JPH0574452A - New secondary battery - Google Patents
New secondary batteryInfo
- Publication number
- JPH0574452A JPH0574452A JP3231659A JP23165991A JPH0574452A JP H0574452 A JPH0574452 A JP H0574452A JP 3231659 A JP3231659 A JP 3231659A JP 23165991 A JP23165991 A JP 23165991A JP H0574452 A JPH0574452 A JP H0574452A
- Authority
- JP
- Japan
- Prior art keywords
- carbonaceous material
- secondary battery
- negative electrode
- weight
- surface area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電流効率、出力特性、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。さらに詳しくは、本発明は特定構造
を有する炭素質材料を負極活物質に用いる二次電池にお
いて平均粒径０．１〜３μのＢＥＴ比表面積Ａ（ｍ2 ／
ｇ）がＡ＝０．１〜１０の炭素質材料を１〜１５重量％
添加することにより、電流効率、出力特性のバランスの
とれた電池を実現しようとするものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel secondary battery having excellent current efficiency, output characteristics, cycleability, storage characteristics and safety. More specifically, the present invention relates to a secondary battery using a carbonaceous material having a specific structure as a negative electrode active material, and has a BET specific surface area A (m 2 / m 2) having an average particle diameter of 0.1 to 3 μm.
g) 1 to 15% by weight of carbonaceous material having A = 0.1 to 10
By adding it, it is intended to realize a battery in which current efficiency and output characteristics are well balanced.
【０００２】[0002]
【従来の技術】近年、電子機器の小型化、軽量化は目覚
ましく、それに伴い電源となる電池に対しても小型軽量
化の要望が非常に大きい。一次電池の分野では既にリチ
ウム電池等の小型軽量電池が実用化されているが、これ
らは一次電池であるが故に繰り返し使用できず、その用
途分野は限られたものであった。一方、二次電池の分野
では従来より鉛電池、ニッケル−カドミ電池が用いられ
てきたが両者共、小型軽量化という点で大きな問題点を
有している。かかる観点から、非水系二次電池が非常に
注目されてきているが、未だ実用化に至っていない。そ
の理由の一つは該二次電池に用いる負極活物質でサイク
ル性、自己放電特性等の実用物性を満足するものが見出
されていない点にある。2. Description of the Related Art In recent years, electronic devices have been remarkably reduced in size and weight, and accordingly, there has been a great demand for reduction in size and weight of batteries as power sources. In the field of primary batteries, small and lightweight batteries such as lithium batteries have already been put into practical use, but since they are primary batteries, they cannot be repeatedly used, and their fields of use have been limited. On the other hand, lead batteries and nickel-cadmium batteries have been conventionally used in the field of secondary batteries, but both have a serious problem in that they are smaller and lighter. From this viewpoint, non-aqueous secondary batteries have received a great deal of attention, but they have not yet been put to practical use. One of the reasons is that no negative electrode active material used for the secondary battery has been found to satisfy practical physical properties such as cycle property and self-discharge property.
【０００３】一方、従来のニッケル−カドミ電池、鉛電
池などと本質的に異なる充放電メカニズムであるドーピ
ング現象、又は電気二重層形成、又は層間化合物のイン
ターカレーションを利用した新しい群の電極活物質が注
目を集めている。かかる新しい電極活物質は、その充
電、放電における電気化学的反応において、複雑な化学
反応を起こさないことから、極めて優れた充放電サイク
ル性が期待されている。On the other hand, a new group of electrode active materials utilizing a doping phenomenon, which is a charging / discharging mechanism which is essentially different from that of conventional nickel-cadmium batteries, lead batteries, etc., electric double layer formation, or intercalation of intercalation compounds. Is attracting attention. Such a new electrode active material does not cause a complicated chemical reaction in the electrochemical reaction during charging and discharging, and thus is expected to have an extremely excellent charge / discharge cycle property.
【０００４】ドーピング現象を利用した電極活物質の例
として、例えば導電性高分子を電極材料に用いた新しい
タイプの二次電池が例えば特開昭５６−１３６４６９号
公報に記載されている。しかしながら、かかる導電性高
分子を用いた二次電池も、不安定性、即ち低いサイクル
性、大きな自己放電等の問題点が未解決で未だ実用化に
至っていない。As an example of an electrode active material utilizing the doping phenomenon, for example, a new type secondary battery using a conductive polymer as an electrode material is described in, for example, JP-A-56-136469. However, the secondary battery using such a conductive polymer has not yet been put to practical use because problems such as instability, that is, low cycleability and large self-discharge have not been solved.
