JP2003272634A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JP2003272634A JP2003272634A JP2002067137A JP2002067137A JP2003272634A JP 2003272634 A JP2003272634 A JP 2003272634A JP 2002067137 A JP2002067137 A JP 2002067137A JP 2002067137 A JP2002067137 A JP 2002067137A JP 2003272634 A JP2003272634 A JP 2003272634A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- secondary battery
- graft polymer
- active material
- 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.)
- Withdrawn
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、非水二次電池に関
し、さらに詳しくは、高容量で貯蔵特性およびサイクル
特性などの信頼性にすぐれた非水二次電池に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous secondary battery, and more particularly to a non-aqueous secondary battery having a high capacity and excellent reliability such as storage characteristics and cycle characteristics.
【０００２】[0002]
【従来の技術】電子機器の小型化、携帯電話の普及に伴
い、高エネルギー密度を有する二次電池への要求がます
ます高まっている。現在、この要求に応える高容量二次
電池としては、正極活物質としてＬｉＣｏＯ2 を用い、
負極活物質として炭素系材料を用いたリチウムイオン二
次電池が商品化されている。2. Description of the Related Art With the miniaturization of electronic devices and the spread of mobile phones, the demand for secondary batteries having high energy density is increasing more and more. Currently, as a high-capacity secondary battery that meets this demand, LiCoO 2 is used as a positive electrode active material,
A lithium ion secondary battery using a carbon-based material as a negative electrode active material has been commercialized.
【０００３】このリチウムイオン二次電池は、平均駆動
電圧が３．６Ｖと高く、従来のニッケルーカドミウム電
池やニッケル水素電池の平均駆動電圧の約３倍である。
また、負極活物質として炭素系材料を用い、充放電に関
与するモビリティーが軽金属であるリチウムであること
から、軽量化も期待できる。This lithium-ion secondary battery has a high average driving voltage of 3.6 V, which is about three times the average driving voltage of conventional nickel-cadmium batteries and nickel-hydrogen batteries.
Further, since a carbon-based material is used as the negative electrode active material and the mobility involved in charging / discharging is lithium, which is a light metal, weight reduction can be expected.
【０００４】リチウムイオン二次電池は、従来のリチウ
ム金属を負極とする非水二次電池とは異なり、活物質を
結着剤などとともに溶液中に分散させたペーストとし、
このペーストを用いて、正極集電体、負極集電体ともに
集電体の両面にそれぞれ活物質を含有する塗膜を形成
し、帯状の正負極を作製する。これらの帯状の電極はセ
パレータを介して渦巻状に巻回して電極体を形成し、電
池缶に挿入して、電池が構成されている。The lithium-ion secondary battery is a paste in which an active material is dispersed in a solution together with a binder, unlike a conventional non-aqueous secondary battery using lithium metal as a negative electrode.
Using this paste, a coating film containing an active material is formed on both surfaces of both the positive electrode current collector and the negative electrode current collector to form a strip-shaped positive and negative electrode. These strip-shaped electrodes are spirally wound through a separator to form an electrode body, which is inserted into a battery can to form a battery.
【０００５】今後、携帯電話などの長時間連続使用、機
能を追加することによる消費電力の増加に対して、リチ
ウムイオン二次電池の一層の高容量化が望まれる。正極
活物質のひとつであるＬｉＣｏＯ2 は、理論放電容量が
２７４ｍＡｈ／ｇであるが、深い充放電を行うとＬｉＣ
ｏＯ2 が相変化を起こしてサイクル寿命に影響を与える
ため、実際のリチウムイオン二次電池における実用的な
放電容量は１２５〜１４０ｍＡｈ／ｇの範囲となる。In the future, it is desired to further increase the capacity of the lithium-ion secondary battery in response to an increase in power consumption due to long-term continuous use of a mobile phone or the like and addition of functions. LiCoO 2 , which is one of the positive electrode active materials, has a theoretical discharge capacity of 274 mAh / g.
Since oO 2 causes a phase change and affects the cycle life, the practical discharge capacity in an actual lithium ion secondary battery is in the range of 125 to 140 mAh / g.
【０００６】また、正極活物質の他のひとつであるＬｉ
ＣｏＯ2 は、理論放電容量がＬｉＣｏＯ2 と同様に２７
４ｍＡｈ／ｇであるが、Ｌｉ極を基準とした作動電位が
ＬｉＣｏＯ2 に比べて低く、放電末期における電圧降下
が急激でないため、Ｌｉ極に対して３．０〜４．０Ｖ領
域での放電容量がＬｉＣｏＯ2 よりも大きく、実用的な
電位範囲（Ｌｉ極に対して３．０〜４．０Ｖ領域）での
放電容量が、合成条件によっても異なるが、一般に１６
０〜２００ｍＡｈ／ｇである。Li, which is another positive electrode active material,
CoO 2 has a theoretical discharge capacity of 27 as well as LiCoO 2.
Although it is 4 mAh / g, the working potential based on the Li electrode is lower than that of LiCoO 2, and the voltage drop at the end of discharge is not abrupt, so the discharge capacity in the 3.0 to 4.0 V region with respect to the Li electrode is Is larger than LiCoO 2 , and the discharge capacity in a practical potential range (3.0 to 4.0 V region with respect to the Li electrode) varies depending on the synthesis conditions.
It is 0 to 200 mAh / g.
【０００７】したがって、正極活物質として、ＬｉＣｏ
Ｏ2 を用いるよりも、ＬｉＮｉＯ2を用いた方が、より
高容量の電池を作製できるものと期待される。ＬｉＮｉ
Ｏ2の真密度は４．６〜４．８ｇ／cm3 であるため、Ｌ
ｉＣｏＯ2 とほぼ同程度の充填性が得られ、ＬｉＣｏＯ
2 をＬｉＮｉＯ2 で置き換えても、電極作製時に充填性
が劣ることはほとんどない。しかしながら、ＬｉＮｉＯ
2 は、合成条件などにより、層間にＮｉイオンが混入し
やすく、この層間のＮｉイオンがＬｉイオンの移動を阻
害するため、ＬｉＮｉＯ2 の電気化学的容量が減少しや
すい。しかも、ＬｉＮｉＯ2 の合成は、酸素雰囲気下で
注意深く制御する必要があるため、ＬｉＣｏＯ2 に比べ
て、製造コストが高くなる。Therefore, as a positive electrode active material, LiCo
It is expected that using LiNiO 2 will produce a battery with a higher capacity than using O 2 . LiNi
Since the true density of O 2 is 4.6 to 4.8 g / cm 3 ,
Almost the same filling property as that of iCoO 2 was obtained.
Be replaced 2 with LiNiO 2, it is hardly inferior filling properties during electrode fabrication. However, LiNiO
In No. 2 , Ni ions are easily mixed between the layers due to synthesis conditions and the Ni ions between the layers inhibit the movement of Li ions, so that the electrochemical capacity of LiNiO 2 is likely to decrease. Moreover, since the synthesis of LiNiO 2 needs to be carefully controlled in an oxygen atmosphere, the manufacturing cost is higher than that of LiCoO 2 .
【０００８】また、正極活物質のさらに他のひとつであ
るＬｉＭｎＯ2 は、理論放電容量が１４８ｍＡｈ／ｇと
小さく、しかもＬｉＣｏＯ2 と同様に充放電中に相変化
を起こし、さらにＬｉＣｏＯ2 の真密度が４．９〜５．
１ｇ／cm3 であるのに対し、ＬｉＭｎＯ2 の真密度は
４．０〜４．２ｇ／cm3 であり、正極活物質としての充
填性を考えると、体積あたりの容量面でも不利を生じる
ことになる。LiMnO 2 , which is another positive electrode active material, has a small theoretical discharge capacity of 148 mAh / g and, like LiCoO 2 , undergoes a phase change during charge and discharge, and further has a true density of LiCoO 2 . Is 4.9-5.
In contrast to 1 g / cm 3 , the true density of LiMnO 2 is 4.0 to 4.2 g / cm 3 , and considering the filling property as a positive electrode active material, there is a disadvantage in terms of capacity per volume. become.
【０００９】このように、正極活物質として、ＬｉＣｏ
Ｏ2 、ＬｉＮｉＯ2 またはＬｉＭｎＯ2 の中から選ばれ
る単独あるいは２種以上の混合物を用いる場合、これら
正極活物質の上記したような充放電特性から、これら正
極活物質の小粒径化あるいはタップ密度の向上により、
正極塗膜中での正極活物質の充填性を向上させ、これに
より高容量化をはかることが望まれる。Thus, as the positive electrode active material, LiCo
When using a single material or a mixture of two or more materials selected from O 2 , LiNiO 2 and LiMnO 2 , due to the above-mentioned charge and discharge characteristics of these positive electrode active materials, it is possible to reduce the particle size or tap density of these positive electrode active materials. By improving
It is desired to improve the filling property of the positive electrode active material in the positive electrode coating film, thereby increasing the capacity.
