性を与える上
で、好ましいからである。The modified vinylidene fluoride polymer (B) having a carboxyl group or an epoxy group has an intrinsic viscosity of preferably 0.2-5.0 dl / by suspension polymerization, emulsion polymerization, solution polymerization or the like. g, more preferably 0.5-
Prepared as 2.0 dl / g. The vinylidene fluoride polymer (B) preferably has an intrinsic viscosity smaller than that of the polymer (A). In particular, the intrinsic viscosity of the polymer (B) is η B and the intrinsic viscosity of the polymer (A) is η B / η a is taken as eta a is 0.9 or less, more preferably 0.8 or less, more preferably preferably has an intrinsic viscosity that is 0.7 or less. This is because it takes not only an extremely long time for the modified vinylidene fluoride-based polymer (B) to have a high molecular weight to the same level as the vinylidene fluoride-based polymer (A) due to a decrease in the polymerizability. In addition to the negative reason that the thermal stability of the modified vinylidene fluoride polymer (B) tends to be lowered, the molecular weight of the modified polymer (B) is relatively lowered to increase the high molecular weight. The relatively broad molecular weight distribution characteristics obtained by combination with the combination (A) form a binder solution and an electrode mixture slurry or paste, and form an electrode mixture layer on the current collecting substrate by coating and drying the same. This is because it is preferable in that the viscosity can be easily adjusted, a uniform electrode mixture layer can be provided through improved coating suitability, and good adhesion to the current collecting substrate can be obtained.
【００１７】すなわち、非改質の高分子量重合体（Ａ）
と改質重合体（Ｂ）には、物理的な分子絡み合い増強効
果と、化学的な集電基体への接着補強効果とに分離した
機能をそれぞれ分担させ、且つそれらが均質な電極合剤
層中に混在して生ずる相乗効果により、改善された集電
基体への接着性と良好な耐非水電解液特性を発揮させる
ことが好ましい。That is, the unmodified high molecular weight polymer (A)
The modified polymer (B) and the modified polymer (B) are divided into a function of enhancing physical entanglement of molecules and a function of chemically reinforcing adhesion to the current collecting substrate, and an electrode mixture layer in which they are homogeneous. It is preferable to exhibit improved adhesion to the current collecting substrate and good non-aqueous electrolyte resistance by a synergistic effect that occurs when they are mixed together.
【００１８】上述したようにフッ化ビニリデン系重合体
（Ａ）および（Ｂ）は、いずれも、懸濁重合、乳化重
合、溶液重合等の方法により製造することができる。重
合方法としては、後処理の容易さ等の点から、水系の懸
濁重合、乳化重合が好ましく、水系懸濁重合が特に好ま
しい。As described above, each of the vinylidene fluoride polymers (A) and (B) can be produced by a method such as suspension polymerization, emulsion polymerization or solution polymerization. As the polymerization method, aqueous suspension polymerization and emulsion polymerization are preferable, and aqueous suspension polymerization is particularly preferable, from the viewpoint of easy post-treatment and the like.
【００１９】水を分散媒とした懸濁重合においては、メ
チルセルロース、メトキシ化メチルセルロース、プロポ
キシ化メチルセルロース、ヒドロキシエチルセルロー
ス、ヒドロキシプロピルセルロース、ポリビニルアルコ
ール、ポリエチレンオキシド、ゼラチン等の懸濁剤を、
水に対して０．００５〜１．０重量％、好ましくは０．
０１〜０．４重量％の範囲で添加して使用する。In suspension polymerization using water as a dispersion medium, a suspending agent such as methyl cellulose, methoxylated methyl cellulose, propoxylated methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyethylene oxide and gelatin is used.
0.005-1.0 wt% with respect to water, preferably 0.1.
It is used by adding in the range of 01 to 0.4% by weight.
【００２０】重合開始剤としては、ジイソプロピルパー
オキシジカーボネート、ジノルマルプロピルパーオキシ
ジカーボネート、ジノルマルヘプタフルオロプロピルパ
ーオキシジカーボネート、イソブチリルパーオキサイ
ド、ジ（クロロフルオロアシル）パーオキサイド、ジ
（パーフルオロアシル）パーオキサイド等が使用でき
る。その使用量は、単量体合計量に対して０．１〜５重
量％、好ましくは０．５〜２重量％である。Examples of the polymerization initiator include diisopropyl peroxydicarbonate, dinormal propyl peroxy dicarbonate, dinormal heptafluoropropyl peroxy dicarbonate, isobutyryl peroxide, di (chlorofluoroacyl) peroxide, di (peroxide). Fluoroacyl) peroxide or the like can be used. The amount used is 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the total amount of monomers.
【００２１】酢酸エチル、酢酸メチル、アセトン、エタ
ノール、ｎ−プロパノール、アセトアルデヒド、プロピ
ルアルデヒド、プロピオン酸エチル、四塩化炭素等の連
鎖移動剤を添加して、得られる重合体の重合度を調節す
ることも可能である。その使用量は、通常は、単量体合
計量に対して０．１〜５重量％、好ましくは０．５〜３
重量％である。Controlling the degree of polymerization of the resulting polymer by adding a chain transfer agent such as ethyl acetate, methyl acetate, acetone, ethanol, n-propanol, acetaldehyde, propyl aldehyde, ethyl propionate or carbon tetrachloride. Is also possible. The amount used is usually 0.1 to 5% by weight, preferably 0.5 to 3% by weight based on the total amount of monomers.
% By weight.
【００２２】単量体の合計仕込量は、単量体合計量：水
の重量比で、１：１〜１：１０、好ましくは１：２〜
１：５であり、重合は温度１０〜５０℃で１０〜１００
時間行う。The total charging amount of the monomers is 1: 1 to 1:10, preferably 1: 2 to 1 in the weight ratio of total monomer: water.
1: 5, the polymerization is 10-100 at a temperature of 10-50 ° C.
Do time.
【００２３】本発明のバインダーは、上記フッ化ビニリ
デン系重合体（Ａ）とフッ化ビニリデン系重合体（Ｂ）
とを、両者の合計量に対する重合体（Ａ）の割合が５〜
７５重量％、好ましくは１０〜５０重量％、となるよう
に混合することにより得られる。The binder of the present invention comprises the above vinylidene fluoride polymer (A) and vinylidene fluoride polymer (B).
