JPH11317228A - Negative electrode material for lithium ion secondary battery and its manufacture - Google Patents
Negative electrode material for lithium ion secondary battery and its manufactureInfo
- Publication number
- JPH11317228A JPH11317228A JP10137698A JP13769898A JPH11317228A JP H11317228 A JPH11317228 A JP H11317228A JP 10137698 A JP10137698 A JP 10137698A JP 13769898 A JP13769898 A JP 13769898A JP H11317228 A JPH11317228 A JP H11317228A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- resin
- secondary battery
- lithium ion
- ion secondary
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】 本発明は高容量、サイクル特性
に優れたリチウムイオン二次電池用負極材およびその製
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 negative electrode material for a lithium ion secondary battery having high capacity and excellent cycle characteristics, and a method for producing the same.
【０００２】[0002]
【従来技術】 リチウムイオン二次電池は高エネルギー
密度、貯蔵特性および信頼性に優れた二次電池の一種で
あり、近年注目されている。しかしながら金属リチウム
を二次電池の負極活物質に用いた場合、充電時に負極表
面にデントライトと称される針状結晶の金属リチウムが
析出し、この針状結晶がセパレーターを突き破り正極と
負極の間で内部短絡を起こすことがあった。このためリ
チウムを炭素材料に挿入させた負極材が用いられてい
る。この場合用いる炭素材料として非晶質系のものと黒
鉛のように高度に結晶化したものがある。非晶質系の炭
素材料をリチウムイオン二次電池用負極材に用いた場
合、容量が大きくなるが、サイクル劣化も大きくなる。
これに対して黒鉛を用いると容量は小さくなるが、サイ
クル特性が安定するため、現在リチウムイオン二次電池
用負極材では黒鉛系が主流となりつつある。すなわち黒
鉛にリチウムを担持させたリチウムイオン二次電池用負
極材は黒鉛層間にリチウムをインターカレートさせた組
成としてLiC6であり、その理論容量は372Ah/kgであり、
実際の容量もこの値前後である。一方ポリアセン構造を
持つ非晶質炭素材料からのリチウムイオン二次電池用負
極材では600〜800Ah/kgの高容量になるが、サイクル劣
化は著しく、サイクル数が多くなると黒鉛以下の容量に
なることが知られている。2. Description of the Related Art A lithium ion secondary battery is a type of secondary battery having high energy density, excellent storage characteristics, and high reliability, and has attracted attention in recent years. However, when metallic lithium is used as a negative electrode active material of a secondary battery, needle-like crystals of metallic lithium called dentite precipitate on the surface of the negative electrode during charging, and the needle-like crystals break through the separator and form a gap between the positive electrode and the negative electrode. Sometimes caused an internal short circuit. Therefore, a negative electrode material in which lithium is inserted into a carbon material is used. In this case, there are an amorphous carbon material and a highly crystallized carbon material such as graphite. When an amorphous carbon material is used for a negative electrode material for a lithium ion secondary battery, the capacity increases, but the cycle deterioration also increases.
On the other hand, when graphite is used, the capacity is reduced, but the cycle characteristics are stabilized. Therefore, the graphite material is currently becoming the mainstream negative electrode material for lithium ion secondary batteries. In other words, the negative electrode material for a lithium ion secondary battery in which graphite is supported on graphite is LiC6 as a composition in which lithium is intercalated between graphite layers, and its theoretical capacity is 372 Ah / kg,
The actual capacity is also around this value. On the other hand, the negative electrode material for lithium ion secondary batteries made of amorphous carbon material with a polyacene structure has a high capacity of 600 to 800 Ah / kg, but the cycle deterioration is remarkable, and when the number of cycles increases, the capacity becomes less than graphite. It has been known.
【０００３】黒鉛化構造を有する炭素粒子表面に非晶質
炭素被膜を形成し、これをリチウムイオン二次電池用負
極材に用いた公知のものとしては、特開平４−３６８７
７８およびＵＳＰ５３４４７２６がある。しかしながら
この方法では黒鉛粒子表面にプロパンガス等の炭化水素
ガスを流しながら焼成することにより黒鉛粒子表面に非
晶質炭素被膜を形成している。この方法では炭化水素ガ
スに直接接触する部分には非晶質炭素被膜が形成し易い
が、黒鉛粒子は凝集するため黒鉛粒子同士が密着してい
る部分にはＣＶＤ法をもってしても非晶質炭素被膜を形
成しない。[0003] A well-known material in which an amorphous carbon film is formed on the surface of a carbon particle having a graphitized structure and used as a negative electrode material for a lithium ion secondary battery is disclosed in Japanese Patent Application Laid-Open No. Hei 4-3687.
