JP2002237301A - Nonaqueous electrolytic solution secondary battery - Google Patents
Nonaqueous electrolytic solution secondary batteryInfo
- Publication number
- JP2002237301A JP2002237301A JP2001031362A JP2001031362A JP2002237301A JP 2002237301 A JP2002237301 A JP 2002237301A JP 2001031362 A JP2001031362 A JP 2001031362A JP 2001031362 A JP2001031362 A JP 2001031362A JP 2002237301 A JP2002237301 A JP 2002237301A
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- Japan
- Prior art keywords
- positive electrode
- active material
- lithium
- secondary battery
- electrode active
- Prior art date
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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、非水電解質二次電
池に関する。TECHNICAL FIELD The present invention relates to a non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】近年、ビデオカメラや携帯型電話機等の
コードレス電子機器の発達がめざましく、これらの民生
用途の電源として電池電圧が高く、高エネルギーを有し
た非水電解質二次電池としてのリチウム二次電池が注目
されて実用化されてきている。2. Description of the Related Art In recent years, cordless electronic devices such as video cameras and portable telephones have been remarkably developed, and lithium-ion batteries as non-aqueous electrolyte secondary batteries having a high battery voltage and high energy have been used as power sources for these consumer applications. Secondary batteries have attracted attention and have been put to practical use.
【０００３】上記電池の正極活物質としては４Ｖ程度の
電池電圧を示すＬｉＣｏＯ2、ＬｉＮｉＯ2、ＬｉＭｎ2
Ｏ4などのリチウム遷移金属複合酸化物、ポリアニリン
など軽量かつ理論容量の高い導電性高分子、さらにはリ
チウム遷移金属複合酸化物と導電性高分子を複合した系
（特開平１０−１８８９８５等）などが使用（一部実用
化）または検討されている。As the positive electrode active material of the battery, LiCoO 2 , LiNiO 2 , LiMn 2 showing a battery voltage of about 4 V
Lithium transition metal composite oxides such as O 4 , light-weight and high-conductivity conductive polymers such as polyaniline, and composites of lithium transition metal composite oxides and conductive polymers (JP-A-10-188895, etc.) Are being used (partially put into practical use) or being studied.
【０００４】また現在では、環境問題等からは自動車の
分野でも電気自動車のハイブリッド自動車の開発がなさ
れており、この様な車載用の電源としてもリチウム二次
電池が注目されている。At present, hybrid vehicles of electric vehicles are also being developed in the field of automobiles due to environmental problems and the like, and lithium secondary batteries are attracting attention as such power sources for vehicles.
【０００５】しかし車載用の電源として用いる場合、民
生用途と比較して使用条件が厳しくなる。すなわち高エ
ネルギー密度の要求に加えて、大電流での充放電や高出
力密度・高回生密度、さらには高温環境下における長寿
命特性等の優れた特性を併せ持つことが要求される。[0005] However, when used as a power supply for a vehicle, operating conditions are more severe than those for consumer use. That is, in addition to the demand for a high energy density, it is also required to have excellent characteristics such as charge / discharge at a large current, a high output density, a high regenerative density, and a long life property in a high temperature environment.
【０００６】これに対し、例えば大電流での充放電、高
出力化等の特性を改善を解決するために、電極の薄膜化
による低抵抗化などが試みられ、ある程度の特性改善さ
れた非水電解質二次電池の提供が可能となっている。On the other hand, in order to solve the characteristics such as charging and discharging at a large current and increasing the output, for example, attempts have been made to reduce the resistance by reducing the thickness of the electrodes. It has become possible to provide an electrolyte secondary battery.
【０００７】[0007]
【発明が解決しようとする課題】しかしながら上記従来
技術の非水電解質二次電池は、その他の特性、たとえば
電池寿命の低下や電池エネルギー密度の低下を招き非水
電解質二次電池に要求される特性をすべて満足すること
は非常に難しかった。However, the above-mentioned prior art non-aqueous electrolyte secondary battery has other characteristics, for example, the characteristics required for the non-aqueous electrolyte secondary battery, such as a reduction in battery life and a reduction in battery energy density. It was very difficult to satisfy all.
【０００８】すなわち、一般的に電池の電極は活物質が
含有される合材層と、アルミ箔や銅箔からなる集電体層
から構成されている。したがって低抵抗化を図り、電極
（合材層）を薄膜化した場合、電池全体における単位体
積または単位重量当たりの電極合材量が減少し、電池の
エネルギー密度が低下してしまう。That is, a battery electrode generally comprises a mixture layer containing an active material and a current collector layer made of aluminum foil or copper foil. Therefore, when the resistance (resistance) is reduced and the electrode (mixture layer) is thinned, the amount of the electrode mixture per unit volume or unit weight in the entire battery decreases, and the energy density of the battery decreases.
【０００９】本発明は、従来技術の問題点に鑑みてなさ
れたものであり、特定のリチウム複合酸化物に導電性高
分子を組み合わせることにより、高エネルギー密度・高
温環境下における長寿命特性を有し、大電流での充放電
が可能で、高出力・回生特性を満足する非水電解液二次
電池を提供することを解決すべき課題とする。The present invention has been made in view of the problems of the prior art, and has a long life characteristic in a high energy density and high temperature environment by combining a specific lithium composite oxide with a conductive polymer. Another object of the present invention is to provide a non-aqueous electrolyte secondary battery which can be charged and discharged with a large current and satisfies high output and regenerative characteristics.
【００１０】[0010]
【課題を解決するための手段】本発明者らは上記課題を
解決する目的で鋭意研究を重ねた結果、正極を所定の構
成とすることで、高エネルギー密度・高温環境下におけ
る長寿命特性に加えて、大電流での充放電が可能で、高
出力密度・高回生密度の電池を得ることを見出した。以
下に説明する。Means for Solving the Problems The inventors of the present invention have conducted intensive studies for the purpose of solving the above-mentioned problems, and as a result, by setting the positive electrode to a predetermined structure, a long life characteristic under a high energy density and high temperature environment is obtained. In addition, it has been found that a battery capable of charging and discharging with a large current and having a high output density and a high regenerative density is obtained. This will be described below.
【００１１】π共役系導電性高分子はπ電子の授受によ
り無機物質からなる活物質（以下、「無機系活物質」と
称する。）と同様に電池反応に関与することができる。
その中で正極活物質として利用できるＰ型導電性高分子
の電池反応の機構に関して考えてみると、酸化時にはそ
のエネルギー準位において最高占有準位（ＨＯＭＯ）に
存在する電子が引き抜かれ導電性高分子が正電荷を帯
び、電荷を補償するためにアニオンが吸着する。The π-conjugated conductive polymer can participate in a battery reaction by transferring π electrons, similarly to an active material made of an inorganic material (hereinafter referred to as “inorganic active material”).