【００１０】正極を作製する場合、正極活物質、導電助
剤、結着剤および有機溶媒などを混合し分散してペース
ト状の正極塗料を調製し、この塗料を正極集電体上に塗
布し乾燥したのち圧縮成形して、正極塗膜を形成する。
正極の体積当たりの容量を向上させるためには、正極塗
膜の高密度化と、塗膜中の正極活物質量の増加とが考え
られ、このうち、前者の高密度化は、圧縮工程での圧力
を高くすることにより実施できるが、この場合、電解液
の浸透が抑制されるため、充放電時に容量の低下が生じ
たり、サイクル特性が悪くなるという問題がある。When manufacturing a positive electrode, a positive electrode active material, a conductive auxiliary agent, a binder, an organic solvent and the like are mixed and dispersed to prepare a paste-like positive electrode coating material, and this coating material is applied onto a positive electrode current collector. After drying, compression molding is performed to form a positive electrode coating film.
In order to improve the capacity per volume of the positive electrode, it is conceivable that the positive electrode coating film should be densified and the amount of the positive electrode active material in the coating film should be increased. This can be carried out by increasing the pressure of 1. However, in this case, since the permeation of the electrolytic solution is suppressed, there is a problem that the capacity is lowered at the time of charging and discharging, and the cycle characteristics are deteriorated.
【００１１】後者の正極活物質量の増加は、結着剤また
は導電助剤の量の低減を行うことで実施できる。しか
し、結着剤量の低減は、正極塗膜の強度低下、集電体と
の密着性の悪化に繋がるため、極めて難しい。導電助剤
量の低減は、正極塗膜の導電性をいかに確保するかが重
要となるため、導電助剤の種類や表面処理などについて
種々の提案がなされている（特開平５−１７４８１０号
公報、特開平１０−３１２８１１号公報）。しかし、い
ずれの提案も、正極塗膜中での導電助剤の均一な分散が
難しく、初期の電池容量を向上させることができても、
貯蔵特性およびサイクル特性などの信頼性試験において
十分な特性が得られない。The latter increase in the amount of the positive electrode active material can be carried out by reducing the amount of the binder or the conductive auxiliary agent. However, it is extremely difficult to reduce the amount of the binder, because it leads to a decrease in the strength of the positive electrode coating film and a deterioration in the adhesion with the current collector. Since it is important to secure the conductivity of the positive electrode coating film in order to reduce the amount of the conductive additive, various proposals have been made regarding the type of the conductive additive and the surface treatment (Japanese Patent Laid-Open No. 174810/1993). , JP-A-10-312811). However, in any of the proposals, it is difficult to uniformly disperse the conductive additive in the positive electrode coating film, and even if the initial battery capacity can be improved,
Sufficient characteristics cannot be obtained in reliability tests such as storage characteristics and cycle characteristics.
【００１２】[0012]
【発明が解決しようとする課題】このように、従来の技
術では、正極塗膜中の正極活物質量の増加などにより、
初期の電池容量を向上させることができたとしても、貯
蔵特性およびサイクル特性などの信頼性を向上させるこ
とは難しかった。本発明は、この課題を解決することに
より、貯蔵特性およびサイクル特性などの信頼性にすぐ
れた非水二次電池を提供することを目的としている。As described above, according to the conventional technique, due to an increase in the amount of the positive electrode active material in the positive electrode coating film,
Even if the initial battery capacity could be improved, it was difficult to improve reliability such as storage characteristics and cycle characteristics. An object of the present invention is to provide a non-aqueous secondary battery having excellent reliability such as storage characteristics and cycle characteristics by solving this problem.
【００１３】[0013]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するため、鋭意検討した結果、正極、負極およ
び電解質を有する非水二次電池において、正極中に、正
極活物質としてのＬｉ複合酸化物、導電助剤および結着
剤とともに、グラフトポリマーを含ませると、高密度で
かつ正極活物質量の多い正極塗膜を形成でき、貯蔵特性
およびサイクル特性などの信頼性にすぐれた非水二次電
池が得られることがわかった。Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and as a result, in a non-aqueous secondary battery having a positive electrode, a negative electrode and an electrolyte, a positive electrode active material was used in the positive electrode. If a graft polymer is included together with the Li complex oxide, the conductive auxiliary agent and the binder, it is possible to form a positive electrode coating film with high density and a large amount of positive electrode active material, and it has excellent reliability such as storage characteristics and cycle characteristics. It was found that a non-aqueous secondary battery was obtained.
【００１４】Ｌｉ複合酸化物は、表面に水酸基などの親
水性基を含むことが知られており、その表面に結着剤で
ある樹脂が吸着して、正極塗膜中で良好に分散する。一
方、導電助剤には、一般的に、鱗片状黒鉛やカーボンブ
ラックが使用されているが、これらの導電助剤の表面は
芳香環基や炭化水素基などの疎水性基を含んでおり、表
面に結着剤である樹脂が吸着し難く、そのため、正極塗
膜中での分散性が不十分になる。このように、正極活物
質と導電助剤との表面性が異なり、正極塗膜中で導電助
剤が不均一に存在しやすい状態にある。It is known that the Li composite oxide contains hydrophilic groups such as hydroxyl groups on the surface, and the resin as the binder is adsorbed on the surface and is well dispersed in the positive electrode coating film. On the other hand, as the conductive additive, generally, flaky graphite or carbon black is used, but the surface of these conductive additives contains a hydrophobic group such as an aromatic ring group or a hydrocarbon group, It is difficult for the resin, which is the binder, to be adsorbed on the surface, so that the dispersibility in the positive electrode coating film becomes insufficient. In this way, the positive electrode active material and the conductive additive have different surface properties, and the conductive additive is likely to be unevenly present in the positive electrode coating film.
【００１５】ところが、正極塗料の調製に際し、グラフ
トポリマー、とくに（１）溶解パラメーター（ＳＰ）が
１０．５以上、１３未満のセグメントと、（２）ＳＰが
７．５以上、１０未満のセグメントとからなるグラフト
ポリマーを添加すると、上記（２）のセグメントが導電
助剤の表面に吸着し、かつ塗料中での分散安定性にも好
結果を与え、しかも上記（１）のセグメントが正極塗料
の有機溶媒として用いられるＮ−メチルピロリドンなど
の非プロトン性極性溶媒に可溶なため、正極活物質と導
電助剤が均一に分散した正極塗料が得られる。However, in the preparation of the positive electrode paint, a graft polymer, particularly (1) a segment having a solubility parameter (SP) of 10.5 or more and less than 13 and (2) a segment of SP of 7.5 or more and less than 10 are used. When the graft polymer consisting of (2) is added, the above segment (2) is adsorbed on the surface of the conductive additive, and the dispersion stability in the paint is also obtained with good results. Since it is soluble in an aprotic polar solvent such as N-methylpyrrolidone used as an organic solvent, a positive electrode coating material in which the positive electrode active material and the conductive additive are uniformly dispersed can be obtained.
【００１６】このような正極塗料を集電体に塗布して正
極を作製すると、高密度でかつ正極活物質量の多い正極
塗膜を形成でき、貯蔵特性およびサイクル特性などの信
頼性にすぐれた非水二次電池が得られる。このような効
果は、従来の低分子の界面活性剤では奏し得られない。
これは、導電助剤表面に吸着する部分と安定化する部分
がともに短いため、吸着能および分散安定性が弱くなる
ためである。とくに、正極塗膜中ではイオン性基の使用
は電池性能の低下に繋がるため、分散安定性の向上にイ
オン性基による静電反発を使用することは難しい。When such a positive electrode coating material is applied to a current collector to prepare a positive electrode, a positive electrode coating film having a high density and a large amount of positive electrode active material can be formed, and the storage characteristics and cycle characteristics are excellent. A non-aqueous secondary battery can be obtained. Such an effect cannot be obtained with a conventional low-molecular-weight surfactant.
This is because both the adsorption portion and the stabilizing portion on the surface of the conductive additive are short, so that the adsorption ability and the dispersion stability are weakened. In particular, since the use of ionic groups in the positive electrode coating film leads to a decrease in battery performance, it is difficult to use electrostatic repulsion by ionic groups to improve dispersion stability.
【００１７】本発明は、以上の知見をもとにして、完成
されたものである。すなわち、本発明は、正極、負極お
よび電解質を有する非水二次電池において、正極中に、
正極活物質としてのＬｉ複合酸化物、導電助剤および結
着剤とともに、グラフトポリマーを含むことを特徴とす
る非水二次電池に係るものであり、とくに、上記グラフ
トポリマーが（１）溶解パラメーター（ＳＰ）が１０．
５以上、１３未満のセグメントと（２）ＳＰが７．５以
上、１０未満のセグメントとからなる上記構成の非水二
次電池、上記グラフトポリマーの分子量が２，０００〜
５０，０００である上記構成の非水二次電池に係るもの
である。The present invention has been completed based on the above findings. That is, the present invention, in a non-aqueous secondary battery having a positive electrode, a negative electrode and an electrolyte, in the positive electrode,
The present invention relates to a non-aqueous secondary battery characterized by comprising a graft polymer together with a Li composite oxide as a positive electrode active material, a conductive auxiliary agent and a binder. (SP) is 10.
