JPH09274920A - Nonaqueous electrolyte battery - Google Patents
Nonaqueous electrolyte batteryInfo
- Publication number
- JPH09274920A JPH09274920A JP8084357A JP8435796A JPH09274920A JP H09274920 A JPH09274920 A JP H09274920A JP 8084357 A JP8084357 A JP 8084357A JP 8435796 A JP8435796 A JP 8435796A JP H09274920 A JPH09274920 A JP H09274920A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- battery
- positive electrode
- aqueous electrolyte
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- 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]
【発明の属する技術分野】本発明は、正極電極と負極電
極の少なくともいずれかが、集電体の表面に活物質粉体
と結着剤とを含有する塗膜が形成されてなるものである
非水電解液電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is one in which at least one of a positive electrode and a negative electrode has a coating film containing an active material powder and a binder formed on the surface of a current collector. The present invention relates to a non-aqueous electrolyte battery.
【０００２】[0002]
【従来の技術】携帯用電子機器の小型軽量化、高性能化
に伴い、使用される電源にも、小型化、高容量化、高エ
ネルギー密度化、高信頼性が求められている。これらの
要求を満たす電池として負極にリチウムを用いた非水電
解液一次電池や、負極にリチウム金属、またはその合
金、または炭素材料などのリチウムを吸蔵放出可能な材
料を用い、正極にもリチウムを脱挿入可能な酸化物、あ
るいはリチウム含有複合酸化物等を用いた非水電解液二
次電池が開発されている。2. Description of the Related Art As portable electronic devices have become smaller and lighter and have higher performance, power supplies to be used have been required to have smaller size, higher capacity, higher energy density and higher reliability. As a battery satisfying these requirements, a non-aqueous electrolyte primary battery using lithium in the negative electrode, a material capable of inserting and extracting lithium such as lithium metal, or an alloy thereof, or a carbon material is used in the negative electrode, and lithium is also used in the positive electrode. Non-aqueous electrolyte secondary batteries have been developed that use oxides that can be inserted and removed, or lithium-containing composite oxides.
【０００３】これらの電池においては、水溶液系の電解
液に比べ電導度の低い非水電解液を用いるため、高出力
化が比較的困難である。このため高出力を得るには、電
極を薄型化し電極面積を拡大して単位面積当たりの電流
値を低く抑える手法が用いられる。In these batteries, since a nonaqueous electrolytic solution having a lower conductivity than that of an aqueous electrolytic solution is used, it is relatively difficult to increase the output. Therefore, in order to obtain a high output, a method is used in which the electrode is thinned and the electrode area is enlarged to keep the current value per unit area low.
【０００４】実際の電池においは、薄くシート状に成形
された電極を短冊状に切断して用いられる。例えば、円
筒型の電池においては、短冊状電極をセパレーターと共
に渦巻き状に巻回して用いられる。In an actual battery, a thin sheet-shaped electrode is cut into strips for use. For example, in a cylindrical battery, a strip electrode and a separator are spirally wound and used.
【０００５】金属リチウムおよび金属リチウムを合金化
したものを活物質として用いる場合は、金属リチウムお
よびリチウム合金自身を短冊状に成形し電極とする。粉
末状の活物質（以下、活物質粉体と称す。）を用いる場
合は、通常、短冊状電極は次のようにして作成される。
水、または有機溶媒中で、活物質粉体と結着剤を混練し
スリラー化した後、集電体に塗布して乾燥させ、さらに
プレスしてシート状に成形してから、短冊状に切断し電
極とする。正極の場合は活物質粉体と結着剤以外に導電
剤を添加して用いることが多い。When metallic lithium or an alloy of metallic lithium is used as an active material, metallic lithium and a lithium alloy themselves are formed into strips to form electrodes. When a powdery active material (hereinafter referred to as active material powder) is used, the strip electrode is usually prepared as follows.
After kneading the active material powder and the binder in water or an organic solvent to make a chiller, apply it to a current collector, dry it, press it to form a sheet, and then cut it into strips. And use it as an electrode. In the case of the positive electrode, a conductive agent is often used in addition to the active material powder and the binder.
【０００６】結着剤としてはポリテトラフルオロエチレ
ン（ＰＴＦＥ）、ポリフッ化ビニリデン（ＰＶＤＦ）、
フッ素ゴム等のフッ素樹脂、スチレンブタジエンゴム、
スチレンブタジエンラテックス、カルボキシメチルセル
ロース（ＣＭＣ）等の有機重合体が用いられる。As the binder, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF),
Fluororesin and other fluororesins, styrene-butadiene rubber,
Organic polymers such as styrene butadiene latex and carboxymethyl cellulose (CMC) are used.
【０００７】その中でもＰＶＤＦは、化学的安定性が高
く、また、良好なスラリー性状により高い生産性が得ら
れるため、非水電解液電池の結着剤として良く用いられ
ている。Among them, PVDF is often used as a binder for non-aqueous electrolyte batteries because it has high chemical stability and high productivity due to good slurry properties.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、ＰＶＤ
Ｆは比較的結着性が低いため、ＰＶＤＦを用いた非水電
解液電池においては、電極の搬送や、電極巻回時のスト
レスによって、短冊状電極の切断面あるいは電極表面か
ら活物質粉体が脱落し、正極と負極を隔離しているセパ
レーターにダメージを与え、これによって、放電不良が
発生するという可能性があった。また、非水電解液二次
電池においては、充放電に伴う電極の寸法変化等により
電極にストレスが加わり、活物質粉体、導電剤、結着剤
等からなる塗膜が集電体から剥離し、これがサイクル特
性が劣化する原因となっていた。[Problems to be Solved by the Invention] However, PVD
Since F has a relatively low binding property, in the non-aqueous electrolyte battery using PVDF, the active material powder is cut off from the cut surface of the strip-shaped electrode or the electrode surface due to stress during electrode transportation and electrode winding. Could fall off and damage the separator that separates the positive electrode from the negative electrode, which could cause discharge failure. In non-aqueous electrolyte secondary batteries, stress is applied to the electrodes due to dimensional changes of the electrodes due to charging and discharging, and the coating film composed of active material powder, conductive agent, binder, etc. peels off from the current collector. However, this has been a cause of deterioration in cycle characteristics.
【０００９】このようにＰＶＤＦの結着力が十分でない
場合、電池の信頼性、生産性を劣化させることになる。When the binding force of PVDF is not sufficient as described above, the reliability and productivity of the battery are deteriorated.
【００１０】そこで、本発明においては、活物質粉体と
結着剤とを含有する塗膜と集電体との結着力を向上さ
せ、活物質粉体の脱落が抑制された電極を用いることに
より、高性能でありながら、信頼性、生産性の高い非水
電解液電池を提供することを目的とする。Therefore, in the present invention, an electrode is used in which the binding force between the coating film containing the active material powder and the binder and the current collector is improved, and the active material powder is prevented from falling off. Accordingly, it is an object of the present invention to provide a non-aqueous electrolyte battery having high performance, high reliability and high productivity.
【００１１】[0011]
【課題を解決するための手段】本発明は、上述の目的を
達成するものであり、正極電極と負極電極の少なくとも
いずれかが、集電体の表面に活物質粉体と結着剤とを含
有する塗膜が形成されてなる非水電解液電池において、
前記結着剤が、数平均分子量Ｍｎが１．０×１０5 以上
のＰＶＤＦよりなるものである。The present invention achieves the above-mentioned object, and at least one of a positive electrode and a negative electrode has an active material powder and a binder on the surface of a current collector. In a non-aqueous electrolyte battery formed by containing a coating film,
The binder is made of PVDF having a number average molecular weight Mn of 1.0 × 10 5 or more.
【００１２】または、正極電極と負極電極の少なくとも
いずれかが、集電体の表面に活物質粉体と結着剤とを含
有する塗膜が形成されてなる非水電解液電池において、
前記結着剤が、Ｎ−メチル−２−ピロリドン（ＮＭＰ）
９０重量％に対して１０重量％溶解させたときの見かけ
粘度が１５０ｍＰａ・ｓ以上となるＰＶＤＦよりなるも
のである。Alternatively, in a non-aqueous electrolyte battery in which at least one of the positive electrode and the negative electrode has a coating film containing active material powder and a binder formed on the surface of a current collector,
The binder is N-methyl-2-pyrrolidone (NMP)
It is made of PVDF having an apparent viscosity of 150 mPa · s or more when dissolved by 10% by weight with respect to 90% by weight.
【００１３】なお、ここで「見かけ粘度」とはＪＩＳ−
Ｋ７１１７によって規定される見かけ粘度であり、上述
したとおり、ＮＭＰ９０重量％に対して１０重量％溶解
させたときの粘度とする。以下、単に「見かけ粘度」と
称す。The term "apparent viscosity" as used herein means JIS-
It is an apparent viscosity defined by K7117, and as described above, it is a viscosity when dissolved in 10% by weight with respect to 90% by weight of NMP. Hereinafter, it is simply referred to as "apparent viscosity".
【００１４】ＰＶＤＦの数平均分子量Ｍｎあるいは見か
け粘度が上述した数値に満たない場合には、活物質粉体
の脱落が起こってセパレータにダメージを与える。ま
た、非水電解液二次電池の場合、集電体から活物質粉体
と結着剤とを含有する塗膜が剥離してサイクル特性が劣
化するといった問題も生じる。When the number average molecular weight Mn of PVDF or the apparent viscosity is less than the above-mentioned values, the active material powder falls off and the separator is damaged. Further, in the case of the non-aqueous electrolyte secondary battery, there is a problem that the coating film containing the active material powder and the binder is peeled off from the current collector to deteriorate cycle characteristics.
