JPH0574494A - Nonaqueous secondary battery - Google Patents
Nonaqueous secondary batteryInfo
- Publication number
- JPH0574494A JPH0574494A JP3261301A JP26130191A JPH0574494A JP H0574494 A JPH0574494 A JP H0574494A JP 3261301 A JP3261301 A JP 3261301A JP 26130191 A JP26130191 A JP 26130191A JP H0574494 A JPH0574494 A JP H0574494A
- Authority
- JP
- Japan
- Prior art keywords
- active material
- electrode active
- positive electrode
- negative electrode
- current collector
- 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
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はサイクル性，保存特性，
安全性に優れた新規な二次電池に関するものである。BACKGROUND OF THE INVENTION The present invention has a cycle property, a storage property,
The present invention relates to a novel secondary battery with excellent safety.
【０００２】[0002]
【従来の技術】近年、従来の酸−鉛電池、ニッケル／カ
ドミウム電池に変わる小型，軽量二次電池として、種々
の非水系二次電池が提案されている。中でも、例えば特
開昭６２−９０，８６３号公報，特開昭６３−１２１，
２６０号公報，特開平３−４９，１５５号公報等におい
て開示されている正極にＬｉ，Ｃｏを主成分とする複合
金属酸化物を用い、負極に炭素質材料を用いる新しい二
次電池系が注目されている。従来かかる非水系二次電池
として提案されているのは負極活物質として、金属Ｌ
ｉ、もしくはＬｉ合金を用いるものであった。かかる金
属Ｌｉ等を負極に用いた二次電池は、小型，軽量という
観点からは満足されるものの、デンドライト析出に基
く、サイクル性，保存特性等の性能上の問題、又、同じ
くデンドライト析出によるセパレーターの突き破りから
内部短絡を引き起こすという寿命の問題、更には金属Ｌ
ｉの活性な化学反応性に基く安全上の問題、等実用化へ
の大きな障害を有していた。これに対し、前記の負極活
物質に炭素質材料を用いる新しい電池系は、このような
デンドライト析出を起こすことなく、優れたサイクル
性，保存特性を有すると共に、金属Ｌｉのような活性な
化学反応性を有していないことから、安全性が非常に優
れているという特徴を有しているものである。2. Description of the Related Art In recent years, various non-aqueous secondary batteries have been proposed as small and lightweight secondary batteries replacing conventional acid-lead batteries and nickel / cadmium batteries. Among them, for example, JP-A-62-90,863, JP-A-63-121,
A new secondary battery system using a composite metal oxide containing Li and Co as a main component in the positive electrode and a carbonaceous material in the negative electrode is disclosed in JP-A No. 260 and JP-A-3-49,155. Has been done. Conventionally proposed as such a non-aqueous secondary battery is metal L as a negative electrode active material.
i or Li alloy was used. Although a secondary battery using such a metallic Li as a negative electrode is satisfactory from the viewpoint of small size and light weight, it has a problem in performance such as cycleability and storage characteristics due to dendrite precipitation, and also a separator due to dendrite precipitation. Life problem of causing internal short circuit due to breakthrough of metal, and further metal L
There were major obstacles to practical use, such as safety problems based on the active chemical reactivity of i. On the other hand, the new battery system using the carbonaceous material as the negative electrode active material has excellent cycleability and storage characteristics without causing such dendrite precipitation, and has an active chemical reaction such as metallic Li. Since it does not have the property, it has a feature that the safety is very excellent.
【０００３】特に、正極活物質としてＬｉ，Ｃｏを主成
分とする複合金属酸化物と組合せた場合、高電圧，高容
量の電池ができるものとして期待されている。In particular, when a positive electrode active material is combined with a composite metal oxide containing Li and Co as a main component, it is expected that a battery having a high voltage and a high capacity can be obtained.
