JPH09106807A - Sheet-like carbon and negative material for lithium battery using same - Google Patents
Sheet-like carbon and negative material for lithium battery using sameInfo
- Publication number
- JPH09106807A JPH09106807A JP7261332A JP26133295A JPH09106807A JP H09106807 A JPH09106807 A JP H09106807A JP 7261332 A JP7261332 A JP 7261332A JP 26133295 A JP26133295 A JP 26133295A JP H09106807 A JPH09106807 A JP H09106807A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- sheet
- negative electrode
- lithium battery
- base material
- 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.)
- Pending
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)
- Ceramic Products (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、シート化カーボン
に関し、またこれを用いたリチウム電池用負極材料に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet carbon and a negative electrode material for a lithium battery using the carbon.
【０００２】[0002]
【従来の技術】近年の電子機器のコードレス化、高性能
化の急速な進歩に伴い、これらの駆動用電源としての電
池に対しても、ますます小型・軽量且つ高エネルギー密
度のものが求められている。これらの要求に対して、リ
チウム等のアルカリ金属を負極活物質に用いた非水電解
質電池は種々の電池の中でエネルギー密度が格段に高い
ため注目されている。しかし負極に用いられたリチウム
は充放電を繰り返すと、デンドライトが成長して内部短
絡を引き起こす等の危険があり、実用化への大きな障害
となっている。この問題点を解消すべく、負極にリチウ
ム合金を用いる方法、あるいは炭素材料がリチウムイオ
ンを吸蔵・放出する性質を利用して炭素繊維成形体にリ
チウムを吸蔵させた複合体を用いる方法等が提案されて
いる。しかし、負極にリチウム合金を用いる方法では充
放電の繰り返しによるデンドライトの抑制が十分ではな
く、炭素繊維成形体を用いる方法では微細炭素粉末を扱
うため工程が複雑となり、実用に供さない欠点があっ
た。2. Description of the Related Art With the recent rapid progress in cordless electronic devices and high performance, electronic devices are required to be smaller and lighter and have high energy density. ing. In order to meet these requirements, non-aqueous electrolyte batteries using an alkali metal such as lithium as a negative electrode active material have attracted attention because of their remarkably high energy density among various batteries. However, the lithium used for the negative electrode has a risk of dendrite growing and causing an internal short circuit when it is repeatedly charged and discharged, which is a major obstacle to practical use. In order to solve this problem, a method of using a lithium alloy for the negative electrode, a method of using a composite in which lithium is occluded in a carbon fiber molded body by utilizing the property of a carbon material to occlude and release lithium ions, etc. are proposed. Has been done. However, the method of using a lithium alloy for the negative electrode does not sufficiently suppress dendrite due to repeated charging / discharging, and the method of using a carbon fiber compact has a drawback that the process is complicated because a fine carbon powder is handled and it cannot be put to practical use. It was
【０００３】[0003]
【発明が解決しようとする課題】本発明の目的とすると
ころは、前記問題点に鑑み高電圧、高放電容量の優れた
電池特性を有し、安全性及び充放電サイクル特性に優れ
たリチウム電池用負極に用いることのできるシート化カ
ーボンを提供することにある。In view of the above-mentioned problems, the object of the present invention is to provide a lithium battery having excellent battery characteristics such as high voltage and high discharge capacity, and excellent safety and charge / discharge cycle characteristics. It is to provide a sheet of carbon that can be used as a negative electrode for automobiles.