Considering the mechanism of the battery reaction of the P-type conductive polymer that can be used as the positive electrode active material, during oxidation, electrons present at the highest occupied level (HOMO) in the energy level are extracted and the conductivity is increased. The molecule is positively charged and anions are adsorbed to compensate for the charge.
【００１２】逆に還元時には負電荷を帯び、アニオンが
電荷の補償のため脱着する。したがって、無機系活物質
の電池反応（化学反応）に比べると、よりマイルドな現
象（吸・脱着）を利用しているため、高速な充放電が可
能となる。また高分子材料であるがゆえに多孔質とする
ことができ、比表面積（すなわち電池反応面積）が大き
いため、大電流での充放電が可能となる。Conversely, it takes a negative charge during reduction and anions desorb to compensate for the charge. Therefore, as compared with the battery reaction (chemical reaction) of the inorganic active material, since a milder phenomenon (absorption / desorption) is used, high-speed charging / discharging becomes possible. In addition, since it is a polymer material, it can be made porous and has a large specific surface area (that is, a battery reaction area).
【００１３】したがって、リチウム−金属複合酸化物の
無機系活物質をもつ電極に、導電性高分子を含有させる
ことにより、無機系活物質の充放電能力（高容量）は維
持しながら、それと平行して導電性高分子の高速充放電
特性を利用することにより高出力密度、高回生密度化お
よび更なる高容量化が可能となる。（なお、正極におい
て一般的に活物質間および集電体間に結着材としてのＰ
ＶＤＦ等を含有させているが、導電性高分子自体が結着
材として機能できるため、電池反応に関与しないＰＶＤ
Ｆ等を含有させる必要がなく、より高容量化することが
可能となる。）しかし、単純に無機系活物質と導電性高
分子とを混合させるだけでは、電池の長寿命化を満足さ
せることができず、無機系活物質と導電性高分子とのマ
ッチングが必要となる。リチウム二次電池における（特
に）高温下での劣化は、主として電解液と正極活物質と
の副反応に起因すると考えられる。Therefore, by adding a conductive polymer to an electrode having a lithium-metal composite oxide inorganic active material, the charge / discharge capability (high capacity) of the inorganic active material can be maintained while maintaining the same. By utilizing the high-speed charge / discharge characteristics of the conductive polymer, high output density, high regenerative density, and further higher capacity can be achieved. (In general, P as a binder between the active material and the current collector in the positive electrode
Although it contains VDF etc., since the conductive polymer itself can function as a binder, PVD which does not participate in the battery reaction
It is not necessary to contain F or the like, and it is possible to further increase the capacity. However, simply mixing the inorganic active material with the conductive polymer cannot satisfy the requirement for longer battery life, and requires matching between the inorganic active material and the conductive polymer. . It is considered that deterioration of the lithium secondary battery at (especially) high temperature is mainly caused by a side reaction between the electrolyte and the positive electrode active material.
【００１４】したがって、長寿命化させるためにはこの
副反応を抑制する必要がある。本発明者らの検討の結
果、主たる活物質としてＢＥＴ比表面積が１．５ｍ2／
ｇ以下のリチウム−金属複合酸化物を用いることによ
り、高温下（６０℃）でのサイクル特性（寿命）が顕著
に向上することを発見した。すなわち、主たる活物質の
リチウム−金属複合酸化物のＢＥＴ比表面積を一定以下
に規定することにより、無機系活物質と電解液との反応
面積を低下できるため副反応の進行も抑制できたものと
考えられる。なお、含有する導電性高分子は、マイルド
な充放電反応特性をもつので、比表面積が大きくても、
充放電時の化学的な副反応による劣化が非常に小さくて
済むので、導電性高分子の比表面積が電池性能に与える
影響は非常に小さくて済んだものと考えられる。Therefore, in order to extend the life, it is necessary to suppress this side reaction. As a result of the study by the present inventors, the BET specific surface area was 1.5 m 2 /
It has been found that by using a lithium-metal composite oxide of not more than g, the cycle characteristics (life) at a high temperature (60 ° C.) are remarkably improved. That is, by defining the BET specific surface area of the lithium-metal composite oxide of the main active material to be equal to or less than a certain value, the reaction area between the inorganic active material and the electrolyte can be reduced, so that the progress of the side reaction can be suppressed. Conceivable. In addition, since the conductive polymer contained has mild charge-discharge reaction characteristics, even if the specific surface area is large,
Since the deterioration due to the chemical side reaction at the time of charge / discharge can be very small, it is considered that the influence of the specific surface area of the conductive polymer on the battery performance is very small.
【００１５】本発明は以上の知見に基づいてなされたも
のである。すなわち、本発明の非水電解質二次電池は、
リチウムを電気化学的に吸蔵・放出し得る材料で形成さ
れた負極と、リチウム−金属複合酸化物からなる主たる
正極活物質と導電性高分子とをもつ正極と、非水電解質
とを有する非水電解質二次電池であって、前記リチウム
−金属複合酸化物はＢＥＴ比表面積が１．５ｍ2／ｇ以
下であることを特徴とする。The present invention has been made based on the above findings. That is, the non-aqueous electrolyte secondary battery of the present invention,
A negative electrode formed of a material capable of electrochemically storing and releasing lithium, a positive electrode having a main positive electrode active material composed of a lithium-metal composite oxide and a conductive polymer, and a non-aqueous solution having a non-aqueous electrolyte An electrolyte secondary battery, wherein the lithium-metal composite oxide has a BET specific surface area of 1.5 m 2 / g or less.
【００１６】そして、前記正極活物質が前記導電性高分
子により被覆されていることが好ましい。導電性高分子
は電子伝導性があるので電極合材中（無機系活物質間）
の電子伝導性を高めることができると同時に、無機系活
物質表面への電解液の直接的な接触を低減することが可
能であり前述の電解液−無機系活物質間での副反応を抑
制することができる。したがって、より高い出力密度お
よび回生密度と、さらなる長寿命化とを図ることができ
る。Preferably, the positive electrode active material is coated with the conductive polymer. Since the conductive polymer has electronic conductivity, it is in the electrode mixture (between inorganic active materials)
And at the same time, it is possible to reduce the direct contact of the electrolyte with the surface of the inorganic active material, thereby suppressing the above-mentioned side reaction between the electrolyte and the inorganic active material. can do. Therefore, higher output density and regenerative density and further extension of life can be achieved.
