JP2002117834A - Positive electrode for nonaqueous secondary battery and nonaqueous secondary battery - Google Patents
Positive electrode for nonaqueous secondary battery and nonaqueous secondary batteryInfo
- Publication number
- JP2002117834A JP2002117834A JP2000310765A JP2000310765A JP2002117834A JP 2002117834 A JP2002117834 A JP 2002117834A JP 2000310765 A JP2000310765 A JP 2000310765A JP 2000310765 A JP2000310765 A JP 2000310765A JP 2002117834 A JP2002117834 A JP 2002117834A
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- Prior art keywords
- positive electrode
- weight
- parts
- secondary battery
- binder
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Classifications
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- 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
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- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウムおよび遷
移金属を含む複合酸化物を正極活物質として有する非水
系二次電池用正極およびそれを具備した高容量および長
寿命の非水系二次電池に関する。The present invention relates to a positive electrode for a non-aqueous secondary battery having a composite oxide containing lithium and a transition metal as a positive electrode active material, and a high-capacity and long-life non-aqueous secondary battery comprising the same. .
【０００２】[0002]
【従来の技術】近年、民生用電子機器のポータブル化、
コードレス化が急激に進んでいる。現在、これら電子機
器の駆動用電源を担う小型かつ軽量で高エネルギー密度
を有する電池への要望が高まっている。このような観点
から非水系二次電池、とりわけリチウムイオン二次電池
は高電圧かつ高エネルギー密度を有する電池として、ノ
ートパソコン、携帯電話、ＡＶ機器などに使用されてい
る。非水系二次電池は、上述の機器に使用されることか
ら、良好な寿命特性を有すことが求められる。そこで、
正極板の電子伝導性を向上させることによる寿命特性の
改善が検討されている。2. Description of the Related Art In recent years, portable electronic devices have become more portable.
Cordless use is rapidly progressing. At present, there is an increasing demand for a small and lightweight battery having a high energy density, which serves as a power supply for driving these electronic devices. From such a viewpoint, non-aqueous secondary batteries, particularly lithium ion secondary batteries, are used in notebook computers, mobile phones, AV equipment, and the like as batteries having high voltage and high energy density. Since the non-aqueous secondary battery is used for the above-described devices, it is required to have good life characteristics. Therefore,
Improvement of the life characteristics by improving the electron conductivity of the positive electrode plate has been studied.
【０００３】正極の電子伝導性を向上させる具体的手段
として、活物質であるリチウムおよび遷移金属を含む複
合酸化物に対し、導電剤を添加する方法が挙げられる。
導電剤としては、アセチレンブラックやケッチェンブラ
ックに代表されるカーボンブラックまたはグラファイト
などが用いられる。また、正極は、極板構造を保持する
ために必要な結着剤や、必要であれば合剤ペーストの粘
度を調整するための増粘剤などを含んでいる。前記結着
剤としては、ポリフッ化ビニリデン、ポリテトラフルオ
ロエチレンなどが用いられる。すなわち、一般に正極
は、活物質、導電剤、結着剤および増粘剤を分散媒と混
合して合剤ペーストを得、合剤ペーストを芯材である金
属箔に塗布し、乾燥して製造される。前記分散媒として
は、Ｎ−メチル−２−ピロリドン、水などが用いられ
る。As a specific means for improving the electron conductivity of the positive electrode, there is a method of adding a conductive agent to a composite oxide containing lithium and a transition metal as active materials.
As the conductive agent, carbon black represented by acetylene black or Ketjen black, graphite, or the like is used. Further, the positive electrode contains a binder necessary for maintaining the electrode plate structure, and, if necessary, a thickener for adjusting the viscosity of the mixture paste. As the binder, polyvinylidene fluoride, polytetrafluoroethylene, or the like is used. That is, in general, a positive electrode is manufactured by mixing an active material, a conductive agent, a binder, and a thickener with a dispersion medium to obtain a mixture paste, applying the mixture paste to a metal foil as a core material, and drying the mixture. Is done. As the dispersion medium, N-methyl-2-pyrrolidone, water and the like are used.
【０００４】従来の結着剤には、２つのタイプがある。
一方は、一旦合剤ペーストの分散媒に溶解し、芯材上に
合剤ペーストを塗布し、乾燥する際に分散媒の揮発に伴
って析出し、その結着機能を発現する。例えば、結着剤
がポリフッ化ビニリデンであり、分散媒がＮ−メチル−
２−ピロリドンである場合がこれに該当する。このよう
な結着剤は、活物質や導電剤を被覆して析出する。その
ため正極内において活物質と導電剤との間隙に結着剤が
有効に配置されず、極板構造を保持するためには多量の
結着剤を要する。[0004] There are two types of conventional binders.
One dissolves in the dispersion medium of the mixture paste once, applies the mixture paste on the core material, and precipitates with the volatilization of the dispersion medium when drying, thereby exhibiting its binding function. For example, the binder is polyvinylidene fluoride, and the dispersion medium is N-methyl-
This is the case with 2-pyrrolidone. Such a binder is deposited by coating the active material and the conductive agent. Therefore, the binder is not effectively disposed in the gap between the active material and the conductive agent in the positive electrode, and a large amount of the binder is required to maintain the electrode plate structure.
【０００５】もう一方は、ポリテトラフルオロエチレン
のように分散媒に溶解せずに合剤ペースト中で粒子状を
維持する。この結着剤は合剤と芯材からなる正極板の圧
延時にかかるせん断応力により、微細繊維（フィブリ
ル）を発生する。そして、微細繊維が活物質や導電剤と
絡み合うことで結着作用が発現する。この場合も、活物
質や導電剤に多量の微細繊維を絡ませる必要があるた
め、多量の結着剤を要する。On the other hand, unlike polytetrafluoroethylene, it does not dissolve in a dispersing medium and maintains a particulate state in a mixture paste. The binder generates fine fibers (fibrils) due to shear stress applied during rolling of the positive electrode plate composed of the mixture and the core material. Then, the binding action is exhibited by the fine fibers entangled with the active material and the conductive agent. In this case, too, a large amount of fine fibers need to be entangled with the active material and the conductive agent, so that a large amount of binder is required.