【０００４】[0004]
【課題を解決するための手段】本発明者は、リチウム電
池用負極材料として種々の炭素材料について検討した結
果、繊維基材に熱硬化性樹脂を含浸させ、高温で炭素質
化させることにより、優れた特性を発揮することを見い
だした。本発明は、熱硬化性樹脂を塗布又は含浸した繊
維基材を８００℃以上２０００℃以下の温度で焼成して
なることを特徴とするシート化カーボンであり、このシ
ート化カーボンを銅箔の両面に接着してなることを特徴
とするリチウム電池用負極であり、熱硬化性樹脂を塗布
又は含浸した繊維基材を８００℃以上２０００℃以下の
温度で焼成して得たシート化カーボンを銅箔の両面に接
着することを特徴とするリチウム電池用負極の製造方法
である。Means for Solving the Problems As a result of studying various carbon materials as negative electrode materials for lithium batteries, the present inventor has found that by impregnating a fiber base material with a thermosetting resin and carbonizing at a high temperature, It has been found that it exhibits excellent characteristics. The present invention is a sheet carbon which is obtained by firing a fiber base material coated or impregnated with a thermosetting resin at a temperature of 800 ° C. or higher and 2000 ° C. or lower. The sheet carbon is formed on both sides of a copper foil. Is a negative electrode for a lithium battery, characterized in that it is adhered to a sheet of carbon foil obtained by firing a fibrous base material coated or impregnated with a thermosetting resin at a temperature of 800 ° C. or higher and 2000 ° C. or lower. Is a method for producing a negative electrode for a lithium battery, characterized in that it is adhered to both surfaces of
【０００５】[0005]
【発明の実施の形態】本発明で用いられる熱硬化性樹脂
は、フェノール樹脂、アミノ樹脂等のホルムアルデヒド
樹脂、及び不飽和ポリエステル、エポキシ樹脂、ジアリ
ルフタレート樹脂等の架橋型樹脂のいずれをも用いるこ
とができるが、繊維基材への含浸性及び経済性からフェ
ノール樹脂が特に好ましい。本発明で用いられるフェノ
ール樹脂組成物は、フェノール類とアルデヒド類とを反
応して得られる特定のレゾール型フェノール樹脂に対
し、さらにフルフリルアルコール及び又はフルフラール
を含有してなるものである。フェノール類としては、フ
ェノール、クレゾール、レゾルシノールやビスフェノー
ルＡなどを使用することができるが、フェノール樹脂を
合成する場合に一般的に使用されているフェノール化合
物であれば特に限定することなく使用でき、数種を混合
して使用してもよい。アルデヒド類は、ホルムアルデヒ
ド、アセトアルデヒド、ベンズアルデヒドなどを使用で
きるが、特に限定されることはなく、アルデヒド基を含
有する化合物であれば使用することができ、数種を混合
して使用してもよい。本発明で用いられる繊維基材は、
紙、布、不織布等シート状繊維基材のいずれをも用いる
ことができる。BEST MODE FOR CARRYING OUT THE INVENTION As the thermosetting resin used in the present invention, any of formaldehyde resin such as phenol resin and amino resin and cross-linking type resin such as unsaturated polyester, epoxy resin and diallyl phthalate resin can be used. However, a phenolic resin is particularly preferable from the viewpoint of impregnation property into a fiber base material and economical efficiency. The phenolic resin composition used in the present invention comprises a specific resol type phenolic resin obtained by reacting phenols with aldehydes and further contains furfuryl alcohol and / or furfural. As the phenols, phenol, cresol, resorcinol, bisphenol A and the like can be used, but any phenol compound generally used when synthesizing a phenol resin can be used without particular limitation. You may mix and use a seed. Formaldehyde, acetaldehyde, benzaldehyde and the like can be used as the aldehydes, but there is no particular limitation, and any compound containing an aldehyde group can be used, and a mixture of several types may be used. The fiber base material used in the present invention is
Any sheet-shaped fiber base material such as paper, cloth, and non-woven fabric can be used.
【０００６】本発明のシート化カーボンを製造するに際
して、熱硬化性樹脂を適切な溶媒にて溶解した樹脂ワニ
ス中に紙、布等の繊維基材を連続的に通過させることに
よって樹脂を繊維基材に塗布含浸させることができる。
塗布工程の後、樹脂を含浸した繊維基材は直ちに乾燥炉
にて１００〜１８０℃に加熱することにより、べたつき
をなくしたいわゆるＢステージのプリプレグを得る。次
いで、得られたプリプレグを窒素ガス等の不活性ガス雰
囲気下で８００〜２０００℃の温度にて１〜数時間保持
し、熱硬化性樹脂及び繊維基材を炭素質化し、シート化
カーボンを得ることができる。In the production of the sheet carbon of the present invention, the resin is made into a fibrous base material by continuously passing a fibrous base material such as paper or cloth through a resin varnish prepared by dissolving a thermosetting resin in an appropriate solvent. The material can be applied and impregnated.
Immediately after the coating step, the resin-impregnated fiber base material is immediately heated to 100 to 180 ° C. in a drying oven to obtain a so-called B-stage prepreg without stickiness. Next, the obtained prepreg is kept at a temperature of 800 to 2000 ° C. for 1 to several hours under an atmosphere of an inert gas such as nitrogen gas to carbonize the thermosetting resin and the fiber base material to obtain sheet carbon. be able to.
