JP2002075357A - Lithium ion secondary battery - Google Patents
Lithium ion secondary batteryInfo
- Publication number
- JP2002075357A JP2002075357A JP2000253833A JP2000253833A JP2002075357A JP 2002075357 A JP2002075357 A JP 2002075357A JP 2000253833 A JP2000253833 A JP 2000253833A JP 2000253833 A JP2000253833 A JP 2000253833A JP 2002075357 A JP2002075357 A JP 2002075357A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- amino
- phenol resin
- type phenol
- lithium ion
- 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
- Carbon And Carbon Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は高容量のリチウムイオン
二次電池に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high capacity lithium ion secondary battery.
【０００２】[0002]
【従来の技術】近年、リチウムを用いた有機電解質二次
電池は高エネルギー密度を有し、機器の小型化や軽量化
に大きな役割を演じている。しかしながら、機器のいっ
そうの小型化、軽量化の要求が強く、より高容量の二次
電池が求められている。2. Description of the Related Art In recent years, an organic electrolyte secondary battery using lithium has a high energy density and plays a major role in reducing the size and weight of equipment. However, there is a strong demand for further downsizing and weight reduction of devices, and a higher capacity secondary battery is required.
【０００３】現在のリチウムイオン二次電池は、通常、
炭素質材料を負極に、リチウム含有化合物を正極に使用
し、正極と負極の間でリチウムイオンを移動させること
により充放電を行う。リチウムイオン二次電池の特性
は、負極材料の特性に大きく依存しており、黒鉛のよう
な高結晶性の炭素を使用すると出力電圧がほぼ一定で充
放電の可逆性に優れた電池となる。しかし、Ｃ6Ｌiの理
論容量以上の充電は困難であるといわれている。一方、
層状構造の未発達な炭素を用いると、Ｃ6Ｌiの理論容量
以上の充電が可能となるが、十分な放電容量が得られて
いない。そこで石炭または石油系ピッチ、熱硬化性樹
脂、炭素繊維などを原料とした炭素負極材料の開発が試
みられている。例えば、特開平３−２４５４５８号公報
にはホウ素を０．１〜０．２重量％含有する炭素材を負
極材とする方法が、特開平６−１１９９２３号公報には
グラファイト結晶部と非晶質部とを有する炭素材にリチ
ウムイオンを注入して負極材とする方法が、特開平６−
３３３５５９号公報には気相成長炭素繊維にカーボンブ
ラックを１〜３０重量％含有させた組成物を負極材とす
る方法が開示されている。しかしながら、いずれにおい
ても十分な放電容量を有する負極材は開発されていない
のが現状である。[0003] Current lithium ion secondary batteries are usually
Using a carbonaceous material for the negative electrode and a lithium-containing compound for the positive electrode, charge and discharge are performed by moving lithium ions between the positive electrode and the negative electrode. The characteristics of a lithium ion secondary battery greatly depend on the characteristics of a negative electrode material. If a highly crystalline carbon such as graphite is used, the output voltage is almost constant and the battery has excellent reversibility of charge and discharge. However, it is said that charging beyond the theoretical capacity of C 6 Li is difficult. on the other hand,
When undeveloped carbon having a layered structure is used, charging at or above the theoretical capacity of C 6 Li is possible, but sufficient discharge capacity has not been obtained. Therefore, development of a carbon anode material using coal or petroleum pitch, thermosetting resin, carbon fiber, or the like as a raw material has been attempted. For example, JP-A-3-245458 discloses a method in which a carbon material containing 0.1 to 0.2% by weight of boron is used as a negative electrode material. JP-A-6-119923 discloses a method in which a graphite crystal part and an amorphous material are used. Japanese Patent Application Laid-Open No.
JP-A-333559 discloses a method of using a composition in which 1 to 30% by weight of carbon black is contained in a vapor-grown carbon fiber as a negative electrode material. However, in any case, a negative electrode material having a sufficient discharge capacity has not been developed at present.