【０００６】多量の結着剤を用いる場合、正極の電子伝
導性を確保するためには多量の導電剤が必要となる。例
えば、結着剤としてホルムアルデヒドに溶解させたポリ
アクリロニトリルを用いる場合、活物質１００重量部あ
たり４重量部以上の導電剤を添加しなければ、良好なサ
イクル寿命を有する電池を得ることができない（特許第
３０４６０５５号）。When a large amount of a binder is used, a large amount of a conductive agent is required to secure the electron conductivity of the positive electrode. For example, when using polyacrylonitrile dissolved in formaldehyde as a binder, a battery having a good cycle life cannot be obtained unless 4 parts by weight or more of a conductive agent is added per 100 parts by weight of the active material (Patent No. 3046055).
【０００７】[0007]
【発明が解決しようとする課題】多量の導電剤と結着剤
を含む正極は、体積あたりの正極合剤に含まれる活物質
重量（以下活物質密度という、単位はｇ／ｍｌ)が低い
ため、その正極を有する電池容量も小さくなる。本発明
は、導電剤および結着剤の量を減らして正極の活物質密
度を向上させることにより、高容量かつ良好な寿命特性
を有する非水系二次電池を提供することを目的とする。The positive electrode containing a large amount of a conductive agent and a binder has a low active material weight per unit volume (hereinafter referred to as an active material density in units of g / ml). Thus, the capacity of the battery having the positive electrode is also reduced. An object of the present invention is to provide a non-aqueous secondary battery having high capacity and good life characteristics by reducing the amounts of a conductive agent and a binder to increase the active material density of the positive electrode.
【０００８】[0008]
【課題を解決するための手段】本発明は、リチウムおよ
び遷移金属を含む複合酸化物からなる活物質、グラファ
イト（Ａ）およびカーボンブラック（Ｂ）からなる導電
剤ならびに有機重合体からなる粒子状結着剤を有する非
水系二次電池用正極であって、前記活物質１００重量部
あたり０．４重量部以上２重量部以下の前記結着剤およ
び２重量部以上４重量部未満の前記導電剤を含み、前記
導電剤におけるグラファイト（Ａ）とカーボンブラック
（Ｂ）との重量比（Ａ／Ｂ）が２０／８０〜８０／２０
であることを特徴とする非水系二次電池用正極に関す
る。SUMMARY OF THE INVENTION The present invention provides an active material comprising a composite oxide containing lithium and a transition metal, a conductive agent comprising graphite (A) and carbon black (B), and a particulate binder comprising an organic polymer. A positive electrode for a non-aqueous secondary battery having a binder, wherein the binder is 0.4 parts by weight or more and 2 parts by weight or less and the conductive agent is 2 parts by weight or more and less than 4 parts by weight per 100 parts by weight of the active material. And the weight ratio (A / B) of graphite (A) and carbon black (B) in the conductive agent is 20/80 to 80/20.
And a positive electrode for a non-aqueous secondary battery.
【０００９】本発明は、また、前記正極、リチウムを吸
蔵、放出可能な材料からなる負極およびリチウムイオン
伝導性の非水電解質を有する非水系二次電池に関する。The present invention also relates to a non-aqueous secondary battery having the positive electrode, a negative electrode made of a material capable of occluding and releasing lithium, and a lithium ion conductive non-aqueous electrolyte.
【００１０】[0010]
【発明の実施の形態】本発明の非水系二次電池用正極
は、リチウムおよび遷移金属を含む複合酸化物を活物質
として含んでいる。前記活物質としては、一般式：Ｌｉ
ＭＯ2（ただし、Ｍ＝Ｃｏ、ＮｉまたはＭｎ）またはＬ
ｉ〔ＬｉxＭｎ2-x 〕Ｏ4(ただし、０≦ｘ≦０．１８）
で示されるものが好ましく用いられる。具体的には、Ｌ
ｉＣｏＯ 2、ＬｉＮｉＯ2、ＬｉＭｎ2Ｏ4などが挙げられ
る。これらは単独で用いてもよく、２種以上を組み合わ
せて用いてもよい。BEST MODE FOR CARRYING OUT THE INVENTION A positive electrode for a non-aqueous secondary battery of the present invention
Is a composite oxide containing lithium and transition metal
Included as The active material has a general formula: Li
MOTwo(Where M = Co, Ni or Mn) or L
i [LixMn2-x OFour(However, 0 ≦ x ≦ 0.18)
Are preferably used. Specifically, L
iCoO Two, LiNiOTwo, LiMnTwoOFourEtc.
You. These may be used alone or in combination of two or more.
May be used.
【００１１】本発明の非水系二次電池用正極は、グラフ
ァイト（Ａ）およびカーボンブラック（Ｂ）からなる導
電剤を含んでいる。グラファイト（Ａ）は、その粒子径
が比較的大きいことから、正極内において主として活物
質と金属箔の芯材との間のマクロな電気的接続経路を形
成していると考えられる。一方、カーボンブラック
（Ｂ）は、その粒子径が比較的小さいことから、正極内
において主として活物質粒子間のミクロな電気的接続経
路を形成していると考えられる。したがって、グラファ
イトとカーボンブラックのどちらか一方しか含まない正
極内には緻密な集電経路が形成されず、電子伝導性が不
充分となる。The positive electrode for a non-aqueous secondary battery of the present invention contains a conductive agent comprising graphite (A) and carbon black (B). Since graphite (A) has a relatively large particle diameter, it is considered that a macro electrical connection path is mainly formed between the active material and the core material of the metal foil in the positive electrode. On the other hand, since carbon black (B) has a relatively small particle size, it is considered that mainly a micro electrical connection path between active material particles is formed in the positive electrode. Therefore, a dense current collecting path is not formed in the positive electrode containing only one of graphite and carbon black, and the electron conductivity becomes insufficient.
【００１２】上記のようなグラファイト（Ａ）とカーボ
ンブラック（Ｂ）との相違点を活用し、緻密な集電経路
を正極内に形成するには、正極に含まれるグラファイト
（Ａ）とカーボンブラック（Ｂ）との重量比を（Ａ／
Ｂ）＝２０／８０〜８０／２０の範囲とする必要があ
る。（Ａ）および（Ｂ）の一方が多すぎても、少なすぎ
ても、緻密な集電経路を形成することはできない。In order to utilize the above-mentioned difference between graphite (A) and carbon black (B) to form a dense current collection path in the positive electrode, graphite (A) and carbon black contained in the positive electrode must be used. The weight ratio with (B) is (A /
B) = 20/80 to 80/20. If one of (A) and (B) is too large or too small, a dense current collecting path cannot be formed.