【０００４】[0004]
【発明が解決しようとする課題】ところで、Ｌｉ，Ｃｏ
を主成分とする複合金属酸化物を正極活物質として用
い、炭素質材料を負極活物質として用いる電池系は前記
の如く高容量というポテンシャルを有しているものの実
際に実用的な電池として高容量を実現する為には、正，
負両電極のみかけ密度，正，負両活物質と金属集電体と
の重量比率により、実際の電池としての重量当たり、体
積当たりの電池容量は大きく左右される。By the way, Li, Co
Although the battery system that uses a composite metal oxide containing as a main component as a positive electrode active material and a carbonaceous material as a negative electrode active material has the potential of high capacity as described above, it has a high capacity as a practical battery. To achieve
Depending on the apparent density of both negative electrodes and the weight ratio between the positive and negative active materials and the metal current collector, the battery capacity per weight and volume as an actual battery is greatly influenced.
【０００５】従って、これらを最適化しなければ実用的
な観点からの高容量電池は実現できなかった。Therefore, a high capacity battery cannot be realized from a practical point of view unless these are optimized.
【０００６】[0006]
【課題を解決するための手段及び作用】本発明者等は、
かかる観点から、正，負両電極のみかけ密度，金属集電
体との重量比率について詳細に検討した結果、ある特定
領域範囲において電池性能のバランスを保ちながら高容
量化を実現できることを見出した。Means and Actions for Solving the Problems The present inventors have
From this point of view, as a result of detailed examination of the apparent densities of both the positive and negative electrodes and the weight ratio with the metal current collector, it was found that a high capacity can be realized while maintaining the balance of battery performance in a certain specific region range.
【０００７】本発明は、かかる知見に基づいてなされた
ものであり、基本構成要素として正極，負極，電解液か
らなる非水二次電池において、該正極活物質がＬｉ，Ｃ
ｏを主成分とする複合金属酸化物であり、該負極活物質
が炭素質材料であり、かつ、以下の（１）〜（４）の条
件を満たすことを特徴とするものである。 （１）正極活物質層のみかけ密度が２．８５〜３．２０
ｇ／ｃｍ3 の範囲にあること。 （２）正極活物質と金属正極集電体との重量比が４〜２
５であること。 （３）負極活物質層のみかけ密度が０．９５〜１．１８
ｇ／ｃｍ3 であること。 （４）負極活物質と金属負極集電体との重量比が１．０
〜７．０であること。The present invention has been made on the basis of such findings, and in a non-aqueous secondary battery comprising a positive electrode, a negative electrode and an electrolytic solution as basic constituent elements, the positive electrode active material is Li, C
It is a composite metal oxide containing o as a main component, the negative electrode active material is a carbonaceous material, and the following conditions (1) to (4) are satisfied. (1) The apparent density of the positive electrode active material layer is 2.85 to 3.20.
Must be in the range of g / cm 3 . (2) The weight ratio of the positive electrode active material and the metal positive electrode current collector is 4 to 2
Must be 5. (3) Apparent density of the negative electrode active material layer is 0.95 to 1.18.
Must be g / cm 3 . (4) The weight ratio of the negative electrode active material and the metal negative electrode current collector is 1.0.
~ 7.0.
【０００８】本発明でいうＬｉ，Ｃｏを主成分とする複
合金属酸化物とは、層状構造を有し電気化学的にＬｉイ
オンがインターカレート，ディインターカレートし得る
化合物であり、少なくともＣｏを金属成分の中で５０重
量％以上含むものである。特に限定されないが、かかる
複合金属酸化物の一例を示せば、例えば特開昭５５−１
３６，１３１号公報で開示されるＬｉＣｏＯ2 ，特開昭
６２−９０，８６３号公報で開示されている一般式Ｌｉ
x Ｃｏy Ｎz Ｏ2 （但し、ＮはＡｌ，Ｉｎ，Ｓｎの群か
ら選ばれた少なくとも一種を表わし、ｘ，ｙ，ｚは各々
０．０５≦ｘ≦１．１０，０．８５≦ｙ≦１．００，
０．００１≦ｚ≦０．１０の数を表わす。）、又、特開
平３−４９，１５５号公報で開示されるＬｉx Ｎｉy Ｃ
ｏ(1-y) Ｏ2 （但し、０＜ｘ≦１，０≦ｙ＜０．５０）
等が挙げられる。The composite metal oxide containing Li and Co as the main components in the present invention is a compound having a layered structure and capable of electrochemically intercalating and deintercalating Li ions, and at least Co Is contained in the metal component in an amount of 50% by weight or more. Although not particularly limited, an example of such a composite metal oxide is shown in, for example, JP-A-55-1.