【００１５】これに対し、本発明を適用して、数平均分
子量Ｍｎあるいは見かけ粘度が大きいＰＶＤＦを用いる
と、活物質粉体の脱落が抑制され、また、活物質粉体と
結着剤とを含有する塗膜と集電体との剥離が抑制できる
ようになる。On the other hand, when the present invention is applied to use PVDF having a large number average molecular weight Mn or a large apparent viscosity, the active material powder is prevented from falling off, and the active material powder and the binder are combined. It becomes possible to suppress peeling between the coating film and the current collector.
【００１６】これは、以上のような数平均分子量Ｍｎあ
るいは見かけ粘度が大きいＰＶＤＦは、分子量が大き
く、分子鎖が長いため、活物質粉体、集電体との接触状
態が良好になり、また、一本の分子鎖でより多くの活物
質粉体、集電体を結着することができる等の理由によ
る。This is because PVDF having a large number average molecular weight Mn or a large apparent viscosity as described above has a large molecular weight and a long molecular chain, so that the state of contact with the active material powder and the current collector is good, and The reason is that a single molecular chain can bind more active material powders and current collectors.
【００１７】このようにＰＶＤＦの結着力は、数平均分
子量Ｍｎあるいは見かけ粘度に依存して向上するが、数
平均分子量Ｍｎが１．５×１０5 以上、あるいは、見か
け粘度が３４０ｍＰａ・ｓ以上とされると、活物質粉体
と結着剤とを含有する塗膜と集電体との剥離を抑制する
効果が十分となる。さらに、数平均分子量Ｍｎが１．８
×１０5 以上、あるいは、見かけ粘度が６００ｍＰａ・
ｓ以上とされると、ＰＶＤＦの結着力がほぼ最大に発揮
されるようになる。As described above, the binding force of PVDF improves depending on the number average molecular weight Mn or the apparent viscosity, but the number average molecular weight Mn is 1.5 × 10 5 or more, or the apparent viscosity is 340 mPa · s or more. Then, the effect of suppressing peeling between the coating film containing the active material powder and the binder and the current collector becomes sufficient. Furthermore, the number average molecular weight Mn is 1.8.
× 10 5 or more, or apparent viscosity of 600 mPa
If it is s or more, the binding force of PVDF will be maximized.
【００１８】なお、ＰＶＤＦの数平均分子量Ｍｎ、見か
け粘度には特に上限はないが、これらの値が大きくなり
すぎる、即ち、ＰＶＤＦの分子量が大きくなりすぎる
と、塗料化が困難となることも考えられる。このため、
ＰＶＤＦの数平均分子量Ｍｎは１．０×１０7 以下とし
て好適である。なお、数平均分子量Ｍｎが１．０×１０
7 程度のＰＶＤＦについては、粘度が高すぎて測定が不
可能である。このため、あえて見かけ粘度の上限を設定
するとすれば、測定が可能な最大値とすればよい。The number average molecular weight Mn of PVDF is
There is no particular upper limit to the viscosity, but these values increase
Too much, that is, the molecular weight of PVDF becomes too large
Therefore, it may be difficult to make paint. For this reason,
The number average molecular weight Mn of PVDF is 1.0 × 10.7As follows
It is suitable. The number average molecular weight Mn is 1.0 × 10.
7For PVDF, the viscosity is too high to measure.
It is possible. Therefore, the upper limit of the apparent viscosity is intentionally set.
Then, the maximum value that can be measured may be set.
【００１９】[0019]
【発明の実施の形態】以下、本発明を適用した具体的な
実施の形態について図面を参照しながら説明する。ここ
では、本発明を図１に示されるような円筒型の非水電解
液電池に適用した。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments to which the present invention is applied will be described below with reference to the drawings. Here, the present invention was applied to a cylindrical non-aqueous electrolyte battery as shown in FIG.
【００２０】この非水電解液電池は、負極集電体１０の
両面に負極活物質粉体と結着剤とを含有する塗膜（以
下、負極活物質含有塗膜と称す。）１５が形成されてな
る負極電極１と、正極集電体１１の両面に正極活物質粉
体と結着剤とを含有する塗膜（以下、正極活物質含有塗
膜と称す。）１６が形成されてなる正極電極２とがセパ
レータ３を介して重ね合わせらて巻回され、電池缶５内
に収納されたものである。In this non-aqueous electrolyte battery, a coating film (hereinafter referred to as a negative electrode active material-containing coating film) 15 containing negative electrode active material powder and a binder is formed on both surfaces of the negative electrode current collector 10. A coating film (hereinafter referred to as a positive electrode active material-containing coating film) 16 containing a positive electrode active material powder and a binder is formed on both surfaces of the negative electrode 1 and the positive electrode current collector 11 thus formed. The positive electrode 2 and the positive electrode 2 are stacked and wound via the separator 3 and housed in the battery can 5.
【００２１】ここで、この非水電解液電池を一次電池と
して用いる場合には、正極活物質として、二酸化マンガ
ン、フッ化炭素、ＦｅＳ、ＦｅＳ2 、ＣｕＯ等が使用で
き、負極活物質として、リチウム金属や、リチウム金属
をＡｌ、Ｐｂ、Ｉｎ等と合金化したものが使用できる。When this non-aqueous electrolyte battery is used as a primary battery, manganese dioxide, fluorocarbon, FeS, FeS 2 , CuO, etc. can be used as the positive electrode active material, and lithium as the negative electrode active material. A metal or a lithium metal alloyed with Al, Pb, In or the like can be used.
【００２２】また、この非水電解液電池を二次電池とし
て用いる場合には、正極活物質として、リチウムイオン
を可逆的に脱挿入可能な物質が用いられる。例えば、Ｔ
ｉＳ 2 、ＭｏＳ2 、Ｖ2 Ｏ5 、Ｖ6 Ｏ13、ＭｎＯ2 、Ｌ
ｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＮｉx Ｃｏy Ｏ2 、Ｌ
ｉＭｎ2 Ｏ4 、ＬｉＭｎＯ2 等が挙げられる。粉体状で
用いられる正極活物質には、一般的に、集電体との電子
電導を確保するため導電剤が添加される。この導電剤と
しては、特に限定されないが、金属粉、炭素粉等が用い
られる。例えば、カーボンブラック等の熱分解炭素、お
よびその黒鉛化品、人造あるいは天然の鱗片状黒鉛粉、
炭素繊維とその黒鉛化品等の炭素粉を用いて好適であ
る。また、これら炭素の混合品も使用可能である。The non-aqueous electrolyte battery is used as a secondary battery.
When used as a positive electrode active material, lithium ion
A substance capable of reversibly inserting and removing is used. For example, T
iS Two, MoSTwo, VTwoOFive, V6O13, MnOTwo, L
iCoOTwo, LiNiOTwo, LiNixCoyOTwo, L
iMnTwoOFour, LiMnOTwoAnd the like. In powder form
The positive electrode active material used is generally an electron with a current collector.
A conductive agent is added to ensure conductivity. With this conductive agent
Is not particularly limited, but metal powder, carbon powder, etc. are used.
Can be For example, pyrolytic carbon such as carbon black,
And its graphitized products, artificial or natural flake graphite powder,
It is suitable to use carbon powder and carbon powder such as graphitized product.
You. Also, a mixture of these carbons can be used.
【００２３】この非水電解液電池を二次電池として用い
る場合の負極活物質としては、リチウム金属や、リチウ
ム金属とＡｌ、Ｐｂ、Ｉｎ等とを合金化したものが用い
られる。また、リチウムを吸蔵放出可能な炭素材料を負
極活物質として用いることにより、さらにサイクル寿命
の優れた電池を得ることができる。この負極用炭素材料
としては、特に限定されないが、種々の有機化合物の熱
分解または焼成炭化により得られるものが使用できる。
また、これらの黒鉛化品も用いられる。さらに天然に産
出する天然黒鉛も使用できる。As the negative electrode active material when the non-aqueous electrolyte battery is used as a secondary battery, lithium metal or an alloy of lithium metal and Al, Pb, In or the like is used. Further, by using a carbon material capable of inserting and extracting lithium as the negative electrode active material, it is possible to obtain a battery having further excellent cycle life. The carbon material for the negative electrode is not particularly limited, but those obtained by thermal decomposition or calcining carbonization of various organic compounds can be used.
Further, these graphitized products are also used. Furthermore, naturally occurring natural graphite can also be used.
【００２４】難黒鉛化性炭素類は、重量あたりの充放電
量能力が大きく、サイクル特性に優れる。特に、（００
２）面の面間隔が０．３７０ｎｍ以上、真密度１．７０
ｇ／ｃｍ3 未満であり、且つ空気気流中における示差熱
分析で７００℃以上に発熱ピークを有しないものが好適
である。このような性質を有する材料としては、有機材
料を焼成等の手法により炭素化して得られる炭素質材料
が挙げられ、炭素化の出発原料としてはフルフリルアル
コールあるいはフルフラールのホモポリマー、コポリマ
ーよりなるフラン樹脂が好適である。具体的には、フル
フラール＋フェノール、フルフリルアルコール＋ジメチ
ロール尿素、フルフリルアルコール、フルフリルアルコ
ール＋ホルムアルデヒド、フルフリルアルコール＋フル
フラール、フルフラール＋ケトン類等よりなる重合体が
挙げられる。あるいは、原料として水素／炭素原子比
０．６〜０．８の石油ピッチを用い、これに酸素を含む
官能基を導入し、いわゆる酸素架橋を施して酸素含有量
１０〜２０重量％の前駆体とした後、焼成して得られる
炭素質材料も使用できる。さらには、フラン樹脂や石油
ピッチ等を炭素化する際、リン化合物あるいはホウ素化
合物を添加することにより、リチウムに対するドープ量
を大きなものとした炭素質材料も使用可能である。The non-graphitizable carbons have a large charge / discharge capacity per weight and are excellent in cycle characteristics. In particular, (00
2) The surface spacing is 0.370 nm or more, and the true density is 1.70.