【００１７】また、前記正極活物質の結晶構造が主とし
て層状構造であることが好ましい。層状構造の材料を用
いると、充放電時の構造変化の影響と考えられるが、充
放電による電圧の偏りが少なく（平均電圧：約３．８Ｖ
以下）、バランスよく高出力密度および高回生密度を得
ることができる。結晶構造が層状構造をもつ正極活物質
としては、リチウムニッケルコバルトアルミ含有複合酸
化物、リチウムマンガンアルミ含有複合酸化物、リチウ
ムマンガンクロム含有複合酸化物から選ばれる１種以上
を含有することがさらに好ましい。It is preferable that the crystal structure of the positive electrode active material is mainly a layered structure. The use of a material having a layered structure is considered to be affected by a structural change during charge and discharge.
Below), high output density and high regenerative density can be obtained in a well-balanced manner. As the positive electrode active material having a crystal structure having a layered structure, it is more preferable to contain at least one selected from a lithium nickel cobalt aluminum-containing composite oxide, a lithium manganese aluminum-containing composite oxide, and a lithium manganese chromium-containing composite oxide. .
【００１８】さらに、前記導電性高分子はポリアニリン
であることが好ましい。ポリアニリンを用いた場合に、
その電池反応は４Ｖ程度（以上）まで可能であり、上記
４Ｖ級の無機系リチウム−金属複合酸化物とのマッチン
グ（電池としての使用電圧範囲の調整）が容易であるか
らである。Further, it is preferable that the conductive polymer is polyaniline. When using polyaniline,
This is because the battery reaction can be performed up to about 4 V (or more), and matching with the above-mentioned 4 V-class inorganic lithium-metal composite oxide (adjustment of the operating voltage range as a battery) is easy.
【００１９】そして、前記負極は負極活物質として炭素
材料をもつことが好ましい。一般的に負極活物質として
はリチウム、リチウムスズ合金、リチウムアルミ合金等
の金属負極、また炭素のようにリチウムを電気化学的に
吸蔵、放出し得る材料などがある。そのなかで、炭素材
料を用いると、比表面積が非常に大きいので反応面積も
大きくでき、大電流を流した時の充放電特性や高出力特
性を向上できるからである。なお、炭素材料を用いれ
ば、内部抵抗は正極に比べて圧倒的に小さくなるため、
負極側の影響はほとんど無視できる。The negative electrode preferably has a carbon material as a negative electrode active material. In general, as the negative electrode active material, there are a metal negative electrode such as lithium, a lithium tin alloy, and a lithium aluminum alloy, and a material such as carbon that can electrochemically occlude and release lithium. Among them, when a carbon material is used, the reaction area can be increased because the specific surface area is very large, and the charge / discharge characteristics and high output characteristics when a large current flows can be improved. If a carbon material is used, the internal resistance is significantly smaller than that of the positive electrode,
The effect on the negative electrode side can be almost ignored.
【００２０】さらに前記正極は炭素材料からなる導電助
剤をもつことが好ましい。正極に炭素材料を用いること
で正極内部の材料の表面積が増加し、その表面に導電性
高分子が被覆でき（導電性高分子の比表面積が増加す
る。）、電池の高出力化が可能となる。Further, it is preferable that the positive electrode has a conductive assistant made of a carbon material. By using a carbon material for the positive electrode, the surface area of the material inside the positive electrode increases, and the surface can be coated with a conductive polymer (the specific surface area of the conductive polymer increases), which can increase the output of the battery. Become.
【００２１】そしてさらに前記導電性高分子は可溶性で
あることが好ましい。溶媒に溶解させることが可能とな
り、正極を作成する場合に容易に表面を被覆することが
できるからである。Further, it is preferable that the conductive polymer is soluble. This is because it can be dissolved in a solvent and the surface can be easily coated when a positive electrode is prepared.
【００２２】[0022]
【発明の実施の形態】以下に本発明の非水電解質二次電
池をリチウム二次電池に適用した実施形態に基づいて説
明する。なお、本発明は、以下の実施形態により限定さ
れるものではない。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The non-aqueous electrolyte secondary battery of the present invention will be described below based on an embodiment in which it is applied to a lithium secondary battery. Note that the present invention is not limited by the following embodiments.
【００２３】本実施形態のリチウム二次電池は、正極と
負極と電解液とその他必要に応じた要素とからなる。本
実施形態のリチウム二次電池は、その形状には特に制限
を受けず、コイン型、円筒型、角型等、種々の形状の電
池として使用できる。本実施形態では、円筒型のリチウ
ム二次電池に基づいて説明を行う。The lithium secondary battery of the present embodiment comprises a positive electrode, a negative electrode, an electrolytic solution, and other elements as required. The shape of the lithium secondary battery of the present embodiment is not particularly limited, and can be used as batteries of various shapes such as a coin shape, a cylindrical shape, and a square shape. In the present embodiment, description will be given based on a cylindrical lithium secondary battery.
【００２４】本実施形態のリチウム二次電池は、正極お
よび負極をシート形状として両者をセパレータを介して
積層し渦巻き型に多数回巻き回した巻回体を空隙を満た
す電解液とともに所定の円筒状のケース内に収納したも
のである。正極と正極端子部とについて、そして負極と
負極端子部とについては、それぞれ電気的に接合されて
いる。In the lithium secondary battery of this embodiment, the positive electrode and the negative electrode are formed in a sheet shape, both of which are laminated via a separator, and wound in a spiral shape many times. Is stored in the case. The positive electrode and the positive electrode terminal are electrically connected to each other, and the negative electrode and the negative electrode terminal are electrically connected to each other.
【００２５】正極は、リチウムイオンを充電時には放出
し、かつ放電時には吸蔵することができるリチウム−金
属複合酸化物としての正極活物質を主成分とし、さらに
導電性高分子をもつ。ここで、正極活物質と導電性高分
子との混合比としては３．５〜２９（＝正極活物質／導
電性高分子）程度が好ましい。The positive electrode contains, as a main component, a positive electrode active material as a lithium-metal composite oxide which can release lithium ions during charging and occlude during discharging, and further has a conductive polymer. Here, the mixing ratio of the positive electrode active material and the conductive polymer is preferably about 3.5 to 29 (= positive electrode active material / conductive polymer).
【００２６】リチウム−金属複合酸化物は、電子とリチ
ウムイオンの拡散性能に優れるなど活物質の性能に優れ
る。そのため、このようなリチウムおよび遷移金属の複
合酸化物を正極活物質に用いれば、高い充放電効率と良
好なサイクル特性とが得られる。さらに正極は、正極活
物質、導電性高分子、導電助材および結着材を混合して
得られた正極合材が集電体に塗布されてなるものを用い
ることが好ましい。なお、適正な導電性高分子を選択す
ることによって、導電助材および／又は結着材をある程
度代替することができる。The lithium-metal composite oxide has excellent performance of the active material, such as excellent diffusion performance of electrons and lithium ions. Therefore, when such a composite oxide of lithium and transition metal is used for the positive electrode active material, high charge / discharge efficiency and good cycle characteristics can be obtained. Further, it is preferable to use a positive electrode obtained by applying a positive electrode mixture obtained by mixing a positive electrode active material, a conductive polymer, a conductive auxiliary material, and a binder to a current collector. By selecting an appropriate conductive polymer, the conductive auxiliary and / or the binder can be replaced to some extent.