【０００４】[0004]
【発明が解決しようとする課題】本発明の課題は、上記
問題点を解決するため、大きな充放電容量を有するリチ
ウムイオン二次電池を提供することである。An object of the present invention is to provide a lithium ion secondary battery having a large charge / discharge capacity in order to solve the above-mentioned problems.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、鋭意研究
した結果、レゾール型フェノール樹脂とアミノ樹脂とを
混合および／または反応させてなるアミノ樹脂変性レゾ
ール型フェノール樹脂（ａ）、および／または、フェノ
ール類とアミノ化合物とホルムアルデヒドとをアルカリ
性触媒下で反応させたアミノ変性レゾール型フェノール
樹脂（ｂ）を熱処理して得られる炭素を負極として用い
ることにより大きな充放電容量を有するリチウムイオン
二次電池が得られること等を見い出し、本発明を完成す
るに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that an amino resin-modified resol phenol resin (a) obtained by mixing and / or reacting a resol phenol resin and an amino resin, and / or Alternatively, a lithium ion secondary battery having a large charge / discharge capacity can be obtained by using, as a negative electrode, carbon obtained by heat-treating an amino-modified resol type phenol resin (b) obtained by reacting a phenol, an amino compound and formaldehyde under an alkaline catalyst. They found that a battery could be obtained, and completed the present invention.
【０００６】即ち、本発明は、 １．レゾール型フェノール樹脂とアミノ樹脂とを混合お
よび／または反応させてなるアミノ樹脂変性レゾール型
フェノール樹脂（ａ）、および／または、フェノール類
とアミノ化合物とホルムアルデヒドとをアルカリ性触媒
下で反応させたアミノ変性レゾール型フェノール樹脂
（ｂ）を熱処理して得られる炭素を、負極として用いて
なることを特徴とする、リチウムイオン二次電池、 ２．アミノ樹脂変性レゾール型フェノール樹脂（ａ）が
レゾール型フェノール樹脂１００重量部に対して、アミ
ノ樹脂を固形分重量比が１〜３０重量部となる範囲で用
いて得られたものであり、アミノ変性レゾール型フェノ
ール樹脂（ｂ）がフェノール類１００重量部に対して、
アミノ化合物が１〜２０重量部となる範囲で用いて得ら
れたものである、上記１記載のリチウムイオン二次電
池、 ３．アミノ樹脂変性レゾール型フェノール樹脂（ａ）お
よびアミノ変性レゾール型フェノール樹脂（ｂ）の数平
均分子量が、２５０〜５００である、上記１または２記
載のリチウムイオン二次電池、 ４．熱処理が、不活性雰囲気中または真空中で、８００
〜１４００での熱処理である、上記１、２または３記載
のリチウムイオン二次電池、および、 ５．負極が、アミノ樹脂変性レゾール型フェノール樹脂
（ａ）および／またはアミノ変性レゾール型フェノール
樹脂（ｂ）を熱処理して得られる炭素を、導電性箔上に
塗布してなるものである、上記１〜４のいずれか１つに
記載のリチウムイオン二次電池、を提供するものであ
る。That is, the present invention provides: Amino resin-modified resole-type phenolic resin (a) obtained by mixing and / or reacting a resole-type phenolic resin with an amino resin, and / or amino-modified by reacting a phenol with an amino compound and formaldehyde under an alkaline catalyst 1. A lithium ion secondary battery, characterized in that carbon obtained by heat-treating a resol-type phenol resin (b) is used as a negative electrode. Amino resin-modified resol type phenol resin (a) is obtained by using an amino resin in a range of 1 to 30 parts by weight of solid content with respect to 100 parts by weight of resol type phenol resin. The resole type phenol resin (b) is based on 100 parts by weight of phenols.
2. The lithium ion secondary battery according to the above 1, wherein the lithium compound is obtained using the amino compound in a range of 1 to 20 parts by weight. 3. The lithium ion secondary battery according to the above 1 or 2, wherein the amino resin-modified resol-type phenol resin (a) and the amino-modified resol-type phenol resin (b) have a number average molecular weight of 250 to 500. The heat treatment is performed in an inert atmosphere or in a vacuum at 800
4. The lithium ion secondary battery according to the above 1, 2, or 3, wherein the heat treatment is performed at 1400. The negative electrode is obtained by applying carbon obtained by heat-treating an amino resin-modified resol-type phenol resin (a) and / or an amino-modified resol-type phenol resin (b) onto a conductive foil. 4. A lithium ion secondary battery according to any one of 4.