36,131, LiCoO 2 , and the general formula Li disclosed in JP-A-62-90,863.
x Co y N z O 2 (wherein N represents at least one selected from the group consisting of Al, In and Sn, and x, y and z are each 0.05 ≦ x ≦ 1.10 and 0.85 ≦ y. ≤1.00,
It represents a number of 0.001 ≦ z ≦ 0.10. ), And Li x Ni y C disclosed in JP-A-3-49,155.
o (1-y) O 2 (where 0 <x ≦ 1, 0 ≦ y <0.50)
Etc.
【０００９】かかる化合物を得るには、水酸化リチウ
ム，酸化リチウム，炭酸リチウム，硝酸リチウム等のＬ
ｉ化合物と酸化コバルト，水酸化コバルト，炭酸コバル
ト，硝酸コバルト等のコバルト化合物と、更に要すれ
ば、他金属化合物との焼成反応により容易に得られるも
のである。To obtain such a compound, L compounds such as lithium hydroxide, lithium oxide, lithium carbonate and lithium nitrate are used.
It can be easily obtained by a firing reaction between the i compound and a cobalt compound such as cobalt oxide, cobalt hydroxide, cobalt carbonate, or cobalt nitrate, and if necessary, another metal compound.
【００１０】これらの複合酸化物は何れも正極活物質と
して、高電圧，高容量という他の活物質には見られない
優れた特性を有している。特に前記一般式Ｌｉx Ｃｏy
ＮzＯ2 （但し、ＮはＡｌ，Ｉｎ，Ｓｎの群から選ばれ
た少なくとも一種を表わし、ｘ，ｙ，ｚは各々０．０５
≦ｘ≦１．１０，０．８５≦ｙ≦１．００，０．００１
≦ｚ≦０．１０の数を表わす。）は特にサイクル性等の
特性に優れており本発明で好ましく用いられる複合酸化
物である。As a positive electrode active material, all of these composite oxides have excellent characteristics such as high voltage and high capacity, which are not found in other active materials. In particular, the above general formula Li x Co y
N z O 2 (where N represents at least one selected from the group consisting of Al, In and Sn, and x, y and z are each 0.05
≤ x ≤ 1.10, 0.85 ≤ y ≤ 1.00, 0.001
Represents a number ≦ z ≦ 0.10. ) Is a complex oxide which is particularly preferably used in the present invention because it has excellent characteristics such as cycle characteristics.
【００１１】又、本発明でいう炭素質材料とは、特に限
定されるものではないが、その一例を示せば特開昭５８
−３５，８８１号公報に記載の高表面積炭素材料、又特
開昭５８−２０９，８６４号公報に記載のフェノール系
樹脂等の焼成炭化物、又特開昭６１−１１１，９０７号
公報に記載の縮合多環炭化水素系化合物の焼成炭化物等
が挙げられる。中でも特開昭６２−９０，８６３号公報
で開示されるＢＥＴ法比表面積Ａ（ｍ2 ／ｇ）が０．１
＜Ａ＜１００の範囲でＸ線回折における結晶厚みＬｃ
（Å）と真密度ρ（ｇ／ｃｍ3 ）の値が下記条件１．７
０＜ρ＜２．１８かつ１０＜Ｌｃ＜１２０ρ−１８９を
満たす範囲にある炭素質材料は高容量かつ優れたサイク
ル特性を有しており、本発明において特に好ましく用い
られる。The carbonaceous material referred to in the present invention is not particularly limited.