【００２７】正極活物質（無機系活物質）は、ＢＥＴ比
表面積が１．５ｍ2／ｇ以下、好ましくは１．０ｍ2／ｇ
以下であって、少なくとも１種以上のリチウム−金属複
合酸化物を含む。ＢＥＴ比表面積は窒素を用いて測定し
た値である。The positive electrode active material (inorganic active material) has a BET specific surface area of 1.5 m 2 / g or less, preferably 1.0 m 2 / g.
And at least one or more lithium-metal composite oxides. The BET specific surface area is a value measured using nitrogen.
【００２８】正極活物質の比表面積の制御方法としては
特に制限されるものではないが、比表面積は原材料の比
表面積に大きく影響をうけるため、各正極組成に対し所
定の条件で原材料を粉砕および／又は分級し制御するこ
とが好ましい。なお、焼成し作製した後に粉砕および／
又は分級してもよい。Although the method for controlling the specific surface area of the positive electrode active material is not particularly limited, the specific surface area is greatly affected by the specific surface area of the raw material. It is preferable to control by classifying. In addition, after baking and producing, pulverization and / or
Or you may classify.
【００２９】正極活物質としては層状構造のリチウム−
金属複合酸化物であることが好ましい。層状構造のリチ
ウムニッケルコバルトアルミ含有複合酸化物、リチウム
マンガンアルミ含有複合酸化物またはリチウムマンガン
クロム含有複合酸化物を含むことが好ましい。As the positive electrode active material, lithium having a layered structure is used.
It is preferably a metal composite oxide. It is preferable to include a lithium nickel cobalt aluminum-containing composite oxide, a lithium manganese aluminum-containing composite oxide, or a lithium manganese chromium-containing composite oxide having a layered structure.
【００３０】これは、一定電圧範囲（例えば４．２Ｖ〜
３Ｖ）で充放電を行う場合、スピネル構造のリチウムマ
ンガン含有複合酸化物等は充放電電圧が高電位側に偏っ
ているため（平均充放電電圧：約４Ｖ）、充電により高
出力密度は得られるものの、充電による回生密度が小さ
くなってしまうのに対して、層状構造の材料を用いる
と、充放電時の構造変化の影響と考えられるが、充放電
による電圧の偏りが少なく（平均電圧：約３．８Ｖ以
下）、バランスよく高出力密度および高回生密度を得る
ことができる。また、層状構造のリチウムニッケル含有
複合酸化物、リチウムマンガン含有複合酸化物は、その
組成の一部をアルミやクロムで置換することがより好ま
しい。活物質内部の電子状態が変化し結晶構造が強化さ
れ高温環境下での無機正極活物質の劣化が小さくなるか
らである。This corresponds to a constant voltage range (for example, 4.2 V to
When charge / discharge is performed at 3 V), the charge / discharge voltage of the lithium manganese-containing composite oxide having a spinel structure is biased toward the high potential side (average charge / discharge voltage: about 4 V), so that a high output density can be obtained by charging. However, while the regenerative density due to charging is reduced, the use of a layered material is considered to be affected by the structural change during charging / discharging, but the bias in voltage due to charging / discharging is small (average voltage: about (3.8 V or less), and high output density and high regenerative density can be obtained in a well-balanced manner. Further, in the lithium nickel-containing composite oxide and the lithium manganese-containing composite oxide having a layered structure, it is more preferable that a part of the composition is replaced with aluminum or chromium. This is because the electronic state inside the active material changes, the crystal structure is strengthened, and the deterioration of the inorganic positive electrode active material in a high temperature environment is reduced.
【００３１】また、その他にも必要に応じて一般的なリ
チウム−金属酸化物を１種以上、混合して用いることも
できる。たとえば、Ｌｉ(1-x)ＮｉＯ2、Ｌｉ(1-x)Ｍｎ
Ｏ2、Ｌｉ(1-x)Ｍｎ2Ｏ4、Ｌｉ(1-x)ＣｏＯ2や、各々に
Ｌｉ、Ａｌ、そしてＣｒ等の遷移金属を添加または置換
した材料等である。この正極活物質の例示におけるｘは
０〜１の数を示す。In addition, if necessary, one or more kinds of general lithium-metal oxides may be used in combination. For example, Li (1-x) NiO 2 , Li (1-x) Mn
O 2 , Li (1-x) Mn 2 O 4 , Li (1-x) CoO 2, and materials to which transition metals such as Li, Al, and Cr are added or substituted, respectively. X in the example of this positive electrode active material shows the number of 0-1.
【００３２】なお、これらの正極活物質は単独で用いる
ばかりでなくこれらの正極活物質を複数混合して用いて
も良い。It should be noted that these positive electrode active materials may be used alone, or a plurality of these positive electrode active materials may be mixed and used.
【００３３】導電性高分子としては、ポリアセチレン、
ポリアニリン、ポリピロール、ポリチオフェン、ポリパ
ラフェニレン、ポリアセン、ポリアズレン、ポリフェニ
レンビニレン等が例示できる。この中で導電性高分子と
してはポリアニリンであることが好ましい。As the conductive polymer, polyacetylene,
Examples thereof include polyaniline, polypyrrole, polythiophene, polyparaphenylene, polyacene, polyazulene, and polyphenylenevinylene. Among them, the conductive polymer is preferably polyaniline.
【００３４】さらに正極活物質が導電性高分子により被
覆されていることが好ましい。導電性高分子によって正
極活物質を被覆するためには導電性高分子の性状として
可溶性であることが好ましい。つまり、溶媒に可溶性の
導電性高分子材料を用いれば、製造時点で導電性高分子
材料が無機活物質等の粒子の表面を均一に覆うことがで
きる。その結果、導電性高分子は電子電導性があるため
に電極合材中（無機活物質間）の電子電導性を高めるこ
とができ、更に無機正極活物質の表面での電解液の直接
的な接触を低減でき副反応（電解液との副反応等）をも
抑えることができる。したがってより出力密度・回生密
度の向上、さらなる長寿命化が図れる。It is preferable that the positive electrode active material is coated with a conductive polymer. In order to coat the positive electrode active material with the conductive polymer, it is preferable that the conductive polymer is soluble in properties. That is, when a conductive polymer material soluble in a solvent is used, the conductive polymer material can uniformly cover the surface of particles of the inorganic active material or the like at the time of manufacturing. As a result, since the conductive polymer has electron conductivity, it can enhance the electron conductivity in the electrode mixture (between the inorganic active materials), and furthermore, the direct flow of the electrolyte on the surface of the inorganic positive electrode active material can be improved. Contact can be reduced and side reactions (such as side reactions with the electrolytic solution) can also be suppressed. Therefore, the output density and the regenerative density can be further improved and the service life can be further extended.