And the ratio of the polymer (A) to the total amount of both is 5 to
It is obtained by mixing so as to be 75% by weight, preferably 10 to 50% by weight.
【００２４】エポキシ基を有するフッ化ビニリデン系重
合体（Ｂ）（特にそれ自体にカルボキシル基等のエポキ
シ硬化作用を有する基を有さないもの）を用いるときに
は、エポキシ基１モルに対し、０．３〜３．０モルの硬
化剤を併用することが好ましい。この硬化剤としては、
アミン、酸無水物、グリシジルエーテルのアミン付加物
等の一般にエポキシ樹脂の硬化剤として用いられる低分
子量化合物を用いることも可能であるが、上記したカル
ボキシル基を有するフッ化ビニリデン系重合体（Ｂ）を
硬化剤として併用することがより好ましい。When the vinylidene fluoride polymer (B) having an epoxy group (in particular, one which does not have a group having an epoxy-curing action such as a carboxyl group in itself) is used, the amount of the compound is 0. It is preferable to use a curing agent in an amount of 3 to 3.0 mol in combination. As this curing agent,
Although it is possible to use a low molecular weight compound generally used as a curing agent for epoxy resins such as amines, acid anhydrides and amine adducts of glycidyl ether, the above vinylidene fluoride polymer (B) having a carboxyl group. Is more preferably used as a curing agent.
【００２５】本発明のバインダーは、上記フッ化ビニリ
デン系重合体（Ａ）とフッ化ビニリデン系重合体（Ｂ）
とを粉体混合し、後述する粉末電極材料と混合して、溶
融成形あるいは粉末成形により集電基体上に電極合剤層
を形成する態様で用いることも可能である。しかし、よ
り好ましくは、その良好な有機溶媒溶解適性ならびに皮
膜形成特性を利用して、有機溶媒に溶解してバインダー
溶液を形成し、更に粉末電極材料を分散させて電極合剤
スラリーを形成させることにより、粉末電極材料に対し
より少なる使用量でバインダー効果を発生させ、電極合
剤層の内部抵抗の増大を防止することが好ましい。The binder of the present invention comprises the above vinylidene fluoride polymer (A) and vinylidene fluoride polymer (B).
It is also possible to powder-mix and mix with the powder electrode material described later to form an electrode mixture layer on the current collecting substrate by melt molding or powder molding. However, more preferably, by utilizing the good suitability for dissolving in an organic solvent and the film forming property, it is possible to dissolve in an organic solvent to form a binder solution and further disperse the powder electrode material to form an electrode mixture slurry. Therefore, it is preferable to generate a binder effect with a smaller amount used for the powder electrode material and prevent an increase in internal resistance of the electrode mixture layer.
【００２６】上記フッ化ビニリデン系重合体（Ａ）およ
び（Ｂ）を溶解して、本発明のバインダー溶液を得るた
めに用いられる有機溶媒は、好ましくは極性のものであ
り、例えばＮ−メチル−２−ピロリドン、ジメチルフォ
ルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−
ジメチルスルフォキシド、ヘキサメチルフォスフォアミ
ド、ジオキサン、テトラヒドロフラン、テトラメチルウ
レア、トリエチルフォスフェイト、トリメチルフォスフ
ェイト、などが挙げられる。上記の極性有機溶媒の中で
も、溶解力の大きいＮ−メチル−２−ピロリドン、ジメ
チルフォルムアミド、Ｎ，Ｎ−ジメチルアセトアミドな
どの含窒素系有機溶媒がより好ましく用いられる。ま
た、これら有機溶媒は単独での使用のみならず二種以上
を混合した混合溶媒として用いることも出来る。The organic solvent used to obtain the binder solution of the present invention by dissolving the above vinylidene fluoride polymers (A) and (B) is preferably a polar solvent, for example, N-methyl- 2-pyrrolidone, dimethylformamide, N, N-dimethylacetamide, N, N-
Examples thereof include dimethyl sulfoxide, hexamethylphosphoamide, dioxane, tetrahydrofuran, tetramethylurea, triethylphosphate, trimethylphosphate, and the like. Among the above polar organic solvents, nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and N, N-dimethylacetamide, which have high solubility, are more preferably used. These organic solvents can be used not only alone but also as a mixed solvent of two or more.
【００２７】本発明のバインダー溶液を得るに当り、こ
れら有機溶媒１００重量部当り、前記フッ化ビニリデン
系重合体（Ａ）および（Ｂ）を、合計量で、０．１〜２
０重量部、更に好ましくは０．５〜１５重量部、特に１
〜１０重量部、の割合で溶解することが好ましい。０．
１重量部未満では、溶液中での重合体の占める割合が小
さすぎ、粉末電極材料を相互に結着させるバインダーと
しての効果が得られない。また、２０重量部を越える
と、高重合度フッ化ビニリデン系重合体（Ａ）を含むた
め、溶液自体の粘度が異常に高くなり過ぎて電極合剤の
調整が困難になることがある。In obtaining the binder solution of the present invention, the vinylidene fluoride polymers (A) and (B) are added in a total amount of 0.1 to 2 per 100 parts by weight of these organic solvents.
0 parts by weight, more preferably 0.5 to 15 parts by weight, especially 1
It is preferable to dissolve at a ratio of 10 to 10 parts by weight. 0.
If it is less than 1 part by weight, the proportion of the polymer in the solution is too small, and the effect as a binder for binding the powder electrode materials to each other cannot be obtained. On the other hand, if it exceeds 20 parts by weight, since the vinylidene fluoride polymer (A) having a high degree of polymerization is contained, the viscosity of the solution itself becomes excessively high, which may make it difficult to adjust the electrode mixture.
【００２８】上記のようにして得られた本発明のフッ化
ビニリデン系重合体バインダー溶液に、粉末電極材料
（電極活物質および必要に応じて加えられる導電助剤、
その他の助剤）を分散混合することにより電極合剤スラ
リーが得られる。また、上記のように一旦バインダー溶
液を形成後、粉末電極材料を形成するのでなく、重合体
（Ａ）、（Ｂ）および粉末電極材料をほぼ同時に有機溶
媒中に混合分散させて、一挙に電極合剤スラリーを形成
することも好ましい。Powdered electrode material (electrode active material and conductive auxiliary agent added as necessary, to the vinylidene fluoride polymer binder solution of the present invention obtained as described above,
The other mixture is dispersed and mixed to obtain an electrode mixture slurry. Further, as described above, the powder electrode material is not formed after the binder solution is once formed, but the polymers (A) and (B) and the powder electrode material are mixed and dispersed in the organic solvent almost at the same time, and the electrode is formed at once. It is also preferable to form a mixture slurry.