【０００５】又、特開昭５８−２０９８６４号公報には
フェノール系繊維の炭化物で水素原子／炭素原子の比が
０．３３〜０．１５の範囲の炭素質材料を電極材料に用
いることが記載されている。主に陰イオンでｐ−ドープ
し正極材料として用いた場合に優れた特性を発揮すると
されており、同時に陽イオンでｎ−ドープし負極材料と
して用い得る旨の記載もなされている。しかしながら、
かかる材料もやはりそのｎ−ドープ体を負極として用い
た場合、サイクル性、自己放電特性に大きな欠点を有す
ると共に、利用率も極めて低く実用上大きな欠点を有す
るものであった。Further, JP-A-58-209864 discloses that a carbonaceous material, which is a carbide of a phenolic fiber and has a hydrogen atom / carbon atom ratio of 0.33 to 0.15, is used as an electrode material. Has been done. It is said that it exhibits excellent characteristics mainly when it is p-doped with an anion and used as a positive electrode material, and at the same time, it is described that it can be n-doped with a cation and used as a negative electrode material. However,
When such an n-doped material is used as the negative electrode, such a material also has a large defect in cycle property and self-discharge characteristic, and also has a very low utilization factor and a large practical defect.
【０００６】又、特開昭５８−３５８８１、特開昭５９
−１７３９７９、特開昭５９−２０７５６８号公報に
は、活性炭等の高表面積炭素材料を電極材料に用いるこ
とが提案されている。かかる電極材料はドーピング現象
と異なるその高表面積に基く電気二重層形成によると思
われる特異な現象が見出されており、特に正極に用いた
場合に優れた性能を発揮するとされている。又、一部に
は負極にも用いられることが記載されているが、かかる
高表面積炭素材料を負極として用いた場合はサイクル特
性、自己放電特性に大きな欠点を有しており、又、利用
率、即ち炭素１原子当りに可逆的に出入りし得る電子、
（又は対陽イオン）の割合が極めて低く、０．０５以
下、通常は０．０１〜０．０２であり、これは二次電池
の負極として用いた場合重量、体積共に極めて大きくな
ることを意味し、実用化に際しての大きな欠点を有して
いる。Further, JP-A-58-35881 and JP-A-59
In Japanese Patent Laid-Open No. 173979/1984, Japanese Patent Application Laid-Open No. 59-207568, it is proposed to use a high surface area carbon material such as activated carbon as an electrode material. Such an electrode material has been found to have a peculiar phenomenon which is considered to be due to the formation of an electric double layer based on its high surface area, which is different from the doping phenomenon, and is said to exhibit excellent performance particularly when used for a positive electrode. Although it is described that it is also used for a negative electrode in some cases, when such a high surface area carbon material is used as a negative electrode, it has great defects in cycle characteristics and self-discharge characteristics. That is, electrons that can reversibly enter and exit per carbon atom,
The ratio of (or counter cation) is extremely low, 0.05 or less, usually 0.01 to 0.02, which means that when used as a negative electrode of a secondary battery, both weight and volume become extremely large. However, it has a major drawback in practical application.
【０００７】又、層状化合物のインターカレーションを
利用した例として古くから黒鉛層間化合物を二次電池電
極材料として用いられ得ることが知られており、特にＢ
ｒ- ，ＣｌＯ4 - ，ＢＦ4 - イオン等の陰イオンを取り
込んだ黒鉛層間化合物を正極として用いることは公知で
ある。一方Ｌｉ+ イオン等の陽イオンを取り込んだ黒鉛
層間化合物を負極として用いることは当然考えられ、事
実、例えば特開昭５９−１４３２８０号公報に、陽イオ
ンを取り込んだ黒鉛層間化合物を負極として用いること
が記載されている。Further, as an example of utilizing intercalation of a layered compound, it has long been known that a graphite intercalation compound can be used as a secondary battery electrode material.
It is known to use a graphite intercalation compound incorporating anions such as r − , ClO 4 − and BF 4 − ions as a positive electrode. On the other hand, it is naturally conceivable to use a graphite intercalation compound incorporating cations such as Li + ions as a negative electrode, and in fact, for example, in JP-A-59-143280, a graphite intercalation compound incorporating cations is used as a negative electrode. Is listed.