【０００７】[0007]
【発明の実施の形態】本発明で用いるアミノ樹脂変性レ
ゾール型フェノール樹脂（ａ）としては、レゾール型フ
ェノール樹脂とアミノ樹脂とを混合および／または反応
させたものであればよく、特に限定されない。ここで用
いるレゾール型フェノール樹脂としては、フェノール類
とホルムアルデヒドとをアルカリ性触媒下で反応させて
なるものが挙げられ、アミノ樹脂としては、例えば、メ
ラミン樹脂、ベンゾグアナミン樹脂、ジシアンジアミド
樹脂、尿素樹脂等が挙げられる。また、レゾール型フェ
ノール樹脂とアミノ樹脂とを反応させる方法は、特に限
定されないが、通常は加熱により反応させる方法が採用
される。BEST MODE FOR CARRYING OUT THE INVENTION The amino resin-modified resol type phenol resin (a) used in the present invention is not particularly limited as long as it is a mixture of a resole type phenol resin and an amino resin and / or a reaction. Examples of the resol type phenol resin used herein include those obtained by reacting phenols and formaldehyde under an alkaline catalyst, and examples of the amino resin include melamine resin, benzoguanamine resin, dicyandiamide resin, and urea resin. Can be The method of reacting the resole type phenol resin with the amino resin is not particularly limited, but a method of reacting by heating is usually employed.
【０００８】アミノ樹脂変性レゾール型フェノール樹脂
（ａ）におけるレゾール型フェノール樹脂とアミノ樹脂
の使用割合としては、レゾール型フェノール樹脂１００
重量部に対して、アミノ樹脂を固形分重量比が１〜３０
重量部となる範囲で用いることが好ましく、なかでも大
きな充放電容量を有するリチウムイオン二次電池が得ら
れることから５〜１６重量部となる範囲が特に好まし
い。In the amino resin-modified resol type phenol resin (a), the ratio of the resole type phenol resin to the amino resin used is 100 resole type phenol resin.
The amino resin has a solid content weight ratio of 1 to 30 parts by weight.
It is preferably used in an amount of 5 parts by weight, particularly preferably 5 to 16 parts by weight, since a lithium ion secondary battery having a large charge / discharge capacity can be obtained.
【０００９】上記レゾール型フェノール樹脂を製造する
のに用いるフェノール類としては、例えば、フェノー
ル、クレゾール、キシレノール、レゾルシン、ビスフェ
ノールＡ等の化合物が挙げられ、２種類以上の併用であ
っても構わないが、特にフェノールが望ましい。フェノ
ール類とフォルムアルデヒドの比率は、特に規定される
ものではない。アルカリ性触媒としては、例えば、アル
カリ金属の水酸化物、アルカリ土類金属の水酸化物や酸
化物、アルカノールアミン、アルキルアミン、アンモニ
ア等の化合物が挙げられる。また、レゾール型フェノー
ル樹脂の製造方法は公知の方法が適応でき、特に限定す
るものではない。Examples of the phenols used for producing the above resole type phenol resin include compounds such as phenol, cresol, xylenol, resorcin, bisphenol A, etc., and two or more compounds may be used in combination. Particularly, phenol is desirable. The ratio of phenols to formaldehyde is not particularly limited. Examples of the alkaline catalyst include hydroxides of alkali metals, hydroxides and oxides of alkaline earth metals, and compounds such as alkanolamines, alkylamines, and ammonia. In addition, a known method can be applied to the method for producing the resol-type phenol resin, and the method is not particularly limited.
【００１０】本発明で用いるアミノ変性レゾール型フェ
ノール樹脂（ｂ）としては、フェノール類とアミノ化合
物とホルムアルデヒドとをアルカリ性触媒下で反応させ
たものであればよく、特に限定されない。ここで用いる
フェノール類とアルカリ性触媒としては、上記レゾール
型フェノール樹脂を製造するのに用いるフェノール類と
アルカリ性触媒がいずれもに使用できる。フェノール類
とフォルムアルデヒドの比率は、特に規定されるもので
はない。アミノ化合物としては、例えば、メラミン、ベ
ンゾグアナミン、ジシアンジアミド、尿素等が挙げられ
る。また、製造方法は公知の方法が適応でき、特に限定
されるものではない。The amino-modified resol type phenol resin (b) used in the present invention is not particularly limited as long as it is obtained by reacting a phenol, an amino compound and formaldehyde under an alkaline catalyst. As the phenols and the alkaline catalyst used herein, any of the phenols and the alkaline catalyst used for producing the above-mentioned resol-type phenol resin can be used. The ratio of phenols to formaldehyde is not particularly limited. Examples of the amino compound include melamine, benzoguanamine, dicyandiamide, urea and the like. In addition, a known method can be applied to the production method, and is not particularly limited.