【００２９】本発明の電極合剤は、非水系電池の正極合
剤、負極合剤のいずれにも適用可能である。The electrode mixture of the present invention can be applied to both a positive electrode mixture and a negative electrode mixture of a non-aqueous battery.
【００３０】リチウムイオン二次電池用の活物質として
は、正極の場合は、一般式ＬｉＭＹ2 （Ｍは、Ｃｏ、Ｎ
ｉ、Ｆｅ、Ｍｎ、Ｃｒ、Ｖ等の遷移金属の少なくとも一
種：ＹはＯ、Ｓ等のカルコゲン元素）で表わされる複合
金属カルコゲン化合物、特にＬｉＮｉx Ｃｏ1-x Ｏ
2 （０≦ｘ≦１）をはじめとする複合金属酸化物やＬｉ
Ｍｎ2 Ｏ4 などのスピネル構造をとる複合金属酸化物が
好ましい。負極の場合は、黒鉛、活性炭、あるいはフェ
ノール樹脂やピッチ等を焼成炭化したもの等の粉末状炭
素質材料に加えて、金属酸化物系のＧｅＯ、ＧｅＯ2 、
ＳｎＯ、ＳｎＯ2 、ＰｂＯ、ＰｂＯ2 など、あるいはこ
れらの複合金属酸化物（例えば特開平７−２４９４０９
号公報に開示されるもの）等が用いられる。As an active material for a lithium ion secondary battery, in the case of a positive electrode, a general formula LiMY 2 (M is Co, N
i, Fe, Mn, Cr, at least one transition metal of V such: Y is O, complex metal chalcogen compound represented by chalcogen element such as S), in particular LiNi x Co 1-x O
2 (0 ≦ x ≦ 1) and other complex metal oxides and Li
A composite metal oxide having a spinel structure such as Mn 2 O 4 is preferable. In the case of the negative electrode, in addition to graphite, activated carbon, or a powdery carbonaceous material such as a phenol resin or a material obtained by firing and carbonizing pitch, metal oxide GeO, GeO 2 ,
SnO, SnO 2 , PbO, PbO 2 , or a composite metal oxide thereof (for example, see JP-A-7-249409)
And the like disclosed in Japanese Patent Application Laid-Open Publication No. H10-209, for example.
【００３１】電池における導電助剤は、ＬｉＣｏＯ2 等
の電子伝導性の小さい活物質を使用する場合に、電極合
剤層の導電性を向上する目的で添加するもので、カーボ
ンブラック、黒鉛微粉末あるいは繊維等の炭素質物質や
ニッケル、アルミニウム等の金属微粉末あるいは、繊維
が使用される。活物質として導電性の大きい物質を用い
る場合はこれらの導電材は使用する必要がない。The conductive assistant in the battery is added for the purpose of improving the conductivity of the electrode mixture layer when using an active material having low electron conductivity such as LiCoO 2. Alternatively, carbonaceous materials such as fibers, fine metal powders such as nickel and aluminum, or fibers are used. When a substance having high conductivity is used as the active material, it is not necessary to use these conductive materials.
【００３２】本発明の電極合剤は、粉末電極材料１００
重量部と、重合体固形分として合計量で０．１〜５０重
量部、特に１〜２０重量部のフッ化ビニリデン系重合体
（Ａ）および（Ｂ）を含むバインダー溶液とを混合し
て、形成することが好ましい。The electrode mixture of the present invention is a powder electrode material 100.
Parts by weight and a binder solution containing a total of 0.1 to 50 parts by weight, particularly 1 to 20 parts by weight, of vinylidene fluoride-based polymers (A) and (B) as polymer solids, are mixed, It is preferably formed.
【００３３】上述のようにして形成された電極合剤スラ
リーを、例えば図１に断面図を示すように、鉄、ステン
レス鋼、鋼、銅、アルミニウム、ニッケル、チタン等の
金属箔あるいは金属網等からなり、厚さが５〜１００μ
ｍ、小規模の場合には例えば５〜２０μｍとなるような
集電体１１の少なくとも一面、好ましくは両面に塗布
し、例えば５０〜１７０℃で乾燥して、例えば小規模の
場合厚さが１０〜１０００μｍの電極合剤層１２ａ、１
２ｂを形成することにより、非水系電池用電極１０が形
成される。The electrode mixture slurry formed as described above is treated with a metal foil or metal mesh of iron, stainless steel, steel, copper, aluminum, nickel, titanium or the like, for example, as shown in the sectional view of FIG. Consisting of 5 to 100μ thick
m, in the case of a small scale, it is applied to at least one side, preferably both sides, of the current collector 11 having a thickness of, for example, 5 to 20 μm, and dried at 50 to 170 ° C. ~ 1000 μm electrode mixture layer 12a, 1
By forming 2b, the nonaqueous battery electrode 10 is formed.
【００３４】図２は、このようにして形成された電極を
含む本発明の非水系電池の一例としての、リチウム二次
電池の部分分解斜視図である。FIG. 2 is a partially exploded perspective view of a lithium secondary battery as an example of the non-aqueous battery of the present invention including the electrode thus formed.
【００３５】すなわち、この二次電池は、基本的には正
極１および負極２間に、電解液を含浸したポリプロピレ
ン、ポリエチレン等の高分子物質の微多孔性膜からなる
セパレータ３を配置積層したものを渦巻き状に巻き回し
た発電素子が、負極端子５ａを形成する有底の金属ケー
シング５中に収容された構造を有する。この二次電池は
更に、負極は負極端子と電気的に接続され、頂部におい
てガスケット６および安全弁７を配置したのち、凸部に
おいて前記正極１と電気的に接続された正極端子８ａを
構成する頂部プレート８を配置し、ケーシング５の頂部
リム５ｂをかしめて、全体を封止した構造をなしてい
る。正極１および／または負極２は、例えば図１に示し
た電極構造体１０の構造を示す。That is, this secondary battery is basically a positive electrode 1 and a negative electrode 2, and a separator 3 made of a microporous film of a polymer material such as polypropylene or polyethylene impregnated with an electrolytic solution, which is arranged and laminated. The power generating element having a spirally wound structure is housed in a bottomed metal casing 5 forming the negative electrode terminal 5a. In this secondary battery, the negative electrode is further electrically connected to the negative electrode terminal, and the gasket 6 and the safety valve 7 are arranged at the top, and then the positive terminal 8a electrically connected to the positive electrode 1 at the convex portion. The plate 8 is arranged, the top rim 5b of the casing 5 is caulked, and the entire structure is sealed. The positive electrode 1 and / or the negative electrode 2 show, for example, the structure of the electrode structure 10 shown in FIG.