The non-aqueous secondary battery having the above-mentioned constitution, which comprises segments of 5 or more and less than 13 and (2) segments of SP of 7.5 or more and less than 10, and the molecular weight of the graft polymer is 2,000 to
The present invention relates to the non-aqueous secondary battery having the above structure of 50,000.
【００１８】[0018]
【発明の実施の形態】本発明におけるグラフトポリマー
は、基本的に、極性の異なる主鎖部分とグラフト部分と
を有するポリマーであり、とくに好適には、（１）溶解
パラメーター（ＳＰ）が１０．５以上、１３未満のセグ
メントと、（２）ＳＰが７．５以上、１０未満のセグメ
ントとから構成されたものが用いられる。このポリマー
には、ａ）上記（１）のセグメントが主鎖部分、上記
（２）のセグメントがグラフト部分となるものと、ｂ）
上記（１）のセグメントがグラフト部分、上記（２）の
セグメントが主鎖部分となるものとが含まれる。いずれ
のグラフトポリマーでも、導電助剤に対し十分な分散性
改善効果を発揮するが、ｂのグラフトポリマーは、より
少ない添加量で電池特性を向上できるので、とくに好ま
しい。BEST MODE FOR CARRYING OUT THE INVENTION The graft polymer according to the present invention is basically a polymer having a main chain portion and a graft portion having different polarities, and particularly preferably (1) the solubility parameter (SP) is 10. What is comprised from the segment of 5 or more and less than 13 and the segment of (2) SP of 7.5 or more and less than 10 is used. In this polymer, a) the above-mentioned segment (1) serves as a main chain portion and the above-mentioned segment (2) serves as a graft portion, and b)
The segment of (1) above is a graft part, and the segment of (2) above is a main chain part. Any of the graft polymers exhibits a sufficient effect of improving the dispersibility with respect to the conductive additive, but the graft polymer of b can improve the battery characteristics with a smaller addition amount, and is therefore particularly preferable.
【００１９】上記（１）のセグメントを構成する単量体
には、ビニルピロリドンまたはその誘導体、ビニルオキ
サゾリン、２−メチル−２−オキサゾリンまたは２−エ
チル−２−オキサゾリンなどがある。上記（２）のセグ
メントを構成する単量体には、スチレンまたはその誘導
体、エチレンやプロピレンなどのアルケン類、ブチルメ
タクリレート、ヘキシルメタクリレート、ラウリルメタ
クリレート、ステアリルメタクレートなどのアルキルメ
タクリレート類、ブチルアクリレート、ヘキシルアクリ
レート、ラウリルアクリレート、ステアリルアクリレー
トなどのアルキルアクリレート類などがある。これらの
両単量体を、適宜の手法により、グラフト共重合させる
ことにより、前記構成のグラフトポリマーが得られる。Monomers constituting the above-mentioned segment (1) include vinylpyrrolidone or a derivative thereof, vinyloxazoline, 2-methyl-2-oxazoline or 2-ethyl-2-oxazoline. Examples of the monomer constituting the segment (2) include styrene or a derivative thereof, alkenes such as ethylene and propylene, butyl methacrylate, hexyl methacrylate, lauryl methacrylate, alkyl methacrylates such as stearyl methacrylate, butyl acrylate, hexyl. Examples include alkyl acrylates such as acrylate, lauryl acrylate, and stearyl acrylate. By graft-copolymerizing these both monomers by an appropriate method, the graft polymer having the above-mentioned constitution can be obtained.
【００２０】このようなグラフトポリマーは、数平均分
子量が２，０００〜５０，０００であるのが好ましい。
数平均分子量が２，０００未満となると、導電助剤に吸
着したポリマーの立体反発が弱くなるため、導電助剤の
分散が不十分となる。また、５０，０００を超えると、
導電助剤の表面に吸着したポリマー鎖が長くなって、導
電助剤同士の導電パスの形成を阻害するおそれがある。Such a graft polymer preferably has a number average molecular weight of 2,000 to 50,000.
When the number average molecular weight is less than 2,000, the steric repulsion of the polymer adsorbed on the conductive additive is weakened, resulting in insufficient dispersion of the conductive additive. If it exceeds 50,000,
The polymer chains adsorbed on the surface of the conductive additive may become long, which may hinder the formation of conductive paths between the conductive auxiliary agents.
【００２１】本発明においては、正極中に上記構成のグ
ラフトポリマーを含ませたことを特徴とするが、その含
有量は、正極活物質に対して、０．００１〜１重量％と
なる割合とするのが望ましい。０．００１重量％より少
ないと、グラフトポリマーを含ませたことによる効果が
十分に発現されず、１重量％を超えると、正極塗料の粘
度が増大し、正極活物質と導電助剤の両方の分散性が低
下する。The present invention is characterized in that the positive electrode contains the graft polymer having the above-mentioned constitution. The content thereof is 0.001 to 1% by weight based on the positive electrode active material. It is desirable to do. If it is less than 0.001% by weight, the effect due to the inclusion of the graft polymer is not sufficiently exhibited, and if it exceeds 1% by weight, the viscosity of the positive electrode coating material increases and both the positive electrode active material and the conductive auxiliary agent are increased. Dispersibility decreases.
【００２２】本発明において、正極は、正極活物質、導
電助剤および結着剤を有機溶媒中に均一に溶解分散した
ペースト状の正極塗料を調製し、これを正極集電体上に
塗布し、乾燥工程や圧縮工程を経て、正極塗膜を形成す
ることにより、作製される。この正極塗膜中に上記構成
のグラフトポリマーを含ませるには、正極塗料の調製に
際し、この塗料中に添加しておけばよい。In the present invention, the positive electrode is prepared by preparing a paste-like positive electrode coating material in which a positive electrode active material, a conductive auxiliary agent and a binder are uniformly dissolved and dispersed in an organic solvent, and the paste is applied onto the positive electrode current collector. It is produced by forming a positive electrode coating film through a drying process and a compression process. In order to include the graft polymer having the above constitution in the positive electrode coating film, it may be added to the positive electrode coating material during the preparation thereof.
【００２３】正極塗料の調製方法は、とくに限定されな
いが、導電助剤とグラフトポリマーを混合し、これに正
極活物質と結着剤を加えて、有機溶媒中で混合分散する
方法を採用すると、本発明の効果がより良く発現させる
ことができる。これ以外に、各成分を一緒に混合し溶解
分散する方法、結着剤やグラフトポリマーなどの樹脂成
分を有機溶媒中に溶解させた溶液をつくり、これに正極
活物質や導電助剤などの固体粒子を混合分散する方法な
どを採用してもよい。これらの方法において、有機溶媒
としては、たとえば、Ｎ−メチルピロリドン、ジメチル
アセトアミド、ジメチルホルムアミド、テトラヒドロフ
ランなどの非プロトン性有機溶媒が、単独でまたは２種
以上の混合系で、用いられる。The method for preparing the positive electrode coating material is not particularly limited, but if a method of mixing a conductive auxiliary agent and a graft polymer, adding a positive electrode active material and a binder to the mixture, and mixing and dispersing in an organic solvent is adopted, The effects of the present invention can be better expressed. In addition to this, a method of mixing and dissolving each component together, making a solution in which a resin component such as a binder or a graft polymer is dissolved in an organic solvent, and then adding a solid such as a positive electrode active material or a conduction aid to the solution A method of mixing and dispersing particles may be adopted. In these methods, as the organic solvent, for example, aprotic organic solvents such as N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and tetrahydrofuran are used alone or in a mixture of two or more kinds.
【００２４】正極活物質としては、Ｌｉ複合酸化物を使
用する。これには、ＬｉＣｏＯ2 などのリチウムコバル
ト酸化物、ＬｉＮｉＯ2 などのリチウムニッケル酸化
物、ＬｉＭｎＯ2 などのリチウムマンガン酸化物などが
用いられる。また、導電助剤としては、鱗片状黒鉛など
の黒鉛系導電材料、アセチレンブラック、ケッチェンブ
ラック、カーボンブラックなどが用いられる。Li composite oxide is used as the positive electrode active material. For this, lithium cobalt oxide such as LiCoO 2 , lithium nickel oxide such as LiNiO 2 and lithium manganese oxide such as LiMnO 2 are used. Further, as the conductive aid, a graphite-based conductive material such as flake graphite, acetylene black, Ketjen black, carbon black, or the like is used.
【００２５】結着剤には、熱可塑性樹脂、ゴム弾性を有
するポリマーまたは多糖類が、１種または２種以上の混
合物として用いられる。具体的には、ポリテトラフルオ
ロエチレン、ポリフッ化ビニリデン、ポリエチレン、ポ
ロプロピレン、エチレン−プロピレン−ジエン共重合樹
脂、スチレンブタジエンゴム、ポリブタジエン、フッ素
ゴム、ポリエチレンオキシド、ポリビニルピロリドン、
ポリエステル樹脂、アクリル樹脂、フェノール樹脂、エ
ポキシ樹脂、ポリビニルアルコール、ヒドロキシプロピ
ルセルロースなどのセルロース樹脂などが挙げられる。
中でも、ポリフッ化ビニリデンは、本発明の効果を得る
上で、とくに好ましい。As the binder, a thermoplastic resin, a polymer having rubber elasticity or a polysaccharide is used as one kind or as a mixture of two or more kinds. Specifically, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, ethylene-propylene-diene copolymer resin, styrene butadiene rubber, polybutadiene, fluororubber, polyethylene oxide, polyvinylpyrrolidone,
Examples thereof include polyester resins, acrylic resins, phenol resins, epoxy resins, polyvinyl alcohol, and cellulose resins such as hydroxypropyl cellulose.