【０００８】しかしながらかかる陽イオンを取り込んだ
黒鉛層間化合物は極めて不安定であり、特に電解液と極
めて高い反応性を有していることは、エイ・エヌ・ディ
（Ａ．Ｎ．Ｄｅｙ）等の「ジャーナル・オブ・エレクト
ロケミカル・ソサエティー（Ｊｏｕｒｎａｌ ｏｆ Ｅ
ｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ）ｖｏ
ｌ．１１７．Ｎｏ２，Ｐ．２２２〜２２４，１９７０
年」の記載から明らかであり、層間化合物を形成し得る
黒鉛、グラファイトを負極として用いた場合、自己放電
等電池としての安定性に欠けると共に、前述の利用率も
極めて低く実用に耐え得るものではなかった。However, graphite intercalation compounds incorporating such cations are extremely unstable, and in particular, have extremely high reactivity with an electrolytic solution, as described by A.N.D.Y. "The Journal of Electrochemical Society (Journal of E
microchemical Society) vo
l. 117. No2, P. 222-224, 1970
It is clear from the description of `` Year '', and when graphite that can form an intercalation compound or graphite is used as a negative electrode, it lacks stability as a battery such as self-discharge, and the above-mentioned utilization rate is extremely low and it is not practical. There wasn't.
【０００９】かかる点に鑑み、本発明者らは、特開昭６
２−９０８６３号に記載の如く、特定な構造を有する炭
素質材料のｎ−ドープ体が、負極として高性能である、
即ち、サイクル寿命、自己放電特性等、電池としての安
定性に優れ、又、利用効率が高く、小型軽量二次電池を
提供し得ることを見出した。しかしながら、初充電、初
放電における電流効率が低く、正極との組合せの電池に
おいては、初回の負極側の電流効率に見合った正極の
量、即ち、過剰量の正極が必要であり、小型・軽量な電
池の実用化に際し、大きな欠点を有していた。In view of this point, the inventors of the present invention disclosed in Japanese Patent Laid-Open No.
As described in No. 2-90863, an n-doped body of a carbonaceous material having a specific structure has high performance as a negative electrode,
That is, it has been found that a small and lightweight secondary battery having excellent stability as a battery such as cycle life and self-discharge characteristics and high utilization efficiency can be provided. However, the current efficiency in initial charge and initial discharge is low, and in the battery combined with the positive electrode, the amount of the positive electrode commensurate with the current efficiency on the negative electrode side at the first time, that is, the excess amount of the positive electrode is required, which is small and lightweight. There was a big defect in practical application of such a battery.
【００１０】[0010]
【発明が解決しようとする課題】前述の如く、ドーピン
グを利用した炭素質材料活物質は本来期待されている性
能は未だに実用的な観点からは実現されていないのが現
状である。As described above, in the present circumstances, the originally expected performance of the carbonaceous material active material utilizing doping has not been realized from a practical point of view.
【００１１】[0011]
【課題を解決するための手段】本発明は前述の問題点を
解決し、電池性能、特にサイクル性、自己放電特性に優
れた高性能、高エネルギー密度の小型軽量二次電池を提
供するためになされたものである。本発明によれば、少
くとも正電極、負電極、セパレーター及び非水電解液を
有する二次電池であって、該負電極の活物質が、ＢＥＴ
法比表面積Ａ（ｍ2 ／ｇ）が０．１＜Ａ＜１００の範囲
で、かつ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 １．８０＜ρ＜２．１８，１５＜Ｌｃかつ １２０ρ−２２７＜Ｌｃ＜１２０ρ−１８９ を満たす範囲にある炭素質材料（以下炭素質材料１とい
う）を８５重量％〜９９重量％と、平均粒径０．１〜３
μのＢＥＴ法比表面積Ａ（ｍ2 ／ｇ）がＡ＝０．１〜１
０、炭素質材料（以下、炭素質材料２という）１５重量
％〜１重量％とからなることを特徴とするものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and provides a compact and lightweight secondary battery having high performance, high energy density and excellent battery performance, particularly cycleability and self-discharge characteristics. It was made. According to the present invention, there is provided a secondary battery having at least a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte, wherein the negative electrode active material is BET.
The specific surface area A (m 2 / g) is in the range of 0.1 <A <100, and the values of the crystal thickness Lc (Å) and the true density ρ (g / cm 3 ) in X-ray diffraction are as follows. 85 wt% to 99 wt% of a carbonaceous material (hereinafter referred to as carbonaceous material 1) in a range satisfying 80 <ρ <2.18, 15 <Lc and 120ρ-227 <Lc <120ρ-189, and an average particle diameter. 0.1-3
BET specific surface area A (m 2 / g) of μ is A = 0.1 to 1
0, and 15% by weight to 1% by weight of carbonaceous material (hereinafter referred to as carbonaceous material 2).
