JPH0574451A - Nonaqueous battery - Google Patents
Nonaqueous batteryInfo
- Publication number
- JPH0574451A JPH0574451A JP3231367A JP23136791A JPH0574451A JP H0574451 A JPH0574451 A JP H0574451A JP 3231367 A JP3231367 A JP 3231367A JP 23136791 A JP23136791 A JP 23136791A JP H0574451 A JPH0574451 A JP H0574451A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- battery
- lithium
- cobalt
- positive 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な二次電池に関し、
特にサイクル特性に優れた二次電池に関するものであ
る。FIELD OF THE INVENTION The present invention relates to a novel secondary battery,
In particular, the present invention relates to a secondary battery having excellent cycle characteristics.
【０００２】[0002]
【従来の技術】従来より非水系二次電池は水溶液系二次
電池に比べ高電圧、高エネルギ−密度であり、自己放電
に優れるなど大いに期待されている。すなわち、従来の
鉛電池、ニッケルーカドミ電池などに代わり、層状化合
物のインターカレーションを利用する新しい型の二次電
池が注目を集めている。2. Description of the Related Art Conventionally, non-aqueous secondary batteries are highly expected to have higher voltage and higher energy density than aqueous solution secondary batteries and to be excellent in self-discharge. That is, a new type of secondary battery, which utilizes intercalation of a layered compound, has been attracting attention in place of conventional lead batteries, nickel-cadmium batteries and the like.
【０００３】例えば、層状化合物のインターカレーショ
ンを利用した例として、カルコゲナイト系化合物が挙げ
られる。例えばＬｉｘＴｉＳ2 、ＬｉｘＭｏＳ3 等のカ
ルコゲナイト系化合物正極は比較的優れたサイクル性を
有しているものの、卑な電位を有する金属リチウムを負
極に用いた場合でも、実用的な放電電圧はせいぜい２Ｖ
前後であり、非水系電池の特徴の一つである高起電力と
いう点で必ずしも満足のいくものではなかった。For example, chalcogenite compounds are mentioned as an example of utilizing the intercalation of a layered compound. For example, the positive electrode of chalcogenite compounds such as LixTiS 2 and LixMoS 3 has a relatively excellent cycle property, but even when metallic lithium having a base potential is used for the negative electrode, the practical discharge voltage is at most 2V.
However, the high electromotive force, which is one of the features of non-aqueous batteries, was not always satisfactory.
【０００４】また、リチウム複合酸化物にとらわれず、
ナトリウム、カリウムといったアルカリ金属元素を含有
する複合酸化物については、ＥＰ−Ｂ１−００１７４０
０、ＵＳ−４４９７７２６等で報告されている。一方、
バナジウム、マンガン、コバルト、ニッケル等を中心金
属とするリチウム複合酸化物を正極活物質として用いた
場合には高起電力が得られる点で注目されている。特に
特開昭５５−１３６１３１号公報、特開昭６２−９０８
６３号公報、特開昭６３−１２１２５８号公報等で開示
されているリチウムと遷移金属、更に要すれば非遷移金
属等からなる複合酸化物を正極活物質とする非水系二次
電池は３Ｖ以上の高起電力が得られ極めてエネルギ−密
度が高く、次世代の高性能二次電池として大いに期待さ
れている。更にかかる複合酸化物を正極として用いた場
合の特徴としてリチウム複合酸化物そのものが既にリチ
ウムをイオンとして含有しており、負極活物質として必
ずしも金属リチウムを用いなくても電池系を形成し得る
という特徴をも有しており、安全性の面でも優れた電池
として期待されている。Further, regardless of the lithium composite oxide,
Regarding complex oxides containing alkali metal elements such as sodium and potassium, EP-B1-001740
0, US-4497726 and the like. on the other hand,
Attention has been paid to the fact that a high electromotive force can be obtained when a lithium composite oxide containing vanadium, manganese, cobalt, nickel or the like as a central metal is used as a positive electrode active material. Particularly, JP-A-55-136131 and JP-A-62-908.
No. 63, JP-A No. 63-112258, etc., a non-aqueous secondary battery using a composite oxide composed of lithium and a transition metal and, if necessary, a non-transition metal as a positive electrode active material is 3 V or more. High electromotive force is obtained and the energy density is extremely high, and it is highly expected as a next-generation high-performance secondary battery. Further, a feature of using such a composite oxide as a positive electrode is that the lithium composite oxide itself already contains lithium as an ion, and a battery system can be formed without necessarily using metallic lithium as a negative electrode active material. Since it also has a battery, it is expected to be an excellent battery in terms of safety.
【０００５】特開昭５５ー１３６１３１号公報で開示さ
れているＬｉＣｏＯ2 は層状化合物で、コバルト酸化物
の層間にリチウムがインターカレートした構造をとって
いる。これを用いた非水系二次電池の充電反応は、正極
の複合酸化物のリチウムイオンがデインタ−カレ−ショ
ンして負極に移動し、逆に放電する場合には負極活物質
からリチウムイオンが正極活物質の層間へインタ−カレ
−ションすることによって進行する。すなわち正極の複
合酸化物のリチウムイオンが出入りする反応を繰り返す
ことによって、充放電を繰り返すことができる。LiCoO 2 disclosed in JP-A-55-136131 is a layered compound, and has a structure in which lithium is intercalated between layers of cobalt oxide. In the charging reaction of the non-aqueous secondary battery using this, the lithium ions of the composite oxide of the positive electrode deintercalate and move to the negative electrode, and in the contrary, when discharging, the lithium ions from the negative electrode active material become the positive electrode. The process proceeds by intercalating the layers of the active material. That is, charge and discharge can be repeated by repeating the reaction of lithium ions in and out of the composite oxide of the positive electrode.