-35,881 high surface area carbon material, JP-A-58-209,864 JP-A No. 61-111,907 JP Examples include calcined carbides of condensed polycyclic hydrocarbon compounds. Above all, the BET specific surface area A (m 2 / g) disclosed in JP-A-62-90,863 is 0.1.
Crystal thickness Lc in X-ray diffraction in the range of <A <100
The value of (Å) and true density ρ (g / cm 3 ) are the following conditions 1.7.
The carbonaceous material in the range of 0 <ρ <2.18 and 10 <Lc <120ρ-189 has a high capacity and excellent cycle characteristics, and is particularly preferably used in the present invention.
【００１２】これらの活物質を用い、実際の正電極，負
電極を得るには金属集電体上にバインダーを用いて結着
させる必要がある。その結着方法は種々の方法が採用さ
れるが本発明の場合塗工法によるのが最も好ましい。In order to obtain actual positive and negative electrodes by using these active materials, it is necessary to bind them on the metal current collector with a binder. As the binding method, various methods are adopted, but in the present invention, the coating method is most preferable.
【００１３】この電極において、みかけ密度は電池容
量、特に容積当たりの電池容量に大きく影響する。In this electrode, the apparent density greatly affects the battery capacity, particularly the battery capacity per volume.
【００１４】即ち、正電極の場合、活物質層のみかけ密
度は２．８５〜３．２０ｇ／ｃｍ3の範囲でなければな
らない。好ましくは２．９０〜３．１５ｇ／ｃｍ3 、更
に好ましくは２．９５〜３．１０ｇ／ｃｍ3 の範囲であ
る。That is, in the case of the positive electrode, the apparent density of the active material layer should be in the range of 2.85 to 3.20 g / cm 3 . The range is preferably 2.90 to 3.15 g / cm 3 , and more preferably 2.95 to 3.10 g / cm 3 .
【００１５】２．８５ｇ／ｃｍ3 未満の場合は、体積当
たりの電池容量が低下し好ましくない。又、３．２０ｇ
／ｃｍ3 を越す場合は出力特性が著しく低下し好ましく
ない。If it is less than 2.85 g / cm 3 , the battery capacity per volume is lowered, which is not preferable. Also, 3.20g
When it exceeds / cm 3 , the output characteristics are remarkably deteriorated, which is not preferable.
【００１６】負電極の場合は、活物質層のみかけ密度は
０．９５〜１．１８ｇ／ｃｍ3 の範囲でなければならな
い。この範囲を外れる場合には、正電極の場合と同じ理
由により用いられない。正，負両電極共にみかけ密度を
この範囲にする為には、上記塗工後の電極を圧延するこ
とにより達成される。その圧延方法は特に限定されない
が、生産性を考えた場合カレンダーロール等のロール圧
延法が好ましい圧延方法として挙げられる。In the case of a negative electrode, the apparent density of the active material layer should be in the range of 0.95 to 1.18 g / cm 3 . If it is out of this range, it is not used for the same reason as in the case of the positive electrode. In order to set the apparent density of both the positive and negative electrodes within this range, it is achieved by rolling the coated electrode. The rolling method is not particularly limited, but a roll rolling method such as a calender roll is mentioned as a preferable rolling method in view of productivity.
【００１７】次に、正，負両電極共に活物質重量と金属
集電体との重量比、活物質重量／金属集電体重量も電池
容量、特に重量当たりの電池容量に大きく影響する。Next, in both the positive and negative electrodes, the weight ratio of the active material to the metal current collector and the weight of the active material / metal current collector also greatly affect the battery capacity, particularly the battery capacity per weight.