【００１２】本発明で用いられる炭素質材料１は後述の
ＢＥＴ法比表面積Ａ（ｍ2 ／ｇ）が０．１より大きく、
１００未満でなければならない。好ましくは０．１より
大きく５０未満、更に好ましくは０．１より大きく２５
未満の範囲である。０．１ｍ2 ／ｇ以下の場合は余りに
表面積が小さく、電極表面での円滑な電気化学的反応が
進行しにくく好ましくない。又、１００ｍ2 ／ｇ以上の
比表面積を有する場合は、サイクル寿命特性、自己放電
特性、更には電流効率特性等の面で特性の低下が見られ
好ましくない。かかる現象は余りに表面積が大きいが故
に電極表面での種々の副反応が起こり、電池性能に悪影
響を及ぼしているものと推察される。The carbonaceous material 1 used in the present invention has a BET specific surface area A (m 2 / g) described later of more than 0.1,
Must be less than 100. Preferably more than 0.1 and less than 50, more preferably more than 0.1 and 25.
The range is less than. When it is 0.1 m 2 / g or less, the surface area is too small and a smooth electrochemical reaction on the electrode surface is difficult to proceed, which is not preferable. Further, when the specific surface area is 100 m 2 / g or more, the characteristics are deteriorated in terms of cycle life characteristics, self-discharge characteristics, and current efficiency characteristics, which is not preferable. It is presumed that such a phenomenon causes a variety of side reactions on the electrode surface because the surface area is too large and adversely affects the battery performance.
【００１３】又、後述の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、即ち １．８０＜ρ＜２．１８，１５＜ＬＣかつ １２０ρ−２２７＜Ｌｃ＜１２０ρ−１８９の範囲でな
ければならない。好ましくは１．９６＜ρ＜２．１６
かつ１５＜Ｌｃ＜１２０ρ−１９６かつＬｃ＞１２０ρ
−２２７の範囲である。The crystal thickness Lc in X-ray diffraction, which will be described later,
The values of (Å) and the true density ρ (g / cm 3 ) must be within the following conditions: 1.80 <ρ <2.18, 15 <LC and 120ρ-227 <Lc <120ρ-189. Preferably 1.96 <ρ <2.16
And 15 <Lc <120ρ-196 and Lc> 120ρ
The range is -227.
【００１４】本発明において、該炭素質材料１のｎ−ド
ープ体を安定な電極活物質として用いる場合、前述のＸ
線回折における結晶厚みＬｃ（Å）と真密度ρ（ｇ／ｃ
ｍ3 ）の値は極めて重要である。即ち、ρの値が１．８
０以下又はＬｃの値が１５以下の場合は、炭素質材料１
が十分に炭化していない、即ち炭素の結晶成長が進んで
おらず、無定形部分が非常に多いことを意味する。又、
その為、この範囲にある炭素質材料１はその炭化過程に
おいて表面積が必然的に大きくなり、本発明の範囲のＢ
ＥＴ法比表面積の値を逸脱する。かかる炭素質材料１の
ｎ−ドープ体は極めて不安定であり、ドープ量も低く、
実質的にｎ−ドープ体として安定に存在することができ
ず、電池活物質として用いることはできない。In the present invention, when the n-doped body of the carbonaceous material 1 is used as a stable electrode active material, the above X
Crystal thickness Lc (Å) and true density ρ (g / c) in line diffraction
The value of m 3 ) is extremely important. That is, the value of ρ is 1.8
When the value of 0 or less or the value of Lc is 15 or less, the carbonaceous material 1
Is not carbonized sufficiently, that is, the crystal growth of carbon has not progressed, and there are a large number of amorphous portions. or,
Therefore, the carbonaceous material 1 in this range inevitably has a large surface area in the carbonization process, and the B
The value of the specific surface area by the ET method deviates. The n-doped body of the carbonaceous material 1 is extremely unstable and has a low doping amount,
It cannot substantially exist as an n-dope and cannot be used as a battery active material.
【００１５】一方、ρの値が２．１８以上又はＬｃの値
が１２０ρ−１８９の値以上の場合、炭素質材料１の炭
化が余りに進み過ぎ、即ち炭素の結晶化の進んだ黒鉛、
グラファイトに近い構造を有していることを意味する。
かかる炭素質材料１の構造を示すパラメーターとして、
本発明で限定する、真密度ρ（ｇ／ｃｍ3 ）、結晶厚み
Ｌｃ（Å）、ＢＥＴ法比表面積Ａ（ｍ2 ／ｇ）以外に、
例えばＸ線回折における層間面間隔ｄ002 （Å）が挙げ
られる。かかる面間隔ｄ002 （Å）の値は結晶化の進行
と共に小さくなり、特に限定はしないが、３．４３Å未
満、更には３．４６Å未満の値を有する炭素質材料１
は、本発明で限定する範囲から逸脱する。On the other hand, when the value of ρ is 2.18 or more or the value of Lc is 120ρ-189 or more, carbonization of the carbonaceous material 1 is too advanced, that is, graphite in which carbon crystallization is advanced,
It means that it has a structure close to that of graphite.