78 and USP 5,344,726. However, in this method, an amorphous carbon film is formed on the surface of the graphite particles by firing while flowing a hydrocarbon gas such as propane gas on the surface of the graphite particles. According to this method, an amorphous carbon film is easily formed on a portion directly in contact with the hydrocarbon gas, but the graphite particles are agglomerated because the graphite particles are agglomerated. Does not form a carbon coating.
【０００４】[0004]
【発明が解決しようとする課題】 従って、本発明は従
来のＣＶＤ法では得られなかった炭素粒子表面に均質化
してかつ結晶構造の異なる薄膜層を少なくとも一層以上
付着させることにより高容量、サイクル特性に優れたリ
チウムイオン二次電池用負極活物質を提供することを主
な目的とする。SUMMARY OF THE INVENTION Accordingly, the present invention provides a high capacity and cycle characteristic by homogenizing and depositing at least one thin film layer having a different crystal structure on the surface of carbon particles which cannot be obtained by the conventional CVD method. It is a main object of the present invention to provide a negative electrode active material for a lithium ion secondary battery which is excellent.
【０００５】[0005]
【課題を解決するための手段】 本発明者はリチウムイ
オン二次電池用負極材として、高容量ではあるがサイク
ル特性の劣る非晶質炭素材料の特徴とサイクル特性に優
れているが低容量である黒鉛質炭素材料とをハイブリッ
ド化することによりその目的を達成し得ることを見出し
た。MEANS TO SOLVE THE PROBLEMS The present inventor has proposed, as a negative electrode material for a lithium ion secondary battery, the characteristics of an amorphous carbon material having a high capacity but inferior cycle characteristics and excellent in cycle characteristics but a low capacity. It has been found that the purpose can be achieved by hybridizing with a certain graphitic carbon material.
【０００６】従来のＣＶＤ法では黒鉛粒子表面に有機ガ
スを流し、このガスの熱分解によって黒鉛粒子表面に非
晶質炭素被膜を形成するのであるが、黒鉛粉末粒子塊の
表面層と内部層では非晶質炭素被膜の形成の程度が異な
る。すなわち、表面層は非晶質炭素被膜が厚く、内部
層、とりわけ中心部ではほとんどの場合非晶質炭素被膜
の被覆層が形成しない。In the conventional CVD method, an organic gas is flowed on the surface of graphite particles, and an amorphous carbon film is formed on the surface of the graphite particles by the thermal decomposition of the gas. The degree of formation of the amorphous carbon film is different. That is, the surface layer is thick in the amorphous carbon film, and the inner layer, especially in the center, is almost not formed with the amorphous carbon film.
【０００７】本発明者は炭素粉末粒子中に樹脂、ヒ゜ッ
チなどの有機系の粉末粒子を均一に混合したものを非酸
化雰囲気下で焼成することにより熱分解ガスにより炭素
粉末粒子表面に新たな炭素被膜の形成が可能なことを見
出した。あるいは炭素粉末粒子を液状樹脂中に浸すこと
により炭素粉末粒子表面を樹脂コートし、これを焼成す
ることにより炭素被膜を形成させた。この場合、黒鉛粒
子表面に非晶質炭素被膜を形成するばかりでなく、非晶
質炭素粒子表面に黒鉛被膜層の形成も可能である。The inventor of the present invention has proposed a method in which organic powder particles such as a resin and a switch are uniformly mixed in a carbon powder particle and fired in a non-oxidizing atmosphere. It has been found that a film can be formed. Alternatively, the carbon powder particles were immersed in a liquid resin to coat the surface of the carbon powder particles with a resin, and then fired to form a carbon coating. In this case, it is possible not only to form an amorphous carbon coating on the surface of the graphite particles, but also to form a graphite coating layer on the surface of the amorphous carbon particles.