【００１１】アミノ変性レゾール型フェノール樹脂
（ｂ）におけるフェノール類とアミノ化合物の使用割合
としては、フェノール類１００重量部に対して、アミノ
化合物が１〜２０重量部となる範囲で用いることが好ま
しく、なかでも大きな充放電容量を有するリチウムイオ
ン二次電池が得られることから５〜１０重量部となる範
囲が特に好ましい。The use ratio of the phenol and the amino compound in the amino-modified resol type phenol resin (b) is preferably in the range of 1 to 20 parts by weight of the amino compound with respect to 100 parts by weight of the phenol. Above all, a range of 5 to 10 parts by weight is particularly preferable since a lithium ion secondary battery having a large charge / discharge capacity can be obtained.
【００１２】アミノ樹脂変性レゾール型フェノール樹脂
（ａ）および／またはアミノ変性レゾール型フェノール
樹脂（ｂ）は、樹脂溶液として使用することができ、溶
媒としては、特に限定はなく、例えば、水；メタノー
ル、エタノール、イソプロプルアルコールで代表される
アルコール類；アセトン、メチルエチルケトンのような
ケトン類などが挙げられる。The amino resin-modified resol type phenol resin (a) and / or the amino-modified resol type phenol resin (b) can be used as a resin solution, and the solvent is not particularly limited. , Ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone.
【００１３】アミノ樹脂変性レゾール型フェノール樹脂
（ａ）および／またはアミノ変性レゾール型フェノール
樹脂（ｂ）の数平均分子量としては、電池特性に優れる
ものが得られることから、２５０〜５００であることが
好ましい。The number-average molecular weight of the amino-resin-modified resol-type phenolic resin (a) and / or the amino-modified resol-type phenolic resin (b) is preferably from 250 to 500 in order to obtain a battery having excellent battery characteristics. preferable.
【００１４】上記のようにして得られたアミノ樹脂変性
レゾール型フェノール樹脂（ａ）および／またはアミノ
変性レゾール型フェノール樹脂（ｂ）を炭素化する方法
としては、例えば、不活性雰囲気中または真空中で８０
０〜１４００℃で熱処理する方法が、炭素化が十分に進
み、炭素以外の元素の残存が少なく、このために電気伝
導度が十分で電池特性に優れるものが得られることから
好ましいThe method for carbonizing the amino-resin-modified resol-type phenol resin (a) and / or the amino-modified resol-type phenol resin (b) obtained as described above includes, for example, an inert atmosphere or a vacuum. At 80
The method of performing heat treatment at 0 to 1400 ° C. is preferable because carbonization proceeds sufficiently, the remaining of elements other than carbon is small, and a substance having sufficient electric conductivity and excellent battery characteristics is obtained.
【００１５】以上のようにして得られた炭素を電極とし
て利用する場合には適当なバインダーと混合して導電性
箔上に塗布することが望ましい。導電性箔としてはいろ
いろなものを用いることが可能であるが、なかでも金属
箔、例えば銅箔が好ましい。このようにして得られた電
極はリチウムイオン二次電池の負極として最適である。When the carbon obtained as described above is used as an electrode, it is desirable to mix it with an appropriate binder and apply it on a conductive foil. Various conductive foils can be used. Among them, a metal foil, for example, a copper foil is preferable. The electrode thus obtained is most suitable as a negative electrode of a lithium ion secondary battery.
【００１６】[0016]
【実施例】以下に実施例および比較例を示して本発明の
実施の形態を具体的に説明するが、もちろん本発明はこ
れらの限定されるものではない。なお、例中の％は重量
基準である。The present invention will now be described in detail with reference to Examples and Comparative Examples, but it should be understood that the present invention is by no means restricted to such specific Examples. The percentages in the examples are on a weight basis.
【００１７】また、以下の実施例および比較例では本来
負極として用いる本発明の炭素材料を正極として用い、
負極として金属リチウムを用いる。これはリチウムイオ
ンの供給源として金属リチウムを用いることにより炭素
材料へのリチウムの挿入と脱離を単純化し、より明白に
本発明の炭素材料の特性を証明することを意図したもの
である。そして、本発明の実施例における構成が本来の
目的であるリチウムイオン電池における負極としての有
用性が証明されることは当業者には明白である。In the following Examples and Comparative Examples, the carbon material of the present invention, which is originally used as a negative electrode, is used as a positive electrode.
Metal lithium is used as the negative electrode. This is intended to simplify the insertion and desorption of lithium into the carbon material by using metallic lithium as a source of lithium ions, and to more clearly prove the properties of the carbon material of the present invention. It is apparent to those skilled in the art that the configuration of the embodiment of the present invention proves usefulness as a negative electrode in a lithium ion battery, which is the original purpose.