As a parameter indicating the structure of the carbonaceous material 1,
In addition to the true density ρ (g / cm 3 ), the crystal thickness Lc (Å), and the BET specific surface area A (m 2 / g), which are limited in the present invention,
For example, the interlayer spacing d 002 (Å) in X-ray diffraction may be mentioned. The value of the interplanar spacing d 002 (Å) decreases with the progress of crystallization, and is not particularly limited, but is less than 3.43 Å, and further less than 3.46 Å
Deviates from the scope limited by the present invention.
【００１６】かかる本発明の条件を満たす炭素質材料１
として例えば、種々の有機化合物の熱分解、又は焼成炭
化により得られる。この場合、熱履歴温度条件は重要で
あり、前記の如く、余りに熱履歴温度が低い場合には炭
化が十分でなく、電気電導度の小さいのみならず本発明
の条件とする炭素質材料とならない。その温度下限は物
により若干異なるが、通常６００℃以上、好ましくは８
００℃以上である。更に重要なのは熱履歴温度上限であ
り、通常の黒鉛、グラファイトや炭素繊維製造で行われ
ている３，０００℃に近い温度での熱処理は、結晶の成
長が余りに進み過ぎ、二次電池としての機能が著しく損
われる。２，４００℃以下、好ましくは１，８００℃以
下、更には１，４００℃以下が好ましい範囲である。か
かる熱処理条件において、昇温速度、冷却速度、熱処理
時間等は目的に応じ任意の条件を選択することができ
る。又、比較的低温領域で熱処理をした後、所定の温度
に昇温する方法も採用される。The carbonaceous material 1 satisfying the conditions of the present invention
For example, it can be obtained by thermal decomposition of various organic compounds or carbonization by firing. In this case, the heat history temperature condition is important, and as described above, when the heat history temperature is too low, the carbonization is not sufficient, the electric conductivity is small, and the carbonaceous material is not the condition of the present invention. .. The lower limit of temperature is slightly different depending on the object, but is usually 600 ° C or higher, preferably 8 ° C.
It is at least 00 ° C. What is more important is the upper limit of the thermal history temperature, and heat treatment at temperatures close to 3,000 ° C., which is performed in ordinary graphite, graphite and carbon fiber production, causes crystal growth too much and functions as a secondary battery. Is significantly impaired. 2,400 ° C or lower, preferably 1,800 ° C or lower, and more preferably 1,400 ° C or lower is a preferable range. Under such heat treatment conditions, the heating rate, the cooling rate, the heat treatment time, etc. can be arbitrarily selected according to the purpose. In addition, a method of raising the temperature to a predetermined temperature after heat treatment in a relatively low temperature region is also adopted.
【００１７】本発明の条件を満たす炭素質材料１の具体
例については前記特開昭６２−９０８６３号公報に記載
の通りであり、気相成長法炭素繊維、ピッチ焼成体、高
分子化合物焼成体等が挙げられる。本発明において前記
特定構造を有する炭素質材料１、８５重量％〜９９重量
％に平均粒径０．１〜３μ、ＢＥＴ法比個よ面積Ａ（ｍ
2 ／ｇ）がＡ＝０．１〜１０の炭素質材料２、１５重量
％〜１重量％混合して用いることにより電流効率を維持
したまま出力特性を向上させることができる。Specific examples of the carbonaceous material 1 satisfying the conditions of the present invention are as described in the above-mentioned JP-A-62-90863, and vapor-grown carbon fiber, pitch fired body, polymer compound fired body. Etc. In the present invention, the carbonaceous material 1 having the above specific structure has an average particle size of 0.1 to 3 μ in 85% by weight to 99% by weight and an area A (m
By using a mixture of the carbonaceous materials 2 having 2 / g) of A = 0.1 to 10 and 15% by weight to 1% by weight, the output characteristics can be improved while maintaining the current efficiency.