【００１８】即ち、正電極の場合この重量比は４〜２５
の範囲でなければならない。好ましくは５〜２０であ
る。That is, in the case of the positive electrode, this weight ratio is 4 to 25.
Must be in the range. It is preferably 5 to 20.
【００１９】４未満の場合、即ち金属集電体の相対重量
が大きくなった場合には重量当たりの電池容量が低下し
好ましくない。逆に、２０を越す場合には電池容量的に
は増大する方向ではあるが、金属集電体の抵抗値が上が
り、内部抵抗上昇，出力特性低下等の影響が現われ用い
られない。かかる正極活物質と金属集電体との重量比を
本発明の範囲にする為には金属集電体の形状，材質の選
択が重要である。When it is less than 4, that is, when the relative weight of the metal current collector is large, the battery capacity per weight is reduced, which is not preferable. On the other hand, when the number exceeds 20, the battery capacity tends to increase, but the resistance value of the metal current collector increases, and the effects of an increase in internal resistance, a decrease in output characteristics, and the like appear, and the battery cannot be used. In order to set the weight ratio of the positive electrode active material and the metal current collector within the range of the present invention, it is important to select the shape and material of the metal current collector.
【００２０】形状としては、箔状が最も好ましく、材質
としてはＡｌ，Ｔｉが好ましく、特にコストの点からＡ
ｌが好ましい。A foil shape is most preferable as a shape, and Al and Ti are preferable as a material.
1 is preferred.
【００２１】負電極の場合には重量比は１．０〜７．０
の範囲でなければならない。この範囲を外れる場合には
正電極の場合と同じ理由により用いられない。In the case of the negative electrode, the weight ratio is 1.0 to 7.0.
Must be in the range. If it is out of this range, it is not used for the same reason as in the case of the positive electrode.
【００２２】負電極の場合も形状としては箔状が最も好
ましく材質としてはＣｕ，Ｎｉが好ましい。Also in the case of the negative electrode, the foil shape is most preferable, and Cu and Ni are preferable as the material.
【００２３】又、特に限定するものではないが正極活物
質と負極活物質との重量比、正極活物質重量／負極活物
質重量は１．７５〜２．０５が好ましい。１．７５未満
の場合は容量が低下し、好ましくなく、２．０５を越す
場合にはサイクル特性等が低下し好ましくない。又、こ
れも特に限定するものではないが、集電体を含めた正極
と負極の膜厚比、正極膜厚／負極膜厚は０．６〜０．９
が好ましい。０．６未満の場合は容量が低下し好ましく
なく、０．９を越す場合にはサイクル特性が低下し好ま
しくない。Although not particularly limited, the weight ratio of the positive electrode active material and the negative electrode active material, the weight of the positive electrode active material / the weight of the negative electrode active material, is preferably 1.75 to 2.05. When it is less than 1.75, the capacity is lowered, which is not preferable, and when it exceeds 2.05, cycle characteristics and the like are lowered, which is not preferable. Although not particularly limited, the film thickness ratio between the positive electrode and the negative electrode including the current collector, positive electrode film thickness / negative electrode film thickness is 0.6 to 0.9.
Is preferred. When it is less than 0.6, the capacity is undesirably lowered, and when it exceeds 0.9, the cycle characteristics are unfavorably lowered.
【００２４】本発明の非水系二次電池を組立てる場合の
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 an electrode using the active material of the present invention, a separator, and a non-aqueous electrolyte. The separator is not particularly limited, and examples thereof include 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.