【０００８】即ち、本発明は、下記のリチウムイオン二
次電池用負極材料を提供するものである；１． 負極の
構成要素として用いられる炭素粉末粒子表面にこれと結
晶構造の違う炭素の薄膜を均一に、少なくとも一層被覆
してなるリチウムイオン二次電池用負極材およびその製
造方法。That is, the present invention provides the following negative electrode material for a lithium ion secondary battery: A negative electrode material for a lithium ion secondary battery comprising a carbon powder particle used as a constituent element of a negative electrode and a carbon thin film having a different crystal structure from the surface of the carbon powder particle uniformly and at least one layer, and a method for producing the same.
【０００９】２ 黒鉛粉末粒子表面を液状樹脂により均
一に付着させ、これを焼成することにより非晶質炭素薄
膜を形成してなる上記項１に記載のリチウムイオン二次
電池用負極材およびその製造方法。Item 2. The negative electrode material for a lithium ion secondary battery according to the above item 1, wherein the surface of the graphite powder particles is uniformly adhered to a liquid resin, and the resultant is fired to form an amorphous carbon thin film, and the production thereof. Method.
【００１０】３．黒鉛粉末粒子表面を表面処理すること
により液状樹脂の付着性を改善してなる上記項２に記載
のリチウムイオン二次電池用負極材およびその製造方
法。[0010] 3. Item 3. The negative electrode material for a lithium ion secondary battery according to Item 2, wherein the surface of the graphite powder particles is surface-treated to improve the adhesion of the liquid resin, and the method for producing the same.
【００１１】４．難黒鉛化性樹脂粉末粒子表面に易黒鉛
化性樹脂を被覆し、これを黒鉛化温度まで焼成して得ら
れる上記項１に記載のリチウムイオン二次電池用負極材
およびその製造方法。4. Item 2. The negative electrode material for a lithium ion secondary battery according to the above item 1, which is obtained by coating the surface of the non-graphitizable resin powder particles with a graphitizable resin and calcining the resin to a graphitization temperature.
【００１２】５．黒鉛粉末粒子および非晶質炭素粉末粒
子を均一に混合してなるリチウムイオン二次電池用負極
材およびその製造方法。5. A negative electrode material for a lithium ion secondary battery obtained by uniformly mixing graphite powder particles and amorphous carbon powder particles, and a method for producing the same.
【００１３】６．黒鉛粉末粒子および難黒鉛化性樹脂粉
末粒子を均一に混合し、これを焼成して樹脂分を炭素化
してなるリチウムイオン二次電池用負極材およびその製
造方法。6. A negative electrode material for a lithium ion secondary battery, which is obtained by uniformly mixing graphite powder particles and non-graphitizable resin powder particles, baking the mixture, and carbonizing the resin component, and a method for producing the same.
【００１４】７．黒鉛粉末粒子表面を化学的気相含浸法
により表面処理することにより非晶質炭素薄膜を形成し
てなる請求項１に記載のリチウムイオン二次電池用負極
材およびその製造方法。7. 2. The negative electrode material for a lithium ion secondary battery according to claim 1, wherein an amorphous carbon thin film is formed by subjecting the surface of the graphite powder particles to a surface treatment by a chemical vapor impregnation method.
【００１５】[0015]
【発明の実施の形態】本発明に用いる結晶性炭素粒子は
黒鉛に相当し、特に限定するわけでは無いが、平均粒径
５〜５０μｍ、より望ましくは１０〜３０μｍ程度であ
り、天然黒鉛、人造黒鉛、キッシュ黒鉛等、黒鉛の種類
は限定しないが、結晶構造が発達したものが望ましい。BEST MODE FOR CARRYING OUT THE INVENTION The crystalline carbon particles used in the present invention correspond to graphite and are not particularly limited, but have an average particle size of 5 to 50 μm, more preferably about 10 to 30 μm, and include natural graphite and artificial graphite. The type of graphite such as graphite and quiche graphite is not limited, but those having a developed crystal structure are desirable.