【００３６】セパレータ３に含浸される非水電解液とし
ては、例えばリチウム塩などの電解質を非水系溶媒（有
機溶媒）に溶解したものを用いることができる。As the non-aqueous electrolytic solution with which the separator 3 is impregnated, for example, a solution obtained by dissolving an electrolyte such as a lithium salt in a non-aqueous solvent (organic solvent) can be used.
【００３７】ここで電解質としては、ＬｉＰＦ6 、Ｌｉ
ＡｓＦ6 、ＬｉＣｌＯ4 、ＬｉＢＦ4 、ＣＨ3 ＳＯ3 Ｌ
ｉ、ＣＦ3 ＳＯ3 Ｌｉ、ＬｉＣｌ、ＬｉＢｒ等がある。
また、電解質の有機溶媒としてはプロピレンカーボネー
ト、エチレンカーボネート、１，２−ジメトキシエタ
ン、１，２−ジエトキシエタン、ジメチルカーボネー
ト、ジエチルカーボネート、メチルエチルカーボネー
ト、γ−ブチロラクトン、プロピオン酸メチル、プロピ
オン酸エチル、およびこれらの混合溶媒などが用いられ
るが、必ずしもこれらに限定されるものではない。Here, as the electrolyte, LiPF 6 , Li
AsF 6 , LiClO 4 , LiBF 4 , CH 3 SO 3 L
i, CF 3 SO 3 Li, LiCl, LiBr and the like.
Further, as the organic solvent of the electrolyte, propylene carbonate, ethylene carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, γ-butyrolactone, methyl propionate, ethyl propionate. , And a mixed solvent thereof are used, but not limited thereto.
【００３８】なお、上記においては円筒形電池の例を示
したが、本発明の非水系電池を、コイン形、角形または
ペーパー形電池として構成することも可能である。Although an example of a cylindrical battery has been shown above, the non-aqueous battery of the present invention can be configured as a coin battery, a prismatic battery or a paper battery.
【００３９】[0039]
【実施例】以下、実施例、比較例により本発明を更に具
体的に説明する。The present invention will be described more specifically with reference to examples and comparative examples.
【００４０】得られたカルボキシル基を有するフッ化ビ
ニリデン系重合体（Ｂ）については、以下の方法によっ
てカルボニル基含有量を求めた。The carbonyl group content of the obtained vinylidene fluoride polymer (B) having a carboxyl group was determined by the following method.
【００４１】［カルボニル基含有量の測定］ポリフッ化
ビニリデン樹脂とポリメチルメタクリレート樹脂を所定
割合で混合した試料についてのＩＲスペクトルの８８１
ｃｍ-1の吸収に対する１７２６ｃｍ-1の吸収の比とカル
ボニル基含有量の関係をプロットし検量線を作成する。[Measurement of Carbonyl Group Content] 881 of IR spectrum of a sample in which a polyvinylidene fluoride resin and a polymethylmethacrylate resin are mixed at a predetermined ratio.
plotting the relationship between the specific and the carbonyl group content of the absorption of 1726 cm -1 for absorption of cm -1 to prepare a calibration curve.
【００４２】試料重合体を熱水洗浄後、ベンゼンにて８
０℃で２４時間のソックスレー抽出により、ポリマー中
に残留している未反応モノマー及びホモポリマーを除去
したものについて、ＩＲスペクトルのカルボニル基によ
る１７４７ｃｍ-1の吸収の、８８１ｃｍ-1の吸収に対す
る比を求め、先に作成した検量線からカルボニル基含有
量を求める。After washing the sample polymer with hot water, it was washed with benzene.
The 24-hour Soxhlet extraction with 0 ° C., about what to remove unreacted monomers and homopolymers remaining in the polymer, the absorption of 1747cm -1 due to carbonyl group of IR spectrum, the ratio of absorption of 881 -1 Then, the carbonyl group content is calculated from the previously prepared calibration curve.
【００４３】（実施例１）内容積２リットルのオートク
レーブに、イオン交換水１０７５ｇ、メチルセルロース
０．４ｇ、フッ化ビニリデン４２０ｇ、ジノルマルプロ
ピルパーオキシジカーボネート２．５ｇ、酢酸エチル５
ｇの各量を仕込み、２５℃で懸濁重合してフッ化ビニリ
デン重合体を得た。得られた粉末状重合体（Ａ１）の固
有粘度は１．７ｄｌ／ｇであった。(Example 1) In an autoclave having an internal volume of 2 liters, 1075 g of ion-exchanged water, 0.4 g of methyl cellulose, 420 g of vinylidene fluoride, 2.5 g of dinormal propyl peroxydicarbonate, and 5 ethyl acetate.
Each amount of g was charged and suspension polymerization was carried out at 25 ° C. to obtain a vinylidene fluoride polymer. The powdery polymer (A1) thus obtained had an intrinsic viscosity of 1.7 dl / g.
【００４４】次に内容積２リットルのオートクレーブ
に、イオン交換水１０４０ｇ、メチルセルロース０．８
ｇ、ジイソプロピルパーオキシジカーボネート４ｇ、酢
酸エチル２．５ｇ、フッ化ビニリデン３９５ｇ、マレイ
ン酸モノメチルエステル４ｇ（フッ化ビニリデン：マレ
イン酸モノメチルエステル＝１００：１．０１）の各量
を仕込み２８℃で懸濁重合して、カルボキシル基含有フ
ッ化ビニリデン系重合体を得た。Next, in an autoclave having an internal volume of 2 liters, 1040 g of ion-exchanged water and 0.8 of methyl cellulose
g, diisopropyl peroxydicarbonate 4 g, ethyl acetate 2.5 g, vinylidene fluoride 395 g, maleic acid monomethyl ester 4 g (vinylidene fluoride: maleic acid monomethyl ester = 100: 1.01) were charged at 28 ° C. Suspension polymerization was performed to obtain a carboxyl group-containing vinylidene fluoride polymer.