Among them, polyvinylidene fluoride is particularly preferable in order to obtain the effects of the present invention.
【００２６】正極集電体としては、アルミニウム、銅、
チタン、ニッケル、ステンレス鋼などの金属の箔、網、
エキスバンドメタル、パンチドメタル、フォームメタル
などが用いられ、とくにアルミニウム箔が好ましい。正
極集電体の厚さは、５〜６０μｍ、とくに８〜４０μｍ
が好ましい。As the positive electrode current collector, aluminum, copper,
Metal foil, mesh, such as titanium, nickel, stainless steel,
Extract band metal, punched metal, foam metal and the like are used, and aluminum foil is particularly preferable. The thickness of the positive electrode current collector is 5 to 60 μm, particularly 8 to 40 μm
Is preferred.
【００２７】このような正極集電体上に正極塗料を塗布
する際には、常法にしたがい、押出しコーター、リバー
スローラー、ドクターブレードなどの各種の塗布方法が
用いられる。この塗布後、乾燥工程や圧縮工程を経て形
成される正極塗膜、つまり、正極活物質含有塗膜の厚さ
としては、片面当たり、通常は、３０〜３００μｍ、と
くに５０〜１５０μｍであるのが好ましい。When applying the positive electrode coating material on such a positive electrode current collector, various coating methods such as an extrusion coater, a reverse roller and a doctor blade are used according to a conventional method. The thickness of the positive electrode coating film formed through a drying step and a compression step after this application, that is, the positive electrode active material-containing coating film, is usually 30 to 300 μm, and particularly 50 to 150 μm per one surface. preferable.
【００２８】本発明において、負極に用いる材料はリチ
ウムイオンをドープ、脱ドープできる物質であればよ
く、このような物質を負極活物質という。この負極活物
質は、とくに限定はないが、黒鉛、熱分解炭素類、コー
クス類、ガラス状炭素類、有機高分子化合物の焼成体、
メソカーボンマイクロビーズ、炭素繊維、活性炭などの
炭素材料、Ｓｉ、Ｓｎ、Ｉｎなどの合金またはＬｉに近
い低電圧で充放電できるＳｉ、Ｓｎ、Ｉｎなどの酸化物
などを用いることができる。In the present invention, the material used for the negative electrode may be any substance that can be doped with lithium ions and dedoped, and such a substance is called a negative electrode active material. The negative electrode active material is not particularly limited, but includes graphite, pyrolytic carbons, cokes, glassy carbons, a fired body of an organic polymer compound,
It is possible to use carbon materials such as mesocarbon microbeads, carbon fibers and activated carbon, alloys such as Si, Sn and In, or oxides such as Si, Sn and In that can be charged and discharged at a low voltage close to Li.
【００２９】負極活物質として炭素材料を用いる場合、
この炭素材料は、以下のような特性を持つものであるの
が好ましい。まず、その（００２）面の面間距離（ｄ
002 ）は、３．５以下であるのが好ましく、より好まし
くは３．４５以下、さらに好ましくは３．４以下であ
る。つぎに、ｃ軸方向の結晶子の大きさ（Ｌｃ）は、３
０以上であるのが好ましく、より好ましくは８０以上、
さらに好ましくは２５０以上である。また、平均粒径は
８〜２０μｍ、とくに１０〜１５μｍであるのが好まし
く、純度は９９．９重量％以上であるのがよい。When a carbon material is used as the negative electrode active material,
This carbon material preferably has the following characteristics. First, the inter-plane distance (d) of the (002) plane
002 ) is preferably 3.5 or less, more preferably 3.45 or less, and further preferably 3.4 or less. Next, the crystallite size (Lc) in the c-axis direction is 3
It is preferably 0 or more, more preferably 80 or more,
More preferably, it is 250 or more. The average particle size is preferably 8 to 20 μm, particularly 10 to 15 μm, and the purity is preferably 99.9% by weight or more.
【００３０】本発明において、負極は、上記の負極活物
質と、ポリフッ化ビニリデンやポリテトラフルオロエチ
レンなどの前記した正極塗料におけるのと同様の結着剤
と、さらに必要により導電助割とを、有機溶媒中に溶解
分散したペースト状の負極塗料を調製し（結着剤はあら
かじめ有機溶媒に溶解させておいてから負極活物質など
と混合してもよい）、この塗料を負極集電体に塗布し、
乾燥工程や圧縮工程を経て、負極塗膜を形成することに
より、作製される。In the present invention, the negative electrode comprises the above-mentioned negative electrode active material, the same binder as in the above-mentioned positive electrode coating material such as polyvinylidene fluoride or polytetrafluoroethylene, and, if necessary, a conductive assistant. Prepare a paste-like negative electrode coating material that is dissolved and dispersed in an organic solvent (the binder may be dissolved in the organic solvent in advance and then mixed with the negative electrode active material), and this coating material is used as the negative electrode current collector. Apply
It is produced by forming a negative electrode coating film through a drying process and a compression process.
【００３１】負極塗料を調製する際の有機溶媒には、正
極塗料の場合と同様の有機溶媒が用いられる。また、負
極集電体には、正極集電体と同様の材質および厚さのも
のが用いられ，とくに銅箔が好ましい。負極集電体上に
負極塗料を塗布する際の塗布方法、塗布後に乾燥工程や
圧縮工程を経て形成される負極塗膜、つまり負極活物質
含有塗膜の厚さなどについても、正極の場合と同様であ
る。The same organic solvent as in the case of the positive electrode coating material is used as the organic solvent for preparing the negative electrode coating material. The negative electrode current collector is made of the same material and has the same thickness as the positive electrode current collector, and copper foil is particularly preferable. Regarding the coating method when applying the negative electrode coating material on the negative electrode current collector, the negative electrode coating film formed through the drying step and the compression step after coating, that is, the thickness of the negative electrode active material-containing coating film, etc. It is the same.
【００３２】なお、電池の作製に際し、上記の負極にリ
ード体が設けられるが、この負極のリード体は、上記の
ように作製される負極に対し、抵抗溶接、超音波溶接な
どにより、負極集電体の露出部分に溶接される。このリ
ード体の断面積は、大電流が流れた場合の抵抗を低減し
発熱量を低減するため、０．１〜１．０mm2 、とくに
０．３〜０．７mm2 であるのが望ましい。このリード体
の材質は、ニッケルが一般的であるが、銅、チタン、ス
テンレス鋼などであってもよい。During the production of the battery, a lead body is provided on the above-mentioned negative electrode, and the lead body of this negative electrode is assembled on the negative electrode produced as described above by resistance welding or ultrasonic welding. It is welded to the exposed part of the electric body. Sectional area of the lead body, in order to reduce a reduced calorific resistance when a large current flows, 0.1 to 1.0 mm 2, in particular is preferably a 0.3 to 0.7 mm 2. The lead material is generally nickel, but may be copper, titanium, stainless steel, or the like.
【００３３】本発明において、電解質には、通常、液状
電解質（以下、これを「電解液」という）が用いられ
る。この電解液には、有機溶媒に溶質を溶解させた有機
溶媒系の非水電解液が用いられる。有機溶媒は、とくに
限定されないが、鎖状エステルを主溶媒としたものが望
ましい。鎖状エステルには、ジエチルカーボネート、ジ
メチルカーボネート、エチルメチルカーボネート、酢酸
エチル、プロピオン酸メチルなどの鎖状のＣＯＯ−結合
を有する有機溶媒が用いられる。鎖状エステルを主溶媒
とするとは、鎖状エステルが有機溶媒全体の５０体積％
より多い体積を占めることを意味し、とくに好ましくは
６５体積％以上、より好ましくは７０体積％以上、さら
に好ましくは７５体積％以上を占めるのがよい。In the present invention, a liquid electrolyte (hereinafter referred to as "electrolyte solution") is usually used as the electrolyte. As the electrolytic solution, an organic solvent-based nonaqueous electrolytic solution in which a solute is dissolved in an organic solvent is used. The organic solvent is not particularly limited, but it is desirable to use a chain ester as the main solvent. As the chain ester, an organic solvent having a chain COO-bond such as diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, ethyl acetate, methyl propionate, etc. is used. The chain ester is the main solvent means that the chain ester is 50% by volume of the whole organic solvent.
It means occupying a larger volume, particularly preferably 65% by volume or more, more preferably 70% by volume or more, further preferably 75% by volume or more.