【００３５】導電助剤としては炭素材料からなることが
好ましい。炭素材料は比表面積が大きくその表面に前述
の導電性高分子を高比表面積で被覆することができ、高
出力化に寄与することができるからである。It is preferable that the conductive assistant is made of a carbon material. This is because the carbon material has a large specific surface area and the surface thereof can be coated with the above-mentioned conductive polymer with a high specific surface area, which can contribute to high output.
【００３６】負極については、リチウムイオンを充電時
には吸蔵し、かつ放電時には放出することができれば、
その材料構成で特に限定されるものではなく、公知の材
料構成のものを用いることができる。たとえば、リチウ
ム金属、グラファイト又は非晶質炭素等の炭素材料等で
ある。そしてリチウムを電気化学的に吸蔵・放出し得る
インターカレート材料で形成された電極、特に炭素材料
を用いることが好ましい。比表面積が比較的大きく、吸
蔵、放出速度が速いため大電流での充放電特性、出力・
回生密度に対して良好となるこのように負極活物質とし
て炭素材料を用いた場合には、これに導電助材および結
着材を混合して得られた負極合材が集電体に塗布されて
なるものを用いることが好ましい。負極活物質として
は、その活物質の種類で特に限定されるものではなく、
公知の負極活物質を用いることができる。なお、出力・
回生密度のバランスを考慮すると、充放電に伴ない電圧
変化の比較的大きい炭素材料を使用することが好まし
い。また、このような炭素材料を負極活物質に用いれ
ば、高い充放電効率と良好なサイクル特性とが得られ
る。For the negative electrode, if lithium ions can be inserted during charging and released during discharging,
The material configuration is not particularly limited, and a known material configuration can be used. For example, a carbon material such as lithium metal, graphite, or amorphous carbon is used. Then, it is preferable to use an electrode formed of an intercalating material capable of occluding and releasing lithium electrochemically, particularly, a carbon material. Since the specific surface area is relatively large and the absorption and desorption rates are fast, the charge / discharge characteristics and output
When a carbon material is used as the negative electrode active material, which is good for the regenerative density, the negative electrode mixture obtained by mixing the conductive material and the binder with the carbon material is applied to the current collector. It is preferable to use those made of The negative electrode active material is not particularly limited by the type of the active material,
A known negative electrode active material can be used. In addition, output
In consideration of the balance of the regenerative density, it is preferable to use a carbon material having a relatively large voltage change accompanying charge / discharge. In addition, when such a carbon material is used for the negative electrode active material, high charge / discharge efficiency and good cycle characteristics can be obtained.
【００３７】電解液は、有機溶媒に支持塩を溶解させた
ものである。The electrolytic solution is obtained by dissolving a supporting salt in an organic solvent.
【００３８】有機溶媒は、通常リチウム二次電池の電解
液の用いられる有機溶媒であれば特に限定されるもので
はなく、例えば、カーボネート類、ハロゲン化炭化水
素、エーテル類、ケトン類、ニトリル類、ラクトン類、
オキソラン化合物等を用いることができる。特に、プロ
ピレンカーボネート、エチレンカーボネート、１，２−
ジメトキシエタン、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等及びそれらの
混合溶媒が適当である。The organic solvent is not particularly limited as long as it is an organic solvent usually used for an electrolyte of a lithium secondary battery, and examples thereof include carbonates, halogenated hydrocarbons, ethers, ketones, nitriles, and the like. Lactones,
An oxolane compound or the like can be used. In particular, propylene carbonate, ethylene carbonate, 1,2-
Dimethoxyethane, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and the like and a mixed solvent thereof are suitable.
【００３９】例に挙げたこれらの有機溶媒のうち、特
に、カーボネート類、エーテル類からなる群より選ばれ
た一種以上の非水溶媒を用いることにより、支持塩の溶
解性、誘電率および粘度において優れ、電池の充放電効
率も高いので、好ましい。By using one or more nonaqueous solvents selected from the group consisting of carbonates and ethers among these organic solvents mentioned in the examples, the solubility, dielectric constant and viscosity of the supporting salt can be improved. It is preferable because it is excellent and the charge and discharge efficiency of the battery is high.
【００４０】支持塩は、その種類が特に限定されるもの
ではないが、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣｌＯ4及び
ＬｉＡｓＦ6から選ばれる無機塩、該無機塩の誘導体、
ＬｉＳＯ3ＣＦ3、ＬｉＣ（ＳＯ3ＣＦ3）2およびＬｉＮ
（ＳＯ3ＣＦ3）2、ＬｉＮ（ＳＯ 2Ｃ2Ｆ5）2およびＬｉ
Ｎ（ＳＯ2ＣＦ3）（ＳＯ2Ｃ4Ｆ9）から選ばれる有機
塩、並びに該有機塩の誘導体の少なくとも１種であるこ
とが好ましい。The kind of the supporting salt is not particularly limited.
Not LiPF6, LiBFFour, LiClOFouras well as
LiAsF6An inorganic salt selected from: a derivative of the inorganic salt,
LiSOThreeCFThree, LiC (SOThreeCFThree)TwoAnd LiN
(SOThreeCFThree)Two, LiN (SO TwoCTwoFFive)TwoAnd Li
N (SOTwoCFThree) (SOTwoCFourF9Organic)
At least one of a salt and a derivative of the organic salt.
Is preferred.
【００４１】この支持塩により、電池性能をさらに優れ
たものとすることができ、かつその電池性能を室温以外
の温度域においてもさらに高く維持することができる。With this supporting salt, the battery performance can be further improved, and the battery performance can be maintained even higher in a temperature range other than room temperature.
【００４２】支持塩の濃度についても特に限定されるも
のではなく、用途に応じ、支持塩および有機溶媒の種類
を考慮して適切に選択することが好ましい。The concentration of the supporting salt is not particularly limited, either, and it is preferable to appropriately select the concentration in consideration of the types of the supporting salt and the organic solvent depending on the application.
【００４３】セパレータは、正極および負極を電気的に
絶縁し、電解液を保持する役割を果たすものである。た
とえば、多孔性合成樹脂膜、特にポリオレフィン系高分
子（ポリエチレン、ポリプロピレン）の多孔膜を用いれ
ばよい。なおセパレータは、正極と負極との絶縁を担保
するため、正極および負極よりもさらに大きいものとす
るのが好ましい。The separator serves to electrically insulate the positive electrode and the negative electrode and retain the electrolyte. For example, a porous synthetic resin film, particularly a porous film of a polyolefin polymer (polyethylene, polypropylene) may be used. Note that the separator is preferably larger than the positive electrode and the negative electrode in order to ensure insulation between the positive electrode and the negative electrode.
