JPH0574454A - Manufacture of carbon for battery activator - Google Patents
Manufacture of carbon for battery activatorInfo
- Publication number
- JPH0574454A JPH0574454A JP3234814A JP23481491A JPH0574454A JP H0574454 A JPH0574454 A JP H0574454A JP 3234814 A JP3234814 A JP 3234814A JP 23481491 A JP23481491 A JP 23481491A JP H0574454 A JPH0574454 A JP H0574454A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- substrate
- reaction
- base
- battery
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は電池活物質用炭素の製
造方法に関するものであり、特に熱分解による炭素の製
造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing carbon for a battery active material, and more particularly to a method for producing carbon by thermal decomposition.
【０００２】[0002]
【従来の技術】高エネルギ密度を有するリチウム電池を
二次電池にする研究が進められている。このリチウム電
池の電池活物質として炭素体が用いられる。電池活物質
とは電池の構成要素となる物質のことであり、ここでい
う炭素体は電極の材料となる。2. Description of the Related Art Studies are underway to use lithium batteries having a high energy density as secondary batteries. A carbon body is used as a battery active material of this lithium battery. A battery active material is a material that is a constituent element of a battery, and the carbon body here is a material of an electrode.
【０００３】炭素体として活性炭を用いた場合、活性炭
は無定形炭素であるためリチウムイオンのインターカレ
ーションができない。したがって、電解液と活性炭との
電気二重層を利用するのみなので、電池に必要な容量と
ならない。When activated carbon is used as the carbon body, lithium ion cannot be intercalated because the activated carbon is amorphous carbon. Therefore, since only the electric double layer of the electrolytic solution and the activated carbon is used, the capacity is not required for the battery.
【０００４】また、炭素体としてグラファイトを用いた
場合、グラファイトは結晶性が高いのでリチウムイオン
のインターカレーションができる。しかし、グラファイ
トを用いた場合は有機溶媒の分解反応が起こることが知
られている〔Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，
１１７，２２２（１９７０）〕。有機溶媒の分解反応が
起きると充電量と放電量との差が大きくなり電池の効率
が悪くなる。Further, when graphite is used as the carbon body, graphite has high crystallinity, and therefore lithium ions can be intercalated. However, it is known that decomposition reaction of an organic solvent occurs when graphite is used [J. Electrochem. Soc. ，
117, 222 (1970)]. When the decomposition reaction of the organic solvent occurs, the difference between the charge amount and the discharge amount becomes large and the efficiency of the battery deteriorates.
【０００５】これに対し、炭素体としてある種の熱分解
炭素を用いると、熱分解炭素はグラファイト状構造と無
定形構造とを有するので、前記２つの炭素体の問題を解
決し良好な電気特性を示すことが知られている（たとえ
ば特開昭６３−２４５５５号公報）。この熱分解炭素
は、炭化水素または炭化水素化合物の気体を熱分解さ
せ、それを基板上に堆積させることにより得られる。On the other hand, when a certain kind of pyrolytic carbon is used as the carbon body, the pyrolytic carbon has a graphite-like structure and an amorphous structure. Is known (for example, JP-A-63-24555). This pyrolytic carbon is obtained by pyrolyzing a gas of a hydrocarbon or a hydrocarbon compound and depositing it on a substrate.
【０００６】[0006]
【発明が解決しようとする課題】この熱分解炭素の生産
量を高めることができればこの熱分解炭素を用いた電池
のコストを下げることが可能となる。If the production amount of the pyrolytic carbon can be increased, the cost of the battery using the pyrolytic carbon can be reduced.
【０００７】この発明にかかる従来の問題点を解決する
ためになされたものである。この発明の目的は、熱分解
炭素の生産量を向上させることができる電池活物質用炭
素の製造方法を提供することである。The present invention has been made to solve the conventional problems of the present invention. An object of the present invention is to provide a method for producing carbon for a battery active material, which can improve the amount of pyrolytic carbon produced.
【０００８】[0008]
【課題を解決するための手段】この発明に従った電池活
物質用炭素の製造方法は、基体表面に鉄族元素または鉄
族元素を含有する化合物のうち少なくともいずれか一方
を含有する物質を位置させる工程と、炭化水素または炭
化水素化合物のうち少なくともいずれか一方を含有する
気体を熱分解させる工程と、熱分解させた炭素を基体表
面に堆積させる工程とを備えている。According to the method for producing carbon for a battery active material according to the present invention, a substance containing at least one of an iron group element and a compound containing an iron group element is located on the surface of a substrate. And a step of thermally decomposing a gas containing at least one of a hydrocarbon and a hydrocarbon compound, and a step of depositing thermally decomposed carbon on the surface of the substrate.