【００３４】また、有機溶媒としては、上記の鎖状エス
テルのみで構成するよりも、電池容量の向上をはかるた
めに、上記の鎖状エステルに誘電率の高いエステル（誘
電率３０以上のエステル）を混合して用いるのが望まし
い。このような誘電率の高いエステルの使用割合は、有
機溶媒全体の１０体積％以上であるのが好ましく、とく
に好ましくは２０体積％以上であるのがよい。Further, as the organic solvent, an ester having a higher dielectric constant (ester having a dielectric constant of 30 or more) is added to the above chain ester in order to improve the battery capacity as compared with the case where only the above chain ester is used. It is desirable to mix and use. The proportion of the ester having such a high dielectric constant used is preferably 10% by volume or more, and particularly preferably 20% by volume or more, based on the whole organic solvent.
【００３５】上記の誘電率の高いエステルとしては、エ
チレンカーボネート、プロピレンカーボネート、ブチレ
ンカーボネート、γ−ブチロラクトン、エチレングリコ
ールサルファイトなどが挙げられ、とくにエチレンカー
ボネート、プロピレンカーボネートなどの環状構造のも
のが好ましく、とりわけ環状のカーボネートが好まし
く、具体的にはエチレンカーボネートが最も好ましい。Examples of the above-mentioned ester having a high dielectric constant include ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, ethylene glycol sulfite and the like, and those having a cyclic structure such as ethylene carbonate and propylene carbonate are particularly preferable. Cyclic carbonates are particularly preferable, and ethylene carbonate is most preferable.
【００３６】さらに、有機溶媒としては、上記の誘電率
の高いエステルのほか、必要によりその他の有機溶媒を
使用してもよい。具体的には、１，２−ジメトキシエタ
ン、１，３−ジオキソラン、テトラヒドロフラン、２−
メチル−テトラヒドロフラン、ジエチルエーテルなどが
用いられ、その他、アミン系またはイミド系有機溶媒
や、含イオウ系または含フッ素系有機溶媒なども使用で
きる。Further, as the organic solvent, in addition to the above-mentioned ester having a high dielectric constant, other organic solvent may be used if necessary. Specifically, 1,2-dimethoxyethane, 1,3-dioxolane, tetrahydrofuran, 2-
Methyl-tetrahydrofuran, diethyl ether and the like are used, and in addition, amine-based or imide-based organic solvents, sulfur-containing or fluorine-containing organic solvents and the like can also be used.
【００３７】非水電解液において、有機溶媒に溶解させ
る溶質としては、ＬｉＣｌＯ4 、ＬｉＰＦ6 、ＬｉＢＦ
4 、ＬｉＡｓＦ6 、ＬｉＳｂＦ6 、ＬｉＣＦ3 ＳＯ3 、
ＬｉＣ4 Ｆ9 ＳＯ3 、ＬｉＣＦ3 ＣＯ2 、Ｌｉ2 Ｃ2 Ｆ
4 （ＳＯ3 ）2 、ＬｉＮ（ＣＦ3 ＳＯ2 ）2 、ＬｉＣ
（ＣＦ3 ＳＯ2 ）3 、ＬｉＣn Ｆ2n+1ＳＯ3 （ｎ≧２）
などが単独でまたは２種以上混合して用いられる。これ
らの中でも、ＬｉＰＦ6やＬｉＣ4 Ｆ9 ＳＯ3 などが、
充放電特性が良好なため、好ましい。電解液中の溶質の
濃度は、とくに限定されないが、通常、０．３〜１．７
モル／リットル、とくに０．４〜１．５モル／リットル
であるのが望ましい。In the non-aqueous electrolyte, solutes to be dissolved in an organic solvent include LiClO 4 , LiPF 6 and LiBF
4 , LiAsF 6 , LiSbF 6 , LiCF 3 SO 3 ,
LiC 4 F 9 SO 3 , LiCF 3 CO 2 , Li 2 C 2 F
4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC
(CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ≧ 2)
Etc. are used alone or in combination of two or more. Among these, LiPF 6 and LiC 4 F 9 SO 3 are
It is preferable because it has good charge and discharge characteristics. The concentration of the solute in the electrolytic solution is not particularly limited, but is usually 0.3 to 1.7.
It is preferably mol / liter, particularly 0.4 to 1.5 mol / liter.
【００３８】本発明において、電解質としては、上記電
解液のほかに、固体状またはゲル状の電解質を用いるこ
ともできる。このような電解質としては、無機固体電解
質のほか、ポリエチレンオキサイド、ポリプロピレンオ
キサイドまたはこれらの誘導体などを主剤とした有機固
体電解質などが用いられる。In the present invention, in addition to the above-mentioned electrolytic solution, a solid or gel electrolyte can be used as the electrolyte. As such an electrolyte, in addition to an inorganic solid electrolyte, an organic solid electrolyte containing polyethylene oxide, polypropylene oxide, or a derivative thereof as a main component is used.
【００３９】本発明の非水二次電池は、たとえば、正極
と負極とを両者間にセパレータを介して重ね合わせ、こ
れを渦巻状、楕円状、長円形状などに巻回した構造の電
極体や、上記重ね合わせた積層構造の電極体を、ニッケ
ルメッキを施した鉄やステンレス鋼製またはアルミニウ
ムやアルミニウム合金製の電池ケース、あるいは金属ラ
ミネートフィルム内に挿入し、これにさらに電解液を注
入するなどして電解質を装填し、最後に、封口する工程
を経て、作製される。この電池には、通常は、電池内部
に発生したガスをある一定圧力まで上昇した段階で電池
外部に排出し、電池の高圧下での破裂を防止する防爆機
構が取り入れられる。The non-aqueous secondary battery of the present invention is, for example, an electrode body having a structure in which a positive electrode and a negative electrode are superposed on each other with a separator interposed therebetween, and which are wound into a spiral shape, an elliptical shape, an oval shape or the like. Alternatively, the above-mentioned laminated laminated electrode body is inserted into a nickel-plated battery case made of iron or stainless steel, aluminum or aluminum alloy, or a metal laminate film, and an electrolytic solution is further injected into the battery case. It is manufactured by, for example, loading an electrolyte and finally sealing it. Usually, an explosion-proof mechanism is incorporated in this battery so that the gas generated inside the battery is discharged to the outside of the battery when the gas pressure rises to a certain constant pressure to prevent the battery from bursting under high pressure.
【００４０】上記のセパレータとしては、強度が十分で
しかも電解液を多く保持できるものが好ましく、そのよ
うな観点から、厚さが５〜５０μｍで、開孔率が３０〜
７０％の微孔性フィルムや不織布などが好ましく用いら
れる。微孔性フィルム材としては、ポリプロピレン、ポ
リエチレン、エチレン−プロピレン共重合体などが挙げ
られ、不織布材としては、ポリプロピレン、ポリエチレ
ン、ポリエチレンテレフタレート、ポリブチレンテレフ
タレートなどが挙げられる。The separator is preferably one having sufficient strength and capable of holding a large amount of electrolytic solution. From such a viewpoint, the thickness is 5 to 50 μm and the porosity is 30 to 30.
A 70% microporous film or a non-woven fabric is preferably used. Examples of the microporous film material include polypropylene, polyethylene, ethylene-propylene copolymer, and the like, and examples of the nonwoven material include polypropylene, polyethylene, polyethylene terephthalate, polybutylene terephthalate, and the like.
【００４１】[0041]
【実施例】つぎに、実施例を記載して、本発明をより具
体的に説明する。ただし、本発明はそれらの実施例のみ
に限定されるものではない。なお、以下において、部と
あるのは重量部を意味する。また、以下の実施例で使用
したグラフトポリマーＡ〜Ｄは、下記の合成例１〜４に
より合成したものである。EXAMPLES Next, the present invention will be described more concretely with reference to examples. However, the present invention is not limited to only those examples. In the following, "parts" means "parts by weight". Further, the graft polymers A to D used in the following examples were synthesized by the following Synthesis Examples 1 to 4.
【００４２】合成例１（グラフトポリマーＡの合成）
片末端スチリル基含有ポリビニルピロリドンマクロモノ
マー（数平均分子量：３，０００）１０部、スチレン１
０部、メチルエチルケトン４０部、過酸化ベンゾイル
０．２部を、冷却管を付けた三つ口フラスコに投入し
て、窒素雰囲気下、８０℃で４時間加熱後、過酸化ベン
ゾイル０．１部をメチルエチルケトン５部に溶かした溶
液を加えて、さらに８０℃で２時間加熱した。減圧下
で、メチルエチルケトンを除いたのち、４０℃で減圧乾
燥を２４時間行った。このようにして得られたグラフト
ポリマーＡは、ＧＰＣ（ゲルパーミエーションクロマト
グラフィー）測定によるポリスチレン換算で数平均分子
量が１０，０００であった。また、このグラフトポリマ
ーＡは、主鎖部分のポリスチレン鎖の溶解パラメーター
（ＳＰ）が９．４であり、枝部分（グラフト部分）のポ
リビニルピロリドン鎖のＳＰが１０．８であった。Synthesis Example 1 (Synthesis of Graft Polymer A) 10 parts of polyvinylpyrrolidone macromonomer (number average molecular weight: 3,000) containing a styryl group at one end, 1 part of styrene
0 parts, 40 parts of methyl ethyl ketone, and 0.2 parts of benzoyl peroxide were put into a three-necked flask equipped with a cooling tube, heated at 80 ° C. for 4 hours under a nitrogen atmosphere, and then 0.1 part of benzoyl peroxide was added. A solution dissolved in 5 parts of methyl ethyl ketone was added, and the mixture was further heated at 80 ° C. for 2 hours. After removing methyl ethyl ketone under reduced pressure, vacuum drying was performed at 40 ° C. for 24 hours. The graft polymer A thus obtained had a number average molecular weight of 10,000 in terms of polystyrene by GPC (gel permeation chromatography) measurement. In this graft polymer A, the solubility parameter (SP) of the polystyrene chain of the main chain portion was 9.4, and the SP of the polyvinylpyrrolidone chain of the branch portion (graft portion) was 10.8.