It is preferably less than g / cm 3 and has no exothermic peak at 700 ° C. or higher in differential thermal analysis in an air stream. Materials having such properties include carbonaceous materials obtained by carbonizing an organic material by a method such as firing, and the starting material for carbonization is furfuryl alcohol or a furfural homopolymer or furan furan copolymer. Resins are preferred. Specific examples thereof include polymers composed of furfural + phenol, furfuryl alcohol + dimethylol urea, furfuryl alcohol, furfuryl alcohol + formaldehyde, furfuryl alcohol + furfural, furfural + ketones and the like. Alternatively, a petroleum pitch having a hydrogen / carbon atom ratio of 0.6 to 0.8 is used as a raw material, a functional group containing oxygen is introduced into the petroleum pitch, and so-called oxygen cross-linking is performed to produce a precursor having an oxygen content of 10 to 20% by weight. After that, a carbonaceous material obtained by firing can also be used. Furthermore, when carbonizing furan resin, petroleum pitch, or the like, a carbonaceous material having a large doping amount with respect to lithium by adding a phosphorus compound or a boron compound can also be used.
【００２５】黒鉛材料は、真密度が高く、電極充填性が
高められるため、高容量の電池を得るのに好ましい。使
用可能な黒鉛材料としては、より高い負極合剤充填性を
得るために、真比重は２．１０ｇ／ｃｍ3 以上であるこ
とが必要であり、２．１８ｇ／ｃｍ3 以上であることが
より好ましい。このような真比重を得るには、Ｘ線回折
法で得られる（００２）面の面間隔が０．３３５ｎｍ〜
０．３４ｎｍであることが必要であり、０．３３５ｎｍ
〜０．３３７ｎｍであることがより好ましい。Ｃ軸方向
の結晶子厚みは１６．０nm以上であることが好ましく、
２４．０nm以上であることがより好ましい。ＪＩＳ−Ｋ
１４６９によって求められた嵩比重は０．３ｇ／ｃｍ3
以上であることが必要である。さらに、黒鉛材料粒子形
状の扁平度を表す平均形状パラメータ（Ｘ）は、ｘ≦１
２５であることが望ましい。また、レーザー・ラマン分
光法は炭素材料の結晶構造の振動に関する情報が高感度
に反映される測定法であるが、ラマンスペクトルより求
められるＧ値はミクロな構造欠陥を評価する有効な指標
の一つである。Ｇ値は炭素材料中の非晶質構造に由来す
るラマンバンドの面積強度に対する、完全な黒鉛構造に
由来するラマンバンドの面積強度の比で表され、Ｇ値は
２．５以上が好ましい。Ｇ値が２．５未満の場合には
２．１ｇ／ｃｍ3 以上の真比重が得られない場合があ
る。The graphite material is preferable for obtaining a high capacity battery since it has a high true density and an improved electrode filling property. As the usable graphite material, the true specific gravity needs to be 2.10 g / cm 3 or more, and 2.18 g / cm 3 or more is more preferable in order to obtain higher negative electrode mixture filling property. preferable. In order to obtain such a true specific gravity, the plane spacing of the (002) plane obtained by the X-ray diffraction method is 0.335 nm to
Must be 0.34 nm, 0.335 nm
More preferably, it is about 0.337 nm. The crystallite thickness in the C-axis direction is preferably 16.0 nm or more,
It is more preferably 24.0 nm or more. JIS-K
The bulk specific gravity determined by 1469 is 0.3 g / cm 3.
It is necessary to be above. Further, the average shape parameter (X) representing the flatness of the graphite material particle shape is x ≦ 1.
It is preferably 25. Further, laser Raman spectroscopy is a measurement method in which the information on the vibration of the crystal structure of the carbon material is reflected with high sensitivity, but the G value obtained from the Raman spectrum is an effective index for evaluating microscopic structural defects. Is one. The G value is represented by the ratio of the area intensity of the Raman band derived from the complete graphite structure to the area intensity of the Raman band derived from the amorphous structure in the carbon material, and the G value is preferably 2.5 or more. If the G value is less than 2.5, a true specific gravity of 2.1 g / cm 3 or more may not be obtained.
【００２６】また、上述したような負極活物質粉体が保
持される負極集電体１０としては、厚さ５〜２０μｍの
銅箔、ステンレス箔、ニッケル箔等が使用できる。一
方、正極集電体１１としては、厚さ１０〜４０μｍのア
ルミニウム箔、ステンレス箔、ニッケル箔等が使用でき
る。なお、いずれの集電体１０、１１においても、箔状
に限られず、メッシュ状や、エキスパンドメタル等より
なる網状のものも使用可能である。Further, as the negative electrode current collector 10 holding the negative electrode active material powder as described above, a copper foil, stainless steel foil, nickel foil or the like having a thickness of 5 to 20 μm can be used. On the other hand, as the positive electrode current collector 11, an aluminum foil, a stainless steel foil, a nickel foil or the like having a thickness of 10 to 40 μm can be used. Note that any of the current collectors 10 and 11 is not limited to the foil shape, and a mesh shape or a mesh shape made of expanded metal or the like can be used.
【００２７】さらに、上述したような負極電極１と正極
電極との間に介在させるセパレータ３としては、特に限
定されないが、織布、不織布、合成樹脂微多孔膜等が挙
げられる。薄型で大面積の電極を用いる場合には、合成
樹脂微多孔膜、特にポリオレフィン系微多孔膜を用いて
好適である。具体的には、ポリエチレンおよびポリプロ
ピレン製微多孔膜、またはこれらを複合した微多孔膜が
用いられる。Further, the separator 3 to be interposed between the negative electrode 1 and the positive electrode as described above is not particularly limited, and examples thereof include woven fabric, non-woven fabric, synthetic resin microporous film and the like. When a thin electrode having a large area is used, a synthetic resin microporous film, particularly a polyolefin microporous film is preferably used. Specifically, a microporous membrane made of polyethylene and polypropylene, or a microporous membrane obtained by combining these is used.
【００２８】上述したような負極電極１、セパレータ
３、正極電極２とを重ね合わせて巻回されたもの（以
下、渦巻状電極体と称す。）が収納される電池缶５とし
ては、例えば、ニッケルメッキを施した鉄よりなる円筒
状のケースが使用できる。なお、上述の渦巻状電極体
は、センターピン１４を中心として巻回されている。As the battery can 5 for accommodating the one in which the negative electrode 1, the separator 3 and the positive electrode 2 as described above are wound and stacked (hereinafter referred to as a spiral electrode body), for example, A cylindrical case made of nickel-plated iron can be used. The spiral electrode body described above is wound around the center pin 14.
【００２９】そして、この渦巻状電極体を電池缶５に収
納するに際しては、その上下両面に絶縁板４が配設され
ると共に、負極集電体１０から導出した負極リード１２
が電池缶５の底部に電気的に接続され、また、正極集電
体１１から導出した正極リード１３が安全弁装置８を介
して電池蓋７に電気的に接続される。When the spirally wound electrode body is housed in the battery can 5, the insulating plates 4 are arranged on both upper and lower surfaces thereof, and the negative electrode lead 12 led out from the negative electrode current collector 10 is provided.
Is electrically connected to the bottom of the battery can 5, and the positive electrode lead 13 led out from the positive electrode current collector 11 is electrically connected to the battery lid 7 via the safety valve device 8.
【００３０】なお、電池缶５内には、有機溶媒に電解質
を溶解させてなる有機電解液が注入されており、電池蓋
７は、アスファルトが塗布された絶縁封口ガスケット６
を介してかしめられて固定されている。An organic electrolytic solution prepared by dissolving an electrolyte in an organic solvent is injected into the battery can 5, and the battery lid 7 has an insulating sealing gasket 6 coated with asphalt.
It is fixed by being caulked through.
【００３１】ここで、有機電解液に含有される電解質と
しては、この種の電池に用いられるものであればいずれ
も使用可能である。例えば、ＬｉＰＦ6 の他、ＬｉＣｌ
Ｏ4、ＬｉＡｓＦ6 、ＬｉＰＦ6 、ＬｉＢＦ4 、ＬｉＢ
（Ｃ6 Ｈ5 ）4 、ＬｉＣｌ、ＬｉＳＯ3 ＣＨ3 、ＬｉＮ
（ＳＯ2 ＣＦ3 ）2 、ＬｉＣ（ＳＯ2 ＣＦ3 ）3 等が挙
げられる。有機溶媒としては、特に限定されないが、例
えばエチレンカーボネート、プロピレンンカーボネー
ト、ブチレンカーボネート、ジエチルカーボネート、メ
チルエチルカーボネート、メチルプロピルカーボネー
ト、γ−ブチロラクトン、スルホラン、１，２−ジメト
キシエタン、１，３−ジメトキシプロパン、ジエチルエ
ーテル、テトラヒドロフラン、２−メチルテトラヒドロ
フランから選ばれる少なくとも１種以上を混合して用い
ることができる。Here, as the electrolyte contained in the organic electrolytic solution, any electrolyte can be used as long as it is used in this type of battery. For example, in addition to LiPF 6 , LiCl
O 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiB
(C 6 H 5) 4, LiCl, LiSO 3 CH 3, LiN
(SO 2 CF 3) 2, LiC (SO 2 CF 3) 3 and the like. The organic solvent is not particularly limited, for example, ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, γ-butyrolactone, sulfolane, 1,2-dimethoxyethane, 1,3-dimethoxy. At least one selected from propane, diethyl ether, tetrahydrofuran and 2-methyltetrahydrofuran can be mixed and used.