【０００９】[0009]
【作用】この発明に従った電池活物質用炭素の製造方法
は、金属基体表面に鉄族元素または鉄族元素を含有する
化合物のうち少なくともいずれか一方を含有する物質を
位置させている。鉄族元素は有機分子の分解反応および
炭素生成反応に対し反応促進の触媒作用を有するので
（たとえば炭素，１９８０（Ｎｏ．１０２），１２４：
大谷朝男）、この物質を位置させない場合に比べ熱分解
炭素の生産量を高めることができる。In the method for producing carbon for a battery active material according to the present invention, a material containing at least one of an iron group element and a compound containing an iron group element is located on the surface of a metal substrate. The iron group element has a catalytic action for accelerating the decomposition reaction of the organic molecule and the carbon production reaction (for example, carbon, 1980 (No. 102), 124:
Asahi Otani), the production of pyrolytic carbon can be increased compared to the case where this substance is not located.
【００１０】[0010]
【実施例】（実施例）図１に示す装置を用いてこの発明
の一実施例を行なった。反応管３の周囲には加熱炉５が
ある。Ｎｉ基板４上に硝酸ニッケル粉末５０ｍｇを載置
した後、Ｎｉ基板４を反応管３内に入れた。そして、加
熱炉５よりＮｉ基板４を加熱した。Ｎｉ基板４の温度は
約７５０℃になるように維持した。EXAMPLE An example of the present invention was carried out using the apparatus shown in FIG. A heating furnace 5 is provided around the reaction tube 3. After placing 50 mg of nickel nitrate powder on the Ni substrate 4, the Ni substrate 4 was put into the reaction tube 3. Then, the Ni substrate 4 was heated from the heating furnace 5. The temperature of the Ni substrate 4 was maintained at about 750 ° C.
【００１１】反応用混合ガス供給器１からアルゴンガス
とプロパンガスとの混合ガスを反応管３へ送った。アル
ゴンガスとプロパンガスとの体積比が８：２となるよう
にニードル弁２で調整した。この雰囲気中でプロパンガ
スを熱分解し、２００分かけてＮｉ基板４上に炭素を堆
積させた。反応終了後、残留ガスは排気装置６で除去し
た。A mixed gas of argon gas and propane gas was sent to the reaction tube 3 from the reaction mixed gas supply device 1. The needle valve 2 was used to adjust the volume ratio of argon gas to propane gas to 8: 2. Propane gas was thermally decomposed in this atmosphere, and carbon was deposited on the Ni substrate 4 for 200 minutes. After the reaction was completed, the residual gas was removed by the exhaust device 6.
【００１２】このようにして得られた炭素をＮｉ基板４
から剥離し、炭素の重量を測定すると１２０ｍｇあっ
た。このうち２０ｍｇとポリオレフィン系結着剤とを混
練した。ポリオレフィン系結着剤の量は炭素粉末に対し
て５ｗｔ％とした。この混練物をニッケルメッシュ上に
乗せ、１１０℃、４００ｋｇｃｍ- 2 の条件でホットプ
レスを行ない電極Ａを作製した。The carbon thus obtained is used for the Ni substrate 4
The carbon was peeled off and the weight of carbon was measured and found to be 120 mg. 20 mg of this and a polyolefin-based binder were kneaded. The amount of the polyolefin-based binder was 5 wt% with respect to the carbon powder. Place the kneaded material on a nickel mesh, 110 ℃, 400kgcm - to produce an electrode A subjected to hot pressing under 2 conditions.
【００１３】（比較例）Ｎｉ基板４上に硝酸ニッケル粉
末を載置しない以外は（実施例）とまったく同じ条件で
炭素を製造した。重量は２５ｍｇであった。そして（実
施例）と同じ条件で電極Ｂを作成した。(Comparative Example) Carbon was produced under exactly the same conditions as (Example) except that nickel nitrate powder was not placed on the Ni substrate 4. The weight was 25 mg. And the electrode B was produced on the same conditions as (Example).