【００４３】合成例２（グラフトポリマーＢの合成）
片末端スチリル基含有ポリビニルピロリドンマクロモノ
マー（数平均分子量：３，０００）１０部、ブチルメタ
クリレート１０部、メチルエチルケトン４０部、過酸化
ベンゾイル０．１５部を、冷却管を付けた三つ口フラス
コに投入して、窒素雰囲気下、８０℃で４時間加熱後、
過酸化ベンゾイル０．０５部をメチルエチルケトン５部
に溶かした溶液を加え、さらに８０℃で２時間加熱し
た。減圧下で、メチルエチルケトンを除いたのち、４０
℃で減圧乾燥を２４時間行った。このようにして得られ
たグラフトポリマーＢは、ＧＰＣ測定によるポリスチレ
ン換算で数平均分子量が３０，０００であった。また、
主鎖部分のポリブチルメタクリレート鎖の溶解パラメー
ター（ＳＰ）は８．３、枝部分（グラフト部分）のポリ
ビニルピロリドン鎖のＳＰは１０．８であった。Synthesis Example 2 (Synthesis of Graft Polymer B) 10 parts of polyvinylpyrrolidone macromonomer (number average molecular weight: 3,000) containing a styryl group at one end, 10 parts of butyl methacrylate, 40 parts of methyl ethyl ketone, 0.15 parts of benzoyl peroxide. Was charged into a three-necked flask equipped with a cooling tube, heated at 80 ° C. for 4 hours in a nitrogen atmosphere,
A solution of 0.05 part of benzoyl peroxide dissolved in 5 parts of methyl ethyl ketone was added, and the mixture was further heated at 80 ° C. for 2 hours. After removing methyl ethyl ketone under reduced pressure, 40
Drying under reduced pressure was performed at 24 ° C. for 24 hours. The graft polymer B thus obtained had a number average molecular weight of 30,000 in terms of polystyrene by GPC measurement. Also,
The solubility parameter (SP) of the polybutylmethacrylate chain in the main chain part was 8.3, and the SP of the polyvinylpyrrolidone chain in the branch part (graft part) was 10.8.
【００４４】合成例３（グラフトポリマーＣの合成）
片末端スチリル基含有ポリ（２−メチル−２−オキサゾ
リン）マクロモノマー（数平均分子量：２，５００）１
０部、ブチルメタクリレート１０部、メチルエチルケト
ン４０部、過酸化ベンゾイル０．１５部を、冷却管を付
けた三つ口フラスコに投入して、窒素雰囲気下、８０℃
で４時間加熱後、過酸化ベンゾイル０．０５部をメチル
エチルケトン５部に溶かした溶液を加えて、さらに８０
℃で２時間加熱した。減圧下で、メチルエチルケトンを
除いたのち、４０℃で減圧乾燥を２４時間行った。この
ようにして得られたグラフトポリマーＣは、ＧＰＣ測定
によるポリスチレン換算で数平均分子量が１５，０００
であった。また、このグラフトポリマーＣは、主鎖部分
のポリブチルメタクリレート鎖の溶解パラメーター（Ｓ
Ｐ）が８．３であり、枝部分（グラフト部分）のポリ
（２−メチル−２−オキサゾリン）鎖のＳＰが１１．８
であった。Synthesis Example 3 (Synthesis of Graft Polymer C) Poly (2-methyl-2-oxazoline) macromonomer (number average molecular weight: 2,500) containing a styryl group at one end 1
0 parts, 10 parts of butyl methacrylate, 40 parts of methyl ethyl ketone, and 0.15 parts of benzoyl peroxide were placed in a three-necked flask equipped with a cooling tube, and the temperature was set to 80 ° C. under a nitrogen atmosphere.
After heating for 4 hours at 0.degree. C., a solution of 0.05 part of benzoyl peroxide in 5 parts of methyl ethyl ketone is added and the mixture is further added to 80 parts.
Heated at ° C for 2 hours. After removing methyl ethyl ketone under reduced pressure, vacuum drying was performed at 40 ° C. for 24 hours. The thus obtained graft polymer C has a number average molecular weight of 15,000 in terms of polystyrene by GPC measurement.
Met. In addition, this graft polymer C has a solubility parameter (S
P) is 8.3, and the SP of the poly (2-methyl-2-oxazoline) chain of the branch portion (graft portion) is 11.8.
Met.
【００４５】合成例４（グラフトポリマーＤの合成）
片末端メタクリロイル基含有ポリスチレンマクロモノマ
ー（数平均分子量：３，０００）１０部、ビニルピロリ
ドン１０部、メチルエチルケトン４０部、過酸化ベンゾ
イル０．１８部を、冷却管を付けた三つ口フラスコに投
入して、窒素雰囲気下、８０℃で４時間加熱後、過酸化
ベンゾイル０．０８部をメチルエチルケトン５部に溶か
した溶液を加えて、さらに８０℃で２時間加熱した。減
圧下で、メチルエチルケトンを除いたのち、４０℃で減
圧乾燥を２４時間行った。このようにして得られたグラ
フトポリマーＤは、ＧＰＣ測定によるポリスチレン換算
で数平均分子量が２２，０００であった。また、このグ
ラフトポリマーＤは、主鎖部分のポリピロリドン鎖の溶
解パラメーター（ＳＰ）が１０．８であり、枝部分（グ
ラフト部分）のポリスチレン鎖のＳＰが９．４であっ
た。Synthesis Example 4 (Synthesis of Graft Polymer D) 10 parts of a polystyrene macromonomer having a methacryloyl group at one end (number average molecular weight: 3,000), 10 parts of vinylpyrrolidone, 40 parts of methyl ethyl ketone, and 0.18 part of benzoyl peroxide were added. Then, the mixture was put into a three-necked flask equipped with a cooling tube, heated at 80 ° C. for 4 hours under a nitrogen atmosphere, and then a solution of 0.08 part of benzoyl peroxide dissolved in 5 parts of methyl ethyl ketone was added, and further at 80 ° C. Heated for 2 hours. After removing methyl ethyl ketone under reduced pressure, vacuum drying was performed at 40 ° C. for 24 hours. The graft polymer D thus obtained had a number average molecular weight of 22,000 in terms of polystyrene by GPC measurement. In this graft polymer D, the solubility parameter (SP) of the polypyrrolidone chain of the main chain portion was 10.8, and the SP of the polystyrene chain of the branch portion (graft portion) was 9.4.
【００４６】実施例１
＜正極の作製＞正極活物質であるＬｉＣｏＯ2 １８０
部、導電助剤であるアセチレンブラック１０部、結着剤
であるポリフツ化ビニリデン６部、合成したグラフトポ
リマーＡ０．１部を、均一になるように混合し、さらに
Ｎ−メチルピロリドン７０部を加えて混合し、ペースト
状の正極塗料を調製した。つぎに、この正極塗料を、７
０メッシュの網を通過させて大きなものを取り除いたの
ち、厚さ１５μｍのアルミニウム箔からなる正極集電体
の両面に均一に塗布し、乾燥して、正極塗膜を形成し
た。その後、厚さ１５８μｍに圧縮成形し、切断後、ア
ルミニウム製リード体を溶接して、帯状の正極を作製し
た。この際、電極密度は３．３０ｇ／cm3 であった。Example 1 <Production of Positive Electrode> LiCoO 2 180 which is a positive electrode active material
Parts, 10 parts of acetylene black which is a conductive aid, 6 parts of polyvinylidene fluoride which is a binder, and 0.1 parts of the synthesized graft polymer A are uniformly mixed, and 70 parts of N-methylpyrrolidone is further added. And mixed to prepare a paste-like positive electrode coating material. Next, apply this positive electrode coating to 7
After passing through a 0-mesh net to remove large ones, the positive electrode current collector made of an aluminum foil having a thickness of 15 μm was uniformly applied on both sides and dried to form a positive electrode coating film. After that, compression molding was performed to a thickness of 158 μm, and after cutting, an aluminum lead body was welded to produce a strip-shaped positive electrode. At this time, the electrode density was 3.30 g / cm 3 .