【００２５】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、ＬｉＣｌＯ4 ，ＬｉＢＦ4 ，Ｌ
ｉＡｓＦ6 ，ＣＦ3 ＳＯ3 Ｌｉ，ＬｉＰＦ6 ，ＬｉＩ，
ＬｉＡｌＣｌ4 ，ＮａＣｌＯ4 ，ＮａＢＦ4 ，ＮａＩ，
（ｎ−Ｂｕ）4 Ｎ+ ＣｌＯ4，（ｎ−Ｂｕ）4 Ｎ+ ＢＦ4
，ＫＰＦ6 等が挙げられる。又、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
化合物等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、ニトリル類、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
好ましくは環状カーボネート類である。The electrolyte of the non-aqueous electrolyte is not particularly limited, but as an example, LiClO 4 , LiBF 4 , L
iAsF 6 , CF 3 SO 3 Li, LiPF 6 , LiI,
LiAlCl 4 , NaClO 4 , NaBF 4 , NaI,
(N-Bu) 4 N + ClO 4 , (n-Bu) 4 N + BF 4
, KPF 6 and the like. Examples of the organic solvent of the electrolytic solution used include ethers, ketones, lactones, nitriles, amines, amides, sulfur compounds, chlorinated hydrocarbons, esters, carbonates,
Nitro compounds, phosphoric acid ester compounds, sulfolane compounds, and the like can be used. Among them, ethers, ketones, nitriles, chlorinated hydrocarbons,
Carbonates and sulfolane compounds are preferable. More preferred are cyclic carbonates.
【００２６】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
溶媒等をあ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。As typical examples of these, 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.
【００２７】更に要すれば、端子、絶縁板等の部品を用
いて電池が構成される。又、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又は複層としたペーパー型電池、積
層型電池、又は正極、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 parts such as terminals and insulating plates. Further, 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 a 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.
【００２８】[0028]
【実施例】以下、実施例により本発明を更に詳しく説明
する。The present invention will be described in more detail with reference to the following examples.
【００２９】みかけ密度の測定法１０ｃｍ×１０ｃｍの
試験片を切り出し、下式により計算する。Measuring method of apparent density A 10 cm × 10 cm test piece is cut out and calculated by the following formula.
【００３０】[0030]
【数１】 実施例１ Ｌｉ1.03Ｃｏ0.92Ｓｎ0.02Ｏ2 の組成を有するＬｉ，Ｃ
ｏ複合酸化物１００重量部とグラファイト２．５重量
部、アセチレンブラック２．５重量部を混合した後、フ
ッ素ゴム２重量部を酢酸エチル／エチルセロソルブの
１：１（重量比）混合溶剤６０重量部に溶解させた液を
混合しスラリー状塗工液を得た。[Equation 1] Example 1 Li, C having a composition of Li 1.03 Co 0.92 Sn 0.02 O 2
o 100 parts by weight of complex oxide, 2.5 parts by weight of graphite and 2.5 parts by weight of acetylene black were mixed, and then 2 parts by weight of fluororubber was mixed with 60 parts by weight of a mixed solvent of ethyl acetate / ethyl cellosolve 1: 1 (weight ratio). The liquid dissolved in the parts was mixed to obtain a slurry coating liquid.
【００３１】ドクターブレードコーターヘッドを有する
塗工機を用い巾６００ｍｍ厚さ１５μのＡｌ箔の両面に
上記塗工液を塗布した。両面塗工後の塗工厚は２９０μ
であった。The coating solution was applied to both sides of an Al foil having a width of 600 mm and a thickness of 15 μm by using a coating machine having a doctor blade coater head. Coating thickness after double-sided coating is 290μ
Met.
【００３２】ニードルコークス粉砕品１００重量部とフ
ッ素ゴム５重量部を酢酸エチル／エチルセロソルブの
１：１（重量比）混合溶剤９０重量部に溶解させた液を
混合しスラリー状塗工液を得た。A solution prepared by dissolving 100 parts by weight of crushed needle coke and 5 parts by weight of fluororubber in 90 parts by weight of a 1: 1 (weight ratio) mixed solvent of ethyl acetate / ethyl cellosolve was mixed to obtain a slurry coating solution. It was
【００３３】ドクターブレードコーターヘッドを有する
塗工機を用い巾６００ｍｍ厚さ１０μのＣｕ箔の両面に
上記塗工液を塗布した。両面塗工後の塗工厚は３５０μ
であった。A coating machine having a doctor blade coater head was used to apply the above coating solution to both sides of a Cu foil having a width of 600 mm and a thickness of 10 μm. Coating thickness after coating on both sides is 350μ
Met.