【００４４】ケースは、特に限定されるものではなく、
公知の材料、形態で作成することができる。The case is not particularly limited.
It can be made of a known material and form.
【００４５】ガスケットは、ケースと正負の両端子部の
間の電気的な絶縁と、ケース内の密閉性とを担保するも
のである。たとえば、電解液にたいして、化学的、電気
的に安定であるポリプロピレンのような高分子等から構
成できる。The gasket ensures electrical insulation between the case and both the positive and negative terminal portions and the hermeticity of the case. For example, it can be composed of a polymer such as polypropylene which is chemically and electrically stable with respect to the electrolytic solution.
【００４６】[0046]
【実施例】以下に本発明の非水電解質二次電池について
実施例に基づいて説明する。以下に示す「％」とは特に
断りのない限り質量百分率である （リチウム２次電池の作製） 〔正極〕表１に示す各試験例の構成比で、リチウム−金
属複合酸化物と、Ｎ−メチル−２−ピロリドンに対して
可溶な導電性高分子としてのポリアニリンと、導電助材
としての平均粒径１０μｍ以下の炭素材と、必要に応じ
て結着材としてのＰＶＤＦとを溶剤のＮ−メチル−２−
ピロリドン中に混合してペーストを作製した。このペー
ストをＡｌ箔集電体上に所定の重量、膜厚で塗布し、乾
燥後直径１４ｍｍの円板状に打ち抜き、加圧成形した
後、真空乾燥することで正極を製作した。EXAMPLES The non-aqueous electrolyte secondary battery of the present invention will be described below with reference to examples. “%” Shown below is a percentage by mass unless otherwise specified. (Preparation of lithium secondary battery) [Positive electrode] In the composition ratio of each test example shown in Table 1, lithium-metal composite oxide and N- Polyaniline as a conductive polymer soluble in methyl-2-pyrrolidone, a carbon material having an average particle diameter of 10 μm or less as a conductive aid, and, if necessary, PVDF as a binder were mixed with N as a solvent. -Methyl-2-
The paste was made by mixing in pyrrolidone. This paste was applied on an Al foil current collector at a predetermined weight and thickness, dried, punched out into a disk having a diameter of 14 mm, pressed, and dried under vacuum to produce a positive electrode.
【００４７】〔負極〕各試験例において用いた負極活物
質の種類を表１に示す。負極活物質としてカーボンを用
いた場合は、メソフェーズ系カーボンを９０％、バイン
ダーのＰＶＤＦを１０％の配合でＮ−メチル−２−ピロ
リドン中に混合してペーストを作製し、このペーストを
Ｃｕ箔集電体上に所定の重量、膜厚で塗布し、乾燥後直
径１５ｍｍの円板状に打ち抜き、加圧成形した後、真空
乾燥することで負極を製作した。[Negative Electrode] Table 1 shows the types of negative electrode active materials used in each test example. When carbon is used as the negative electrode active material, a paste is prepared by mixing 90% of mesophase-based carbon and 10% of PVDF as a binder in N-methyl-2-pyrrolidone to prepare a paste, and paste this paste into a Cu foil. A negative electrode was manufactured by applying a predetermined weight and film thickness on an electric body, drying, punching out into a disk having a diameter of 15 mm, press-forming, and vacuum drying.
【００４８】負極活物質として金属Ｌｉを用いた場合
は、Ｌｉ金属箔を直径１５ｍｍの円板状に打ち抜き、こ
れを用いた。When metal Li was used as the negative electrode active material, a Li metal foil was punched into a disk having a diameter of 15 mm and used.
【００４９】〔電解液〕エチレンカーボネートとジメチ
ルカーボネートとを体積比３：７にて混合した混合溶媒
に、ＬｉＰＦ6を１ｍｏｌ／Ｌの濃度で溶解させ、電解
液とした。 〔電池の組み立て〕上記の正極、負極及び電解液を使用
して、直径２０ｍｍ、厚み約３ｍｍの偏平形の本発明電
池を組み立て各試験例の電池とした。なお、セパレ−タ
にはポリエチレン製の微多孔膜を使用した。[Electrolyte] LiPF 6 was dissolved at a concentration of 1 mol / L in a mixed solvent obtained by mixing ethylene carbonate and dimethyl carbonate at a volume ratio of 3: 7 to prepare an electrolyte. [Assembly of Battery] Using the above-mentioned positive electrode, negative electrode and electrolyte solution, a flat type battery of the present invention having a diameter of 20 mm and a thickness of about 3 mm was assembled as batteries of each test example. In addition, a polyethylene microporous membrane was used as a separator.
【００５０】[0050]
【表１】 [Table 1]
【００５１】（正極活物質の特性評価及びリチウム２次
電池の高温特性評価） 〔正極活物質の評価〕各試験例で用いた無機系活物質の
比表面積を評価した。比表面積はＮ2吸着によるＢＥＴ
法をもちいて測定した。表１に測定結果を示す。(Evaluation of Characteristics of Positive Electrode Active Material and Evaluation of High Temperature Characteristics of Lithium Secondary Battery) [Evaluation of positive electrode active material] The specific surface area of the inorganic active material used in each test example was evaluated. Specific surface area is BET by N 2 adsorption
It measured using the method. Table 1 shows the measurement results.
【００５２】〔充放電容量評価〕各試験例の電池の充放
電容量を評価した。条件としては、室温にて充電を１．
１ｍＡ／ｃｍ2の一定電流で４．２Ｖまで行い、その
後、４．２Ｖの定電圧で充電時間が合計４時間となるま
で行った。そして放電は０．５ｍＡ／ｃｍ2の一定電流
で３Ｖまで行い、これを５サイクル繰り返した。表１に
５サイクル目の放電容量を示す。[Evaluation of Charge / Discharge Capacity] The charge / discharge capacity of the battery of each test example was evaluated. As conditions, charging at room temperature is 1.
The test was performed at a constant current of 1 mA / cm 2 up to 4.2 V, and then at a constant voltage of 4.2 V until the charging time reached a total of 4 hours. The discharge was performed at a constant current of 0.5 mA / cm 2 up to 3 V, and this was repeated 5 cycles. Table 1 shows the discharge capacity at the fifth cycle.