【００４５】重合率は９０重量％で、得られた粉末状重
合体（Ｂ１）の固有粘度は１．１ｄｌ／ｇ、カルボニル
基含有量１．２×１０-4モル／ｇであった。The polymerization rate was 90% by weight, the powdery polymer (B1) thus obtained had an intrinsic viscosity of 1.1 dl / g and a carbonyl group content of 1.2 × 10 -4 mol / g.
【００４６】上記重合体（Ａ１）０．１２５ｇと、重合
体（Ｂ１）０．３７５ｇとを、溶剤であるＮ−メチル−
２−ピロリドン（以下ＮＭＰと略記）４．５ｇとともに
混合し、５０℃で撹拌して均一に溶解し、混合重合体の
バインダー溶液を得た。0.125 g of the polymer (A1) and 0.375 g of the polymer (B1) were mixed with N-methyl-solvent.
4.5 g of 2-pyrrolidone (hereinafter abbreviated as NMP) was mixed and stirred at 50 ° C. to be uniformly dissolved to obtain a binder solution of a mixed polymer.
【００４７】（実施例２）実施例１と同様にして、内容
積２リットルのオートクレーブに、イオン交換水１０７
５ｇ、メチルセルロース０．４ｇ、フッ化ビニリデン４
２０ｇ、ジノルマルプロピルパーオキシジカーボネート
２．５ｇ、酢酸エチル５ｇの各量を仕込み、２５℃で懸
濁重合してフッ化ビニリデン重合体を得た。(Example 2) In the same manner as in Example 1, an ion-exchanged water 107 was placed in an autoclave having an internal volume of 2 liters.
5 g, methyl cellulose 0.4 g, vinylidene fluoride 4
20 g, 2.5 g of dinormal propyl peroxydicarbonate and 5 g of ethyl acetate were charged, and suspension polymerization was carried out at 25 ° C. to obtain a vinylidene fluoride polymer.
【００４８】得られた粉末状重合体（Ａ２）の固有粘度
は２．１ｄｌ／ｇであった。The powdery polymer (A2) thus obtained had an intrinsic viscosity of 2.1 dl / g.
【００４９】重合体（Ａ２）０．１２５ｇと、実施例１
で得た重合体（Ｂ１）０．３７５ｇとを、ＮＭＰ４．５
ｇとともに混合し、５０℃で撹拌して均一に溶解し、混
合重合体のバインダー溶液を得た。0.125 g of polymer (A2) and Example 1
0.375 g of the polymer (B1) obtained in
It was mixed with g and stirred at 50 ° C. to be uniformly dissolved to obtain a binder solution of the mixed polymer.
【００５０】（実施例３）実施例２で得た重合体（Ａ
２）０．２５ｇと、実施例１で得た重合体（Ｂ１）０．
２５ｇとを、ＮＭＰ４．５ｇとともに混合し、５０℃で
撹拌して均一に溶解し、混合重合体のバインダー溶液を
得た。Example 3 The polymer (A obtained in Example 2
2) 0.25 g and the polymer (B1) 0.
25 g was mixed with 4.5 g of NMP, and the mixture was stirred at 50 ° C. and uniformly dissolved to obtain a binder solution of the mixed polymer.
【００５１】（実施例４）実施例１と同様にして、内容
積２リットルのオートクレーブに、イオン交換水１００
０ｇ、メチルセルロース１．２ｇ、ジノルマルプロピル
パーオキシジカーボネート５ｇ、フッ化ビニリデン３９
７ｇ、アリルグリシジルエーテル３ｇの各量を仕込み
（フッ化ビニリデン：アリルグリシジルエーテル（モル
比）＝１００：０．４２）の各量を仕込み、２５℃で懸
濁重合してエポキシ基含有フッ化ビニリデン重合体を得
た。(Example 4) In the same manner as in Example 1, 100 g of ion-exchanged water was placed in an autoclave having an internal volume of 2 liters.
0 g, methyl cellulose 1.2 g, dinormal propyl peroxydicarbonate 5 g, vinylidene fluoride 39
7 g, and 3 g of allyl glycidyl ether were charged (vinylidene fluoride: allyl glycidyl ether (molar ratio) = 100: 0.42), and the suspension was polymerized at 25 ° C. to obtain epoxy group-containing vinylidene fluoride. A polymer was obtained.
【００５２】重合率は８０重量％で、得られた粉末状重
合体（Ｂ２）の固有粘度は１．２ｄｌ／ｇであった。The polymerization rate was 80% by weight, and the powdery polymer (B2) obtained had an intrinsic viscosity of 1.2 dl / g.
【００５３】上記の重合体（Ｂ２）０．２５ｇと、実施
例１で得た重合体（Ａ１）０．２５ｇとを、ＮＭＰ４．
５ｇとともに混合し、５０℃で撹拌して均一に溶解し、
混合重合体のバインダー溶液を得た。0.25 g of the above polymer (B2) and 0.25 g of the polymer (A1) obtained in Example 1 were mixed with NMP4.
Mix with 5g, stir at 50 ° C to dissolve uniformly,
A binder solution of the mixed polymer was obtained.
【００５４】（比較例１）実施例１で製造したフッ化ビ
ニリデン重合体（Ａ１）０．５ｇを、ＮＭＰ４．５ｇと
ともに混合し、５０℃で撹拌して均一に溶解し、Ａ１単
体のバインダー溶液を得た。(Comparative Example 1) 0.5 g of the vinylidene fluoride polymer (A1) produced in Example 1 was mixed with 4.5 g of NMP and stirred at 50 ° C. to dissolve uniformly, and a binder solution of A1 simple substance was mixed. Got
【００５５】（比較例２）実施例１で製造したカルボキ
シル基含有のフッ化ビニリデン系重合体（Ｂ１）０．５
ｇを、ＮＭＰ４．５ｇとともに混合し、５０℃で撹拌し
て均一に溶解し、Ｂ１単体のバインダー溶液を得た。Comparative Example 2 Carboxyl group-containing vinylidene fluoride polymer (B1) 0.5 produced in Example 1
g was mixed with 4.5 g of NMP, and the mixture was stirred at 50 ° C. and uniformly dissolved to obtain a binder solution of B1 simple substance.