【０００６】しかしながら、上述のように正極活物質と
して複合酸化物、負極活物質として金属リチウム等を用
いた電池を作成すると、これらは充放電の進行と共にリ
チウム等が劣化しパウダ−状になって、長期にわたって
使用することが困難である課題を有している。そこで、
このような課題を解決するために炭素質材料を負極電極
材料として、また正極活物質としては高い放電電位を有
することから、リチウムを含む化合物であるＬｉｘＣｏ
Ｏ2 （ｘ＝０．０５〜１．１０）を用いることが提案さ
れている。しかしながら、このような炭素質材料を負極
に用いても、ＬｉｘＣｏＯ2 （ｘ＝０．０５〜１．１
０）を正極材料に用いると、充放電の繰り返しによって
ＬｉｘＣｏＯ2 の結晶構造が徐々に壊れ、複合酸化物に
可逆的に出入り可能なリチウム量（ド−プ量）が減少し
て、サイクル劣化の一因となる。However, when a battery using the composite oxide as the positive electrode active material and metallic lithium or the like as the negative electrode active material is prepared as described above, the lithium or the like deteriorates with the progress of charging and discharging, and becomes a powder. , Has a problem that it is difficult to use for a long time. Therefore,
In order to solve such a problem, a carbonaceous material is used as a negative electrode material, and a positive electrode active material has a high discharge potential. Therefore, LixCo, which is a compound containing lithium, is used.
It has been proposed to use O 2 (x = 0.05 to 1.10). However, even if such a carbonaceous material is used for the negative electrode, LixCoO 2 (x = 0.05 to 1.1) is used.
When 0) is used as the positive electrode material, the crystal structure of LixCoO 2 is gradually broken by repeated charging and discharging, and the amount of lithium (doping amount) that can reversibly move in and out of the composite oxide decreases, resulting in cycle deterioration. Contribute.
【０００７】一方、特開平２−２７８６５７号公報では
負極に金属リチウムを用い、正極にナトリウム・コバル
ト酸化物を用いることを提案している。特開昭５５ー１
３６３１号公報で得られるＬｉＣｏＯ2 はα型構造であ
るのに対し、ここで得られるのはγ型のＮａＣｏＯ2 で
ある。ＮａＣｏＯ2 からＮａを約半分抜いたＮａ0.5 Ｃ
ｏＯ2 を作成し、これを正極に用いるとサイクル性が大
幅に改善されることが開示されている。しかし、γ型の
ＮａＣｏＯ2 の合成には、急速昇温、急速降温を避けて
焼成する必要があるために合成時間が長くかかり、また
電極として使用する場合、予め過剰のＮａを抜くという
煩雑な操作が必要となる。On the other hand, JP-A-2-278657 proposes to use metallic lithium for the negative electrode and sodium-cobalt oxide for the positive electrode. JP 55-1
LiCoO 2 obtained in Japanese Patent No. 3631 has an α-type structure, whereas γ-type NaCoO 2 is obtained here. Na 0.5 C obtained by removing about half of Na from NaCoO 2.
It is disclosed that when oO 2 is prepared and used for the positive electrode, the cycle property is significantly improved. However, the synthesis of γ-type NaCoO 2 requires a long synthesis time because it needs to be fired while avoiding a rapid temperature rise / fall, and when used as an electrode, it is complicated to remove excess Na in advance. Operation is required.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上述のような
問題を解決し、非水系二次電池の充放電の繰り返しによ
る正極活物質の劣化を防止し，長期間充放電を繰り返す
ことのできる信頼性の高い非水系二次電池を提供するこ
とを目的として、提案されたものである。The present invention can solve the above problems, prevent deterioration of the positive electrode active material due to repeated charging / discharging of a non-aqueous secondary battery, and can repeat charging / discharging for a long period of time. It has been proposed for the purpose of providing a highly reliable non-aqueous secondary battery.
【０００９】[0009]
【課題を解決するための手段】上記問題点を解決するた
めに本発明者は鋭意検討した結果、リチウム−コバルト
酸化物のリチウムの一部をナトリウムで置換した複合酸
化物が充放電を繰り返しても構造変化が少なく、サイク
ル性に優れていることを見い出し、本発明を完成するに
至った。すなわち本発明は、ＬｉｘＮａｙＭＯｚ（Ｍは
コバルト、或いはコバルトを主体としニッケル、マンガ
ンの少なくとも一種を少量含む混合金属を表す。ｘは
０．２０≦ｘ≦１．１０、ｙは０．０１≦ｙ≦０．３
０、ｚは１．９５≦ｚ≦２．４５の各数である）を正極
活物質とする非水系二次電池を提供せんとするものであ
る。Means for Solving the Problems As a result of intensive studies by the present inventors in order to solve the above problems, as a result, a composite oxide obtained by substituting a part of lithium of lithium-cobalt oxide with sodium was repeatedly charged and discharged. However, the present invention has been completed by discovering that there is little structural change and excellent cycleability. That is, the present invention represents LixNayMOz (M is cobalt, or a mixed metal mainly containing cobalt and containing a small amount of at least one of nickel and manganese. X is 0.20 ≦ x ≦ 1.10 and y is 0.01 ≦ y ≦. 0.3
0 and z are each numbers of 1.95 ≦ z ≦ 2.45) as a positive electrode active material.