【００４７】＜負極の作製＞負極活物質である黒鉛系炭
素材料〔００２面の面間距離（ｄ002 ）＝３．３７、ｃ
軸方向の結晶子の大きさ（Ｌｃ）＝９５０、平均粒径１
０μｍ、純度９９．９重量％以上〕１８０部を、ポリフ
ッ化ビニリデン１４部をＮ−メチルピロリドン１９０部
に溶解させた溶液と混合して、ペースト状の負極塗料を
調製した。この負極塗料を、厚さ１０μｍの帯状の銅箔
からなる負極集電体の両面に均一に塗布し、乾燥して、
負極塗膜を形成した。その後、厚さ１６７μｍに圧縮成
形し、切断後、ニッケル製リード体を溶接して、帯状の
負極を作製した。<Preparation of Negative Electrode> Graphite carbon material as negative electrode active material [interplanar distance of 002 planes (d 002 ) = 3.37, c
Axial crystallite size (Lc) = 950, average particle size 1
0 μm, purity 99.9% by weight or more] 180 parts was mixed with a solution of 14 parts of polyvinylidene fluoride dissolved in 190 parts of N-methylpyrrolidone to prepare a paste-like negative electrode coating material. This negative electrode coating material is uniformly applied to both surfaces of a negative electrode current collector made of a strip-shaped copper foil having a thickness of 10 μm, and dried,
A negative electrode coating film was formed. After that, compression molding was performed to a thickness of 167 μm, and after cutting, a nickel lead body was welded to produce a strip-shaped negative electrode.
【００４８】＜電解液の調製＞メチルエチルカーボネー
トとエチレンカーボネートとを体積比２：１で混合した
混合溶媒に、電解質（溶質）としてＬｉＰＦ6 を１．２
モル／リットルの濃度となるように混合溶解して、非水
電解液（電解液）を調製した。<Preparation of Electrolyte Solution> LiPF 6 as an electrolyte (solute) was added to a mixed solvent in which methyl ethyl carbonate and ethylene carbonate were mixed at a volume ratio of 2: 1.
A non-aqueous electrolytic solution (electrolytic solution) was prepared by mixing and dissolving so as to have a concentration of mol / liter.
【００４９】＜非水二次電池の作製＞上記の正極と負極
とを、その乾燥処理後、両極間に厚さ２５μｍの微孔性
ポリエチレンフィルムからなるセパレータを介して渦巻
状に巻回し、巻回構造の電極体とした。これを袋状のア
ルミラミネートフィルム内に挿入し、上記の電解液を注
入したのち、真空封止を行い、その状態で３時間室温に
放置し、正極、負極およびセパレータに電解液を十分に
含浸させて、非水二次電池を作製した。<Preparation of Non-Aqueous Secondary Battery> The above positive electrode and negative electrode were dried and then spirally wound between both electrodes with a separator made of a microporous polyethylene film having a thickness of 25 μm interposed therebetween. The electrode body has a spiral structure. After inserting this into a bag-shaped aluminum laminate film, injecting the above-mentioned electrolytic solution, vacuum-sealing, and leaving at room temperature for 3 hours in that state, the positive electrode, negative electrode and separator are sufficiently impregnated with the electrolytic solution. Then, a non-aqueous secondary battery was produced.
【００５０】実施例２
正極塗料の調製に際し、まず、導電助剤であるアセチレ
ンブラック１０部と、合成したグラフトポリマーＡ０．
１部とを均一に混合し、ついで、ＬｉＣｏＯ2１８０
部、結着剤であるポリフッ化ビニリデン６部およびＮ−
メチルピロリドン７０部を加えて、均一に混合分散し、
ペースト状の正極塗料を調製した。この塗料を使用した
以外は、実施例１と同様に処理し、圧縮成形後の厚さが
１５２μｍ、電極密度が３．３５ｇ／cm3 である帯状の
正極を作製した。その他は、実施例１と同様にして、非
水二次電池を作製した。Example 2 In preparing a positive electrode coating material, first, 10 parts of acetylene black as a conductive additive and the synthesized graft polymer A0.
1 part was mixed uniformly and then LiCoO 2 180
Part, 6 parts of polyvinylidene fluoride as a binder and N-
Add 70 parts of methylpyrrolidone, mix and disperse evenly,
A paste-like positive electrode coating material was prepared. The same procedure as in Example 1 was carried out except that this coating material was used to prepare a strip-shaped positive electrode having a thickness after compression molding of 152 μm and an electrode density of 3.35 g / cm 3 . A nonaqueous secondary battery was produced in the same manner as in Example 1 except for the above.
【００５１】実施例３
正極塗料の調製に際し、グラフトポリマーＡ０．１部に
代えて、グラフトポリマーＢ０．１部を使用した以外
は、実施例１と同様にして、ペースト状の正極塗料を調
製した。この塗料を使用した以外は、実施例１と同様に
処理し、圧縮成形後の厚さが１６０μｍ、電極密度が
３．２７ｇ／cm3 である帯状の正極を作製した。その他
は、実施例１と同様にして、非水二次電池を作製した。Example 3 A paste-like positive electrode paint was prepared in the same manner as in Example 1 except that 0.1 part of the graft polymer B was used in place of 0.1 part of the graft polymer A when preparing the positive electrode paint. . The same procedure as in Example 1 was carried out except that this coating material was used to prepare a strip-shaped positive electrode having a thickness after compression molding of 160 μm and an electrode density of 3.27 g / cm 3 . A nonaqueous secondary battery was produced in the same manner as in Example 1 except for the above.
【００５２】実施例４
正極塗料の調製に際し、グラフトポリマーＡ０．１部に
代えて、グラフトポリマーＣ０．１部を使用した以外
は、実施例１と同様にして、ペースト状の正極塗料を調
製した。この塗料を使用した以外は、実施例１と同様に
処理し、圧縮成形後の厚さが１６１μｍ、電極密度が
３．２７ｇ／cm3 である帯状の正極を作製した。その他
は、実施例１と同様にして、非水二次電池を作製した。Example 4 A paste-like positive electrode paint was prepared in the same manner as in Example 1 except that 0.1 part of the graft polymer C was used in place of 0.1 part of the graft polymer A when preparing the positive electrode paint. . The same procedure as in Example 1 was carried out except that this coating material was used to prepare a strip-shaped positive electrode having a thickness after compression molding of 161 μm and an electrode density of 3.27 g / cm 3 . A nonaqueous secondary battery was produced in the same manner as in Example 1 except for the above.
【００５３】実施例５
正極塗料の調製に際し、グラフトポリマーＡ０．１部に
代えて、グラフトポリマーＤ０．１部を使用した以外
は、実施例１と同様にして、ペースト状の正極塗料を調
製した。この塗料を使用した以外は、実施例１と同様に
処理し、圧縮成形後の厚さが１６５μｍ、電極密度が
３．２３ｇ／cm3 である帯状の正極を作製した。その他
は、実施例１と同様にして、非水二次電池を作製した。Example 5 A paste-like positive electrode paint was prepared in the same manner as in Example 1 except that 0.1 part of the graft polymer D was used in place of 0.1 part of the graft polymer A when preparing the positive electrode paint. . The same treatment as in Example 1 was carried out except that this coating material was used to prepare a strip-shaped positive electrode having a thickness after compression molding of 165 μm and an electrode density of 3.23 g / cm 3 . A nonaqueous secondary battery was produced in the same manner as in Example 1 except for the above.
【００５４】比較例１
正極塗料の調製に際し、正極活物質であるＬｉＣｏＯ2
１６２部、導電助剤であるアセチレンブラック１０部、
結着剤であるポリフッ化ビニリデン６部を均一混合し、
さらにＮ−メチルピロリドン７０部を加えて混合分放
し、ペースト状の正極塗料を調製した。この塗料を使用
した以外は、実施例１と同様に処理し、圧縮成形後の厚
さが１７５μｍ、電極密度が３．１５ｇ／cm3 である帯
状の正極を作製した。その他は、実施例１と同様にし
て、非水二次電池を作製した。Comparative Example 1 When preparing a positive electrode coating material, LiCoO 2 as a positive electrode active material was used.
162 parts, 10 parts of acetylene black which is a conductive additive,
Uniformly mix 6 parts of polyvinylidene fluoride, which is a binder,
Further, 70 parts of N-methylpyrrolidone was added and mixed and released to prepare a paste-like positive electrode coating material. The same procedure as in Example 1 was carried out except that this coating material was used to prepare a strip-shaped positive electrode having a thickness after compression molding of 175 μm and an electrode density of 3.15 g / cm 3 . A nonaqueous secondary battery was produced in the same manner as in Example 1 except for the above.
【００５５】上記の実施例１〜５および比較例１の各非
水二次電池について、充放電を繰り返したときの放電容
量の変化および高温貯蔵前後の放電容量の変化を、下記
の方法により、測定した。結果は、表１に示されるとお
りであった。For each of the non-aqueous secondary batteries of Examples 1 to 5 and Comparative Example 1 described above, the change in discharge capacity when charging and discharging were repeated and the change in discharge capacity before and after high temperature storage were measured by the following method. It was measured. The results are as shown in Table 1.