【００１８】本発明の炭素質材料２の例としては、ピッ
チ、フェノール樹脂等の球状炭素前駆体を焼成して得、
球状微細炭素質材料等が挙げられる。炭素質材料２の平
均粒径が０．１μ未満の場合は電流効率の低下が避けら
れず好ましくない。又、３μを越す場合は出力特性の低
下が見られ好ましくない。何故、かかる炭素質材料２を
加えることにより効果が発現するのか定かではないが、
炭素質材料２は粒径的に小さいにもかかわらず比較的表
面積が小さく副反応が起こりにくい為ではないかと推察
される。An example of the carbonaceous material 2 of the present invention is obtained by firing a spherical carbon precursor such as pitch or phenol resin,
Examples include spherical fine carbonaceous materials. When the average particle diameter of the carbonaceous material 2 is less than 0.1 μ, a decrease in current efficiency cannot be avoided, which is not preferable. On the other hand, when it exceeds 3 μ, the output characteristics are deteriorated, which is not preferable. Although it is not clear why the addition of the carbonaceous material 2 produces the effect,
It is presumed that the carbonaceous material 2 has a relatively small surface area and is less likely to cause a side reaction despite its small particle size.
【００１９】この炭素質材料２が１５重量％越す場合に
は電池容量が低下し好ましくない。又、１重量％未満の
場合は電流効率、出力特性のバランスがとれず好ましく
ない。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、前述の如
く、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。If the carbonaceous material 2 exceeds 15% by weight, the battery capacity will decrease, which is not preferable. On the other hand, if it is less than 1% by weight, current efficiency and output characteristics cannot be balanced, which is not preferable. The basic constituent elements 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 electrolytic solution. The separator is not particularly limited, and examples thereof include woven cloth, non-woven cloth, glass woven cloth, and synthetic resin microporous film. When a thin film or large area electrode is used as described above, for example, JP-A-58-59072 is used. The synthetic resin microporous membrane disclosed in JP-A No. 1994-1999, particularly a polyolefin-based microporous membrane is preferable in terms of thickness, strength and membrane resistance.
【００２０】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 ，Ｌｉ
ＡｓＦ6 ，ＣＦ3 ＳＯ3 Ｌｉ，ＬｉＰＦ4 ，ＬｉＩ，Ｌ
ｉＡｌＣｌ4 ，ＮａＣｌＯ4 ，ＮａＢＦ4 ，ＮａＩ，
（ｎ−Ｂｕ）4 Ｎ- ＣｌＯ4 ，（ｎ−Ｂｕ）4 Ｎ- ＢＦ
4 ，ＫＰＦ4 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 , Li
AsF 6 , CF 3 SO 3 Li, LiPF 4 , LiI, L
iAlCl 4 , NaClO 4 , NaBF 4 , NaI,
(N-Bu) 4 N - ClO 4, (n-Bu) 4 N - BF
4 , KPF 4 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.
【００２１】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。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.
【００２２】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。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 components such as a current collector, a terminal and an insulating plate. 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.
【００２３】[0023]
【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。尚、表面積は柴田科学器械工業（株）製
ＢＥＴ表面積測定装置Ｐ−７００型を用いて、窒素吸着
法により測定した。また、Ｘ線回折は「日本学術振興会
法」に準じて行った。また、真密度は、炭素質材料の粉
粒体を試料とし、２５℃でブロモホルム、四塩化炭素混
合溶液を用いる浮沈法により測定した。真密度が分布を
有する試料に関しては、粉末粒子の全体の約５０％が沈
降するところの値を測定値とした。また、平均粒径の測
定は、ＳＹＭＰＡＴＥＣ社製の乾式流動分散ユニットＲ
ＯＤＯＳ及びレーザー回折式粒度分布測定光学システム
ＨＥＲＯＳ−ＢＡＳＩＳ／ＫＡ（０．５〜１７５μレン
ジ）を使用し、気流圧５．０ｂａｒ、吹込み圧１００ｍ
ｂａｒ、カスケード使用の条件で乾式分散させ測定し
た。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. The surface area was measured by a nitrogen adsorption method using a BET surface area measuring device P-700 type manufactured by Shibata Scientific Instruments Co., Ltd. In addition, X-ray diffraction was performed according to the "Japan Society for the Promotion of Science". The true density was measured by a float-sink method at 25 ° C. using a powder of carbonaceous material as a sample and a mixed solution of bromoform and carbon tetrachloride. Regarding the sample having the distribution of true density, the value at which about 50% of the whole powder particles settled was used as the measured value. The average particle size is measured by a dry fluid dispersion unit R manufactured by SYMPATEC.
ODOS and laser diffraction type particle size distribution measurement optical system HEROS-BASIS / KA (0.5 to 175 μ range) are used, and air pressure is 5.0 bar and blowing pressure is 100 m.
The measurement was carried out by dry dispersion under the conditions of bar and cascade.