【００１４】実施例と比較例とを比べればわかるよう
に、硝酸ニッケル粉末をＮｉ基板４上に載置すると、製
造量が９５ｍｇ増加した。As can be seen by comparing the example and the comparative example, when the nickel nitrate powder was placed on the Ni substrate 4, the production amount increased by 95 mg.
【００１５】次に、電極Ａ、Ｂを図２に示す電極特性測
定装置を用いて充放電サイクル試験を行なった。図２に
示す装置について簡単に説明していく。電解槽１２に
は、１ｍｏｌ ｄｍ- 3 の過塩素酸リチウムを溶解させ
たプロピレンカーボネートが入っている。９はリチウム
対極で負極となる。７は電極ＡまたはＢであり、正極と
なる。８は集電体である。１０はリチウム参照極であ
り、正極、負極の電位を測定する基準となる。リチウム
参照極１０だけでは正確な基準にならないので、リチウ
ム参照極１０の周囲にガラスからなる包囲体１３を設け
た。Next, the electrodes A and B were subjected to a charge / discharge cycle test using the electrode characteristic measuring device shown in FIG. The device shown in FIG. 2 will be briefly described. The electrolytic cell 12, 1 mol dm - propylene carbonate dissolved lithium perchlorate 3 is on. 9 is a lithium counter electrode, which serves as a negative electrode. Reference numeral 7 is an electrode A or B, which serves as a positive electrode. 8 is a current collector. Reference numeral 10 is a lithium reference electrode, which serves as a reference for measuring the potentials of the positive electrode and the negative electrode. Since the lithium reference electrode 10 alone does not serve as an accurate reference, an enclosure 13 made of glass is provided around the lithium reference electrode 10.
【００１６】充放電サイクル試験はリチウム参照極１０
に対して０〜２．５Ｖの電位範囲にて行なった。１０サ
イクル後、１００サイクル後の電極Ａ、Ｂの放電容量を
測定した。結果を表１に示す。The charge / discharge cycle test was carried out using a lithium reference electrode 10
In the potential range of 0 to 2.5 V. After 10 cycles and 100 cycles, the discharge capacities of the electrodes A and B were measured. The results are shown in Table 1.
【００１７】[0017]
【表１】 表１を見ればわかるように、電極Ａと電極Ｂとは放電容
量に差がない。[Table 1] As can be seen from Table 1, there is no difference in discharge capacity between the electrodes A and B.
【００１８】なお、この実施例ではニッケルを用いてい
るが、鉄、コバルト等の他の鉄族元素であってもよい。
さらに鉄族元素を含む化合物であってもよい。この化合
物としては、ホウ化物、炭化物、窒化物、フッ化物、塩
化物、硫化物、臭化物、ヨウ化物、ホウフッ化物、ケイ
フッ化物、シアン化物、リン化物、水酸化物、乳酸塩、
硝酸塩、硫酸塩、ギ酸塩、ホスフィン酸塩、酢酸塩、炭
酸塩、クエン酸塩、シュウ酸塩、フマル酸塩、リン酸
塩、ステアリン酸塩、スルファミン酸塩、酒石酸塩、ナ
フテレ酸塩、オクチル酸塩、ピロリン酸塩、アミド硫酸
塩、安息香酸塩、オレイン酸塩、ホウ酸塩がある。Although nickel is used in this embodiment, other iron group elements such as iron and cobalt may be used.
Further, it may be a compound containing an iron group element. As the compound, boride, carbide, nitride, fluoride, chloride, sulfide, bromide, iodide, borofluoride, silicofluoride, cyanide, phosphide, hydroxide, lactate,
Nitrate, sulphate, formate, phosphinate, acetate, carbonate, citrate, oxalate, fumarate, phosphate, stearate, sulfamate, tartrate, naphtherate, octyl There are acid salts, pyrophosphates, amide sulfates, benzoates, oleates and borates.
【００１９】また、この実施例では硝酸ニッケル粉末を
基板上に載置しているが、液状のものやゼリー状のもの
であってもよい。In this embodiment, the nickel nitrate powder is placed on the substrate, but it may be liquid or jelly.
【００２０】また、鉄族元素またはこれらの合金を基体
の材料とすると炭素をさらに多く堆積できる。Further, if an iron group element or an alloy thereof is used as the base material, more carbon can be deposited.