【００１０】以下本発明を詳細に説明する。上記Ｌｉｘ
ＮａｙＭＯｚはＬｉ、Ｎａ、Ｍ各々の金属の酸化物、水
酸化物、炭酸塩、硝酸塩、有機酸塩等を混合せしめた
後、空気中または酸素雰囲気下において６００〜１００
０℃、好ましくは８００〜９６０℃の温度範囲で焼成す
ることにより得られる。ここで、ナトリウムの置換比率
は特に制限されないが、放電容量、自己放電率を考慮す
れば、コバルトに対して１％以上、３０％以下であるこ
とが好ましい。より好ましくは２％以上、２０％以下で
ある。The present invention will be described in detail below. Lix above
NayMOz is a mixture of Li, Na and M metal oxides, hydroxides, carbonates, nitrates, organic acid salts, etc., and then 600 to 100 in air or in an oxygen atmosphere.
It is obtained by firing in a temperature range of 0 ° C, preferably 800 to 960 ° C. Here, the substitution ratio of sodium is not particularly limited, but considering the discharge capacity and the self-discharge rate, it is preferably 1% or more and 30% or less with respect to cobalt. It is more preferably 2% or more and 20% or less.
【００１１】ナトリウムの置換の効果については未だ明
確ではないが、リチウムとはイオン半径の異なるナトリ
ウムで置換することにより、結晶構造が適度に歪み、リ
チウムのインターカレーション、デインターカレーショ
ンが容易になり、さらにリチウムがデインターカレーシ
ョンした際の結晶構造の崩壊を防ぎ、電池のサイクル性
を向上させることが考えられる。Although the effect of sodium substitution has not been clarified yet, substitution with sodium having an ionic radius different from that of lithium causes moderate distortion of the crystal structure and facilitates lithium intercalation and deintercalation. In addition, it is possible to prevent the crystal structure from collapsing when lithium is deintercalated and improve the cycleability of the battery.
【００１２】本発明で正極活物質として用いる一般式Ｌ
ｉｘＮａｙＭＯｚで示されるリチウム複合酸化物におい
て、Ｍはコバルト、あるいはコバルトを主体としニッケ
ル、マンガンの少なくとも一種を少量含む混合金属を表
す。ここで、少量とはコバルトに対し、３０％以下程度
をいう。またｘの値は、充電状態、放電状態により変動
し、その範囲は０．２０≦ｘ≦１．１０である。The general formula L used as the positive electrode active material in the present invention
In the lithium composite oxide represented by ixNayMOz, M represents cobalt or a mixed metal mainly containing cobalt and containing a small amount of at least one of nickel and manganese. Here, the small amount means about 30% or less with respect to cobalt. The value of x varies depending on the charge state and the discharge state, and the range is 0.20 ≦ x ≦ 1.10.
【００１３】またｙの値は０．０１≦ｙ≦０．３０であ
り、基本的には充電、放電により変動しないが、複合酸
化物の焼成条件によっては、充電時に若干のナトリウム
イオンがデインターカレーションすることもある。ｙの
値が０．０１未満、０．３０を超える場合には、放電容
量、サイクル性の低下、自己放電率の増加などの現象が
発生し、二次電池用活物質として充分な性能が得られず
好ましくない。The value of y is 0.01≤y≤0.30 and basically does not fluctuate due to charging and discharging, but some sodium ions may be deintercalated during charging depending on the firing conditions of the composite oxide. Sometimes curated. When the value of y is less than 0.01 or more than 0.30, phenomena such as decrease in discharge capacity, cycleability, increase in self-discharge rate occur, and sufficient performance as an active material for a secondary battery is obtained. It is not preferable because it is not possible.
【００１４】またｚの値は１．９５≦ｚ≦２．４５の範
囲であり、焼成時の雰囲気およびアルカリ金属の組成比
によって変動する。本発明でいうドープ量とは、充放電
時に可逆的に移動するリチウム量をいい、実施例中で用
いられるドープ量は、コバルトを基準として複合酸化物
中のリチウムの何パーセントが可逆的に移動するかを表
す。The value of z is in the range of 1.95≤z≤2.45, and varies depending on the atmosphere during firing and the composition ratio of the alkali metal. The doping amount in the present invention refers to the amount of lithium that reversibly moves during charge and discharge, and the doping amount used in the examples is the percentage of lithium in the composite oxide that moves reversibly based on cobalt. Indicates whether to do.