【００１８】実施例における充放電特性の測定は次の手
法により行った。炭素粉末３ｇを、ポリフッ化ビニリデ
ンをＮ−メチルピロリドンに１０％溶解したバインダー
３ｇに混合し、厚さ２０μｍの銅箔上に塗布、乾燥して
電極板を得た。また、エチレンカーボネートと炭酸ジエ
チルを１：１の体積比で混合した有機溶媒に、ＬiＰＦ6
を１モル／リットルの割合で溶解して電解液を作製し
た。炭素電極と対極として金属リチウムを用い、両者の
間に電解液を多孔質ポリプロピレンに含侵させたものを
はさみ込み、これらを２０１６タイプのコインケース内
に入れ、プレス封口を行なって評価用のコイン電池を作
製した。このようにして得られた電池について、０．２
ｍＡの定電流で電位が０Ｖになるまで充電を行い、さら
に０Ｖの電位を保って電流が１０ｍＡとなった時点で充
電を終了した。つぎに、０．２ｍＡの定電流で電位が
１．５Ｖになるまで放電を行なった。The charging / discharging characteristics in the examples were measured by the following method. 3 g of carbon powder was mixed with 3 g of a binder obtained by dissolving 10% of polyvinylidene fluoride in N-methylpyrrolidone, applied on a copper foil having a thickness of 20 μm, and dried to obtain an electrode plate. Also, LiPF 6 was added to an organic solvent in which ethylene carbonate and diethyl carbonate were mixed at a volume ratio of 1: 1.
Was dissolved at a rate of 1 mol / liter to prepare an electrolytic solution. Metallic lithium is used as a carbon electrode and a counter electrode. A porous polypropylene impregnated with an electrolytic solution is sandwiched between the two, and these are placed in a 2016 type coin case, and press-sealing is performed. A battery was manufactured. For the battery obtained in this way, 0.2
Charging was performed at a constant current of mA until the potential became 0 V, and the charging was terminated when the current became 10 mA while maintaining the potential of 0 V. Next, discharging was performed at a constant current of 0.2 mA until the potential became 1.5 V.
【００１９】実施例１〜４および比較例１ フェノール９４０ｇと３７％フォルマリン９４０ｇをガ
ラス製２リットルフラスコに仕込み、４８％水酸化ナト
リウム水溶液２８．２ｇを添加し、加熱して８０℃にて
３時間反応させ、有効成分５５％、数平均分子量４００
のレゾール型フェノール樹脂を得た。得られたレゾール
型フェノール樹脂１０００ｇに、メラミン樹脂〔大日本
インキ化学工業（株）製ベッカミンＰＭ−Ｎ〕４０ｇ、
１００ｇ、２００ｇ、３００ｇを、それぞれ添加、混合
してして、メラミン樹脂変性レゾール型フェノール樹脂
を得た。Examples 1-4 and Comparative Example 1 940 g of phenol and 940 g of 37% formalin were charged into a 2 liter glass flask, 28.2 g of a 48% aqueous sodium hydroxide solution was added, and the mixture was heated and heated at 80 ° C. for 3 hours. Reaction time, active ingredient 55%, number average molecular weight 400
Was obtained. To 1000 g of the obtained resol-type phenol resin, 40 g of a melamine resin [Beckamine PM-N manufactured by Dainippon Ink and Chemicals, Inc.]
100 g, 200 g, and 300 g were respectively added and mixed to obtain a melamine resin-modified resol-type phenol resin.
【００２０】得られたメラミン樹脂変性レゾール型フェ
ノール樹脂と、未変性のレゾール型フェノール樹脂のそ
れぞれを、遊星ボールミルにて平均粒径が１０μｍにな
るように粉砕を行った後、アルゴン雰囲気中で１０００
℃、１時間の熱処理を行い、それぞれの炭素粉末を得
た。これらの炭素粉末の放電容量と不可逆容量の測定を
行った結果を表１に示す。表１に示すようにメラミン樹
脂の添加による変性で放電容量の増加が見られた。The obtained melamine resin-modified resol-type phenol resin and the unmodified resol-type phenol resin are each pulverized by a planetary ball mill so that the average particle diameter becomes 10 μm, and then 1000 μm in an argon atmosphere.
C. for 1 hour to obtain carbon powders. Table 1 shows the results of measuring the discharge capacity and irreversible capacity of these carbon powders. As shown in Table 1, an increase in the discharge capacity was observed due to the modification by the addition of the melamine resin.