【００２４】累積分布５０％粒径を平均粒径とした。The average particle size was defined as the 50% cumulative distribution particle size.
【００２５】[0025]
【実施例１〜５、比較例１〜４】Ｌｉ1.03Ｃｏ0.92Ｓｎ
0.02Ｏ2 の組成を有するＬｉ，Ｃｏ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。Examples 1 to 5 and Comparative Examples 1 to 4 Li 1.03 Co 0.92 Sn
After mixing 100 parts by weight of Li, Co composite oxide having a composition of 0.02 O 2 , 2.5 parts by weight of graphite and 2.5 parts by weight of acetylene black, 2 parts by weight of fluororubber were mixed with ethyl acetate / ethyl cellosolve 1: 2. A liquid dissolved in 60 parts by weight of a 1 (weight ratio) mixed solvent was mixed to obtain a slurry coating liquid.
【００２６】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さは２９０
μであった。比表面積６．５ｍ2 ／ｇ、真密度２．１
３、Ｌｃ＝４８Åのニードルコークス粉砕品（炭素質材
料１）１００重量部と粒径１．５μ比表面積１．５ｍ2
／ｇの炭素質材料２、５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。Using a coating machine having a doctor blade coater head, the above coating solution was applied to both sides of an al foil having a width of 600 mm and a thickness of 15 μm. Coating thickness after coating on both sides is 290
It was μ. Specific surface area 6.5 m 2 / g, true density 2.1
3, 100 parts by weight of crushed needle coke (carbonaceous material 1) with Lc = 48 Å and particle size 1.5μ specific surface area 1.5m 2
/ G of carbonaceous material (2, 5 parts by weight) and fluororubber (5 parts by weight) dissolved in 90 parts by weight of a 1: 1 (weight ratio) mixed solvent of ethyl acetate / ethyl cellosolve are mixed to form a slurry coating solution. Obtained.
【００２７】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。両面塗工液の塗工厚は３５０μ
であった。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４０３０Ｕ
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５０
ｍｍのＡサイズの電池缶を試作した。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 of both sides coating liquid is 350μ
Met. 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. Li 1.03 Co 0.92 Sn 0.02 O 2 coated product was used as a positive electrode, needle coke coated product was used as a negative electrode, and a polyethylene microporous film (HIPORE 4030U) was used as a separator.
Asahi Kasei Co., Ltd.) and was wound into a coil having an outer diameter of 14.9 mm by a winding machine. This wound coil was placed in a battery can having an outer diameter of 16 mm, and then a 1: 1 concentration of LiBF 4 dissolved in a mixed solvent of propylene carbonate / ethylene carbonate / γ-butyrolactone 1: 1: 2 (weight ratio) was electrolyzed. After being impregnated as a liquid, it is sealed and the height 50 shown in FIG.
A mm size A battery can was prototyped.
【００２８】本電池を４．２Ｖ定電圧で充電し、電池性
能試験を行った。結果を表１に示す。This battery was charged at a constant voltage of 4.2 V and a battery performance test was conducted. The results are shown in Table 1.
【００２９】[0029]
【実施例２〜３、比較例１〜４】実施例１において表１
に示すように炭素質材料２の種類を変えることと、その
混合比を代えた以外は全く同じ操作を行い電池を試作し
た。電池性能試験結果を併せて表１に示す。Examples 2-3, Comparative Examples 1-4 Table 1 in Example 1
As shown in, the same procedure was performed except that the kind of the carbonaceous material 2 was changed and the mixing ratio thereof was changed, to fabricate a battery as a prototype. Table 1 also shows the results of the battery performance test.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【発明の効果】本発明の電池は小型軽量であり、特にサ
イクル特性、自己放電特性に優れ、小型電子機器用、電
気自動車用、電力貯蔵用等の電源として極めて有用であ
る。EFFECTS OF THE INVENTION The battery of the present invention is small and lightweight, and is particularly excellent in cycle characteristics and self-discharge characteristics, and is extremely useful as a power source for small electronic devices, electric vehicles, power storage, etc.