【００５３】〔高温サイクル特性評価〕各試験例の電池
を用い高温サイクル特性評価を行った。条件としては、
充放電容量評価した電池を一定温度（６０℃）とした恒
温槽のなかで、２．２ｍＡ／ｃｍ2の一定電流で、電池
極間電圧が４．２Ｖから３Ｖの間で充放電を繰り返し
た。表１に１サイクル目の放電容量に対する１００サイ
クル目の放電容量の割合、すなわちサイクル後容量維持
率を示す。[Evaluation of high-temperature cycle characteristics] High-temperature cycle characteristics were evaluated using the batteries of the respective test examples. The condition is
The charge / discharge was repeated at a constant current of 2.2 mA / cm 2 at a voltage between the battery electrodes of 4.2 V to 3 V in a constant temperature bath at a constant temperature (60 ° C.) of the battery whose charge / discharge capacity was evaluated. . Table 1 shows the ratio of the discharge capacity at the 100th cycle to the discharge capacity at the first cycle, that is, the capacity retention rate after the cycle.
【００５４】〔出力・回生密度評価〕各試験例の電池を
用いて出力特性および回生特性の評価を行った。まず、
室温にて充電を１．１ｍＡ／ｃｍ2の一定電流で行い、
電池の充電状態ＳＯＣを５０％（ＳＯＣ：Ｓｔａｔｅ
ｏｆ Ｃｈａｒｇｅ）に調整した。そして電池の作動電
圧範囲を４．２Ｖから３Ｖの範囲とし、電池の放電（充
電）電流を変化させ、夫々１０秒間のパルス放電（充
電）を行い、１０秒目の電流−電圧直線を求め、そこか
ら出力および回生特性の値を算出した。表１に試験例
１、６、１１、１６の値に対する出力および回生特性の
値の比を示した。[Evaluation of Output / Regenerative Density] The output characteristics and the regenerative characteristics were evaluated using the batteries of each test example. First,
Charge at room temperature with a constant current of 1.1 mA / cm 2 ,
The state of charge SOC of the battery is reduced to 50% (SOC: State
of Charge). Then, the operating voltage range of the battery was set to a range of 4.2 V to 3 V, and the discharging (charging) current of the battery was changed, pulse discharging (charging) was performed for 10 seconds each, and a current-voltage straight line at 10 seconds was obtained. The output and the value of the regenerative characteristics were calculated therefrom. Table 1 shows the ratios of the output and regeneration characteristics to the values of Test Examples 1, 6, 11, and 16.
【００５５】（リチウム２次電池の特性評価結果）初期
容量評価、高温サイクル評価、出力・回生評価した結果
を表１に示す。(Characteristic Evaluation Results of Lithium Secondary Battery) Table 1 shows the results of the initial capacity evaluation, high-temperature cycle evaluation, output / regeneration evaluation.
【００５６】まず、同一組成を有する正極活物質間で比
較する。比表面積が１．５ｍ2／ｇ以下である試験例
１、２〜６、８〜１１、１３〜１６、１８、１９の電池
は正極活物質の比表面積の値が１．５ｍ2／ｇを超えた
正極活物質を用いた試験例２、７、１２、１７の電池よ
りもサイクル後容量維持率の値が９〜２０％程度高くな
った。したがって、正極活物質の比表面積は１．５ｍ2
／ｇ以下とすることが好ましい。First, a comparison is made between positive electrode active materials having the same composition. The batteries of Test Examples 1, 2 to 6, 8 to 11, 13 to 16, 18, and 19 having a specific surface area of 1.5 m 2 / g or less have a specific surface area of the positive electrode active material of 1.5 m 2 / g. The value of the capacity retention after cycling was higher by about 9 to 20% than in the batteries of Test Examples 2, 7, 12, and 17 using the positive electrode active material in excess. Therefore, the specific surface area of the positive electrode active material is 1.5 m 2
/ G or less.
【００５７】次に負極活物質としてカーボンを用いた試
験例１〜４、６〜９、１１〜１４の電池は負極活物質と
して金属Ｌｉを用いた試験例５、１０、１５の電池と比
較して出力比、回生比の値が著しく向上している。した
がって負極活物質としてはカーボンを用いることが好ま
しい。さらに負極活物質に同じくカーボンを用いた試験
例の電池であっても導電性高分子を正極に含有させた試
験例２〜４、７〜９、１２〜１４の電池は導電性高分子
を含有しない試験例１、６、１１の電池と比較してさら
に出力比および回生比が著しく向上した。これは正極活
物質にＬｉＭｎ 1.75Ａｌ0.25Ｏ4を含有する試験例１６
〜１９の電池についても同様である。したがって、正極
には導電性高分子を含有させることが好ましい。Next, a test using carbon as the negative electrode active material was performed.
The batteries of Experimental Examples 1-4, 6-9, and 11-14 correspond to the negative electrode active material.
To the batteries of Test Examples 5, 10, and 15 using metal Li
In comparison, the values of the output ratio and the regeneration ratio are remarkably improved. did
Therefore, it is preferable to use carbon as the negative electrode active material.
New Further tests using carbon as the negative electrode active material
Even in the case of the example battery, a test was conducted in which the conductive polymer was contained in the positive electrode.
The batteries of Experimental Examples 2 to 4, 7 to 9, and 12 to 14 are conductive polymers.
In comparison with the batteries of Test Examples 1, 6, and 11 containing no
In addition, the output ratio and the regenerative ratio improved remarkably. This is the positive electrode
LiMn for substance 1.75Al0.25OFourTest Example 16 containing
The same applies to the batteries No. to No. 19. Therefore, the positive electrode
Preferably contains a conductive polymer.
【００５８】さらに、層状構造をもつ正極活物質を用い
た試験例１〜１５の電池はスピネル構造をもつ正極活物
質を用いた試験例１６〜１９の電池と比較して回生／出
力の値が大きくでき、効率よく回生できることがわかっ
た。したがって、正極活物質としては層状構造を有する
ことが好ましい。Furthermore, the batteries of Test Examples 1 to 15 using the positive electrode active material having a layered structure had lower regeneration / output values than the batteries of Test Examples 16 to 19 using the positive electrode active material having a spinel structure. It was found that it could be enlarged and regenerated efficiently. Therefore, the positive electrode active material preferably has a layered structure.
【００５９】すなわち、負極としてリチウムを電気化学
的に吸蔵、放出し得る材料で形成された電極を用い、正
極活物質としてＢＥＴ比表面積が１．５ｍ2／ｇ以下の
少なくとも一種以上のリチウム−金属複合酸化物を用い
た正極（電極）において、導電性高分子を含有すること
により、高エネルギー密度、高温環境下における長寿命
特性に加えて、大電流での充放電が可能で、高出力密度
・高回生密度の電池を得ることが可能となることが明ら
かとなった。That is, an electrode made of a material capable of electrochemically absorbing and releasing lithium is used as a negative electrode, and at least one lithium-metal having a BET specific surface area of 1.5 m 2 / g or less is used as a positive electrode active material. Positive electrode (electrode) using composite oxide contains conductive polymer, which enables high energy density, long life under high temperature environment, high charge / discharge with large current, and high output density -It became clear that a battery with high regenerative density can be obtained.