【００２１】[0021]
【表１】 [Table 1]
【００２２】実施例５ フェノール９４０ｇとメラミン９４ｇと３７％フォルマ
リン１０３４ｇをガラス製２リットルフラスコに仕込
み、４８％水酸化ナトリウム水溶液１８．８ｇを添加
し、加熱して８０℃にて３時間反応させ、有効成分５３
％、数平均分子量３９０のメラミン変性レゾール型フェ
ノール樹脂を得た。得られたメラミン変性レゾール型フ
ェノール樹脂を、実施例１と同様の手法により粉砕、熱
処理して、炭素粉末を得た。この炭素粉末の放電容量と
不可逆容量の測定を行ったところ、放電容量６３３ｍＡ
ｈ／ｇ、不可逆容量２００ｍＡｈ／ｇであった。実施例
１のメラミン樹脂変性レゾール型フェノール樹脂のう
ち、メラミンを添加しなかったものと比較して電池特性
の改善が見られた。Example 5 940 g of phenol, 94 g of melamine and 1034 g of 37% formalin were charged into a 2 liter glass flask, 18.8 g of a 48% aqueous sodium hydroxide solution was added, and the mixture was heated and reacted at 80 ° C. for 3 hours. , Active ingredient 53
%, A melamine-modified resol type phenol resin having a number average molecular weight of 390 was obtained. The obtained melamine-modified resol-type phenol resin was pulverized and heat-treated in the same manner as in Example 1 to obtain a carbon powder. When the discharge capacity and the irreversible capacity of this carbon powder were measured, the discharge capacity was 633 mA.
h / g, and the irreversible capacity was 200 mAh / g. Among the melamine resin-modified resol-type phenol resins of Example 1, the battery characteristics were improved as compared with those in which melamine was not added.
【００２３】実施例６ フェノール９４０ｇと３７％フォルマリン９４０ｇをガ
ラス製２リットルフラスコに仕込み、４８％水酸化ナト
リウム水溶液２８．２ｇを添加し、加熱して８０℃にｔ
ｒ３時間反応させ、有効成分５５％、数平均分子量４０
０のレゾール型フェノール樹脂を得た。得られたレゾー
ル型フェノール樹脂１０００ｇに、メラミン樹脂〔大日
本インキ化学工業（株）製ベッカミンＰＭ−Ｎ〕１００
ｇを添加して、メラミン樹脂変性レゾール形フェノール
樹脂を得た。得られたメラミン樹脂変性レゾール型フェ
ノール樹脂を、実施例１と同様の手法により粉砕、熱処
理して、炭素粉末を得た。この炭素粉末の放電容量と不
可逆容量の測定を行ったところ、放電容量６３１ｍＡｈ
／ｇ、不可逆容量２０２ｍＡｈ／ｇであった。Example 6 940 g of phenol and 940 g of 37% formalin were charged into a 2 liter glass flask, 28.2 g of a 48% aqueous sodium hydroxide solution was added, and the mixture was heated to 80.degree.
r3 hours reaction, 55% active ingredient, number average molecular weight 40
0 was obtained. Melamine resin [Beckamine PM-N manufactured by Dainippon Ink and Chemicals, Inc.] 100 g to 1000 g of the obtained resol-type phenol resin.
g was added to obtain a melamine resin-modified resol type phenol resin. The obtained melamine resin-modified resol type phenol resin was pulverized and heat-treated in the same manner as in Example 1 to obtain a carbon powder. When the discharge capacity and the irreversible capacity of this carbon powder were measured, the discharge capacity was 631 mAh.
/ G and an irreversible capacity of 202 mAh / g.
【００２４】実施例７および比較例２ フェノール９４０ｇと３７％フォルマリン８６８ｇをガ
ラス製２リットルフラスコに仕込み、アルカリ性触媒と
してトリエチルアミン３７．６ｇを添加し、７５℃で４
時間の反応を行うことで、有効成分５２％、平均分子量
３４０のレゾール型フェノール樹脂を得た。このレゾー
ル型フェノール樹脂１０００ｇに、メラミン樹脂〔大日
本インキ化学工業（株）製ベッカミンＰＭ−Ｎ〕を２０
０ｇ加えて硬化させることでメラミン樹脂変性レゾール
形フェノール樹脂を得た。得られたメラミン樹脂変性レ
ゾール型フェノール樹脂と、未変性レゾール型フェノー
ル樹脂とを、それぞれ実施例１と同様の手法にて電池特
性の測定を行ったところ、メラミン樹脂で変性した場合
では放電容量が６３１ｍＡｈ／ｇg、 不可逆容量が２０
８ｍＡｈ／ｇであった。一方、メラミン樹脂での変性を
行わなかった場合では放電容量５９８ｍＡｈ／ｇ、不可
逆容量２０１ｍＡｈ／ｇであった。Example 7 and Comparative Example 2 940 g of phenol and 868 g of 37% formalin were charged into a 2 liter glass flask, and 37.6 g of triethylamine was added as an alkaline catalyst.