【図１】本発明に係る電池の半裁断面を示す。FIG. 1 shows a half-cut cross section 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……銅製の負極リード ６……アルミニウム製の正極リード ７……ガスケット 1 ... Positive electrode 2 ... Separator 3 ... Negative electrode 4 ... Insulating plate 5 ... Copper negative electrode lead 6 ... Aluminum positive electrode lead 7 ... Gasket
Claims (1)
及び非水電解液を有する二次電池であって、該負電極の
活物質が、ＢＥＴ法比表面積Ａ（ｍ2 ／ｇ）が０．１＜
Ａ＜１００の範囲で、かつＸ線回折における結晶厚みＬ
ｃ（Å）と真密度ρ（ｇ／ｃｍ3 ）の値が下記条件 １．８０＜ρ＜２．１８，１５＜Ｌｃかつ １２０ρー２２７＜Ｌｃ＜１２０ρ−１８９ を満たす範囲にある炭素質材料を８５重量％〜９９重量
％と、平均粒径０．１〜３μのＢＥＴ法比表面積Ａ（ｍ
2 ／ｇ）がＡ＝０．１〜１０の炭素質材料１５重量％〜
１重量％とからなることを特徴とする新規二次電池。1. A secondary battery comprising at least a positive electrode, a negative electrode, a separator and a non-aqueous electrolyte, wherein the negative electrode active material has a BET specific surface area A (m 2 / g) of 0. 1 <
Crystal thickness L in the range of A <100 and in X-ray diffraction
A carbonaceous material in which the values of c (Å) and true density ρ (g / cm 3 ) satisfy the following conditions: 1.80 <ρ <2.18, 15 <Lc and 120ρ−227 <Lc <120ρ−189 Of 85% by weight to 99% by weight and a BET specific surface area A (m
2 / g) 15% by weight of carbonaceous material with A = 0.1-10
A novel secondary battery comprising 1% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3231659A JPH0574452A (en) | 1991-09-11 | 1991-09-11 | New secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3231659A JPH0574452A (en) | 1991-09-11 | 1991-09-11 | New secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0574452A true JPH0574452A (en) | 1993-03-26 |
Family
ID=16926967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3231659A Withdrawn JPH0574452A (en) | 1991-09-11 | 1991-09-11 | New secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0574452A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054779A1 (en) * | 1997-05-30 | 1998-12-03 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| WO1998054780A1 (en) * | 1997-05-30 | 1998-12-03 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery and method for manufacturing negative electrode of the same |
| JP2004360160A (en) * | 2003-05-09 | 2004-12-24 | Showa Denko Kk | Linear fine carbon fiber and resin composite material given by using the same |
| JP2007066669A (en) * | 2005-08-30 | 2007-03-15 | Lignyte Co Ltd | Electrode material, electrode for secondary battery, carbon material for electric double layer capacitor polarizing electrode, and electric double layer capacitor polarizing electrode |
| EP2105985A1 (en) * | 2008-03-25 | 2009-09-30 | Fuji Jukogyo Kabushiki Kaisha | Carbon Material for Negative Electrode, Electric Storage Device, and Product Having Mounted Thereon Electric Storage Device |
-
1991
- 1991-09-11 JP JP3231659A patent/JPH0574452A/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998054779A1 (en) * | 1997-05-30 | 1998-12-03 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery |
| WO1998054780A1 (en) * | 1997-05-30 | 1998-12-03 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery and method for manufacturing negative electrode of the same |
| US6403259B1 (en) | 1997-05-30 | 2002-06-11 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery comprising carbon particles with a plural-layer structure |
| US6455199B1 (en) | 1997-05-30 | 2002-09-24 | Matsushita Electric Industrial Co., Ltd. | Nonaqueous electrolyte secondary battery and method for manufacturing negative electrode of the same |
| JP2004360160A (en) * | 2003-05-09 | 2004-12-24 | Showa Denko Kk | Linear fine carbon fiber and resin composite material given by using the same |
| JP2010084316A (en) * | 2003-05-09 | 2010-04-15 | Showa Denko Kk | Fine carbon fiber with linearity and composite material using the same |
| US8084121B2 (en) | 2003-05-09 | 2011-12-27 | Showa Denko K.K. | Fine carbon fiber with linearity and resin composite material using the same |
| US8372511B2 (en) | 2003-05-09 | 2013-02-12 | Showa Denko K.K. | Fine carbon fiber with linearity and resin composite material using the same |
| JP2013217011A (en) * | 2003-05-09 | 2013-10-24 | Showa Denko Kk | Linear fine carbon fiber |
| JP2007066669A (en) * | 2005-08-30 | 2007-03-15 | Lignyte Co Ltd | Electrode material, electrode for secondary battery, carbon material for electric double layer capacitor polarizing electrode, and electric double layer capacitor polarizing electrode |
| EP2105985A1 (en) * | 2008-03-25 | 2009-09-30 | Fuji Jukogyo Kabushiki Kaisha | Carbon Material for Negative Electrode, Electric Storage Device, and Product Having Mounted Thereon Electric Storage Device |
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