【０００７】このシート化カーボンからリチウム電池用
負極材料を得るには、両面に接着剤を塗布した導体箔の
両面にシート化カーボンを圧着することにより接着す
る。以下実施例により本発明を詳細に説明するが、これ
らの本発明はこれらの実施例に限定されるものではな
い。To obtain a negative electrode material for a lithium battery from this sheet carbon, sheet carbon is adhered by pressure-bonding to both sides of a conductor foil coated with an adhesive on both sides. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
【０００８】[0008]
《実施例１》＝シート化カーボンの作製 フェノール１０００ｇ、３７％ホルマリン１０００ｇを
撹拌装置付き反応フラスコにとり、１０％水酸化ナトリ
ウム水溶液３５ｇと１０％水酸化カリウム水溶液３５ｇ
を添加し、８５℃で３時間反応の後真空下で脱水して目
的とするレゾール型フェノール樹脂溶液を得た。得られ
た樹脂溶液を坪量８０ｇ／mm2のクラフト紙に含浸させ
た後、１５０℃で５分間乾燥させ、樹脂分５０％、厚さ
１００μｍのシート状のプリプレグを得た。次いで電気
加熱炉内を高純度窒素ガスで充分に置換した後、前記シ
ート状プリプレグを電気加熱炉にセットし、さらに流量
２リットル／分の割合で高純度窒素ガスを流しながら加
熱を開始した。加熱は、２５℃／分の速度で１０００℃
まで昇温し更にその温度で１時間保持して炭化反応を進
めた。その後、電気加熱炉内に高純度窒素ガスを流しな
がら室温まで冷却し、目的とする厚さ９０μｍのシート
化カーボンを得た。Example 1 = Preparation of sheet carbon 1000 g of phenol and 1000 g of 37% formalin are placed in a reaction flask equipped with a stirrer, 35 g of 10% aqueous sodium hydroxide solution and 35 g of 10% aqueous potassium hydroxide solution.
Was added, and the mixture was reacted at 85 ° C. for 3 hours and then dehydrated under vacuum to obtain a desired resol-type phenol resin solution. Kraft paper having a basis weight of 80 g / mm 2 was impregnated with the obtained resin solution and dried at 150 ° C. for 5 minutes to obtain a sheet-like prepreg having a resin content of 50% and a thickness of 100 μm. Next, after the inside of the electric heating furnace was sufficiently replaced with high-purity nitrogen gas, the sheet-like prepreg was set in the electric heating furnace, and heating was started while flowing high-purity nitrogen gas at a flow rate of 2 liters / minute. Heating is 1000 ° C at a rate of 25 ° C / min
The temperature was raised to 1, and the temperature was maintained for 1 hour to proceed with the carbonization reaction. Then, it was cooled to room temperature while flowing high-purity nitrogen gas into the electric heating furnace to obtain a target sheet carbon having a thickness of 90 μm.
【０００９】《実施例２》＝リチウム電池用負極材料の
作製 厚さ１０μｍの圧延銅箔の両面にフッ化ビニリデン系の
接着剤を塗工した後、この両面に先に得られたシート化
カーボンを圧着ロールにて１kgf/cm2の圧力をかけ圧着
しながら接着し、銅箔の両面にシート化カーボンの貼付
されたリチウム電池用負極材料を得た。Example 2 Production of Negative Electrode Material for Lithium Batteries A vinylidene fluoride adhesive was applied to both sides of a rolled copper foil having a thickness of 10 μm, and the sheeted carbon obtained above was applied to both sides. Was bonded by applying a pressure of 1 kgf / cm 2 with a pressure bonding roll while pressure bonding to obtain a negative electrode material for a lithium battery in which sheet carbon was adhered to both surfaces of a copper foil.
【００１０】《実施例３》＝リチウム二次電池の試作 正極にはＶ2Ｏ5粉末２０ｇと（ＮＨ4)3ＰＯ4・３Ｈ2Ｏ粉
末６ｇを混合した後９００℃で３時間溶融した。得られ
た溶融物をドライアイスで冷却してある銅板の上に流下
して急冷し、次いで平均粒径２００μｍに粉砕した。こ
の非晶物質の粉末１０ｇと粉末状ポリテトラフルオロエ
チレン１ｇとを混練し、得られた混練物をロール成形し
て厚み０．４ｍｍのシートとした。このシートの片面を
集電体である線径０．１ｍｍ、６０メッシュのステンレ
ス鋼ネットに圧着して正極体とした。一方、負極には先
に得られたリチウム電池用負極材料を幅５ｃｍ長さ４０
ｃｍに裁断し、負極体とした。上記の正極体及び負極体
をその間にセパレータとしてポリプロピレン不織布を載
置した後、電解液としてホウフッ化リチウムとプロピレ
ンカーボネートとの混合溶液を用いて、本発明のリチウ
ム電池用負極材料を用いた試作二次電池を作製した。こ
のようにして作製した二次電池について、充放電サイク
ル試験を行った。このとき、充電は５００μＡの定電流
で、電池電圧が３．６Ｖになるまで行い、また放電は放
電電流５００μＡで放電終止電圧が２．５Ｖになるまで
行った。このサイクル試験において、本発明のリチウム
電池用負極材料を用いた試作電池は１００サイクル後に
おいても、その充放電効率は１００％を示した。Example 3 = Trial Production of Lithium Secondary Battery A positive electrode was prepared by mixing 20 g of V 2 O 5 powder and 6 g of (NH 4 ) 3 PO 4 .3H 2 O powder and then melting at 900 ° C. for 3 hours. The obtained melt was poured onto a copper plate cooled with dry ice, rapidly cooled, and then ground to an average particle size of 200 μm. 10 g of the powder of the amorphous substance and 1 g of powdery polytetrafluoroethylene were kneaded, and the obtained kneaded product was roll-formed into a sheet having a thickness of 0.4 mm. One side of this sheet was pressure-bonded to a stainless steel net having a wire diameter of 0.1 mm and 60 mesh as a current collector to obtain a positive electrode body. On the other hand, for the negative electrode, the negative electrode material for a lithium battery obtained above was used.