【００３２】そして、本実施の形態においては、上述し
たような渦巻状電極体の各極活物質含有塗膜１５、１６
に活物質粉体と共に用いられる結着剤として、数平均分
子量Ｍｎが１．０×１０5 以上、あるいは、Ｎ−メチル
−２−ピロリドン（ＮＭＰ）９０重量％に対して１０重
量％溶解させたときの見かけ粘度が１５０ｍＰａ・ｓ以
上となるＰＶＤＦを用いている。In the present embodiment, the electrode active material-containing coatings 15 and 16 of the spirally wound electrode body as described above.
As a binder used together with the active material powder, the number average molecular weight Mn was 1.0 × 10 5 or more, or 10% by weight was dissolved in 90% by weight of N-methyl-2-pyrrolidone (NMP). PVDF having an apparent viscosity of 150 mPa · s or more is used.
【００３３】ＰＶＤＦは一般に、１，１−ジフルオロエ
チレンを集合開始剤、懸濁剤、または乳化剤等の添加剤
と共に適当な反応媒体中で、懸濁重合、または乳化重合
して得られる。どちらの製法で得られたものでも化学的
安定性が高く、また、良好なスラリー性状により高い生
産性が得られるため、結着剤として使用可能である。PVDF is generally obtained by suspension polymerization or emulsion polymerization of 1,1-difluoroethylene in an appropriate reaction medium together with an additive such as an assembly initiator, a suspending agent or an emulsifying agent. The product obtained by either of the production methods has high chemical stability, and high productivity can be obtained due to good slurry properties, so that it can be used as a binder.
【００３４】このＰＶＤＦの分子量は、種々の重合度調
整剤、あるいは連鎖移動剤を使用することによりコント
ロール可能である。例えば、懸濁重合ではビスアルキル
等、乳化重合ではクロロフルオルメタン等を用いること
により重合度を調整し、種々の分子量を有するＰＶＤＦ
を得ることができる。ここでは、このようにして、数平
均分子量Ｍｎが１．０×１０5 以上となるように、ある
いは、見かけ粘度が１５０ｍＰａ・ｓ以上となるように
した。これにより、ＰＶＤＦの結着性を向上させること
ができる。The molecular weight of this PVDF can be controlled by using various polymerization degree adjusting agents or chain transfer agents. For example, bisalkyl or the like is used in suspension polymerization, and chlorofluoromethane or the like is used in emulsion polymerization to adjust the degree of polymerization, and PVDF having various molecular weights is used.
Can be obtained. Here, in this way, the number average molecular weight Mn is set to 1.0 × 10 5 or more, or the apparent viscosity is set to 150 mPa · s or more. Thereby, the binding property of PVDF can be improved.
【００３５】なお、ここで示される数平均分子量Ｍｎは
ゲル・パーミエーション・クロマトグラフィー（ＧＰ
Ｃ）により測定したものである。測定装置としては、東
ソー社製、商品名：ＨＬＣ８０２０を用い、カラムとし
ては、商品名：Ｇ５０００Ｈ６、Ｇ４００８Ｈ８、Ｇ３
０００８を３本連結したものを用いた。検出には、ＵＶ
検出器を用い、溶離液としては、０．０１モル／ｌのＬ
ｉＢｒ／ＮＭＰ溶液を用いた。標準試料としては、各種
分子量の単分散ポリスチレンを用いた。溶離液にＬｉＢ
ｒを添加したのは、電解質の添加によりポリマーとカラ
ムのゲルとの静電的相互作用を打ち消し、正常なクロマ
トグラムを得るためである。The number average molecular weight Mn shown here is determined by gel permeation chromatography (GP
It is measured by C). As a measuring device, a product name: HLC8020 manufactured by Tosoh Corporation is used, and as a column, product names: G5000H6, G4008H8, G3.
A product obtained by connecting three 0008 was used. UV for detection
Using a detector, the eluent is 0.01 mol / l L
An iBr / NMP solution was used. Monodisperse polystyrene having various molecular weights was used as a standard sample. LiB as the eluent
The reason for adding r is to cancel the electrostatic interaction between the polymer and the gel of the column by adding the electrolyte and obtain a normal chromatogram.
【００３６】本実施の形態においては、使用するＰＶＤ
Ｆの見かけ粘度についても上述したように規定を設けて
いる。一般に高分子溶液の固有粘度は高分子の分子量の
基準として用いられることがあり、見かけ粘度も分子量
に相関をもつ値となるからである。分子量が大きいＰＶ
ＤＦは溶液粘度が高くなり、スラリー粘度も高くなる。
そして、このようにＰＶＤＦの見かけ粘度を高くすると
結着性が向上する。なお、結着性が向上する理由として
は、分子量が大きくなったこと以外に、スラリー粘度が
上昇し活物質粉体とＰＶＤＦの分散性が向上することも
挙げられる。In this embodiment, the PVD used
The apparent viscosity of F is also specified as described above. This is because the intrinsic viscosity of the polymer solution is generally used as a standard for the molecular weight of the polymer, and the apparent viscosity also has a value having a correlation with the molecular weight. PV with high molecular weight
DF has a high solution viscosity and a high slurry viscosity.
When the apparent viscosity of PVDF is increased in this way, the binding property is improved. The reason why the binding property is improved is that the viscosity of the slurry is increased and the dispersibility of the active material powder and PVDF is improved, in addition to the increase in the molecular weight.
【００３７】ここで、ここで示される見かけ粘度は、Ｊ
ＩＳ−Ｋ７１１７に従って測定されるものである。即
ち、溶媒のＮ−メチル−２−ピロリドン（ＮＭＰ）９０
重量％に対して、ＰＶＤＦを１０重量％溶解し、Ｂ型粘
度計（トキメック社製、商品名：DIGITAL VISCOMETER D
VL-BII）を用い、Ｓ法（単一円筒回転粘度計を使用）に
従って測定した。なお、測定温度は２３℃とし、スピン
ドルとしてはＳＢ３を用い、スピンドル回転数は３０回
／分とした。Here, the apparent viscosity shown here is J
It is measured according to IS-K7117. That is, the solvent N-methyl-2-pyrrolidone (NMP) 90
10% by weight of PVDF is dissolved in the weight%, and a B-type viscometer (manufactured by Tokimec, trade name: DIGITAL VISCOMETER D
VL-BII) according to the S method (using a single cylinder rotational viscometer). The measurement temperature was 23 ° C., SB3 was used as the spindle, and the spindle rotation speed was 30 rpm.
【００３８】以上、本発明を適用した非水電解液電池の
実施の形態について説明したが、本発明が上述した実施
の形態に限定されるものではないことは言うまでもな
く、偏平角型の非水電解液電池に適用する等、本発明の
趣旨を逸脱しない範囲で適宜変形変更が可能である。Although the embodiment of the non-aqueous electrolyte battery to which the present invention is applied has been described above, it goes without saying that the present invention is not limited to the above-described embodiment, and it is needless to say that the flat rectangular non-aqueous electrolyte is used. Modifications and changes can be made as appropriate without departing from the spirit of the present invention, such as application to electrolytic solution batteries.
【００３９】[0039]
【実施例】ここで、上述の実施の形態に示されるような
非水電解液電池を実際に作製し、特性の評価を行った。EXAMPLES Here, a non-aqueous electrolyte battery as shown in the above-mentioned embodiment was actually manufactured and its characteristics were evaluated.
【００４０】実施例１ 本実施例においては、結着剤として、数平均分子量Ｍｎ
が２．４３×１０5 であり、見かけ粘度が１３９１ｍＰ
ａ・ｓであるＰＶＤＦを用いて、非水電解液二次電池を
作製した。 Example 1 In this example, a number average molecular weight Mn was used as a binder.
Is 2.43 × 10 5 , and apparent viscosity is 1391 mP
A non-aqueous electrolyte secondary battery was produced using PVDF of a · s.
【００４１】具体的には、先ず、石油ピッチを１２００
℃で仮焼した後、不活性ガス雰囲気中、３０００℃にて
熱処理し、その後、粉砕することにより、人造黒鉛材料
よりなる負極活物質粉体を得た。この負極活物質粉体に
ついて、粉末Ｘ線回折測定を行った結果、（００２）面
の面間隔は０．３３７ｎｍ、Ｃ軸方向の結晶子の厚みは
３０ｎｍであった。レーザーラマン法によるＧ値は１
３．６、ピクノメータ法による真比重は２．２０ｇ／ｃ
ｍ3 であった。また、レーザー回折式粒度分布測定によ
る平均粒径は３３μｍ、ＪＩＳ−Ｋ１４６９によって求
められた嵩比重は１．１８ｇ／ｃｍ3 、平均形状パラメ
ータは３．６であった。Specifically, first, the petroleum pitch is set to 1200.