【００５６】（比較例３）実施例２で得た重合体（Ａ
２）０．５ｇを、ＮＭＰ４．５ｇとともに混合し、５０
℃で撹拌して均一に溶解し、Ａ２単体のバインダー溶液
を得た。(Comparative Example 3) The polymer (A obtained in Example 2)
2) 0.5g is mixed with 4.5g NMP, 50
The mixture was stirred at 0 ° C. and uniformly dissolved to obtain a binder solution of A2 simple substance.
【００５７】（比較例４）実施例１と同様にして、内容
積２リットルのオートクレーブに、イオン交換水１０４
０ｇ、メチルセルロース０．４ｇ、フッ化ビニリデン４
００ｇ、ジノルマルプロピルパーオキシジカーボネート
２ｇ、酢酸エチル８ｇの各量を仕込み、２５℃で懸濁重
合してフッ化ビニリデン重合体を得た。Comparative Example 4 In the same manner as in Example 1, an autoclave having an internal volume of 2 liters was charged with ion-exchanged water 104.
0 g, methyl cellulose 0.4 g, vinylidene fluoride 4
Each amount of 00 g, dinormal propyl peroxydicarbonate 2 g and ethyl acetate 8 g was charged and suspension polymerization was carried out at 25 ° C. to obtain a vinylidene fluoride polymer.
【００５８】得られた粉末状重合体（Ａ３）の固有粘度
は１．１ｄｌ／ｇであった。The powdery polymer (A3) thus obtained had an intrinsic viscosity of 1.1 dl / g.
【００５９】この重合体（Ａ３）０．５ｇを、ＮＭＰ
４．５ｇとともに混合し、５０℃で撹拌して均一に溶解
し、Ａ３単体のバインダー溶液を得た。0.5 g of this polymer (A3) was added to NMP.
It was mixed with 4.5 g and stirred at 50 ° C. to uniformly dissolve it, to obtain a binder solution of A3 simple substance.
【００６０】（比較例５）比較例４で得られた重合体
（Ａ３）０．１２５ｇと、実施例１で得た重合体（Ｂ
１）０．３７５ｇとを、ＮＭＰ４．５ｇとともに混合
し、５０℃で撹拌して均一に溶解し、混合重合体のバイ
ンダー溶液を得た。Comparative Example 5 0.125 g of the polymer (A3) obtained in Comparative Example 4 and the polymer (B obtained in Example 1)
1) 0.375 g was mixed with 4.5 g of NMP, and the mixture was stirred at 50 ° C. and uniformly dissolved to obtain a binder solution of a mixed polymer.
【００６１】（比較例６）実施例４で得た重合体（Ｂ
２）０．５ｇを、ＮＭＰ４．５ｇとともに混合し、５０
℃で撹拌して均一に溶解し、Ｂ２単体のバインダー溶液
を得た。(Comparative Example 6) The polymer (B
2) 0.5g is mixed with 4.5g NMP, 50
The mixture was stirred at 0 ° C. and uniformly dissolved to obtain a binder solution containing B2 alone.
【００６２】［バインダーの膨潤度評価］前記実施例、
比較例で得られたバインダー溶液を、それぞれガラス板
上にキャストし、１３０℃で２時間乾燥し、室温まで降
温後にガラス板から剥離して、厚さ約２００μｍのフィ
ルムを得た。[Evaluation of degree of swelling of binder]
Each of the binder solutions obtained in Comparative Examples was cast on a glass plate, dried at 130 ° C. for 2 hours, cooled to room temperature, and then peeled off from the glass plate to obtain a film having a thickness of about 200 μm.
【００６３】次いでこれらフィルムを、ＬｉＣｌＯ
4 ８．８重量部、プロピレンカーボネート５３．６、ジ
メトキシエタン３７．６重量部からなる混合液に調整し
て得た電解液に、それぞれ浸漬し、７０℃で７２時間の
浸漬を行い、キャストフィルムの重量増加率（増加重量
／原フィルム重量×１００）による膨潤度を求めた。Then, these films were treated with LiClO.
4 8.8 parts by weight, 53.6 parts of propylene carbonate, 37.6 parts by weight of dimethoxyethane prepared in a mixed solution obtained by immersing each in the obtained electrolytic solution, dipping for 72 hours at 70 ℃, cast film The degree of swelling was determined by the rate of increase in weight (increase weight / weight of original film × 100).
【００６４】上記測定結果をまとめて後記表１に記す。The above measurement results are summarized in Table 1 below.
【００６５】（実施例５）実施例１で得た混合重合体の
バインダー溶液５．０ｇと、平均粒径が約２０μｍ、比
表面積が約３ｍ2 ／ｇのピッチ系炭素質粉末４．５ｇと
を混合し、ホモジナイザーにより６０℃で均一に混合、
分散してスラリー状の電極合剤を製造した。Example 5 5.0 g of the binder solution of the mixed polymer obtained in Example 1 and 4.5 g of pitch-based carbonaceous powder having an average particle size of about 20 μm and a specific surface area of about 3 m 2 / g. , And mix evenly at 60 ° C with a homogenizer,
Dispersed to produce a slurry electrode mixture.
【００６６】この電極合剤を、厚み１０μｍの銅箔の片
面上にドクターブレードで塗布し、これを加熱・乾燥し
て、合計厚み１１０μｍの電極構造体を作成した。This electrode mixture was applied onto one surface of a copper foil having a thickness of 10 μm by a doctor blade, and this was heated and dried to prepare an electrode structure having a total thickness of 110 μm.
【００６７】（実施例６）実施例１で得た混合重合体の
バインダー溶液の代りに、実施例２で得た混合重合体の
バインダー溶液を用いる以外は、実施例５と同様にして
合計厚み１０５μｍの電極構造体を作成した。Example 6 The total thickness was the same as in Example 5 except that the mixed polymer binder solution obtained in Example 1 was used in place of the mixed polymer binder solution obtained in Example 1. A 105 μm electrode structure was created.