【００１５】本発明の複合酸化物を用いて正極を作成す
るときには、有機重合体をバインダーとして用いること
ができる。その際には、該有機重合体を溶媒に溶解せし
めたバインダー溶液に電極活物質を分散せしめたものを
塗工液として用いる方法、また、該有機重合体の水乳化
分散液に電極活物質を分散せしめたものを塗工液として
用いる方法、予め予備成形された電極活物質に該有機重
合体の溶液及び／または分散液を塗布する方法等が一例
として挙げられる。用いるバインダー量は特に限定され
るものではないが、通常、電極活物質１００重量部に対
し０．１〜２０重量部、好ましくは０．５〜１０重量部
の範囲である。When a positive electrode is prepared using the composite oxide of the present invention, an organic polymer can be used as a binder. In that case, a method of using as a coating solution a dispersion of an electrode active material in a binder solution prepared by dissolving the organic polymer in a solvent, and the electrode active material in a water-emulsion dispersion of the organic polymer. As an example, a method of using the dispersed material as a coating solution, a method of applying a solution and / or a dispersion of the organic polymer to a preformed electrode active material, and the like can be given. The amount of binder used is not particularly limited, but is usually in the range of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the electrode active material.
【００１６】ここで用いられる有機重合体は特に限定さ
れるものではないが、該有機重合体が２５℃、周波数１
ｋＨｚにおける比誘電率が４．５以上の値を有する場
合、特に好ましい結果をもたらし、特に電池性能とし
て、サイクル性、過電圧等の面で優れた特性を有する。
かかる条件を満たす有機重合体の一例を示せば、アクリ
ロニトリル、メタクリニトリル、フッ化ビニル、フッ化
ビニリデン、クロロプレン、塩化ビニリデン等の重合体
もしくは共重合体、ニトロセルロース、シアノエチルセ
ルロース、多硫化ゴム等が挙げられる。The organic polymer used here is not particularly limited, but the organic polymer is 25 ° C., frequency 1
When the relative permittivity in kHz has a value of 4.5 or more, particularly preferable results are brought about, and particularly, the battery performance has excellent characteristics in terms of cycleability, overvoltage and the like.
Examples of organic polymers satisfying such conditions include acrylonitrile, methacrylonitrile, vinyl fluoride, vinylidene fluoride, chloroprene, vinylidene chloride, and other polymers or copolymers, nitrocellulose, cyanoethyl cellulose, polysulfide rubber, and the like. Can be mentioned.
【００１７】かかる方法により電極を製造するに際し、
前記塗工液を基材上に塗布乾燥することにより成形され
る。この時要すれば、集電体材料と共に成形しても良い
し、また別法としてアルミ箔、ニッケル箔、チタン箔、
銅箔、ＳＵＳ箔、モリブデン箔等の集電体を基材として
用いることもできる。本発明の活物質を用いて製造され
る電池電極には、前記バインダー、導電補助剤、その他
添加剤、例えば増粘剤、分散剤、増量剤、粘着補助剤等
が添加されても良いが、少なくとも本発明の活物質が２
５重量％以上含まれているものをいう。 導電補助剤と
しては、金属粉、導電金属酸化物粉、カーボン等が挙げ
られる。特にかかる導電補助剤の添加は本発明の活物質
を用いる場合に顕著な効果が見い出せる。When manufacturing an electrode by such a method,
It is formed by coating the coating liquid on a substrate and drying. At this time, if necessary, it may be molded together with the current collector material, or alternatively, aluminum foil, nickel foil, titanium foil,
A current collector such as copper foil, SUS foil, molybdenum foil can also be used as the base material. To the battery electrode manufactured using the active material of the present invention, the binder, the conductive auxiliary agent, and other additives, such as a thickener, a dispersant, a bulking agent, an adhesion auxiliary agent may be added, At least 2 active materials of the present invention
It means that the content is 5% by weight or more. Examples of the conductive auxiliary agent include metal powder, conductive metal oxide powder, carbon and the like. In particular, the addition of such a conductive auxiliary agent can find a remarkable effect when the active material of the present invention is used.
【００１８】中でも、好ましい結果を与えるのはカーボ
ンであり、通常活物質１００重量部に対して１〜３０重
量部の添加により著しい過電圧の低下効果が発現し、優
れたサイクル性を発揮する。ここでいうカーボンとは、
負極炭素質材料とは異なる特性が要求されるものであ
り、必ずしも特定されたカーボンを意味するものではな
いが、一例としてグラファイト、カーボンブラック等が
挙げられる。特に好ましい組合せとして、平均粒径０．
１〜１０ミクロンのカーボンと平均粒径０．０１〜０．
０８ミクロンのカーボンを混合して用いた場合、特に優
れた効果を与える。Among them, carbon gives a preferable result. Usually, the addition of 1 to 30 parts by weight to 100 parts by weight of the active material exerts a remarkable effect of lowering the overvoltage and exhibits excellent cycleability. The carbon here means
It requires properties different from those of the negative electrode carbonaceous material and does not necessarily mean the specified carbon, but examples thereof include graphite and carbon black. A particularly preferred combination is an average particle size of 0.
1 to 10 micron carbon and average particle size 0.01 to 0.
A particularly excellent effect is obtained when 08 micron of carbon is mixed and used.