After calcination at ℃, it was heat-treated at 3000 ℃ in an inert gas atmosphere, and then ground to obtain a negative electrode active material powder made of an artificial graphite material. As a result of powder X-ray diffraction measurement of the negative electrode active material powder, the (002) plane spacing was 0.337 nm, and the crystallite thickness in the C-axis direction was 30 nm. G value by laser Raman method is 1
3.6, true specific gravity by pycnometer method is 2.20 g / c
m 3 . The average particle size measured by laser diffraction type particle size distribution was 33 μm, the bulk specific gravity determined by JIS-K1469 was 1.18 g / cm 3 , and the average shape parameter was 3.6.
【００４２】続いて、数平均分子量Ｍｎが２．４３×１
０5 であり、見かけ粘度が１３９１ｍＰａ・ｓであるＰ
ＶＤＦ（これを試料Ａとする。）を用意し、負極活物質
粉体９０重量部と、試料Ａよりなる結着剤１０重量部と
を混合し、ＮＭＰに分散させてスラリーを調製した。Subsequently, the number average molecular weight Mn was 2.43 × 1.
0 is 5, P apparent viscosity is 1391mPa · s
VDF (this is referred to as sample A) was prepared, 90 parts by weight of the negative electrode active material powder and 10 parts by weight of the binder made of sample A were mixed and dispersed in NMP to prepare a slurry.
【００４３】そして、厚さ１０μｍの帯状の銅箔よりな
る負極集電体１０の表面に、上述のスラリーを塗布し、
乾燥した後、圧縮成形して負極活物質含有塗膜１５を形
成することによって、負極電極１を作製した。Then, the above-mentioned slurry is applied to the surface of the negative electrode current collector 10 made of a strip-shaped copper foil having a thickness of 10 μm,
After drying, the negative electrode 1 was prepared by compression molding to form the negative electrode active material-containing coating film 15.
【００４４】また、炭素リチウム０．５モルと炭素コバ
ルト１モルを混合し、９００℃の空気中で５時間焼成し
た後、これを粉砕し、平均粒径が１５μｍのＬｉＣｏＯ
2 粉末を得た。なお、このＬｉＣｏＯ2 粉末についてＸ
線回折測定を行った結果、ＪＣＰＤＳファイルに登録さ
れたＬｉＣｏＯ2 のピークと良く一致した。続いて、こ
のＬｉＣｏＯ2 粉末９５重量％と炭素リチウム粉末５重
量％からなる正極活物質粉体９１重量％、グラファイト
（導電剤）６重量％、試料Ａよりなる結着剤３重量％を
混合し、ＮＭＰに分散させてスラリーを調製した。Further, 0.5 mol of lithium carbon and 1 mol of carbon cobalt were mixed and baked in air at 900 ° C. for 5 hours and then crushed to obtain LiCoO 2 having an average particle size of 15 μm.
Two powders were obtained. Regarding this LiCoO 2 powder, X
As a result of line diffraction measurement, it was in good agreement with the peak of LiCoO 2 registered in the JCPDS file. Subsequently, 91 wt% of the positive electrode active material powder composed of 95 wt% of this LiCoO 2 powder and 5 wt% of carbon lithium powder, 6 wt% of graphite (conductive agent), and 3 wt% of the binder of Sample A were mixed. , NMP were dispersed to prepare a slurry.
【００４５】そして、厚さ２０μｍの帯状のアルミニウ
ム箔よりなる正極集電体１１の表面に、上述のスラリー
を塗布し、乾燥した後、圧縮成形して正極活物質含有塗
膜１６を形成することによって、正極電極２を作製し
た。Then, the above-mentioned slurry is applied to the surface of the positive electrode current collector 11 made of a strip-shaped aluminum foil having a thickness of 20 μm, dried and then compression-molded to form the positive electrode active material-containing coating film 16. Thus, the positive electrode 2 was produced.
【００４６】次に、厚さ２５μｍの微多孔性ポリプロピ
レンフィルムよりなるセパレータ３を用意し、このセパ
レータ３、正極電極２、セパレータ３、負極電極１の順
に積層してから巻回することにより渦巻状電極体を作製
した。そして、直径１８ｍｍ、高さ６５ｍｍの円筒型の
電池缶５内に、この渦巻状電極体を収納し、エチレンカ
ーボネート５０体積％、ジエチルカーボネート５０体積
％の混合溶媒にＬｉＰＦ6 を１モル／ｌなる濃度で溶解
させた有機電解液を注入して、非水電解液電池を完成し
た。このようにして作製された非水電解液電池を実施例
１のサンプル電池とする。Next, a separator 3 made of a microporous polypropylene film having a thickness of 25 μm is prepared, and the separator 3, the positive electrode 2, the separator 3 and the negative electrode 1 are laminated in this order and then wound to form a spiral shape. An electrode body was produced. Then, the spirally wound electrode body was housed in a cylindrical battery can 5 having a diameter of 18 mm and a height of 65 mm, and 1 mol / l of LiPF 6 was added to a mixed solvent of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate. A non-aqueous electrolyte battery was completed by injecting an organic electrolyte solution dissolved at a concentration. The non-aqueous electrolyte battery manufactured in this manner is used as the sample battery of Example 1.
【００４７】実施例２〜実施例５ ここでは、負極電極１の負極活物質含有塗膜１５に含有
される結着剤として、実施例１とは数平均分子量Ｍｎお
よび見かけ粘度が異なるＰＶＤＦを用いた。 Examples 2 to 5 Here, as the binder contained in the negative electrode active material-containing coating film 15 of the negative electrode 1, PVDF having a number average molecular weight Mn and an apparent viscosity different from those in Example 1 was used. I was there.
【００４８】具体的には、ＰＶＤＦとして、数平均分子
量Ｍｎおよび見かけ粘度が表１に示されるような試料Ｂ
〜使用Ｅを用意した。なお、表１には、実施例１にて用
いた試料Ａについての数平均分子量Ｍｎおよび見かけ粘
度も併せて示す。Concretely, as PVDF, Sample B whose number average molecular weight Mn and apparent viscosity are shown in Table 1 is used.
-Use E was prepared. Table 1 also shows the number average molecular weight Mn and the apparent viscosity of Sample A used in Example 1.
【００４９】[0049]
【表１】 [Table 1]
【００５０】そして、負極電極１の負極活物質含有塗膜
１５に含有される結着剤として、試料Ｂを用いた以外は
実施例１と同様にして非水電解液電池を作製し、これを
実施例２のサンプル電池とした。また、負極活物質含有
塗膜１５に含有される結着剤として、試料Ｃを用いた以
外は実施例１と同様にして非水電解液電池を作製し、こ
れを実施例３のサンプル電池とした。さらに、負極活物
質含有塗膜１５に含有される結着剤として、試料Ｄを用
いた以外は実施例１と同様にして非水電解液電池を作製
し、これを実施例４のサンプル電池とした。また、負極
活物質含有塗膜１５に含有される結着剤として、試料Ｅ
を用いた以外は実施例１と同様にして非水電解液電池を
作製し、これを実施例５のサンプル電池とした。Then, a nonaqueous electrolyte battery was prepared in the same manner as in Example 1 except that Sample B was used as the binder contained in the negative electrode active material-containing coating film 15 of the negative electrode 1. The sample battery of Example 2 was used. Further, a non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that Sample C was used as the binder contained in the negative electrode active material-containing coating film 15, and this was used as the sample battery in Example 3. did. Further, a non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that Sample D was used as the binder contained in the negative electrode active material-containing coating film 15, and this was used as the sample battery of Example 4. did. Further, as a binder contained in the negative electrode active material-containing coating film 15, Sample E
A non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that was used as a sample battery of Example 5.
【００５１】比較例１ ここでも、負極電極１の負極活物質含有塗膜１５に含有
される結着剤として、数平均分子量Ｍｎおよび見かけ粘
度が実施例１とは異なるＰＶＤＦを用いた。 Comparative Example 1 Here, PVDF having a number average molecular weight Mn and an apparent viscosity different from those in Example 1 was used as the binder contained in the negative electrode active material-containing coating film 15 of the negative electrode 1.
【００５２】具体的には、負極活物質含有塗膜１５に含
有される結着剤として、表１に示される試料Ｆを用いた
以外は実施例１と同様にして非水電解液電池を作製し、
これにより比較例１のサンプル電池を得た。Specifically, a non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that the sample F shown in Table 1 was used as the binder contained in the negative electrode active material-containing coating film 15. Then
Thereby, the sample battery of Comparative Example 1 was obtained.
【００５３】実施例６〜実施例９ ここでは、正極電極２の正極活物質含有塗膜１６に含有
される結着剤として、実施例１とは数平均分子量Ｍｎお
よび見かけ粘度が異なるＰＶＤＦを用いた。 Examples 6 to 9 Here, as the binder contained in the positive electrode active material-containing coating film 16 of the positive electrode 2, PVDF having a number average molecular weight Mn and an apparent viscosity different from those in Example 1 was used. I was there.