【００２１】また、この実施例では基体として板状のも
のを用いているが、網状のものやスポンジ状のものであ
ってもよい。In this embodiment, a plate-shaped substrate is used as the substrate, but a net-shaped or sponge-shaped substrate may be used.
【００２２】また、この実施例ではプロパンを用いてい
るが、熱分解の際に使用する炭化水素あるいは炭化水素
化合物としては脂肪族炭化水素、芳香族炭化水素、脂環
族炭化水素などいずれであってもよい。その具体例とし
てはたとえばベンゼン、トルエン、キシレン、ナフタレ
ン、アントラセン、ヘキサメチルベンゼン、１．２−ジ
ブロモエチレン、２−ブチン、アセチレン、ビフェニ
ル、ジフェニルアセチレンおよびその置換体がある。Although propane is used in this embodiment, the hydrocarbon or hydrocarbon compound used in the thermal decomposition may be any of aliphatic hydrocarbon, aromatic hydrocarbon, alicyclic hydrocarbon and the like. May be. Specific examples thereof include benzene, toluene, xylene, naphthalene, anthracene, hexamethylbenzene, 1.2-dibromoethylene, 2-butyne, acetylene, biphenyl, diphenylacetylene and its substitution products.
【００２３】[0023]
【発明の効果】この発明によれば熱分解炭素の生産量を
高めることができるので、この炭素を電池活物質として
用いる電池のコストを下げることが可能となる。According to the present invention, since the production amount of pyrolytic carbon can be increased, the cost of a battery using this carbon as a battery active material can be reduced.
【図１】熱分解炭素の製造に用いる装置の断面図であ
る。FIG. 1 is a sectional view of an apparatus used for producing pyrolytic carbon.
【図２】電極特性測定装置の模式図である。FIG. 2 is a schematic view of an electrode characteristic measuring device.
１ 反応用混合ガス供給器 ３ 反応管 ４ 基板 ５ 加熱炉 1 mixed gas supply device for reaction 3 reaction tube 4 substrate 5 heating furnace
フロントページの続き (72)発明者 山田 和夫 大阪市阿倍野区長池町22番22号 シヤープ 株式会社内Front page continuation (72) Inventor Kazuo Yamada 22-22 Nagaike-cho, Abeno-ku, Osaka
Claims (1)
有する化合物のうち少なくともいずれか一方を含有する
物質を位置させる工程と、 炭化水素または炭化水素化合物のうち少なくともいずれ
か一方を含有する気体を熱分解させる工程と、 熱分解させた炭素を前記基体表面に堆積させる工程と、 を備えた、電池活物質用炭素の製造方法。1. A step of arranging a substance containing at least one of an iron group element and a compound containing an iron group element on the surface of a substrate; and containing at least one of a hydrocarbon and a hydrocarbon compound. A method for producing carbon for a battery active material, comprising: a step of thermally decomposing a gas; and a step of depositing thermally decomposed carbon on the surface of the substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3234814A JP2707171B2 (en) | 1991-09-13 | 1991-09-13 | Method for producing carbon for battery active material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3234814A JP2707171B2 (en) | 1991-09-13 | 1991-09-13 | Method for producing carbon for battery active material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0574454A true JPH0574454A (en) | 1993-03-26 |
| JP2707171B2 JP2707171B2 (en) | 1998-01-28 |
Family
ID=16976810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3234814A Expired - Fee Related JP2707171B2 (en) | 1991-09-13 | 1991-09-13 | Method for producing carbon for battery active material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2707171B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61500561A (en) * | 1984-05-10 | 1986-03-27 | ル・カルボンヌ・ロレ−ヌ | Manufacturing method of carbon fiber by vapor deposition from methane |
| JPS6324555A (en) * | 1986-03-27 | 1988-02-01 | Sharp Corp | Electrode and its manufacture |
-
1991
- 1991-09-13 JP JP3234814A patent/JP2707171B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61500561A (en) * | 1984-05-10 | 1986-03-27 | ル・カルボンヌ・ロレ−ヌ | Manufacturing method of carbon fiber by vapor deposition from methane |
| JPS6324555A (en) * | 1986-03-27 | 1988-02-01 | Sharp Corp | Electrode and its manufacture |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2707171B2 (en) | 1998-01-28 |
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|---|---|---|---|
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Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19970909 |
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