By performing the reaction for a time, a resol type phenol resin having an active ingredient of 52% and an average molecular weight of 340 was obtained. To 1000 g of the resole type phenol resin, 20 parts of a melamine resin [Beckamine PM-N manufactured by Dainippon Ink and Chemicals, Inc.] was added.
By adding 0 g and curing, a melamine resin-modified resol type phenol resin was obtained. When the battery characteristics of the obtained melamine resin-modified resol-type phenol resin and the unmodified resol-type phenol resin were measured in the same manner as in Example 1, the discharge capacity was reduced when the melamine resin was modified. 631 mAh / gg, irreversible capacity is 20
It was 8 mAh / g. On the other hand, when the modification with the melamine resin was not performed, the discharge capacity was 598 mAh / g and the irreversible capacity was 201 mAh / g.
【００２５】実施例８ メラミンの代わりにジシアンジアミドを用いた以外は実
施例５と同様にして、有効成分５３％、平均分子量４０
０のジシアンジアミド変性レゾール型フェノール樹脂を
得た。このジシアンジアミド変性レゾール型フェノール
樹脂を用い、実施例１と同様の手法で炭素粉末を作製し
て、電池特性を測定したところ、放電容量６４０ｍＡｈ
／ｇ、不可逆容量２１０ｍＡｈ／ｇであった。メラミン
をジシアンジアミドに変更しても実施例５の場合と同様
に電池特性の改善が見られた。Example 8 Except that dicyandiamide was used in place of melamine, the same procedure as in Example 5 was carried out to obtain an active ingredient of 53% and an average molecular weight of 40.
0 was obtained. Using this dicyandiamide-modified resol-type phenol resin, a carbon powder was prepared in the same manner as in Example 1, and the battery characteristics were measured. The discharge capacity was 640 mAh.
/ G, and the irreversible capacity was 210 mAh / g. Even when melamine was changed to dicyandiamide, battery characteristics were improved as in Example 5.
【００２６】[0026]
【発明の効果】本発明のリチウムイオン二次電池は、大
きな充放電容量を有するという利点がある。The lithium ion secondary battery of the present invention has the advantage of having a large charge / discharge capacity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｈ０１Ｍ 10/40 Ｈ０１Ｍ 10/40 Ｚ Ｆターム(参考） 4G046 CA04 CB09 CC01 CC02 CC08 4J033 CA02 CA11 CA44 CC02 CC07 FA01 FA04 FA05 FA06 FA11 HA02 HA13 5H029 AJ03 AK06 AL12 AM03 AM05 AM07 BJ03 CJ02 CJ11 CJ22 CJ28 EJ12 HJ01 HJ11 HJ14 5H050 AA08 BA17 CB07 DA04 EA04 GA02 GA22 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) // H01M 10/40 H01M 10/40 Z F term (Reference) 4G046 CA04 CB09 CC01 CC02 CC08 4J033 CA02 CA11 CA44 CC02 CC07 FA01 FA04 FA05 FA06 FA11 HA02 HA13 5H029 AJ03 AK06 AL12 AM03 AM05 AM07 BJ03 CJ02 CJ11 CJ22 CJ28 EJ12 HJ01 HJ11 HJ14 5H050 AA08 BA17 CB07 DA04 EA04 GA02 GA22
Claims (5)
とを混合および／または反応させてなるアミノ樹脂変性
レゾール型フェノール樹脂（ａ）、および／または、フ
ェノール類とアミノ化合物とホルムアルデヒドとをアル
カリ性触媒下で反応させたアミノ変性レゾール型フェノ
ール樹脂（ｂ）を熱処理して得られる炭素を、負極とし
て用いてなることを特徴とする、リチウムイオン二次電
池。1. An amino resin-modified resol type phenol resin (a) obtained by mixing and / or reacting a resol type phenol resin and an amino resin, and / or a phenol, an amino compound and formaldehyde under an alkaline catalyst. A lithium ion secondary battery characterized in that carbon obtained by heat-treating the reacted amino-modified resol-type phenol resin (b) is used as a negative electrode.