【００１３】グラファイトの平均粒子径は、特に限定さ
れるものではないが０．１〜１０μｍであることが、良
好な集電経路を形成するうえで好ましい。また、カーボ
ンブラックの平均粒子径も、特に限定されるものではな
いが０．０１〜０．１μｍであることが、良好な集電経
路を形成するうえで好ましい。また、カーボンブラック
の平均粒子径に対するグラファイトの平均粒子径の比は
２〜１０００であることが好ましい。The average particle size of graphite is not particularly limited, but is preferably from 0.1 to 10 μm in order to form a good current collecting path. The average particle size of the carbon black is not particularly limited, but is preferably from 0.01 to 0.1 μm in order to form a favorable current collecting path. Further, the ratio of the average particle diameter of graphite to the average particle diameter of carbon black is preferably from 2 to 1,000.
【００１４】グラファイトの種類に特に限定はないが、
例えば膨張黒鉛などの人造黒鉛、鱗片状黒鉛などの天然
黒鉛などを用いることができる。また、カーボンブラッ
クの種類に特に限定はないが、例えばアセチレンブラッ
ク、ファーネスブラックなどを用いることができる。There is no particular limitation on the type of graphite,
For example, artificial graphite such as expanded graphite and natural graphite such as flaky graphite can be used. The type of carbon black is not particularly limited, and for example, acetylene black, furnace black, and the like can be used.
【００１５】本発明の非水系二次電池用正極は、少量の
粒子状結着剤を含んでいる。粒子状結着剤は、正極内で
粒子状を維持する必要がある。従って、粒子状結着剤
は、合剤ペーストの分散媒に溶解しないことが必要であ
る。粒子状結着剤は、粒子形状を維持したまま正極内に
含まれるため、活物質粒子や導電剤粒子の表面を被覆す
ることがない。粒子状結着剤は、活物質−活物質間、活
物質−導電剤間および導電剤−導電剤間に有効に配置さ
れる。従って、少量の結着剤を用いるだけで極板形状を
維持するための充分な効果を得ることができる。正極に
含まれる結着剤量が少ないため、導電剤の必要量も少な
くなる。結果として、寿命特性を損じることなく正極の
活物質密度を向上させることができる。The positive electrode for a non-aqueous secondary battery of the present invention contains a small amount of a particulate binder. The particulate binder needs to maintain a particulate state in the positive electrode. Therefore, it is necessary that the particulate binder does not dissolve in the dispersion medium of the mixture paste. Since the particulate binder is contained in the positive electrode while maintaining the particle shape, it does not cover the surfaces of the active material particles and the conductive agent particles. The particulate binder is effectively disposed between the active material and the active material, between the active material and the conductive agent, and between the conductive agent and the conductive agent. Therefore, a sufficient effect for maintaining the electrode plate shape can be obtained only by using a small amount of the binder. Since the amount of the binder contained in the positive electrode is small, the required amount of the conductive agent is also reduced. As a result, the active material density of the positive electrode can be improved without impairing the life characteristics.
【００１６】粒子状結着剤の平均粒子径は、特に限定さ
れるものではないが０．０５〜０．５μｍであることが
好ましい。平均粒子径が０．０５μｍ未満の場合、結着
剤で被覆される活物質表面積が大きくなり、電池反応が
阻害され易くなる。一方、０．５μｍを超える場合、活
物質粒子間の距離が広くなり、正極の電子伝導性が低下
する傾向がある。The average particle size of the particulate binder is not particularly limited, but is preferably from 0.05 to 0.5 μm. When the average particle size is less than 0.05 μm, the surface area of the active material covered with the binder becomes large, and the battery reaction is easily inhibited. On the other hand, if it exceeds 0.5 μm, the distance between the active material particles is increased, and the electron conductivity of the positive electrode tends to decrease.
【００１７】粒子状結着剤としては、例えばＮ−メチル
−２−ピロリドンに分散させたアクリルゴム粒子、水に
分散させたテトラフルオロエチレン−ヘキサフルオロプ
ロピレン共重合体（以下ＦＥＰという）などが入手可能
である。ただし、ＦＥＰが結着の効果を発現するために
はＦＥＰを約２５０℃で加熱する必要があるのに対し、
アクリルゴム粒子は加熱する必要がないため、アクリル
ゴム粒子の方が好ましい。Examples of the particulate binder include acrylic rubber particles dispersed in N-methyl-2-pyrrolidone and tetrafluoroethylene-hexafluoropropylene copolymer (hereinafter referred to as FEP) dispersed in water. It is possible. However, in order for FEP to exhibit the binding effect, it is necessary to heat FEP at about 250 ° C.
Acrylic rubber particles are preferred because they do not require heating.
【００１８】アクリルゴム粒子のなかでも、アクリロニ
トリル単位を含むコア部とアクリル酸エステル単位、２
−エチルヘキシルアクリレート単位等を含む柔軟なシェ
ル部とからなるコアシェル型のゴム粒子が特に好まし
い。この場合、アクリロニトリル単位を含む強固なコア
部が正極内で粒子形状を保持する機能を有し、シェル部
が結着の効果を発現する。Among the acrylic rubber particles, a core containing an acrylonitrile unit and an acrylate unit,
Core-shell type rubber particles comprising a flexible shell portion containing -ethylhexyl acrylate unit and the like are particularly preferred. In this case, the strong core containing acrylonitrile units has a function of maintaining the particle shape in the positive electrode, and the shell exerts a binding effect.
【００１９】本発明の非水系二次電池用正極に含まれる
導電剤の量は、活物質１００重量部あたり２重量部以上
４重量部未満に限定される。導電剤の量が２重量部未満
の場合、正極の電子伝導性が乏しくなって電池の寿命特
性が低下する。一方、４重量部以上の場合、正極の活物
質密度を向上させることができず、高容量な電池を得る
ことができない。The amount of the conductive agent contained in the positive electrode for a non-aqueous secondary battery of the present invention is limited to 2 parts by weight or more and less than 4 parts by weight per 100 parts by weight of the active material. When the amount of the conductive agent is less than 2 parts by weight, the electron conductivity of the positive electrode becomes poor, and the life characteristics of the battery deteriorate. On the other hand, when the amount is 4 parts by weight or more, the active material density of the positive electrode cannot be improved, and a high-capacity battery cannot be obtained.