【００１９】本発明で用いられる負極活物質は特に限定
されるものではないが、金属リチウム、リチウム合金、
ＬｉｘＦｅ2 Ｏ3 、ＬｉｘＷＯ2 等の金属酸化物負極、
ポリアセチレン、ポリーｐ−フェニレン等の導電性高分
子負極、ピッチ系カーボン、気相成長法炭素繊維等の炭
素質系材料等が挙げられる。特に、炭素質材料等のリチ
ウムイオンをインターカレートし得る物質を負極に用い
た場合に優れた効果が発揮される。Although the negative electrode active material used in the present invention is not particularly limited, metallic lithium, lithium alloy,
LixFe 2 O 3 , LixWO 2 and other metal oxide negative electrodes,
Examples thereof include conductive polymer negative electrodes such as polyacetylene and poly-p-phenylene, carbonaceous materials such as pitch-based carbon and vapor grown carbon fiber. In particular, when a substance capable of intercalating lithium ions such as a carbonaceous material is used for the negative electrode, excellent effects are exhibited.
【００２０】本発明の非水系二次電池を組み立てる場合
の基本構成要素として、前記本発明の活物質を用いた電
極、更にはセパレーター、非水電解液が挙げられる。セ
パレーターとしては特に限定されないが、織布、不織
布、ガラス織布、合成樹脂微多孔膜等が挙げられるが、
薄膜、大面積電極を用いる場合には、例えば特開昭５８
−５９０７２号に開示される合成樹脂微多孔膜、特にポ
リオレフィン系微多孔膜が、厚み、強度、膜抵抗の面で
好ましい。The basic components for assembling the non-aqueous secondary battery of the present invention include the electrode using the active material of the present invention, a separator, and a non-aqueous electrolyte. The separator is not particularly limited, and includes woven cloth, non-woven cloth, glass woven cloth, synthetic resin microporous membrane, and the like.
When using a thin film or a large area electrode, for example, Japanese Patent Laid-Open No.
The synthetic resin microporous membrane disclosed in No. 59072, particularly a polyolefin microporous membrane, is preferable in terms of thickness, strength and membrane resistance.
【００２１】非水電解液の電解質としては特に限定され
ないが、一例を示せば、ＬｉＣｌＯ 4 、ＬｉＢＦ4 、Ｌ
ｉＡｓＦ6 、ＣＦ3 ＳＯ3 Ｌｉ、ＬｉＰＦ6 、ＬｉＩ、
ＬｉＡｌＣｌ4 、ＮａＣｌＯ4 、ＮａＢＦ4 、ＮａＩ、
（ｎ−Ｂｕ）4 Ｎ+ ＣｌＯ4 、（ｎ−Ｂｕ）4 Ｎ+ ＢＦ
4 、ＫＰＦ6 等が挙げられる。また、用いられる電解液
の有機溶媒としては、例えばエーテル類、ケトン類、ラ
クトン類、ニトリル類、アミン類、アミド類、硫黄化合
物、塩素化炭化水素類、エステル類、カーボネート類、
ニトロ化合物、リン酸エステル系化合物、スルホラン系
化合物などを用いることができるが、これらのうちでも
エーテル類、ケトン類、ラクトン類、ニトリル類、エス
テル類、塩素化炭化水素類、カーボネート類、スルホラ
ン系化合物が好ましい。更に好ましくは環状ラクトン
類、あるいは環状ラクトンと環状カーボネート類との混
合物である。The electrolyte of the non-aqueous electrolyte is not particularly limited.
No, but as an example, LiClO Four, LiBFFour, L
iAsF6, CF3SO3Li, LiPF6, LiI,
LiAlClFour, NaClOFour, NaBFFour, NaI,
(N-Bu)FourN+ClOFour, (N-Bu)FourN+BF
Four, KPF6Etc. Also used electrolyte
Examples of the organic solvent include ethers, ketones, and
Cutones, nitriles, amines, amides, sulfur compounds
Products, chlorinated hydrocarbons, esters, carbonates,
Nitro compounds, phosphate compounds, sulfolane compounds
Compounds and the like can be used, but among these,
Ethers, ketones, lactones, nitriles, s
Tells, chlorinated hydrocarbons, carbonates, sulfora
Compounds are preferred. More preferably cyclic lactone
Or a mixture of cyclic lactone and cyclic carbonate
It is a combination.
【００２２】これらの代表例としては、テトラヒドロフ
ラン、２−メチルテトラヒドロフラン、１，４−ジオキ
サン、アニソール、モノグライム、アセトニトリル、プ
ロピオニトリル、４−メチル−２−ペンタノン、ブチロ
ニトリル、バレロニトリル、ベンゾニトリル、１，２−
ジクロロエタン、γ−ブチロラクトン、ジメトキシエタ
ン、メチルフォルメイト、プロピレンカーボネート、エ
チレンカーボネート、ビニレンカーボネート、ジメチル
ホルムアミド、ジメチルスルホキシド、ジメチルチオホ
ルムアミド、スルホラン、３−メチル−スルホラン、リ
ン酸トリメチル、リン酸トリエチルおよびこれらの混合
溶媒等を挙げることができるが、必ずしもこれらに限定
されるものではない。Typical examples of these are tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, anisole, monoglyme, acetonitrile, propionitrile, 4-methyl-2-pentanone, butyronitrile, valeronitrile, benzonitrile, 1 , 2-
Dichloroethane, γ-butyrolactone, dimethoxyethane, methyl formate, propylene carbonate, ethylene carbonate, vinylene carbonate, dimethylformamide, dimethylsulfoxide, dimethylthioformamide, sulfolane, 3-methyl-sulfolane, trimethyl phosphate, triethyl phosphate, and triethyl phosphate thereof. Examples of the mixed solvent include, but are not necessarily limited to, these.