脂（ａ）がレゾール型フェノール樹脂１００重量部に対
して、アミノ樹脂を固形分重量比が１〜３０重量部とな
る範囲で用いて得られたものであり、アミノ変性レゾー
ル型フェノール樹脂（ｂ）がフェノール類１００重量部
に対して、アミノ化合物が１〜２０重量部となる範囲で
用いて得られたものである、請求項１記載のリチウムイ
オン二次電池。2. An amino resin-modified resol type phenol resin (a) obtained by using an amino resin in a range of 1 to 30 parts by weight of a solid content relative to 100 parts by weight of a resol type phenol resin. The lithium ion according to claim 1, wherein the amino-modified resol-type phenol resin (b) is obtained by using the amino compound in an amount of 1 to 20 parts by weight based on 100 parts by weight of the phenol. Rechargeable battery.
脂（ａ）およびアミノ変性レゾール型フェノール樹脂
（ｂ）の数平均分子量が、２５０〜５００である、請求
項１または２記載のリチウムイオン二次電池。3. The lithium ion secondary battery according to claim 1, wherein the number average molecular weight of the amino resin-modified resol phenol resin (a) and the amino-modified resol phenol resin (b) is 250 to 500.
で、８００〜１４００での熱処理である、請求項１、２
または３記載のリチウムイオン二次電池。4. The heat treatment according to claim 1, wherein the heat treatment is a heat treatment at 800 to 1400 in an inert atmosphere or in a vacuum.
Or the lithium ion secondary battery according to 3.
ノール樹脂（ａ）および／またはアミノ変性レゾール型
フェノール樹脂（ｂ）を熱処理して得られる炭素を、導
電性箔上に塗布してなるものである、請求項１〜４のい
ずれか１項に記載のリチウムイオン二次電池。5. A negative electrode comprising a conductive foil coated with carbon obtained by heat-treating an amino resin-modified resol-type phenol resin (a) and / or an amino-modified resol-type phenol resin (b). The lithium ion secondary battery according to any one of claims 1 to 4.
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|---|---|---|---|
| JP2000253833A JP2002075357A (en) | 2000-08-24 | 2000-08-24 | Lithium ion secondary battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010082645A1 (en) * | 2009-01-16 | 2010-07-22 | 住友化学株式会社 | Method for producing carbon material |
| JP2011225431A (en) * | 2010-03-30 | 2011-11-10 | Fujifilm Corp | Nitrogen-containing carbon alloy, method for producing the same, and carbon catalyst using the same |
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| JPH07192759A (en) * | 1993-12-24 | 1995-07-28 | Sanyo Electric Co Ltd | Nonaqueous system electrolyte battery |
| JPH11269340A (en) * | 1998-03-20 | 1999-10-05 | Sumitomo Durez Kk | Phenol resin composition |
| JPH11354120A (en) * | 1998-06-10 | 1999-12-24 | Sumitomo Durez Kk | Electrode material composition for lithium-ion secondary battery |
| JP2000001306A (en) * | 1998-06-10 | 2000-01-07 | Sumitomo Durez Co Ltd | Nitrogen-containing carbon material |
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| JPS58109525A (en) * | 1981-12-24 | 1983-06-29 | Sumitomo Deyurezu Kk | Solid resol phenolic resin |
| JPH0127199B2 (en) * | 1982-02-06 | 1989-05-26 | Arakawa Chem Ind | |
| JPS6155176A (en) * | 1984-08-27 | 1986-03-19 | Nippon Sheet Glass Co Ltd | Binder for glass fiber |
| JPH0564989B2 (en) * | 1986-06-04 | 1993-09-16 | Toshiba Chem Prod | |
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| JPH11354120A (en) * | 1998-06-10 | 1999-12-24 | Sumitomo Durez Kk | Electrode material composition for lithium-ion secondary battery |
| JP2000001306A (en) * | 1998-06-10 | 2000-01-07 | Sumitomo Durez Co Ltd | Nitrogen-containing carbon material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010082645A1 (en) * | 2009-01-16 | 2010-07-22 | 住友化学株式会社 | Method for producing carbon material |
| JP2011225431A (en) * | 2010-03-30 | 2011-11-10 | Fujifilm Corp | Nitrogen-containing carbon alloy, method for producing the same, and carbon catalyst using the same |
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