【００５４】具体的には、正極活物質含有塗膜１６に含
有される結着剤として、表１に示される試料Ｂ〜試料Ｅ
を用いた以外は実施例１と同様にして非水電解液電池を
作製した。なお、正極活物質含有塗膜１６に含有される
結着剤として試料Ｂを用いたものを実施例６のサンプル
電池とし、同じく試料Ｃを用いたものを実施例７のサン
プル電池とし、同じく試料Ｄを用いたものを実施例８の
サンプル電池とし、同じく試料Ｅを用いたものを実施例
９のサンプル電池とした。Specifically, as the binder contained in the positive electrode active material-containing coating film 16, samples B to E shown in Table 1 were used.
A non-aqueous electrolyte battery was produced in the same manner as in Example 1 except that was used. Sample B was used as the binder contained in the positive electrode active material-containing coating 16 as the sample battery of Example 6, and Sample B was similarly used as the sample battery of Example 7, and the same sample was used. The sample battery using D was the sample battery of Example 8, and the sample battery using Sample E was the sample battery of Example 9.
【００５５】比較例２ ここでも、正極電極２の正極活物質含有塗膜１６に含有
される結着剤として、数平均分子量Ｍｎおよび見かけ粘
度が実施例１とは異なるＰＶＤＦを用いた。 Comparative Example 2 Here again, PVDF having a number average molecular weight Mn and an apparent viscosity different from those of Example 1 was used as the binder contained in the positive electrode active material-containing coating film 16 of the positive electrode 2.
【００５６】具体的には、正極活物質含有塗膜１６に含
有される結着剤として、表１に示される試料Ｆを用いた
以外は実施例１と同様にして非水電解液電池を作製し、
これにより比較例２のサンプル電池を得た。Specifically, a non-aqueous electrolyte battery was prepared in the same manner as in Example 1 except that Sample F shown in Table 1 was used as the binder contained in the positive electrode active material-containing coating film 16. Then
As a result, a sample battery of Comparative Example 2 was obtained.
【００５７】実施例１０ 本実施例においては、正極電極２の正極活物質含有塗膜
１６に含有される結着剤として試料Ａを用い、非水電解
液一次電池を作製した。 Example 10 In this example, a non-aqueous electrolyte primary battery was prepared by using Sample A as the binder contained in the positive electrode active material-containing coating film 16 of the positive electrode 2.
【００５８】具体的には、先ず、純度９６％のＦｅＳ2
を用意し、これを目開き４４μｍのメッシュを通過さ
せ、平均粒径１３μｍのＦｅＳ2 粉末を得た。続いて、
このＦｅＳ2 粉末９１重量部、グラファイト（導電剤）
６重量％、試料Ａよりなる結着剤３重量％を混合し、Ｎ
ＭＰに分散させてスラリーを調製した。Specifically, first, FeS 2 having a purity of 96% is prepared.
Was prepared and passed through a mesh having an opening of 44 μm to obtain FeS 2 powder having an average particle size of 13 μm. continue,
91 parts by weight of this FeS 2 powder, graphite (conductive agent)
6% by weight and 3% by weight of the binder consisting of sample A are mixed, and N
A slurry was prepared by dispersing in MP.
【００５９】そして、厚さ２０μｍの帯状のアルミニウ
ム箔よりなる正極集電体１１の表面に、上述のスラリー
を塗布し、乾燥した後、圧縮成形して正極活物質含有塗
膜１６を形成することによって、正極電極２を作製し
た。Then, the above-mentioned slurry is applied to the surface of the positive electrode current collector 11 made of a strip-shaped aluminum foil having a thickness of 20 μm, dried and then compression molded to form the positive electrode active material-containing coating film 16. Thus, the positive electrode 2 was produced.
【００６０】また、ロール状に巻取られている金属リチ
ウムを切断して負極電極１を作製し、その端部にニッケ
ルよりなる負極リード１２を圧着した。Further, the metallic lithium wound in a roll shape was cut to prepare the negative electrode 1, and the negative electrode lead 12 made of nickel was pressure-bonded to the end of the negative electrode 1.
【００６１】次に、厚さ２５μｍの微多孔性ポリプロピ
レンフィルムよりなるセパレータ３を用意し、このセパ
レータ３、正極電極２、セパレータ３、負極電極１の順
に積層してから巻回することにより渦巻状電極体を作製
した。そして、直径１８ｍｍ、高さ６５ｍｍの円筒型の
電池缶５内に、この渦巻状電極体を収納し、プロピレン
カーボネート５０体積％、ジメトキシエタン５０体積％
の混合溶媒にＬｉＣＦ 3 ＳＯ3 を０．７モル／ｌなる濃
度で溶解させた有機電解液を注入して、非水電解液電池
を完成した。このようにして作製された非水電解液電池
を実施例１０のサンプル電池とする。Next, a microporous polypropylene having a thickness of 25 μm was prepared.
Prepare a separator 3 made of ren film,
In this order, the generator 3, the positive electrode 2, the separator 3, and the negative electrode 1
Fabricate spiral electrode body by stacking on
did. A cylindrical type with a diameter of 18 mm and a height of 65 mm
The spirally wound electrode body is housed in the battery can 5 and
Carbonate 50% by volume, Dimethoxyethane 50% by volume
LiCF as a mixed solvent of ThreeSOThreeIs 0.7 mol / l
Non-aqueous electrolyte battery by injecting dissolved organic electrolyte
Was completed. Non-aqueous electrolyte battery produced in this way
Is a sample battery of Example 10.
【００６２】実施例１１〜実施例１４ ここでは、正極電極２の正極活物質含有塗膜１６に含有
される結着剤として、実施例１０とは数平均分子量Ｍｎ
および見かけ粘度が異なるＰＶＤＦを用いた。 Examples 11 to 14 Here, as the binder contained in the positive electrode active material-containing coating film 16 of the positive electrode 2, the example 10 is the number average molecular weight Mn.
And PVDF with different apparent viscosities were used.
【００６３】具体的には、正極活物質含有塗膜１６に含
有される結着剤として、表１に示される試料Ｂ〜試料Ｅ
を用いた以外は実施例１０と同様にして非水電解液電池
を作製した。なお、正極活物質含有塗膜１６に含有され
る結着剤として試料Ｂを用いたものを実施例１１のサン
プル電池とし、同じく試料Ｃを用いたものを実施例１２
のサンプル電池とし、同じく試料Ｄを用いたものを実施
例１３のサンプル電池とし、同じく試料Ｅを用いたもの
を実施例１４のサンプル電池とした。Specifically, as the binder contained in the positive electrode active material-containing coating film 16, Samples B to E shown in Table 1 were used.
A nonaqueous electrolyte battery was produced in the same manner as in Example 10 except that was used. Note that the sample B was used as the binder contained in the positive electrode active material-containing coating film 16 as the sample battery of Example 11, and the sample B was similarly used as the sample battery of Example 12.
The sample battery of Example 13 was the sample battery of Example 13, and the sample battery of Example 13 was the sample battery of Example 13.
【００６４】比較例３ ここでも、正極電極２の正極活物質含有塗膜１６に含有
される結着剤として、数平均分子量Ｍｎおよび見かけ粘
度が実施例１０とは異なるＰＶＤＦを用いた。 Comparative Example 3 Here again, PVDF having a number average molecular weight Mn and an apparent viscosity different from those in Example 10 was used as the binder contained in the positive electrode active material-containing coating film 16 of the positive electrode 2.
【００６５】具体的には、正極活物質含有塗膜１６に含
有される結着剤として、表１に示される試料Ｆを用いた
以外は実施例１０と同様にして非水電解液電池を作製
し、これにより比較例３のサンプル電池を得た。Specifically, a non-aqueous electrolyte battery was prepared in the same manner as in Example 10 except that Sample F shown in Table 1 was used as the binder contained in the positive electrode active material-containing coating film 16. Then, a sample battery of Comparative Example 3 was obtained.
【００６６】特性の評価 以下、上述のようにして作製されたサンプル電池に対す
る特性の評価を行う。 Evaluation of Characteristics The characteristics of the sample batteries manufactured as described above will be evaluated below.
【００６７】非水電解液二次電池である実施例１〜９、
比較例１、２のサンプル電池については、負極活物質含
有塗膜１５と負極集電体１０との結着力あるいは正極活
物質含有塗膜１６と正極集電体１１との結着力、サイク
ル維持率を調べ、非水電解液一次電池である実施例１０
〜１４、比較例３のサンプル電池については、正極活物
質含有塗膜１６と正極集電体１１との結着力、良品率を
調べた。Examples 1 to 9 which are non-aqueous electrolyte secondary batteries,
Regarding the sample batteries of Comparative Examples 1 and 2, the binding force between the negative electrode active material-containing coating film 15 and the negative electrode current collector 10 or the binding force between the positive electrode active material-containing coating film 16 and the positive electrode current collector 11, and cycle retention rate. Example 10 which is a non-aqueous electrolyte primary battery
14 and the sample batteries of Comparative Example 3, the binding force between the positive electrode active material-containing coating film 16 and the positive electrode current collector 11 and the non-defective rate were examined.