【００２３】更に要すれば、集電体、端子、絶縁板等の
部品を用いて電池が構成される。また、電池の構造とし
ては、特に限定されるものではないが、正極、負極、更
に要すればセパレーターを単層または複層としたペーパ
ー型電池、積層型電池、または正極、負極、更に要すれ
ばセパレーターをロール状に巻いた円筒状電池等の形態
が一例として挙げられる。Further, if necessary, a battery is constructed by using components such as a current collector, a terminal and an insulating plate. Moreover, the structure of the battery is not particularly limited, but a positive electrode, a negative electrode, and further, if necessary, a paper-type battery having a single-layer or multi-layer separator, a laminated battery, or a positive electrode, a negative electrode, and further required. For example, a form of a cylindrical battery or the like in which a separator is wound in a roll shape can be mentioned.
【００２４】[0024]
【実施例】以下、実施例、比較例により本発明を更に詳
しく説明するが、これらの実施例に限定されるものでは
ない。EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００２５】[0025]
【実施例１】炭酸リチウムと炭酸ナトリウム、酸化コバ
ルトを所定のモル比で混合した後、空気中で９３０℃に
て３時間焼成することによって複合酸化物ＬｉｘＮａｙ
ＭＯｚを得た。この複合酸化物をボールミルで粉砕後、
水洗、乾燥し、平均粒径１５ミクロン以下のＬｉ0.9 Ｎ
ａ0.1 ＣｏＯ2 を正極活物質とし、グラファイトおよび
アセチレングラファイトを導電剤とし、フッ素ゴムを結
着剤とし、各々Ｌｉ0. 9 Ｎａ0.1 ＣｏＯ2 ：グラファイ
ト：アセチレンブラック：フッ素ゴム＝１００：７．
５：２．５：２の重量比で混合したものを、ポリアクリ
ロニトリルのジメチルホルムアミド溶液に混合してペー
スト状としてＡｌ箔に塗布乾燥したシートを正電極とし
た。又、ニードルコークス粉末を負極活物質とし、フッ
素ゴムを結着剤とし、ニードルコークス：フッ素ゴム＝
９５：５の重量比で混合したものをポリアクリロニトリ
ルのジメチルホルムアミド溶液に混合してペースト状と
してＮｉ箔に塗布乾燥したシートを負電極とし、Ｌｉ金
属を参照極とし、図１に示す電池を製造した。なおセパ
レーター７としてポリプロピレン不織布を使用し、電解
液としてプロピレンカーボネートとγ−ブチロラクトン
の混合溶媒（体積比＝１：１）にホウフッ化リチウムを
１．０Ｍの濃度に調整した液を用いた。Example 1 A mixed oxide LixNay was prepared by mixing lithium carbonate, sodium carbonate and cobalt oxide in a predetermined molar ratio and then calcining them in air at 930 ° C. for 3 hours.
MOz was obtained. After crushing this composite oxide with a ball mill,
Li 0.9 N with an average particle size of 15 microns or less after washing with water and drying
and a 0.1 CoO 2 active material, the conductive agent graphite and acetylene graphite, fluorine rubber and binder, each Li 0. 9 Na 0.1 CoO 2: Graphite: acetylene black: fluororubber = 100: 7.
The positive electrode was a sheet prepared by mixing the mixture in a weight ratio of 5: 2.5: 2 with a solution of polyacrylonitrile in dimethylformamide, forming a paste, and coating and drying the Al foil. Also, needle coke powder was used as the negative electrode active material, fluororubber was used as the binder, and needle coke: fluororubber =
The mixture shown in the weight ratio of 95: 5 was mixed with a solution of polyacrylonitrile in dimethylformamide and applied as a paste on a Ni foil, and the dried sheet was used as a negative electrode, and a Li metal was used as a reference electrode to produce the battery shown in FIG. did. A polypropylene non-woven fabric was used as the separator 7, and a solution prepared by adjusting lithium borofluoride to a concentration of 1.0 M in a mixed solvent of propylene carbonate and γ-butyrolactone (volume ratio = 1: 1) was used as an electrolytic solution.
【００２６】この電池を定電圧４．２Ｖで７時間充電し
た後、１．０ｍＡ／ｃｍ2 の定電流で終止電圧２．７Ｖ
まで放電した。この充放電サイクルを繰り返した際の放
電容量の変化を図２に示す。また、表１には１サイクル
目の放電容量（重量基準）、コバルト基準のドープ量、
および１００サイクル目の１サイクル目に対する放電容
量の割合（％）をサイクル性として表す。After charging this battery at a constant voltage of 4.2 V for 7 hours, a constant voltage of 1.0 mA / cm 2 was applied and the final voltage was 2.7 V.