【００５６】＜放電容量の変化の測定＞充電を１Ｃの電
流制限回路を設けて４．２Ｖの定電圧で行い、放電を電
池の電極間電圧が２．７５Ｖに低下するまで行った。サ
イクル特性は、それぞれの電池の充放電の繰り返しにお
ける１サイクル目の放電容量に対する３００サイクル後
の放電容量で求めた。高温貯蔵特性は、それぞれの電池
の初期に対する６０℃，２０日後の放電容量で求めた。<Measurement of Change in Discharge Capacity> Charging was carried out at a constant voltage of 4.2 V with a current limiting circuit of 1 C provided, and discharging was carried out until the inter-electrode voltage of the battery dropped to 2.75 V. The cycle characteristics were determined by the discharge capacity after 300 cycles with respect to the discharge capacity at the first cycle in the repeated charging and discharging of each battery. The high temperature storage characteristics were determined by the discharge capacity after 60 days at 60 ° C. with respect to the initial of each battery.
【００５７】表１ Table 1
【００５８】上記の表１の結果から、正極中にグラフト
ポリマーを含ませた実施例１〜５の各電池は、上記グラ
フトポリマーを含ませなかった比較例１の電池に比べ
て、サイクル特性および高温貯蔵特性にすぐれているこ
とがわかる。From the results shown in Table 1 above, the batteries of Examples 1 to 5 in which the graft polymer was included in the positive electrode were compared with the batteries of Comparative Example 1 in which the above graft polymer was not included, in terms of cycle characteristics and It can be seen that it has excellent high temperature storage characteristics.
【００５９】[0059]
【発明の効果】以上のように、本発明は、正極、負極お
よび電解質を有する非水二次電池において、正極中に、
正極活物質としてのＬｉ複合酸化物、導電助剤および結
着剤とともに、グラフトポリマーを含ませたことによ
り、サイクル特性および貯蔵特性などの信頼性にすぐれ
る非水二次電池を提供することができる。As described above, the present invention provides a non-aqueous secondary battery having a positive electrode, a negative electrode and an electrolyte, in which the positive electrode is
It is possible to provide a non-aqueous secondary battery having excellent reliability such as cycle characteristics and storage characteristics by including a graft polymer together with a Li composite oxide as a positive electrode active material, a conductive auxiliary agent and a binder. it can.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｍ 4/02 Ｈ０１Ｍ 4/02 Ｃ 10/40 10/40 Ｚ (72)発明者 岸 文彦 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 (72)発明者 大桃 義智 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 (72)発明者 宮田 一司 大阪府茨木市丑寅一丁目１番88号 日立マ クセル株式会社内 Ｆターム(参考） 4J002 AB01W AC03W AC09W BB02W BB11W BB15W BD12W BD14W BD15W BE02W BG00W BJ00W BN12X BN23Y CC03W CD00W CF00W CH02W DE046 DE196 GQ00 5H029 AJ04 AJ05 AK03 AL06 AL07 AL08 AL11 AM03 AM04 AM05 AM07 AM12 AM16 CJ08 CJ11 DJ08 EJ12 HJ00 HJ11 5H050 AA07 AA09 BA17 CA08 CA09 CB07 CB08 CB09 CB11 DA09 EA23 GA10 GA11 HA00 HA11─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) H01M 4/02 H01M 4/02 C 10/40 10/40 Z (72) Inventor Fumihiko Kishi Ibaraki City, Osaka Prefecture Yoshira Otomo 1-88, Hitachi Maxel Co., Ltd. (72) Inventor Yoshitomo Otomo Ibaraki City, Osaka Prefecture 1-88, Hitachi Maxel Co., Ltd. (72) Inventor, Koji Miyata, Ibaraki-shi, Osaka chome No. 1 No. 88 Hitachi Maxell, Ltd. in the F-term (reference) 4J002 AB01W AC03W AC09W BB02W BB11W BB15W BD12W BD14W BD15W BE02W BG00W BJ00W BN12X BN23Y CC03W CD00W CF00W CH02W DE046 DE196 GQ00 5H029 AJ04 AJ05 AK03 AL06 AL07 AL08 AL11 AM03 AM04 AM05 AM07 AM12 AM16 CJ08 CJ11 DJ08 EJ12 HJ00 HJ11 5H050 AA07 AA09 BA17 CA08 CA09 CB07 CB08 CB09 CB11 DA09 EA23 GA10 GA11 HA00 HA11
Claims (3)
次電池において、正極中に、正極活物質としてのＬｉ複
合酸化物、導電助剤および結着剤とともに、グラフトポ
リマーを含むことを特徴とする非水二次電池。1. A non-aqueous secondary battery having a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode contains a Li composite oxide as a positive electrode active material, a conductive auxiliary agent and a binder, and a graft polymer. Non-aqueous rechargeable battery.
ーター（ＳＰ）が１０．５以上、１３未満のセグメント
と、（２）ＳＰが７．５以上、１０未満のセグメントと
からなる請求項１に記載の非水二次電池。2. The graft polymer comprises (1) a segment having a solubility parameter (SP) of 10.5 or more and less than 13 and (2) a segment of SP of 7.5 or more and less than 10. The non-aqueous secondary battery described.
２，０００〜５０，０００である請求項１に記載の非水
二次電池。3. The non-aqueous secondary battery according to claim 1, wherein the graft polymer has a number average molecular weight of 2,000 to 50,000.
Priority Applications (1)
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|---|---|---|---|
| JP2002067137A JP2003272634A (en) | 2002-03-12 | 2002-03-12 | Nonaqueous secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002067137A JP2003272634A (en) | 2002-03-12 | 2002-03-12 | Nonaqueous secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JP2003272634A true JP2003272634A (en) | 2003-09-26 |
Family
ID=29198620
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|---|---|---|---|
| JP2002067137A Withdrawn JP2003272634A (en) | 2002-03-12 | 2002-03-12 | Nonaqueous secondary battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011014387A (en) * | 2009-07-02 | 2011-01-20 | Nippon Zeon Co Ltd | All-solid secondary battery |
| JP2011040318A (en) * | 2009-08-17 | 2011-02-24 | Hitachi Vehicle Energy Ltd | Lithium secondary battery |
| WO2012165422A1 (en) * | 2011-05-31 | 2012-12-06 | 日本ゼオン株式会社 | Composite particles for lithium secondary battery positive electrodes, method for producing composite particles for lithium secondary battery positive electrodes, method for producing positive electrode for lithium secondary batteries, positive electrode for lithium secondary batteries, and lithium secondary battery |
| JP2021046491A (en) * | 2019-09-18 | 2021-03-25 | 株式会社日本触媒 | Manufacturing method of graft copolymer |
| CN114914444A (en) * | 2021-02-10 | 2022-08-16 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode plate, preparation method thereof and lithium ion battery |
| KR20220123000A (en) | 2019-12-27 | 2022-09-05 | 니폰 제온 가부시키가이샤 | Electrochemical device, electrode for electrochemical device, coating liquid for electrochemical device, and use thereof |
-
2002
- 2002-03-12 JP JP2002067137A patent/JP2003272634A/en not_active Withdrawn
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011014387A (en) * | 2009-07-02 | 2011-01-20 | Nippon Zeon Co Ltd | All-solid secondary battery |
| JP2011040318A (en) * | 2009-08-17 | 2011-02-24 | Hitachi Vehicle Energy Ltd | Lithium secondary battery |
| WO2012165422A1 (en) * | 2011-05-31 | 2012-12-06 | 日本ゼオン株式会社 | Composite particles for lithium secondary battery positive electrodes, method for producing composite particles for lithium secondary battery positive electrodes, method for producing positive electrode for lithium secondary batteries, positive electrode for lithium secondary batteries, and lithium secondary battery |
| CN103563133A (en) * | 2011-05-31 | 2014-02-05 | 日本瑞翁株式会社 | Composite particles for lithium secondary battery positive electrodes, method for producing composite particles for lithium secondary battery positive electrodes, method for producing positive electrode for lithium secondary batteries, positive elect |
| JPWO2012165422A1 (en) * | 2011-05-31 | 2015-02-23 | 日本ゼオン株式会社 | Composite particle for lithium secondary battery positive electrode, method for producing composite particle for lithium secondary battery positive electrode, method for producing positive electrode for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery |
| JP2021046491A (en) * | 2019-09-18 | 2021-03-25 | 株式会社日本触媒 | Manufacturing method of graft copolymer |
| JP7395297B2 (en) | 2019-09-18 | 2023-12-11 | 株式会社日本触媒 | Method for producing graft copolymer |
| KR20220123000A (en) | 2019-12-27 | 2022-09-05 | 니폰 제온 가부시키가이샤 | Electrochemical device, electrode for electrochemical device, coating liquid for electrochemical device, and use thereof |
| CN114914444A (en) * | 2021-02-10 | 2022-08-16 | 中国石油化工股份有限公司 | Silicon-carbon negative electrode plate, preparation method thereof and lithium ion battery |
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