【００２０】一方、本発明の非水系二次電池用正極に含
まれる結着剤の量は、活物質１００重量部あたり０．４
重量部以上２重量部以下に限定される。結着剤の量が
０．４重量部未満では少なすぎるため、正極の製造工程
で合剤が芯材から剥がれ、製造が困難になる。一方、２
重量部を超える場合、正極の電子伝導性が低下するた
め、電池の寿命特性が低下する。On the other hand, the amount of the binder contained in the positive electrode for a non-aqueous secondary battery of the present invention is 0.4 parts per 100 parts by weight of the active material.
It is limited to not less than 2 parts by weight and not more than 2 parts by weight. If the amount of the binder is less than 0.4 part by weight, the amount is too small, so that the mixture is peeled off from the core material in the production process of the positive electrode, and the production becomes difficult. Meanwhile, 2
If the amount exceeds the weight part, the electron conductivity of the positive electrode decreases, and the life characteristics of the battery deteriorate.
【００２１】粒子状結着剤は合剤ペーストの分散媒に溶
解しないため、合剤ペーストの粘度を調整することがで
きない。そこで、増粘剤を添加して分散媒の粘度を上げ
て、合剤ペーストを芯材への塗工に適した性状にする必
要がある。増粘剤は、結着剤が溶解しない分散媒に溶解
する必要がある。Since the particulate binder does not dissolve in the dispersion medium of the mixture paste, the viscosity of the mixture paste cannot be adjusted. Therefore, it is necessary to increase the viscosity of the dispersion medium by adding a thickener to make the mixture paste a property suitable for application to the core material. The thickener must be dissolved in a dispersion medium in which the binder does not dissolve.
【００２２】例えば結着剤として前記アクリルゴム粒子
を用いる場合、分散媒としてはＮ−メチル−２−ピロリ
ドンが好適である。従って、増粘剤としてはＮ−メチル
−２−ピロリドンに溶解し得る変性ポリエチレンなどの
樹脂が好ましい。また、変性ポリエチレンとしては、ポ
リエチレンの構造にビニルアルコール単位等の極性基を
含ませたものが好ましい。For example, when the acrylic rubber particles are used as a binder, N-methyl-2-pyrrolidone is preferable as a dispersion medium. Therefore, as the thickener, a resin such as a modified polyethylene that can be dissolved in N-methyl-2-pyrrolidone is preferable. Further, as the modified polyethylene, those in which a polar group such as a vinyl alcohol unit is included in the structure of the polyethylene are preferable.
【００２３】結着剤としてＦＥＰを用いる場合、分散媒
としては水が好適である。従って、増粘剤としては水に
溶解し得るカルボキシメチルセルロースなどが好まし
い。When FEP is used as a binder, water is suitable as a dispersion medium. Therefore, carboxymethylcellulose soluble in water and the like are preferable as the thickener.
【００２４】合剤ペーストに含まれる増粘剤の量は、特
に限定されるものではないが、活物質１００重量部あた
り０．１〜１重量部であることが好ましい。増粘剤量が
０．１重量部未満の場合、合剤ペーストを芯材への塗工
に適した性状にすることが困難になり、１重量部を超え
る場合、増粘剤で被覆される活物質表面積が大きくな
り、電池反応が阻害される。The amount of the thickener contained in the mixture paste is not particularly limited, but is preferably 0.1 to 1 part by weight per 100 parts by weight of the active material. When the amount of the thickener is less than 0.1 part by weight, it is difficult to make the mixture paste into a property suitable for application to the core material. When the amount exceeds 1 part by weight, the mixture paste is coated with the thickener. The active material surface area is increased, and the battery reaction is hindered.
【００２５】本発明の非水系二次電池用正極は、例え
ば、上記活物質、導電剤、結着剤および増粘剤を所定の
分散媒とともに練合し、合剤ペーストを得、これをアル
ミニウムなどの金属箔または穿孔板（ラスメタル板）の
両面に塗布し、圧延し、切断する工程などにより作製さ
れる。電池を小型軽量にする観点から、芯材の厚さは金
属箔であれば１０〜２５μｍ、穿孔板であれば１０〜５
０μｍとするのが一般的であり、正極の厚さは８０〜２
００μｍとするのが一般的である。The positive electrode for a non-aqueous secondary battery of the present invention is prepared by, for example, kneading the above-mentioned active material, conductive agent, binder and thickener together with a predetermined dispersion medium to obtain a mixture paste. It is produced by a process such as coating on both sides of a metal foil or a perforated plate (lath metal plate), rolling and cutting. From the viewpoint of reducing the size and weight of the battery, the thickness of the core material is 10 to 25 μm for a metal foil, and 10 to 5 for a perforated plate.
Generally, the thickness of the positive electrode is 80 to 2 μm.
Generally, it is set to 00 μm.
【００２６】一方、負極は、例えば、リチウムイオンを
吸蔵・放出できる炭素を活物質として含む合剤ペースト
を銅などの金属箔または穿孔板（ラスメタル板）の両面
に塗布し、圧延し、切断する工程などにより作製され
る。電池を小型軽量にする観点から、芯材の厚さは金属
箔であれば８〜２０μｍ、穿孔板であれば１０〜５０μ
ｍとするのが一般的であり、負極の厚さは８０〜２００
μｍとするのが一般的である。On the other hand, for the negative electrode, for example, a mixture paste containing carbon capable of occluding and releasing lithium ions as an active material is applied to both surfaces of a metal foil such as copper or a perforated plate (lass metal plate), rolled, and cut. It is produced by a process or the like. From the viewpoint of reducing the size and weight of the battery, the thickness of the core material is 8 to 20 μm for a metal foil and 10 to 50 μm for a perforated plate.
m, and the thickness of the negative electrode is 80 to 200
It is generally set to μm.