【００６８】なお、活物質含有塗膜１５、１６と集電体
１０、１１との結着力は、ＪＩＳ−Ｋ５４００−８．
５．２に規定される碁盤目テープ法による測定結果によ
って評価した。即ち、先ず、負極電極１あるいは正極電
極２の活物質含有塗膜１５、１６の中央１カ所に、カッ
ターナイフにより、等速にて切り傷１本につき約０．５
秒かけて、間隔１ｍｍ、格子１００個の碁盤目状の切り
傷を設けた。続いて、ＪＩＳ−Ｚ１５２２に規定される
幅１８ｍｍ、粘着力２．９４Ｎ／１０ｍｍ以上のセロハ
ン粘着テープを碁盤目の上に接着部分の長さが約５０ｍ
ｍとなるように貼り付けた後、ＪＩＳ−Ｓ６０５０に規
定される消しゴムにて上述の接着部分をこすって、電極
１、２の活物質含有塗膜１５、１６にセロハン粘着テー
プを完全に付着させた。そして、セロハン粘着テープを
付着させてから２分後に、セロハン粘着テープの一端を
持ち、これを活物質含有塗膜１５、１６の塗布面に垂直
に保ちながら、このセロハン粘着テープを瞬間的に引き
剥した。この操作により、活物質含有塗膜１５、１６が
剥離しなかった格子の数を数え、残存した格子の割合を
算出した。そして、この測定を５回繰り返し、平均値を
求め、この数値を結着力を評価するために用いた。な
お、実施例１〜５、比較例１のサンプル電池について
は、負極電極１における負極集電体１０と負極活物質含
有塗膜１５との結着力を求め、実施例６〜９、比較例２
のサンプル電池、実施例１０〜１４、比較例３のサンプ
ル電池については、正極電極２における正極集電体１１
と正極活物質含有塗膜１６との結着力を求めた。The binding force between the active material-containing coatings 15 and 16 and the current collectors 10 and 11 is determined according to JIS-K5400-8.
The evaluation was made based on the measurement results by the cross-cut tape method specified in 5.2. That is, first, about 0.5 per cut and one scratch at a constant speed with a cutter knife at one central portion of the active material-containing coatings 15 and 16 of the negative electrode 1 or the positive electrode 2.
Over a period of 2 seconds, a grid-like cut with 100 mm intervals was provided. Subsequently, a cellophane adhesive tape having a width of 18 mm and an adhesive force of 2.94 N / 10 mm or more specified in JIS-Z1522 is formed on the grid and the length of the adhesive portion is about 50 m.
m, and then rub the above-mentioned adhesive part with an eraser specified in JIS-S6050 to completely adhere the cellophane adhesive tape to the active material-containing coatings 15 and 16 of the electrodes 1 and 2. It was Then, two minutes after applying the cellophane adhesive tape, hold one end of the cellophane adhesive tape, and while holding it vertically to the application surface of the active material-containing coatings 15 and 16, pull this cellophane adhesive tape momentarily. I peeled it off. By this operation, the number of lattices in which the active material-containing coatings 15 and 16 were not peeled off was counted, and the ratio of the remaining lattices was calculated. Then, this measurement was repeated 5 times to obtain an average value, and this numerical value was used to evaluate the binding strength. Regarding the sample batteries of Examples 1 to 5 and Comparative Example 1, the binding force between the negative electrode current collector 10 and the negative electrode active material-containing coating film 15 in the negative electrode 1 was determined, and Examples 6 to 9 and Comparative Example 2 were obtained.
For the sample batteries of Examples, Examples 10 to 14 and the sample batteries of Comparative Example 3, the positive electrode current collector 11 in the positive electrode 2 was used.
The binding force between the positive electrode active material-containing coating film 16 and
【００６９】また、サイクル維持率は、上限電圧を４．
２Ｖ、定電流領域での電流を１Ａに設定して、２．５時
間充電した後、０．７Ａ定電流で２．５Ｖまで放電する
サイクルを繰り返し、２．７５Ｖまでの放電容量を求
め、１０サイクル目の容量に対する１００サイクル目の
容量の割合として算出したものである。As for the cycle maintenance rate, the upper limit voltage is 4.
After setting the current in the constant current region at 2V to 1A and charging the battery for 2.5 hours, the cycle of discharging to 2.5V at 0.7A constant current was repeated to obtain the discharge capacity up to 2.75V. It is calculated as the ratio of the capacity at the 100th cycle to the capacity at the cycle.
【００７０】さらに、良品率は、０．７Ａの定電流で
０．５Ｖまで放電し、０．９Ｖまでの放電容量を求め、
この放電容量の平均値から５％以上放電容量が低い場合
を不良と判定し、不良と判定されなかった割合を算出し
たものである。Further, the non-defective rate is determined by discharging up to 0.5 V with a constant current of 0.7 A and obtaining the discharge capacity up to 0.9 V.
From this average value of the discharge capacity, the case where the discharge capacity is lower than 5% is determined to be defective, and the ratio not determined to be defective is calculated.
【００７１】これら結果を表２〜４に示す。The results are shown in Tables 2-4.
【００７２】[0072]
【表２】 [Table 2]
【００７３】[0073]
【表３】 [Table 3]
【００７４】[0074]
【表４】 [Table 4]
【００７５】また、非水電解液二次電池の負極電極１に
用いられるＰＶＤＦの数平均分子量Ｍｎと、上述した結
着力（碁盤目テープ法による格子残存率）およびサイク
ル維持率との関係を図２に示し、同じくＰＶＤＦの見か
け粘度と結着力およびサイクル維持率との関係を図３に
示す。同様に、非水電解液二次電池の正極電極２に用い
られるＰＶＤＦの数平均分子量Ｍｎと結着力およびサイ
クル維持率との関係を図４に示し、同じくＰＶＤＦの見
かけ粘度と結着力およびサイクル維持率との関係を図５
に示す。さらに、非水電解液一次電池の正極電極２に用
いられるＰＶＤＦの数平均分子量Ｍｎと結着力および良
品率との関係を図６に示し、同じくＰＶＤＦの見かけ粘
度と結着力および良品率との関係を図７に示す。Further, the relationship between the number average molecular weight Mn of PVDF used for the negative electrode 1 of the non-aqueous electrolyte secondary battery and the above-mentioned binding force (lattice residual rate by the cross-cut tape method) and cycle maintenance rate is shown in FIG. 2 as well as the relationship between the apparent viscosity of PVDF and the binding strength and cycle retention rate. Similarly, FIG. 4 shows the relationship between the number average molecular weight Mn of PVDF used for the positive electrode 2 of the non-aqueous electrolyte secondary battery and the binding force and the cycle retention rate. Similarly, the apparent viscosity of PVDF and the binding force and the cycle retention rate were also shown. Figure 5 shows the relationship with the rate
Shown in Furthermore, FIG. 6 shows the relationship between the number average molecular weight Mn of PVDF used for the positive electrode 2 of the non-aqueous electrolyte primary battery and the binding force and the good product ratio. Similarly, the relationship between the apparent viscosity of PVDF and the binding force and the good product ratio is shown. Is shown in FIG.
【００７６】表２〜４、図２〜７より、結着剤として、
数平均分子量Ｍｎおよび見かけ粘度が高いＰＶＤＦを用
いるほど、各極電極１、２における集電体１０、１１と
活物質含有塗膜１５、１６との結着力が向上し、サイク
ル維持率あるいは良品率も向上することがわかる。From Tables 2 to 4 and FIGS. 2 to 7, as the binder,
As PVDF having a higher number average molecular weight Mn and a higher apparent viscosity is used, the binding force between the current collectors 10 and 11 and the active material-containing coatings 15 and 16 in the electrode electrodes 1 and 2 is improved, and the cycle retention rate or the good product rate is improved. It turns out that also improves.
【００７７】そして、数平均分子量Ｍｎが１．０×１０
5 以上、見かけ粘度が１５０ｍＰａ・ｓ以上のＰＶＤＦ
を用いることにより、良好な結着力を得られるようにな
り、サイクル維持率や良品率も優れたものとなることが
わかった。また、数平均分子量Ｍｎが１．８×１０5 以
上、見かけ粘度が６００ｍＰａ・ｓ以上のＰＶＤＦを用
いれば、結着力がほぼ最大に発揮されるようなることも
わかった。The number average molecular weight Mn is 1.0 × 10.
PVDF with an apparent viscosity of 5 or more and an apparent viscosity of 150 mPa · s or more
It was found that, by using, the good binding force can be obtained, and the cycle retention rate and the non-defective rate are also excellent. It was also found that when PVDF having a number average molecular weight Mn of 1.8 × 10 5 or more and an apparent viscosity of 600 mPa · s or more is used, the binding force is almost maximized.
【００７８】[0078]
【発明の効果】以上の説明からも明らかなように、本発
明を適用すると、活物質粉体と結着剤とを含有する塗膜
と集電体との結着力を向上させることができ、活物質粉
体の脱落も抑制できる。このため、高性能でありなが
ら、信頼性、生産性の高い非水電解液電池を提供するこ
とが可能となる。As is apparent from the above description, when the present invention is applied, the binding force between the coating film containing the active material powder and the binder and the current collector can be improved, It is also possible to prevent the active material powder from falling off. Therefore, it is possible to provide a non-aqueous electrolyte battery that has high performance and high reliability and productivity.
【図１】非水電解液電池の一構成例を示す模式的断面図
である。FIG. 1 is a schematic cross-sectional view showing a configuration example of a non-aqueous electrolyte battery.
【図２】非水電解液二次電池の負極電極に用いられるＰ
ＶＤＦの数平均分子量Ｍｎと、碁盤目テープ法による格
子残存率およびサイクル維持率との関係を示す特性図で
ある。FIG. 2 shows P used for a negative electrode of a non-aqueous electrolyte secondary battery.
It is a characteristic view which shows the relationship of the number average molecular weight Mn of VDF, the lattice retention rate by a cross-cut tape method, and a cycle maintenance rate.