【００３４】前記２種類の塗工品をカレンダーロールに
てプレス後、両者共にスリッターを用い４１ｍｍ巾にス
リットした。Ｌｉ1.03Ｃｏ0.92Ｓｎ0.02Ｏ2 塗工品を正
極とし、ニードルコークス塗工品を負極とし、セパレー
ターとしてポリエチレン製微多孔膜（ハイポア４０３０
Ｕ旭化成社製）を用い、捲回機により外径１４．９ｍｍ
のコイル状に捲回した。この捲回コイルを外径１６ｍｍ
の電池缶に入れた後、プロピレンカーボネート／エチレ
ンカーボネート／γ−ブチロラクトンの１：１：２（重
量比）の混合溶剤にＬｉＢＦ4 を１Ｍ濃度に溶かしたも
のを電解液として含浸した後封口し、図１に示す高さ５
０ｍｍのＡサイズの電池缶を試作した。ここで用いた電
極のプレス後の性状は表１に示す通りであった。After pressing the above-mentioned two kinds of coated products with a calendar roll, both were slit to a width of 41 mm using a slitter. The Li 1.03 Co 0.92 Sn 0.02 O 2 coated product was used as the positive electrode, the needle coke coated product was used as the negative electrode, and a polyethylene microporous membrane (hypore 4030) was used as the separator.
U Asahi Kasei Co., Ltd.) with a winding machine, outer diameter 14.9 mm
Was wound into a coil. This winding coil has an outer diameter of 16 mm
After being placed in the battery can, the mixture of propylene carbonate / ethylene carbonate / γ-butyrolactone 1: 1: 2 (weight ratio) in which LiBF 4 was dissolved at a concentration of 1 M was impregnated as an electrolytic solution and then sealed. Height 5 shown in Figure 1
A 0 mm A size battery can was prototyped. The properties of the electrode used here after pressing were as shown in Table 1.
【００３５】この電池の性能評価を併せて表１に示す。The performance evaluation of this battery is also shown in Table 1.
【００３６】実施例２〜４，比較例１〜５ 実施例１において、正，負両電極の塗工量、プレス条件
を変えた以外は全く同じ操作を行った。Examples 2-4 and Comparative Examples 1-5 The same operation as in Example 1 was performed except that the coating amounts of the positive and negative electrodes and the press conditions were changed.
【００３７】この時の各々の正，負電極のプレス後の性
状は表１に示す通りであった。The properties of the positive and negative electrodes after pressing at this time are as shown in Table 1.
【００３８】この電池の性能評価結果を表１に示す。The results of performance evaluation of this battery are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【発明の効果】以上の説明からも明らかなように、Ｌ
ｉ，Ｃｏ複合酸化物を正極活物質とし、炭素質材料を負
極活物質に用いる二次電池において、みかけ密度、活物
質と集電体との重量比率を最適化することにより電池容
量を上げることができる。As is clear from the above description, L
In a secondary battery using a i, Co composite oxide as a positive electrode active material and a carbonaceous material as a negative electrode active material, increasing the battery capacity by optimizing the apparent density and the weight ratio of the active material and the current collector. You can
【図１】本発明に係る電池の半裁断面図FIG. 1 is a half cutaway view of a battery according to the present invention.