【００２７】得られた正極および負極を、両者の間にセ
パレータを介在させて積層し、横断面が略楕円形になる
ように捲回すれば角形電池用の極板群が、横断面が円形
になるように捲回すれば円筒形電池用の極板群がそれぞ
れ得られる。セパレータとしては、ポリエチレンやポリ
プロピレンなどのポリオレフィン製微多孔膜などが用い
られる。その厚さは一般的に１０〜４０μｍである。The obtained positive electrode and negative electrode are laminated with a separator interposed therebetween, and wound so as to have a substantially elliptical cross section. The electrode groups for a cylindrical battery can be obtained by winding such that As the separator, a microporous film made of polyolefin such as polyethylene or polypropylene is used. Its thickness is generally between 10 and 40 μm.
【００２８】極板群を角形または円筒形の金属製電池ケ
ースに収容し、リチウムイオン伝導性の非水電解質を注
入すれば本発明の非水系二次電池を得ることができる。
電池ケース内に注入される非水電解質は、従来からリチ
ウム二次電池に用いられているものを特に制限なく用い
ることができる。一般的には、リチウム塩および非水溶
媒からなる電解質が用いられる。リチウム塩としては、
例えばＬｉＰＦ6、ＬｉＢＦ4などが挙げられる。これら
は単独で用いてもよく、２種以上を組合せて用いてもよ
い。また、非水溶媒としては、エチレンカーボネート、
ジメチルカーボネート、ジエチルカーボネート、エチル
メチルカーボネート、プロピレンカーボネートなどが挙
げられる。これらは単独で用いてもよく、２種以上を組
合せて用いてもよい。The non-aqueous secondary battery of the present invention can be obtained by housing the electrode group in a square or cylindrical metal battery case and injecting a lithium ion conductive non-aqueous electrolyte.
As the non-aqueous electrolyte injected into the battery case, those conventionally used for lithium secondary batteries can be used without any particular limitation. Generally, an electrolyte composed of a lithium salt and a non-aqueous solvent is used. As lithium salts,
For example, LiPF 6 , LiBF 4 and the like can be mentioned. These may be used alone or in combination of two or more. Further, as the non-aqueous solvent, ethylene carbonate,
Dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate and the like can be mentioned. These may be used alone or in combination of two or more.
【００２９】本発明の非水系二次電池の一例である角形
電池の横断図面を図１に示す。図中、１は角形の電池ケ
ースを示し、その内部に極板群が挿入されている。極板
群は、正極２および負極３を、両者の間にセパレータ４
を介在させて積層し、横断面が略楕円形になるように捲
回することにより構成されている。FIG. 1 is a cross-sectional view of a prismatic battery which is an example of the non-aqueous secondary battery of the present invention. In the drawing, reference numeral 1 denotes a rectangular battery case, into which an electrode plate group is inserted. The electrode group includes a positive electrode 2 and a negative electrode 3, and a separator 4 between them.
Are laminated and wound so that the cross section becomes substantially elliptical.
【００３０】[0030]
【実施例】以下、本発明を実施例に基づいて具体的に説
明する。ただし、本発明はこれらの実施例に限定される
ものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. However, the present invention is not limited to these examples.
【００３１】《実施例１》１００重量部のＬｉＣｏＯ2
に対し、結着剤としてＮ−メチル−２−ピロリドンに分
散させたアクリルゴム粒子（日本ゼオン(株)製のＢＭ５
００Ｂ（商品名）、平均粒子径０．２μｍ）を固形分で
０．４重量部、増粘剤としてＮ−メチル−２−ピロリド
ンに溶解させた変性ポリエチレン（日本ゼオン(株)製の
ＢＭ７００Ｈ（商品名））を樹脂成分で０．３重量部、
ならびに導電剤として平均粒子径０．３μｍのグラファ
イト１．５重量部および平均粒子径０．０３μｍのアセ
チレンブラック１．５重量部を混合し、Ｎ−メチル−２
−ピロリドンを分散媒とし、固形分濃度２８重量％の合
剤ペーストを得た。なお、上記結着剤は、アクリロニト
リル単位を含むコア部を有するコアシェル型のアクリル
ゴム粒子である。Example 1 100 parts by weight of LiCoO 2
In contrast, acrylic rubber particles dispersed in N-methyl-2-pyrrolidone as a binder (BM5 manufactured by Zeon Corporation)
00B (trade name, average particle size: 0.2 μm) in a solid content of 0.4 part by weight, modified polyethylene dissolved in N-methyl-2-pyrrolidone as a thickener (BM700H manufactured by Zeon Corporation) 0.3% by weight of the resin component)
Also, 1.5 parts by weight of graphite having an average particle diameter of 0.3 μm and 1.5 parts by weight of acetylene black having an average particle diameter of 0.03 μm were mixed as a conductive agent, and N-methyl-2 was added.
A mixture paste having a solid content of 28% by weight was obtained using pyrrolidone as a dispersion medium. The binder is a core-shell type acrylic rubber particle having a core containing acrylonitrile units.
【００３２】この合剤ペーストを、厚さ２０μｍのアル
ミニウム箔の両面に塗布し、乾燥し、合剤部分における
活物質密度が３．６ｇ／ｍｌとなるように圧延し、幅４
０ｍｍ、長さ４６０ｍｍに切断して正極を得た。This mixture paste was applied to both sides of an aluminum foil having a thickness of 20 μm, dried, and rolled so that the active material density at the mixture portion became 3.6 g / ml.
It was cut to 0 mm and 460 mm in length to obtain a positive electrode.
【００３３】一方、人造黒鉛粉末１００重量部に対し、
結着剤としてスチレンブタジエンゴム３重量部を混合
し、これらをカルボキシメチルセルロース水溶液に懸濁
させて合剤ペーストにした。このペーストを厚さ１５μ
ｍの銅箔の両面に塗布し、乾燥し、圧延後、所定の寸法
に切断して負極を得た。得られた正極と負極との間にセ
パレータを介在させて横断面が略楕円形になるように捲
回し、極板群を得た。セパレータとしては、厚さ２７μ
ｍのポリエチレン製微多孔膜を用いた。On the other hand, for 100 parts by weight of the artificial graphite powder,
3 parts by weight of styrene butadiene rubber was mixed as a binder, and these were suspended in an aqueous solution of carboxymethyl cellulose to form a mixture paste. This paste is 15μ thick
m, coated on both sides of a copper foil, dried, rolled, and cut into predetermined dimensions to obtain a negative electrode. A separator was interposed between the obtained positive electrode and negative electrode and wound so that the cross section became substantially elliptical to obtain an electrode plate group. 27μ thick separator
m of polyethylene microporous membrane was used.