It was cut into cm to obtain a negative electrode body. After placing a polypropylene nonwoven fabric as a separator between the positive electrode body and the negative electrode body, using a mixed solution of lithium borofluoride and propylene carbonate as an electrolytic solution, a trial production using a negative electrode material for a lithium battery of the present invention 2 A secondary battery was produced. A charge / discharge cycle test was performed on the secondary battery thus manufactured. At this time, charging was carried out at a constant current of 500 μA until the battery voltage reached 3.6 V, and discharging was carried out at a discharge current of 500 μA until the discharge end voltage reached 2.5 V. In this cycle test, the prototype battery using the negative electrode material for a lithium battery of the present invention showed 100% charge / discharge efficiency even after 100 cycles.
【００１１】[0011]
【発明の効果】本発明のシート化カーボンを用いたリチ
ウム電池用負極材料は、非常に容易な工程で作製するこ
とができ、またこのリチウム電池用負極材料を用いて作
製した二次電池は充放電サイクル寿命が長く、高信頼性
且つ高性能の二次電池を作製し得るという効果を奏す
る。INDUSTRIAL APPLICABILITY The negative electrode material for a lithium battery using the sheet carbon of the present invention can be manufactured by a very easy process, and the secondary battery manufactured by using the negative electrode material for a lithium battery is charged. The effect is that a secondary battery having a long discharge cycle life and high reliability and high performance can be manufactured.
Claims (3)
材を８００℃以上２０００℃以下の温度で焼成してなる
ことを特徴とするシート化カーボン。1. A sheet carbon, which is obtained by firing a fiber base material coated or impregnated with a thermosetting resin at a temperature of 800 ° C. or higher and 2000 ° C. or lower.
着してなることを特徴とするリチウム電池用負極材料。2. A negative electrode material for a lithium battery, wherein the sheet carbon is adhered to both sides of a copper foil.
材を８００℃以上２０００℃以下の温度で焼成して得た
シート化カーボンを銅箔の両面に接着することを特徴と
するリチウム電池用負極材料の製造方法。3. A lithium battery, characterized in that sheet carbon obtained by firing a fibrous base material coated or impregnated with a thermosetting resin at a temperature of 800 ° C. or higher and 2000 ° C. or lower is adhered to both surfaces of a copper foil. For manufacturing negative electrode material for automobile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7261332A JPH09106807A (en) | 1995-10-09 | 1995-10-09 | Sheet-like carbon and negative material for lithium battery using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7261332A JPH09106807A (en) | 1995-10-09 | 1995-10-09 | Sheet-like carbon and negative material for lithium battery using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09106807A true JPH09106807A (en) | 1997-04-22 |
Family
ID=17360350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7261332A Pending JPH09106807A (en) | 1995-10-09 | 1995-10-09 | Sheet-like carbon and negative material for lithium battery using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09106807A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015141853A1 (en) * | 2014-03-20 | 2015-09-24 | 株式会社クレハ | Carbon molding for electrode, and method for producing same |
-
1995
- 1995-10-09 JP JP7261332A patent/JPH09106807A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015141853A1 (en) * | 2014-03-20 | 2015-09-24 | 株式会社クレハ | Carbon molding for electrode, and method for producing same |
| JPWO2015141853A1 (en) * | 2014-03-20 | 2017-04-13 | 株式会社クレハ | Carbonaceous molded body for electrode and method for producing the same |
| US10388956B2 (en) | 2014-03-20 | 2019-08-20 | Kureha Corporation | Carbonaceous molded article for electrodes and method of manufacturing the same |
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