Discharged up to. FIG. 2 shows the change in discharge capacity when this charging / discharging cycle is repeated. Further, in Table 1, the discharge capacity (weight basis) of the first cycle, the cobalt-based doping amount,
And the ratio (%) of the discharge capacity to the first cycle of the 100th cycle is represented as cycleability.
【００２７】[0027]
【比較例１】ＬｉＣｏＯ2 を正極活物質とし、グラファ
イトおよびアセチレンブラックを導電剤とし、フッ素ゴ
ムを結着剤とし、各々ＬｉＣｏＯ2 ：グラファイト：ア
セチレンブラック：フッ素ゴム＝１００：７．５：２．
５：２の重量比で混合したものをポリアクリロニトリル
のジメチルホルムアミド溶液に混合してペースト状とし
てＡｌ箔に塗布乾燥したシートを正電極とした他は実施
例１と同じ電池を製造し、同様の評価を行った。結果を
図３に示す。Comparative Example 1 LiCoO 2 was used as a positive electrode active material, graphite and acetylene black were used as conductive agents, and fluororubber was used as a binder. LiCoO 2 : graphite: acetylene black: fluororubber = 100: 7.5: 2.
A battery was prepared in the same manner as in Example 1 except that the mixture in a weight ratio of 5: 2 was mixed with a solution of polyacrylonitrile in dimethylformamide to form a paste, and the sheet was dried and used as a positive electrode. An evaluation was made. Results are shown in FIG.
【００２８】比較例１に例示したようにＬｉＣｏＯ2 で
は１００サイクルで放電容量が５３．７％にまで低下す
るのに対して、実施例１に例示したナトリウム含有複合
酸化物の場合には８７．６％と良好なサイクル性を示し
た。また、ＬｉＣｏＯ2 の場合サイクルに伴って過電圧
が増大し、１００サイクルで０．４Ｖに達するのに対し
て、Ｌｉ0.9 Ｎａ0.1 ＣｏＯ2 の場合では０．０５Ｖと
ほとんど増加がみられなかった。As exemplified in Comparative Example 1, the discharge capacity of LiCoO 2 drops to 53.7% after 100 cycles, whereas the sodium-containing composite oxide exemplified in Example 1 has a discharge capacity of 87. It showed a good cycle property of 6%. Further, in the case of LiCoO 2 , the overvoltage increased with the cycle and reached 0.4 V after 100 cycles, whereas in the case of Li 0.9 Na 0.1 CoO 2 , the increase was 0.05 V, which was almost no increase.
【００２９】[0029]
【実施例２〜４】実施例１においてＮａ含有量を表１に
示す通りに変えた以外は全く実施例１と同様に実施し
た。結果を表１に示す。Examples 2 to 4 The same procedure as in Example 1 was carried out except that the Na content was changed as shown in Table 1. The results are shown in Table 1.
【００３０】[0030]
【実施例５】実施例１において、Ｌｉ0.9 Ｎａ0.1 Ｃｏ
Ｏ2 の代わりにＬｉＮａ0.1 ＣｏＮｉ0.1 Ｏ2 を用いた
以外は全く実施例１と同様に実施例した。結果を表２に
示す。Example 5 In Example 1, Li 0.9 Na 0.1 Co
Except that in place of O 2 with Lina 0.1 CoNi 0.1 O 2 was entirely embodiment in the same manner as in Example 1. The results are shown in Table 2.
【００３１】[0031]
【実施例６】実施例１において、Ｌｉ0.9 Ｎａ0.1 Ｃｏ
Ｏ2 の代わりにＬｉＮａ0.1 ＣｏＭｎ0.1 Ｏ2 を用いた
以外は、全く実施例１と同様に実施例した。結果を表２
に示す。Example 6 In Example 1, Li 0.9 Na 0.1 Co
Except for using Lina 0.1 CoMn 0.1 O 2 instead of O 2 was embodiments similarly exactly Example 1. The results are shown in Table 2.
Shown in.
【００３２】[0032]
【実施例７】負極として、ポリアセチレン負極を用いた
他は、実施例１と全く同様に実施した。結果を表３に示
す。ポリアセチレン負極の調製法は以下の通りである。
Ｎ2 雰囲気下、内容積８００ｍｌのガラス容器にトルエ
ン５０ｍｌをとり、テトラブトキシチタン６ｍｌ、トリ
エチルアルミニウム１０ｍｌを加えて触媒を調製した。
容器を−７８℃に冷却後、系内を排気し、容器壁面に触
媒液を塗布し、アセチレンガスを導入した。直ちに壁面
に膜状ポリアセチレンが生成し、１５分放置後系内を排
気した。トルエンで洗浄後０．５Ｎ−ＨＣｌ−ＭｅＯＨ
で５回洗浄した後、乾燥し取り出した。[Example 7] The same operation as in Example 1 was carried out except that a polyacetylene negative electrode was used as the negative electrode. The results are shown in Table 3. The method for preparing the polyacetylene negative electrode is as follows.