【００３４】前記極板群は、その上部および底部に絶縁
リングを配して所定のアルミニウム製ケース内に３．２
ｇの非水電解質とともに収容した。非水電解質として
は、等体積のエチレンカーボネートとエチルメチルカー
ボネートとの混合物に１モル／リットルの濃度になるよ
うにＬｉＰＦ6を溶解したものを用いた。そして、負極
板に取り付けたリードと正極板に取り付けたリードを所
定の箇所に接続した後、ケースの開口部を封口板で封口
し、本発明の非水系二次電池を完成した。この電池は、
幅３０ｍｍ、高さ４８ｍｍ、厚さ５ｍｍの角形であり、
電池の公称容量は６００ｍＡｈである。The electrode group is provided with an insulating ring on the top and bottom thereof and placed in a predetermined aluminum case in 3.2 inches.
g of non-aqueous electrolyte. As the non-aqueous electrolyte, one obtained by dissolving LiPF 6 at a concentration of 1 mol / liter in a mixture of equal volumes of ethylene carbonate and ethyl methyl carbonate was used. Then, the lead attached to the negative electrode plate and the lead attached to the positive electrode plate were connected to predetermined locations, and then the opening of the case was sealed with a sealing plate to complete the non-aqueous secondary battery of the present invention. This battery is
It is a square with a width of 30 mm, a height of 48 mm, and a thickness of 5 mm,
The nominal capacity of the battery is 600 mAh.
【００３５】《実施例２〜４および比較例１〜２》正極
に含まれる結着剤の量を表１に示すように変化させたこ
と以外、実施例１と同様に正極および非水系二次電池を
作製した。<< Examples 2 to 4 and Comparative Examples 1 and 2 >> The same procedure as in Example 1 was carried out except that the amount of the binder contained in the positive electrode was changed as shown in Table 1. A battery was manufactured.
【００３６】《実施例５〜６および比較例３〜４》正極
に含まれる導電剤の総量は変えずにグラファイトとアセ
チレンブラックとの重量比率を表１に示すように変化さ
せたこと以外、実施例２と同様に正極および非水系二次
電池を作製した。<< Examples 5 to 6 and Comparative Examples 3 to 4 >> Except that the weight ratio of graphite to acetylene black was changed as shown in Table 1, without changing the total amount of the conductive agent contained in the positive electrode. A positive electrode and a non-aqueous secondary battery were produced in the same manner as in Example 2.
【００３７】《実施例７〜８および比較例５〜７》正極
に含まれる導電剤におけるグラファイトとアセチレンブ
ラックとの重量比率は変えずに導電剤の総量を表１に示
すように変化させたこと以外、実施例２と同様に正極お
よび非水系二次電池を作製した。Examples 7 to 8 and Comparative Examples 5 to 7 The total amount of the conductive agent was changed as shown in Table 1 without changing the weight ratio of graphite to acetylene black in the conductive agent contained in the positive electrode. A positive electrode and a non-aqueous secondary battery were produced in the same manner as in Example 2 except for the above.
【００３８】《実施例９》正極に含まれる結着剤をＦＥ
Ｐに代え、増粘剤をカルボキシメチルセルロースに代え
るとともにその量を活物質１００重量部に対し１重量部
としたこと以外、実施例４と同様に正極および非水系二
次電池を作製した。Example 9 The binder contained in the positive electrode was FE
A positive electrode and a non-aqueous secondary battery were produced in the same manner as in Example 4, except that carboxymethyl cellulose was used in place of P and the amount was 1 part by weight based on 100 parts by weight of the active material.
【００３９】《比較例８》正極に含まれる結着剤をポリ
フッ化ビニリデン（ＰＶＤＦ）に代え、その量を活物質
１００重量部に対し４重量部とし、増粘剤は用いなかっ
たこと以外、実施例１と同様に正極および非水系二次電
池を作製した。Comparative Example 8 The binder contained in the positive electrode was replaced with polyvinylidene fluoride (PVDF), and the amount was 4 parts by weight with respect to 100 parts by weight of the active material, except that no thickener was used. A positive electrode and a non-aqueous secondary battery were produced in the same manner as in Example 1.
【００４０】次に、前記実施例および比較例の正極およ
び電池の評価を行った。 （ｉ）正極の評価 正極合剤ペーストをアルミニウム箔上に塗布し、乾燥し
た後、アルミニウム箔からの合剤の脱落の有無を目視し
た。そして、不具合のない正極のみ電池の作製に用い
た。結果を表１に示す。次いで、極板群構成後の正極表
面を目視し、同じく不具合のない正極のみ電池の作製に
用いた。結果を表１に示す。Next, the positive electrodes and batteries of the above Examples and Comparative Examples were evaluated. (I) Evaluation of Positive Electrode The positive electrode mixture paste was applied on an aluminum foil and dried, and then the presence or absence of the mixture from the aluminum foil was visually observed. Then, only the positive electrode having no defect was used for producing a battery. Table 1 shows the results. Next, the surface of the positive electrode after the formation of the electrode plate group was visually observed, and only the positive electrode having no defect was used for producing a battery. Table 1 shows the results.
【００４１】（ii）電池の評価 得られた電池のサイクル寿命特性を評価した。具体的に
は、６００ｍＡで電池電圧が４．２Ｖになるまで充電
し、６００ｍＡで電池電圧が３Ｖになるまで放電する操
作を２００回繰り返した。そして、１回目の放電容量に
対する２００回目の放電容量の比を求めた。結果を容量
維持率として百分率で表１に示す。(Ii) Evaluation of Battery The cycle life characteristics of the obtained battery were evaluated. Specifically, the operation of charging at 600 mA until the battery voltage becomes 4.2 V and discharging the battery at 600 mA until the battery voltage becomes 3 V was repeated 200 times. Then, the ratio of the 200th discharge capacity to the first discharge capacity was determined. The results are shown in Table 1 as a percentage of capacity retention.