【図３】非水電解液二次電池の負極電極に用いられるＰ
ＶＤＦの見かけ粘度と、碁盤目テープ法による格子残存
率およびサイクル維持率との関係を示す特性図である。FIG. 3 P used for the negative electrode of a non-aqueous electrolyte secondary battery
It is a characteristic view which shows the relationship between the apparent viscosity of VDF, the lattice residual rate by the cross-cut tape method, and the cycle maintenance rate.
【図４】非水電解液二次電池の正極電極に用いられるＰ
ＶＤＦの数平均分子量Ｍｎと、碁盤目テープ法による格
子残存率およびサイクル維持率との関係を示す特性図で
ある。FIG. 4 P used for a positive electrode of a non-aqueous electrolyte secondary battery
It is a characteristic view which shows the relationship of the number average molecular weight Mn of VDF, the lattice retention rate by a cross-cut tape method, and a cycle maintenance rate.
【図５】非水電解液二次電池の正極電極に用いられるＰ
ＶＤＦの見かけ粘度と、碁盤目テープ法による格子残存
率およびサイクル維持率との関係を示す特性図である。FIG. 5: P used for the positive electrode of a non-aqueous electrolyte secondary battery
It is a characteristic view which shows the relationship between the apparent viscosity of VDF, the lattice residual rate by the cross-cut tape method, and the cycle maintenance rate.
【図６】非水電解液一次電池の正極電極に用いられるＰ
ＶＤＦの数平均分子量Ｍｎと、碁盤目テープ法による格
子残存率およびサイクル維持率との関係を示す特性図で
ある。FIG. 6 P used for a positive electrode of a non-aqueous electrolyte primary battery
It is a characteristic view which shows the relationship of the number average molecular weight Mn of VDF, the lattice retention rate by a cross-cut tape method, and a cycle maintenance rate.
【図７】非水電解液一次電池の正極電極に用いられるＰ
ＶＤＦの見かけ粘度と、碁盤目テープ法による格子残存
率およびサイクル維持率との関係を示す特性図である。FIG. 7: P used for the positive electrode of a non-aqueous electrolyte primary battery
It is a characteristic view which shows the relationship between the apparent viscosity of VDF, the lattice residual rate by the cross-cut tape method, and the cycle maintenance rate.
１ 負極電極、 ２ 正極電極、 ３ セパレータ、
４ 絶縁板、 ５ 電池缶、 ６ 封口ガスケット、
７ 電池蓋、 ８ 安全弁装置、 １０ 負極集電体、
１１ 正極集電体、 １２ 負極リード、 １３ 正
極リード、 １４ センターピン、 １５ 負極活物質
含有塗膜、 １６ 正極活物質含有塗膜1 negative electrode, 2 positive electrode, 3 separator,
4 insulating plates, 5 battery cans, 6 sealing gaskets,
7 battery lid, 8 safety valve device, 10 negative electrode current collector,
11 positive electrode current collector, 12 negative electrode lead, 13 positive electrode lead, 14 center pin, 15 negative electrode active material-containing coating film, 16 positive electrode active material-containing coating film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小野 高志 福島県郡山市日和田町高倉字下杉下１−１ 株式会社ソニー・エナジー・テック内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Ono 1-1 Shimosugishita, Takakura, Hiwada Town, Koriyama City, Fukushima Prefecture Sony Energy Tech Inc.
Claims (4)
かが、集電体の表面に活物質粉体と結着剤とを含有する
塗膜が形成されてなる非水電解液電池において、 前記結着剤が、数平均分子量Ｍｎが１．０×１０5 以上
のポリフッ化ビニリデンよりなることを特徴とする非水
電解液電池。1. A non-aqueous electrolyte battery in which at least one of a positive electrode and a negative electrode has a coating film containing an active material powder and a binder formed on the surface of a current collector. A non-aqueous electrolyte battery, wherein the binder comprises polyvinylidene fluoride having a number average molecular weight Mn of 1.0 × 10 5 or more.
以上であることを特徴とする請求項１記載の非水電解液
電池。2. The number average molecular weight Mn is 1.8 × 10 5.
It is above, The non-aqueous electrolyte battery of Claim 1 characterized by the above-mentioned.
かが、集電体の表面に活物質粉体と結着剤とを含有する
塗膜が形成されてなる非水電解液電池において、 前記結着剤が、Ｎ−メチル−２−ピロリドン９０重量％
に対して１０重量％溶解させたときの見かけ粘度が１５
０ｍＰａ・ｓ以上となるポリフッ化ビニリデンよりなる
ことを特徴とする非水電解液電池。3. A non-aqueous electrolyte battery in which at least one of a positive electrode and a negative electrode has a coating film containing an active material powder and a binder formed on the surface of a current collector. 90% by weight of N-methyl-2-pyrrolidone
And the apparent viscosity when dissolved by 10% by weight is 15
A non-aqueous electrolyte battery comprising a polyvinylidene fluoride having a pressure of 0 mPa · s or more.
であることを特徴とする請求項３記載の非水電解液電
池。4. The non-aqueous electrolyte battery according to claim 3, wherein the apparent viscosity is 600 mPa · s or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8084357A JPH09274920A (en) | 1996-04-05 | 1996-04-05 | Nonaqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8084357A JPH09274920A (en) | 1996-04-05 | 1996-04-05 | Nonaqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09274920A true JPH09274920A (en) | 1997-10-21 |
Family
ID=13828279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8084357A Pending JPH09274920A (en) | 1996-04-05 | 1996-04-05 | Nonaqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09274920A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2002047193A1 (en) * | 2000-12-07 | 2002-06-13 | Tdk Corporation | Electrode composition and lithium secondary battery |
| JP2002270182A (en) * | 2001-03-13 | 2002-09-20 | Shin Kobe Electric Mach Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2003100299A (en) * | 2001-09-21 | 2003-04-04 | Tdk Corp | Lithium secondary battery |
| WO2003038931A1 (en) * | 2001-10-29 | 2003-05-08 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| KR100749650B1 (en) * | 2005-12-29 | 2007-08-14 | 삼성에스디아이 주식회사 | Lithium rechargeable battery |
| KR100859637B1 (en) * | 2007-06-01 | 2008-09-23 | 삼성에스디아이 주식회사 | Lithium rechargeable battery |
| US7709141B2 (en) | 2005-12-29 | 2010-05-04 | Samsung Sdi Co., Ltd. | Lithium ion secondary battery |
| US7842414B2 (en) | 2005-12-29 | 2010-11-30 | Samsung Sdi Co., Ltd. | Lithium secondary battery |
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| JP2016021391A (en) * | 2014-06-19 | 2016-02-04 | 日本ゼオン株式会社 | Conductive material fluid dispersion for electrochemical devices, slurry for electrochemical device positive electrodes, positive electrode for electrochemical devices, and electrochemical device |
| US9444104B2 (en) | 2012-05-21 | 2016-09-13 | Daikin Industries, Ltd. | Electrode mixture |
| WO2024045554A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Binder, preparation method, positive electrode sheet, secondary battery and electric device |
| WO2024045553A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Binder, preparation method, positive electrode sheet, secondary battery and electric device |
-
1996
- 1996-04-05 JP JP8084357A patent/JPH09274920A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002047193A1 (en) * | 2000-12-07 | 2002-06-13 | Tdk Corporation | Electrode composition and lithium secondary battery |
| JP2002270182A (en) * | 2001-03-13 | 2002-09-20 | Shin Kobe Electric Mach Co Ltd | Non-aqueous electrolyte secondary battery |
| JP2003100299A (en) * | 2001-09-21 | 2003-04-04 | Tdk Corp | Lithium secondary battery |
| WO2003038931A1 (en) * | 2001-10-29 | 2003-05-08 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| US7150940B2 (en) | 2001-10-29 | 2006-12-19 | Matsushita Electric Industrial Co., Ltd. | Lithium ion secondary battery |
| US7722983B2 (en) | 2005-12-29 | 2010-05-25 | Samsung Sdi Co., Ltd. | Lithium ion secondary battery |
| US7709141B2 (en) | 2005-12-29 | 2010-05-04 | Samsung Sdi Co., Ltd. | Lithium ion secondary battery |
| KR100749650B1 (en) * | 2005-12-29 | 2007-08-14 | 삼성에스디아이 주식회사 | Lithium rechargeable battery |
| US7842414B2 (en) | 2005-12-29 | 2010-11-30 | Samsung Sdi Co., Ltd. | Lithium secondary battery |
| KR100859637B1 (en) * | 2007-06-01 | 2008-09-23 | 삼성에스디아이 주식회사 | Lithium rechargeable battery |
| WO2013176093A1 (en) * | 2012-05-21 | 2013-11-28 | ダイキン工業株式会社 | Electrode mixture |
| JPWO2013176093A1 (en) * | 2012-05-21 | 2016-01-14 | ダイキン工業株式会社 | Electrode mixture |
| US9444104B2 (en) | 2012-05-21 | 2016-09-13 | Daikin Industries, Ltd. | Electrode mixture |
| US9444103B2 (en) | 2012-05-21 | 2016-09-13 | Daikin Industries, Ltd. | Electrode mixture |
| JP2016021391A (en) * | 2014-06-19 | 2016-02-04 | 日本ゼオン株式会社 | Conductive material fluid dispersion for electrochemical devices, slurry for electrochemical device positive electrodes, positive electrode for electrochemical devices, and electrochemical device |
| WO2024045554A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Binder, preparation method, positive electrode sheet, secondary battery and electric device |
| WO2024045553A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Binder, preparation method, positive electrode sheet, secondary battery and electric device |
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