【００６０】[0060]
【発明の効果】本発明の非水電解質二次電池により、高
エネルギー密度、高温環境下における長寿命特性に加え
て、大電流での充放電が可能で、高出力密度・高回生密
度の電池を得ることが可能となるという効果がある。According to the non-aqueous electrolyte secondary battery of the present invention, in addition to a high energy density and a long life under a high temperature environment, a charge / discharge with a large current is possible, and a high output density and a high regenerative density battery are provided. Is obtained.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 5H029 AJ02 AJ03 AJ05 AK03 AL06 AM03 AM04 AM05 AM07 DJ08 DJ17 EJ13 HJ07 HJ13 5H050 AA02 AA05 AA07 BA17 CA08 CA09 CB07 DA09 DA10 EA08 EA25 FA18 HA07 HA13 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 5H029 AJ02 AJ03 AJ05 AK03 AL06 AM03 AM04 AM05 AM07 DJ08 DJ17 EJ13 HJ07 HJ13 5H050 AA02 AA05 AA07 BA17 CA08 CA09 CB07 DA09 DA10 EA08 EA25 FA18 HA07 HA13
Claims (8)
る材料で形成された負極と、リチウム−金属複合酸化物
からなる主たる正極活物質と導電性高分子とをもつ正極
と、非水電解質とを有する非水電解質二次電池であっ
て、 前記リチウム−金属複合酸化物はＢＥＴ比表面積が１．
５ｍ2／ｇ以下であることを特徴とする非水電解質二次
電池。1. A negative electrode formed of a material capable of electrochemically storing and releasing lithium, a positive electrode having a main positive electrode active material comprising a lithium-metal composite oxide and a conductive polymer, and a non-aqueous electrolyte And a lithium-metal composite oxide having a BET specific surface area of 1.
A non-aqueous electrolyte secondary battery having a density of 5 m 2 / g or less.
り被覆されていることを特徴とする請求項１に記載の非
水電解質二次電池。2. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode active material is coated with the conductive polymer.
状構造である請求項１又は２に記載の非水電解質二次電
池。3. The non-aqueous electrolyte secondary battery according to claim 1, wherein the crystal structure of the positive electrode active material is mainly a layered structure.
ッケルコバルトアルミ含有複合酸化物、リチウムマンガ
ンアルミ含有複合酸化物、リチウムマンガンクロム含有
複合酸化物から選ばれる１種以上を含有する請求項３に
記載の非水電解質二次電池。4. The positive electrode active material according to claim 3, wherein the positive electrode active material contains at least one selected from a lithium nickel cobalt aluminum-containing composite oxide, a lithium manganese aluminum-containing composite oxide, and a lithium manganese chromium-containing composite oxide. Non-aqueous electrolyte secondary battery.
請求項１〜４のいずれかに記載の非水電解質二次電池。5. The non-aqueous electrolyte secondary battery according to claim 1, wherein the conductive polymer is polyaniline.
もつ請求項１〜５のいずれかに記載の非水電解質二次電
池。6. The non-aqueous electrolyte secondary battery according to claim 1, wherein the negative electrode has a carbon material as a negative electrode active material.
もつ請求項１〜６のいずれかに記載の非水電解質二次電
池。7. The non-aqueous electrolyte secondary battery according to claim 1, wherein the positive electrode has a conductive additive made of a carbon material.
１〜７のいずれかに記載の非水電解質二次電池。8. The non-aqueous electrolyte secondary battery according to claim 1, wherein the conductive polymer is soluble.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001031362A JP2002237301A (en) | 2001-02-07 | 2001-02-07 | Nonaqueous electrolytic solution secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001031362A JP2002237301A (en) | 2001-02-07 | 2001-02-07 | Nonaqueous electrolytic solution secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002237301A true JP2002237301A (en) | 2002-08-23 |
Family
ID=18895458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001031362A Pending JP2002237301A (en) | 2001-02-07 | 2001-02-07 | Nonaqueous electrolytic solution secondary battery |
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| Country | Link |
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| JP (1) | JP2002237301A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012248478A (en) * | 2011-05-30 | 2012-12-13 | Denso Corp | Lithium ion secondary battery |
| US9887430B2 (en) | 2010-03-19 | 2018-02-06 | Toyota Jidosha Kabushiki Kaisha | Lithium secondary battery and positive electrode active material for the lithium secondary battery |
| US11031585B2 (en) | 2016-01-28 | 2021-06-08 | Sumitomo Metal Mining Co., Ltd. | Method for producing coated nickel-based lithium-nickel composite oxide particles |
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|---|---|---|---|---|
| JPH08138649A (en) * | 1994-11-09 | 1996-05-31 | Toray Ind Inc | Non-aqueous secondary battery |
| JPH09161771A (en) * | 1995-12-08 | 1997-06-20 | Ricoh Co Ltd | Nonaqueous electrolyte secondary battery |
| JPH11135119A (en) * | 1997-10-27 | 1999-05-21 | Matsushita Electric Ind Co Ltd | Active material and positive plate for nonaqueous electrolyte secondary battery, and the nonaqueous electrolyte secondary battery |
| JPH11260368A (en) * | 1998-03-13 | 1999-09-24 | Mitsubishi Cable Ind Ltd | Positive electrode active material for lithium secondary battery |
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2001
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08138649A (en) * | 1994-11-09 | 1996-05-31 | Toray Ind Inc | Non-aqueous secondary battery |
| JPH09161771A (en) * | 1995-12-08 | 1997-06-20 | Ricoh Co Ltd | Nonaqueous electrolyte secondary battery |
| JPH11135119A (en) * | 1997-10-27 | 1999-05-21 | Matsushita Electric Ind Co Ltd | Active material and positive plate for nonaqueous electrolyte secondary battery, and the nonaqueous electrolyte secondary battery |
| JPH11260368A (en) * | 1998-03-13 | 1999-09-24 | Mitsubishi Cable Ind Ltd | Positive electrode active material for lithium secondary battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9887430B2 (en) | 2010-03-19 | 2018-02-06 | Toyota Jidosha Kabushiki Kaisha | Lithium secondary battery and positive electrode active material for the lithium secondary battery |
| JP2012248478A (en) * | 2011-05-30 | 2012-12-13 | Denso Corp | Lithium ion secondary battery |
| US11031585B2 (en) | 2016-01-28 | 2021-06-08 | Sumitomo Metal Mining Co., Ltd. | Method for producing coated nickel-based lithium-nickel composite oxide particles |
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