【００６８】（実施例７）実施例１で得た混合重合体の
バインダー溶液の代りに、実施例３で得た混合重合体の
バインダー溶液を用いる以外は、実施例５と同様にして
合計厚み１０５μｍの電極構造体を作成した。Example 7 The total thickness was the same as in Example 5 except that the mixed polymer binder solution obtained in Example 3 was used in place of the mixed polymer binder solution obtained in Example 1. A 105 μm electrode structure was created.
【００６９】（実施例８）実施例１で得た混合重合体の
バインダー溶液の代りに実施例４で得た混合重合体のバ
インダー溶液を用いる以外は、実施例５と同様にして合
計厚み１０７μｍの電極構造体を作成した。Example 8 A total thickness of 107 μm was obtained in the same manner as in Example 5 except that the mixed polymer binder solution obtained in Example 4 was used in place of the mixed polymer binder solution obtained in Example 1. The electrode structure of was prepared.
【００７０】（比較例７）実施例１で得た混合重合体の
バインダー溶液の代りに、比較例１で得た重合体（Ａ
１）の単独バインダー溶液を用いる以外は、実施例５と
同様にして合計厚み１１０μｍの電極構造体を作成し
た。COMPARATIVE EXAMPLE 7 Instead of the mixed polymer binder solution obtained in Example 1, the polymer (A) obtained in Comparative Example 1 was used.
An electrode structure having a total thickness of 110 μm was prepared in the same manner as in Example 5 except that the single binder solution of 1) was used.
【００７１】（比較例８）実施例１で得た混合重合体の
バインダー溶液の代りに、比較例２で得た重合体（Ｂ
１）単独のバインダー溶液を用いる以外は、実施例５と
同様にして合計厚み１００μｍの電極構造体を作成し
た。Comparative Example 8 Instead of the binder solution of the mixed polymer obtained in Example 1, the polymer (B obtained in Comparative Example 2 was used.
1) An electrode structure having a total thickness of 100 μm was prepared in the same manner as in Example 5 except that a single binder solution was used.
【００７２】（比較例９）実施例１で得た混合重合体の
バインダー溶液の代りに、比較例３で得た重合体（Ａ
２）単独のバインダー溶液を用いる以外は、実施例５と
同様にして合計厚み１００μｍの電極構造体を作成し
た。(Comparative Example 9) Instead of the mixed polymer binder solution obtained in Example 1, the polymer (A) obtained in Comparative Example 3 was used.
2) An electrode structure having a total thickness of 100 μm was prepared in the same manner as in Example 5 except that a single binder solution was used.
【００７３】（比較例１０）実施例１で得た混合重合体
のバインダー溶液の代りに、比較例５で得た重合体（Ａ
３）と重合体（Ｂ１）との混合バインダー溶液を用いる
以外は、実施例５と同様にして合計厚み１０２μｍの電
極構造体を作成した。(Comparative Example 10) Instead of the binder solution of the mixed polymer obtained in Example 1, the polymer (A) obtained in Comparative Example 5 was used.
An electrode structure having a total thickness of 102 μm was prepared in the same manner as in Example 5 except that the mixed binder solution of 3) and the polymer (B1) was used.
【００７４】（比較例１１）実施例１で得た混合重合体
のバインダー溶液の代りに、比較例５で得た重合体（Ｂ
２）の単独バインダー溶液を用いる以外は、実施例５と
同様にして合計厚み１０２μｍの電極構造体を作成し
た。Comparative Example 11 Instead of the binder solution of the mixed polymer obtained in Example 1, the polymer obtained in Comparative Example 5 (B
An electrode structure having a total thickness of 102 μm was prepared in the same manner as in Example 5 except that the single binder solution of 2) was used.
【００７５】［電極構造体における合剤層の接着性評
価］上記の実施例、比較例で得られた電極構造体におけ
る合剤層（活物質層）と集電体である銅箔との接着力
を、ＪＩＳ Ｋ６８５４に準じて１８０度剥離試験によ
る剥離強度として評価した。結果を表２に示す。[Evaluation of Adhesiveness of Mixture Layer in Electrode Structure] Adhesion of mixture layer (active material layer) in the electrode structures obtained in the above Examples and Comparative Examples and a copper foil as a current collector The force was evaluated as the peel strength by a 180 degree peel test according to JIS K6854. Table 2 shows the results.
【００７６】[0076]
【表１】 [Table 1]
【００７７】[0077]
【表２】 [Table 2]
【００７８】[0078]
【発明の効果】上記表１および表２の結果を見ると、固
有粘度が１．２以上である非改質フッ化ビニリデン系重
合体（Ａ）と、カルボキシル基またはエポキシ基を有す
る改質フッ化ビニリデン系重合体（Ｂ）との組合わせか
らなる本発明のバインダーは、非水電解液に対する耐久
性を、非改質フッ化ビニリデン系重合体（Ａ）単独から
なるバインダーと比べて、それ程低下させることなく
（膨潤性を著しく増大させることなく。表１）、粉末電
極材料と混合して形成した電極合剤層の集電基体（銅
箔）に対する接着性が、フッ化ビニリデン系重合体
（Ａ）単独の場合はもとより、接着性改質を行ったフッ
化ビニリデン系重合体（Ｂ）単独の場合に比べても著し
く向上した接着強度（表２）を与えることが判る。From the results shown in Tables 1 and 2, the unmodified vinylidene fluoride polymer (A) having an intrinsic viscosity of 1.2 or more and the modified fluoride having a carboxyl group or an epoxy group. The binder of the present invention comprising a combination with the vinylidene fluoride-based polymer (B) has a higher durability against a non-aqueous electrolyte than the binder comprising the unmodified vinylidene fluoride-based polymer (A) alone. The adhesiveness of the electrode mixture layer formed by mixing with the powder electrode material to the current collecting substrate (copper foil) without decreasing (without significantly increasing the swelling property), the vinylidene fluoride polymer. It can be seen that not only the case of using (A) alone, but also the adhesive strength (Table 2), which is remarkably improved as compared with the case of using the vinylidene fluoride polymer (B) having the modified adhesion, alone.
【図１】非水系電池に採用される電極構造体の部分断面
図。FIG. 1 is a partial cross-sectional view of an electrode structure used in a non-aqueous battery.
【図２】本発明に従い構成可能な非水溶媒系二次電池の
一部分解斜視図。FIG. 2 is a partially exploded perspective view of a non-aqueous solvent secondary battery that can be configured according to the present invention.