【００４２】（iii）評価結果(Iii) Evaluation results
【００４３】[0043]
【表１】 [Table 1]
【００４４】正極の結着剤として分散媒（Ｎ−メチル−
２−ピロリドン）に溶解するポリフッ化ビニリデンを用
いた比較例８の正極は、極板群構成後に略楕円形に捲回
された極板群を目視したところ、最も曲率が高い箇所に
折り目状の亀裂が発生していることが確認された。比較
例８の正極は多量のポリフッ化ビニリデンを結着剤とし
て含んでいるため、極板内の空隙体積が少なくなり、極
板の柔軟性が著しく損なわれたものと考えられる。正極
の活物質密度を３．３ｇ／ｍｌまで減らせば亀裂が発生
しないことが確認されたが、活物質密度を減らすと極板
の厚さは増加することになる。従って、金属ケースに挿
入するには正極の長さを減ずる（すなわち容量を低下さ
せる）必要がある。As a binder for the positive electrode, a dispersion medium (N-methyl-
In the positive electrode of Comparative Example 8 using polyvinylidene fluoride dissolved in (2-pyrrolidone), a fold-like electrode was formed at a position where the curvature was highest when the electrode group wound substantially elliptical after the formation of the electrode group was visually observed. It was confirmed that cracks had occurred. It is considered that since the positive electrode of Comparative Example 8 contained a large amount of polyvinylidene fluoride as a binder, the void volume in the electrode plate was reduced, and the flexibility of the electrode plate was significantly impaired. It was confirmed that cracking did not occur when the active material density of the positive electrode was reduced to 3.3 g / ml, but when the active material density was reduced, the thickness of the electrode plate increased. Therefore, it is necessary to reduce the length of the positive electrode (that is, reduce the capacity) in order to insert the positive electrode into the metal case.
【００４５】一方、正極の結着剤として分散媒（Ｎ−メ
チル−２−ピロリドン）に溶解しないＢＭ５００Ｂを用
いた実施例１の正極は、少量でも結着効果を発現するた
め、充分な空隙を確保しつつ活物質密度３．６ｇ／ｍｌ
とすることができた。また、実施例１の正極に不具合は
一切生じなかった。実施例１の電池のサイクル寿命特性
も良好であった。結着剤としてＦＥＰを用いた実施例９
の正極でも同様の効果が得られた。ただし、比較例１の
ように結着剤の量が少なすぎると、合剤が極板から脱落
し、比較例２のように結着剤の量が多すぎると、正極内
の電子伝導性が不足するためサイクル寿命特性が低下し
た。このことから、結着剤量の最適範囲は、活物質１０
０重量部あたり０．４重量部以上２重量部以下であるこ
とがわかる。On the other hand, the positive electrode of Example 1 using BM500B, which does not dissolve in a dispersion medium (N-methyl-2-pyrrolidone), as a binder for the positive electrode, exerts a binding effect even in a small amount, and therefore has a sufficient space. Active material density 3.6g / ml while securing
And could be. In addition, no problem occurred in the positive electrode of Example 1. The cycle life characteristics of the battery of Example 1 were also good. Example 9 using FEP as a binder
The same effect was obtained with the positive electrode. However, if the amount of the binder is too small as in Comparative Example 1, the mixture will fall off the electrode plate, and if the amount of the binder is too large as in Comparative Example 2, the electron conductivity in the positive electrode will decrease. Insufficiency reduced the cycle life characteristics. From this, the optimum range of the amount of the binder is 10
It is understood that the content is 0.4 parts by weight or more and 2 parts by weight or less per 0 parts by weight.
【００４６】導電剤の総量は変化させず、グラファイト
（Ａ）とアセチレンブラック（Ｂ）との重量比率を変化
させた場合、比較例３（（Ａ／Ｂ）＝１０／９０）、比
較例４（（Ａ／Ｂ）＝９０／１０）の電池は、いずれも
サイクル寿命特性が低下した。この理由として、比較例
３の正極はグラファイトが不足しているため、また、比
較例４の電池はアセチレンブラックが不足しているた
め、緻密な集電経路を形成することができず、いずれも
正極の電子伝導性が低下したためと考えられる。このこ
とから、グラファイト（Ａ）とアセチレンブラック
（Ｂ）との重量比率の最適範囲は、（Ａ／Ｂ）＝２０／
８０〜８０／２０であることがわかる。When the weight ratio of graphite (A) to acetylene black (B) was changed without changing the total amount of the conductive agent, Comparative Example 3 ((A / B) = 10/90) and Comparative Example 4 The batteries of ((A / B) = 90/10) all had reduced cycle life characteristics. The reason for this is that the positive electrode of Comparative Example 3 lacks graphite and the battery of Comparative Example 4 lacks acetylene black, so that a dense current collecting path cannot be formed. It is considered that the electron conductivity of the positive electrode decreased. From this, the optimal range of the weight ratio between graphite (A) and acetylene black (B) is (A / B) = 20 /
It turns out that it is 80-80 / 20.
【００４７】グラファイト（Ａ）とアセチレンブラック
（Ｂ）との重量比率は変化させず、導電剤の総量を変化
させた場合、活物質１００重量部あたり１．６重量部し
か導電剤を含まない比較例５の正極は、電子伝導性不足
のため電池のサイクル寿命特性が低下した。また、物質
１００重量部あたり４重量部の導電剤を含む比較例６の
正極は、極板群を略楕円形に捲回した際に亀裂が発生し
ていることが確認された。比較例６の場合、極板群の亀
裂が微細であったため、電池を構成するうえで影響がな
いと判断してサイクル寿命特性を評価したところ、実施
例１と同等の結果であった。しかし、活物質１００重量
部あたり４．６重量部の結着剤を含む比較例７の正極に
は、比較例８と同程度の亀裂が確認された。このことか
ら、導電剤量の最適範囲は、活物質１００重量部あたり
２重量部以上４重量部未満であることがわかる。When the weight ratio of graphite (A) and acetylene black (B) was not changed and the total amount of the conductive agent was changed, only 1.6 parts by weight of the conductive material was included per 100 parts by weight of the active material. In the positive electrode of Example 5, the cycle life characteristics of the battery deteriorated due to insufficient electron conductivity. In addition, it was confirmed that the positive electrode of Comparative Example 6, which contained 4 parts by weight of the conductive agent per 100 parts by weight of the substance, had cracks when the electrode plate group was wound into an approximately elliptical shape. In the case of Comparative Example 6, since the electrode group was finely cracked, it was determined that there was no effect on the construction of the battery, and the cycle life characteristics were evaluated. The results were equivalent to those of Example 1. However, in the positive electrode of Comparative Example 7 containing 4.6 parts by weight of the binder per 100 parts by weight of the active material, cracks similar to those in Comparative Example 8 were confirmed. This indicates that the optimal range of the amount of the conductive agent is 2 parts by weight or more and less than 4 parts by weight per 100 parts by weight of the active material.