１ 正極 ２ セパレーター ３ 負極 ４ 絶縁板 ５ 負極リード ６ 正極リード ７ ガスケット 1 positive electrode 2 separator 3 negative electrode 4 insulating plate 5 negative electrode lead 6 positive electrode lead 7 gasket
Claims (2)
からなる非水二次電池において、該正極活物質がＬｉ，
Ｃｏを主成分とする複合金属酸化物であり、該負極活物
質が炭素質材料であり、かつ、以下の（１）〜（４）の
条件を満たすことを特徴とする非水二次電池。 （１）正極活物質層のみかけ密度が２．８５〜３．２０
ｇ／ｃｍ3 の範囲にあること。 （２）正極活物質と金属正極集電体との重量比が４〜２
５であること。 （３）負極活物質層のみかけ密度が０．９５〜１．１８
ｇ／ｃｍ3 であること。 （４）負極活物質と金属負極集電体との重量比が１．０
〜７．０であること。1. A non-aqueous secondary battery comprising a positive electrode, a negative electrode, and an electrolytic solution as basic constituent elements, wherein the positive electrode active material is Li,
A non-aqueous secondary battery comprising a composite metal oxide containing Co as a main component, the negative electrode active material being a carbonaceous material, and satisfying the following conditions (1) to (4). (1) The apparent density of the positive electrode active material layer is 2.85 to 3.20.
Must be in the range of g / cm 3 . (2) The weight ratio of the positive electrode active material and the metal positive electrode current collector is 4 to 2
Must be 5. (3) Apparent density of the negative electrode active material layer is 0.95 to 1.18.
Must be g / cm 3 . (4) The weight ratio of the negative electrode active material and the metal negative electrode current collector is 1.0.
~ 7.0.
１．７５〜２．０５であり、かつ集電体を含めた正極と
負極との膜厚比が０．６〜０．９であることを特徴とす
る請求項１記載の非水二次電池。2. The weight ratio of the positive electrode active material and the negative electrode active material is 1.75 to 2.05, and the film thickness ratio of the positive electrode and the negative electrode including the current collector is 0.6 to 0.9. The non-aqueous secondary battery according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03261301A JP3118655B2 (en) | 1991-09-13 | 1991-09-13 | Non-aqueous secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03261301A JP3118655B2 (en) | 1991-09-13 | 1991-09-13 | Non-aqueous secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0574494A true JPH0574494A (en) | 1993-03-26 |
| JP3118655B2 JP3118655B2 (en) | 2000-12-18 |
Family
ID=17359896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03261301A Expired - Lifetime JP3118655B2 (en) | 1991-09-13 | 1991-09-13 | Non-aqueous secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3118655B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001160391A (en) * | 1999-12-06 | 2001-06-12 | Sanyo Electronic Components Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2004342500A (en) * | 2003-05-16 | 2004-12-02 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and battery charge/discharge system |
| JP2007103130A (en) * | 2005-10-03 | 2007-04-19 | Geomatec Co Ltd | Thin film solid secondary battery and method of manufacturing thin film solid secondary battery |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101904847B1 (en) * | 2015-12-30 | 2018-12-05 | 황인조 | Method of producing cloth gloves |
-
1991
- 1991-09-13 JP JP03261301A patent/JP3118655B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001160391A (en) * | 1999-12-06 | 2001-06-12 | Sanyo Electronic Components Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2004342500A (en) * | 2003-05-16 | 2004-12-02 | Matsushita Electric Ind Co Ltd | Non-aqueous electrolyte secondary battery and battery charge/discharge system |
| JP4604460B2 (en) * | 2003-05-16 | 2011-01-05 | パナソニック株式会社 | Nonaqueous electrolyte secondary battery and battery charge / discharge system |
| US9088035B2 (en) | 2003-05-16 | 2015-07-21 | Panasonic Intellectual Property Management Co., Ltd. | Nonaqueous electrolyte secondary battery and charge/discharge system thereof |
| JP2007103130A (en) * | 2005-10-03 | 2007-04-19 | Geomatec Co Ltd | Thin film solid secondary battery and method of manufacturing thin film solid secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3118655B2 (en) | 2000-12-18 |
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