Under a N 2 atmosphere, 50 ml of toluene was placed in a glass container having an internal volume of 800 ml, and 6 ml of tetrabutoxytitanium and 10 ml of triethylaluminum were added to prepare a catalyst.
After cooling the container to −78 ° C., the inside of the system was evacuated, the catalyst liquid was applied to the wall surface of the container, and acetylene gas was introduced. Immediately, film-like polyacetylene was formed on the wall surface, and after leaving it for 15 minutes, the system was evacuated. After washing with toluene 0.5N-HCl-MeOH
After being washed 5 times with, the product was dried and taken out.
【００３３】この膜状ポリアセチレンを２５０℃で５秒
間熱処理した後用いた。The filmy polyacetylene was used after being heat-treated at 250 ° C. for 5 seconds.
【００３４】[0034]
【比較例２】負極として、ポリアセチレン負極を用いた
他は、比較例１と全く同様に実施した。結果を表３に示
す。[Comparative Example 2] The same operation as in Comparative Example 1 was carried out except that a polyacetylene negative electrode was used as the negative electrode. The results are shown in Table 3.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【表３】 [Table 3]
【００３８】[0038]
【発明の効果】本発明の電池は従来の非水系二次電池の
欠点であったサイクル特性が飛躍的に改良され、小形電
池機器用、電気自動車用等民生用、産業用の電源として
広く有用である。INDUSTRIAL APPLICABILITY The battery of the present invention has drastically improved the cycle characteristics which were the drawbacks of the conventional non-aqueous secondary batteries, and is widely useful as a power source for small battery devices, electric vehicles such as electric vehicles, and industrial use. Is.
【図１】図１は本発明の実施例、比較例で用いた電池の
構造図。FIG. 1 is a structural diagram of batteries used in Examples and Comparative Examples of the present invention.
【図２】図２は本発明電池の１サイクル目の放電容量を
１００としたとき、各充電サイクル毎の放電容量（％）
を示す。FIG. 2 is a discharge capacity (%) at each charge cycle when the discharge capacity at the first cycle of the battery of the present invention is 100.
Indicates.
【図３】図３は比較例１・電池の１サイクル目の放電容
量を１００としたとき、各充電サイクル毎の放電容量
（％）を示す。FIG. 3 shows the discharge capacity (%) for each charge cycle when the discharge capacity of the first cycle of Comparative Example 1 battery is 100.
１ 正極 ２ 負極 ３ 集電棒 ４ ＳＵＳネット ５ 外部電極端子 ６ 電池ケース ７ セパレーター ８ 電解液 1 Positive Electrode 2 Negative Electrode 3 Current Collecting Rod 4 SUS Net 5 External Electrode Terminal 6 Battery Case 7 Separator 8 Electrolyte
Claims (1)
いはコバルトを主体としニッケル、マンガンの少なくと
も一種を少量含む混合金属を表す。ｘは０．２０≦ｘ≦
１．１０、ｙは０．０１≦ｙ≦０．３０、ｚは１．９５
≦ｚ≦２．４５の各数である）を正極活物質とする非水
系二次電池。1. LixNayMOz (M represents cobalt or a mixed metal mainly containing cobalt and containing a small amount of at least one of nickel and manganese. X is 0.20 ≦ x ≦.
1.10, y is 0.01 ≦ y ≦ 0.30, and z is 1.95.
<Z <2.45) as a positive electrode active material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23136791A JP3236317B2 (en) | 1991-09-11 | 1991-09-11 | Non-aqueous battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23136791A JP3236317B2 (en) | 1991-09-11 | 1991-09-11 | Non-aqueous battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0574451A true JPH0574451A (en) | 1993-03-26 |
| JP3236317B2 JP3236317B2 (en) | 2001-12-10 |
Family
ID=16922511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23136791A Expired - Lifetime JP3236317B2 (en) | 1991-09-11 | 1991-09-11 | Non-aqueous battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3236317B2 (en) |
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| JP2007287661A (en) * | 2006-03-20 | 2007-11-01 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2011170994A (en) * | 2010-02-16 | 2011-09-01 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
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| US8048564B2 (en) * | 2007-06-25 | 2011-11-01 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery and method of forming positive electrode |
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1991
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| US8048564B2 (en) * | 2007-06-25 | 2011-11-01 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery and method of forming positive electrode |
| JP2011170994A (en) * | 2010-02-16 | 2011-09-01 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery and method of manufacturing the same |
| CN102208674A (en) * | 2010-03-31 | 2011-10-05 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
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| US9318740B2 (en) * | 2010-03-31 | 2016-04-19 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte secondary battery |
| JP2012094487A (en) * | 2010-09-30 | 2012-05-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery and method for manufacturing the same |
| JP2016091633A (en) * | 2014-10-30 | 2016-05-23 | 住友金属鉱山株式会社 | Substituent element select method, battery positive electrode material manufacturing method, and battery positive electrode material |
| CN109761287A (en) * | 2018-12-29 | 2019-05-17 | 合肥融捷能源材料有限公司 | A kind of high-rate type lithium cobaltate and its preparation method and application |
| CN109761287B (en) * | 2018-12-29 | 2021-08-27 | 合肥融捷能源材料有限公司 | High-rate lithium cobalt oxide and preparation method and application thereof |
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