【００４８】[0048]
【発明の効果】本発明によれば、正極の活物質密度を向
上することができ、高容量かつ良好な寿命特性を有する
非水系二次電池用正極および非水系二次電池を提供する
ことができる。According to the present invention, it is possible to provide a positive electrode for a non-aqueous secondary battery and a non-aqueous secondary battery which can increase the active material density of the positive electrode, and have a high capacity and a good life characteristic. it can.
【図１】本発明の非水系二次電池の一例の横断面図であ
る。FIG. 1 is a cross-sectional view of an example of a non-aqueous secondary battery of the present invention.
１ 電池ケース ２ 正極板 ３ 負極板 ４ セパレータ DESCRIPTION OF SYMBOLS 1 Battery case 2 Positive electrode plate 3 Negative electrode plate 4 Separator
───────────────────────────────────────────────────── フロントページの続き (72)発明者 福永 政雄 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 黒田 明 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 川村 基 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 大畠 積 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 5H029 AJ03 AJ05 AK03 AL07 AM03 AM05 AM07 DJ08 DJ16 EJ04 EJ12 HJ01 5H050 AA07 AA08 BA17 CA08 CA09 CB08 DA02 DA10 DA11 EA09 EA10 EA23 FA17 HA01 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masao Fukunaga 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. 72) Inventor Moto Kawamura 1006 Kadoma Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. AL07 AM03 AM05 AM07 DJ08 DJ16 EJ04 EJ12 HJ01 5H050 AA07 AA08 BA17 CA08 CA09 CB08 DA02 DA10 DA11 EA09 EA10 EA23 FA17 HA01
Claims (2)
物からなる活物質、グラファイト（Ａ）およびカーボン
ブラック（Ｂ）からなる導電剤ならびに有機重合体から
なる粒子状の結着剤を有する非水系二次電池用正極であ
って、 前記活物質１００重量部あたり０．４重量部以上２重量
部以下の前記結着剤および２重量部以上４重量部未満の
前記導電剤を含み、 前記導電剤におけるグラファイト（Ａ）とカーボンブラ
ック（Ｂ）との重量比（Ａ／Ｂ）が２０／８０〜８０／
２０であることを特徴とする非水系二次電池用正極。1. A non-aqueous system comprising an active material comprising a composite oxide containing lithium and a transition metal, a conductive agent comprising graphite (A) and carbon black (B), and a particulate binder comprising an organic polymer. A positive electrode for a secondary battery, comprising 0.4 to 2 parts by weight of the binder and 2 to 4 parts by weight of the conductive agent per 100 parts by weight of the active material. The weight ratio (A / B) of graphite (A) to carbon black (B) is 20 / 80-80 /
20. A positive electrode for a non-aqueous secondary battery, which is 20.
放出可能な材料からなる負極およびリチウムイオン伝導
性の非水電解質を有する非水系二次電池。2. The positive electrode according to claim 1, wherein the positive electrode stores lithium.
A nonaqueous secondary battery having a negative electrode made of a releasable material and a lithium ion conductive nonaqueous electrolyte.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000310765A JP3582823B2 (en) | 2000-10-11 | 2000-10-11 | Positive electrode for non-aqueous secondary battery and non-aqueous secondary battery |
| TW090117687A TW508861B (en) | 2000-08-08 | 2001-07-19 | Non-aqueous electrolyte secondary battery and positive electrode for the same |
| US09/915,946 US6869724B2 (en) | 2000-08-08 | 2001-07-26 | Non-aqueous electrolyte secondary battery and positive electrode for the same |
| KR10-2001-0046908A KR100414720B1 (en) | 2000-08-08 | 2001-08-03 | Non-aqueous electrolyte secondary battery and positive electrode for the same |
| EP01119035A EP1179869B1 (en) | 2000-08-08 | 2001-08-07 | Non-aqueous electrolyte secondary battery and positive electrode for the same |
| EP07113920A EP1858095B1 (en) | 2000-08-08 | 2001-08-07 | Non-aqueous electrolyte secondary battery and positive electrode for the same |
| DE60142371T DE60142371D1 (en) | 2000-08-08 | 2001-08-07 | Non-aqueous electrolyte secondary battery and positive electrode therefor |
| DE60137001T DE60137001D1 (en) | 2000-08-08 | 2001-08-07 | Non-aqueous secondary battery and positive electrode for it |
| CNB011249919A CN1167161C (en) | 2000-08-08 | 2001-08-08 | Positive electrode for non-water electrolyte secondary cell and cell adopting same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000310765A JP3582823B2 (en) | 2000-10-11 | 2000-10-11 | Positive electrode for non-aqueous secondary battery and non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002117834A true JP2002117834A (en) | 2002-04-19 |
| JP3582823B2 JP3582823B2 (en) | 2004-10-27 |
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ID=18790659
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|---|---|---|---|
| JP2000310765A Expired - Fee Related JP3582823B2 (en) | 2000-08-08 | 2000-10-11 | Positive electrode for non-aqueous secondary battery and non-aqueous secondary battery |
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| JP2005533373A (en) * | 2002-07-12 | 2005-11-04 | イドロ−ケベック | Particles comprising a non-conductive core or a semi-conductive core coated with a hybrid conductive layer, a method for its production, and its use in electrochemical devices |
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| JP2018503946A (en) * | 2015-01-13 | 2018-02-08 | エルジー・ケム・リミテッド | Method for producing positive electrode forming composition for lithium secondary battery, and positive electrode and lithium secondary battery produced using the same |
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