１ 正極 ２ 負極 ３ セパレータ ５ ケーシング（５ａ：底部、５ｂ：リム） ６ ガスケット ７ 安全弁 ８ 頂部プレート １０ 電極構造体 １１ 集電体 １２ａ、１２ｂ 電極合剤層 DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 5 Casing (5a: bottom part, 5b: rim) 6 Gasket 7 Safety valve 8 Top plate 10 Electrode structure 11 Current collectors 12a, 12b Electrode mixture layer
Claims (5)
ッ化ビニリデン系重合体（Ａ）と、カルボキシル基また
はエポキシ基を有するフッ化ビニリデン系重合体（Ｂ）
とからなり、重合体（Ａ）と（Ｂ）との合計量に対する
重合体（Ａ）の割合が５〜７５重量％の範囲にある非水
系電池電極形成用バインダー。1. A vinylidene fluoride polymer (A) having an intrinsic viscosity of 1.2 dl / g or more and a vinylidene fluoride polymer (B) having a carboxyl group or an epoxy group.
And a binder for forming a non-aqueous battery electrode, wherein the ratio of the polymer (A) to the total amount of the polymers (A) and (B) is in the range of 5 to 75% by weight.
（Ｂ）とを有機溶媒に溶解してなり、溶液状態にある請
求項１のバインダー。2. The binder according to claim 1, which is obtained by dissolving the vinylidene fluoride polymer (A) and (B) in an organic solvent and is in a solution state.
極材料を分散させてなる電極合剤。3. An electrode mixture obtained by dispersing a powder electrode material in the binder according to claim 1 or 2.
電極合剤層を形成してなる電極構造体。4. An electrode structure formed by forming the electrode mixture layer according to claim 3 on at least one surface of a current collecting substrate.
配置された非水電解液とからなり、該正極および負極の
少なくとも一方が請求項４の電極構造体からなる非水系
電池。5. A non-aqueous battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolytic solution disposed between the positive electrode and the negative electrode, wherein at least one of the positive electrode and the negative electrode comprises the electrode structure according to claim 4.
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| JP15294496A JP3518712B2 (en) | 1996-05-27 | 1996-05-27 | Non-aqueous battery electrode forming binder, electrode mixture, electrode structure and battery |
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|---|---|---|---|
| JP15294496A JP3518712B2 (en) | 1996-05-27 | 1996-05-27 | Non-aqueous battery electrode forming binder, electrode mixture, electrode structure and battery |
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| JP15294496A Expired - Fee Related JP3518712B2 (en) | 1996-05-27 | 1996-05-27 | Non-aqueous battery electrode forming binder, electrode mixture, electrode structure and battery |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998027605A1 (en) * | 1996-12-16 | 1998-06-25 | Daikin Industries, Ltd. | Binder for rechargeable battery with nonaqueous electrolyte and battery electrode depolarizing mix prepared using the same |
| JPH10199536A (en) * | 1997-01-17 | 1998-07-31 | Asahi Chem Ind Co Ltd | Electrode for lithium ion secondary battery |
| JPH10255760A (en) * | 1997-03-14 | 1998-09-25 | Hitachi Maxell Ltd | Lithium secondary battery |
| WO1999034463A1 (en) * | 1997-12-26 | 1999-07-08 | Kureha Kagaku Kogyo Kabushiki Kaisha | Electrode material mixture for nonaqueous battery and nonaqueous battery |
| JP2004146253A (en) * | 2002-10-25 | 2004-05-20 | Sony Corp | Negative electrode and battery, and manufacturing method of these |
| JP2005310747A (en) * | 2004-03-23 | 2005-11-04 | Kureha Chem Ind Co Ltd | Binder for forming nonaqueous electrochemical element electrode, electrode mix, electrode structure, and electrochemical element |
| JPWO2004049475A1 (en) * | 2002-11-22 | 2006-03-30 | 株式会社クレハ | Non-aqueous electrolyte battery electrode binder composition and use thereof |
| WO2010035587A1 (en) * | 2008-09-26 | 2010-04-01 | 株式会社クレハ | Negative electrode mixture for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
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| WO2017056974A1 (en) * | 2015-09-30 | 2017-04-06 | 株式会社クレハ | Binder composition, non-aqueous electrolyte secondary battery electrode, and non-aqueous electrolyte secondary battery |
| WO2018092677A1 (en) * | 2016-11-15 | 2018-05-24 | 株式会社クレハ | Electrode mix, method for producing electrode mix, electrode structure, method for producing electrode structure, and secondary battery |
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-
1996
- 1996-05-27 JP JP15294496A patent/JP3518712B2/en not_active Expired - Fee Related
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998027605A1 (en) * | 1996-12-16 | 1998-06-25 | Daikin Industries, Ltd. | Binder for rechargeable battery with nonaqueous electrolyte and battery electrode depolarizing mix prepared using the same |
| US6265107B1 (en) | 1996-12-16 | 2001-07-24 | Daikin Industries, Ltd. | Binder for rechargeable battery with nonaqueous electrolyte and battery electrode depolarizing mix prepared using the same |
| JPH10199536A (en) * | 1997-01-17 | 1998-07-31 | Asahi Chem Ind Co Ltd | Electrode for lithium ion secondary battery |
| JPH10255760A (en) * | 1997-03-14 | 1998-09-25 | Hitachi Maxell Ltd | Lithium secondary battery |
| WO1999034463A1 (en) * | 1997-12-26 | 1999-07-08 | Kureha Kagaku Kogyo Kabushiki Kaisha | Electrode material mixture for nonaqueous battery and nonaqueous battery |
| JPH11195419A (en) * | 1997-12-26 | 1999-07-21 | Kureha Chem Ind Co Ltd | Depolarizing mix for nonaqueous battery and nonaqueous battery |
| JP2004146253A (en) * | 2002-10-25 | 2004-05-20 | Sony Corp | Negative electrode and battery, and manufacturing method of these |
| US7754381B2 (en) | 2002-10-25 | 2010-07-13 | Sony Corporation | Anode and battery, and manufacturing methods thereof |
| JPWO2004049475A1 (en) * | 2002-11-22 | 2006-03-30 | 株式会社クレハ | Non-aqueous electrolyte battery electrode binder composition and use thereof |
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