【００１６】本発明に用いる非晶性炭素粒子とは２５０
０℃以上の温度で黒鉛化処理して、Ｘ線回折、ラマン分
光分析等の測定をしたときに難黒鉛性を示す炭素粒子を
いう。例えば、ここに掲げるものに限定するわけではな
いが、合成樹脂類（フェノール樹脂、フラン樹脂、ポリ
イミド樹脂、ポリパラフェニレン樹脂、コプナ樹脂、あ
るいはこれらの共重合樹脂）、天然物類（松ヤニ、各種
木材、石炭、石油からの重質油など）等、炭素化したと
きに残炭率の高いものが望ましい。The amorphous carbon particles used in the present invention are 250
Carbon particles exhibiting non-graphitic properties when subjected to graphitization at a temperature of 0 ° C. or higher and measured by X-ray diffraction, Raman spectroscopy, or the like. For example, although not limited to those listed here, synthetic resins (phenolic resin, furan resin, polyimide resin, polyparaphenylene resin, copna resin, or copolymer resins thereof), natural products (pine tar, It is desirable to use a material having a high residual carbon ratio when carbonized, such as various types of wood, coal, and heavy oil from petroleum.
【００１７】次にこれら炭素粒子に結晶構造の違う炭素
被膜を形成する方法として、結晶性炭素粒子上に非晶性
炭素被膜を形成させる場合と非晶性炭素粒子上に結晶性
炭素被膜を形成させる場合がある。結晶性炭素粒子上に
非晶性炭素被膜を形成させる場合としては、黒鉛粒子に
上記した非晶性炭素になり得る樹脂類を被覆させて炭素
化することによりハイブリッド炭素粒子を得る。被覆す
る方法としては、液状樹脂類に黒鉛粒子を浸し、黒鉛粒
子表面に樹脂類を被覆させた後炭素化する方法がある。
この場合、被覆厚みは樹脂濃度に依存する。また黒鉛粒
子と上記した非晶性炭素になり得る樹脂類粉末を均一に
混合し、特に限定するわけではないが、４００〜１００
０℃、より望ましくは５００〜８００℃に熱分解焼成し
て、熱分解ガスの蒸着により黒鉛粒子表面に非晶性炭素
被膜を形成したものがある。この場合では非晶性炭素被
膜を形成した黒鉛粒子と非晶性炭素が混在する。この
他、熱分解して炭素を生成するようなガス、例えばメタ
ン、エタン、プロパン、ブタン、エチレン、アセチレン
等の炭化水素ガスを熱分解温度以上に加熱した黒鉛粉末
上に流し、熱分解炭素を黒鉛粒子表面に形成させる方法
もある。このような手法を化学的蒸着法（ＣＶＤ）とい
うが、さらに黒鉛粉末塊内部まで均一に処理できる化学
的気相含浸法（ＣＶＩ）によりハイブリッド炭素粒子を
得る方法も取ることができる。Next, as a method of forming a carbon film having a different crystal structure on these carbon particles, there are a method of forming an amorphous carbon film on crystalline carbon particles and a method of forming a crystalline carbon film on amorphous carbon particles. May be caused. When the amorphous carbon film is formed on the crystalline carbon particles, hybrid carbon particles are obtained by coating the graphite particles with the above-mentioned resins that can be amorphous carbon and carbonizing the same. As a coating method, there is a method in which graphite particles are immersed in a liquid resin, the surface of the graphite particles is coated with the resin, and then carbonized.
In this case, the coating thickness depends on the resin concentration. In addition, the graphite particles and the above-mentioned resin powder that can be amorphous carbon are uniformly mixed, and are not particularly limited.
There is a material in which an amorphous carbon film is formed on the surface of graphite particles by pyrolytic baking at 0 ° C., more preferably 500 to 800 ° C., and vapor deposition of a pyrolytic gas. In this case, the graphite particles having the amorphous carbon film and the amorphous carbon are mixed. In addition, a gas that generates carbon by pyrolysis, such as methane, ethane, propane, butane, ethylene, or a hydrocarbon gas such as acetylene, is flown over the graphite powder heated to a temperature higher than the pyrolysis temperature, and the pyrolytic carbon There is also a method of forming on the surface of graphite particles. Such a method is called a chemical vapor deposition method (CVD), but a method of obtaining hybrid carbon particles by a chemical vapor impregnation method (CVI) that can further uniformly treat the inside of the graphite powder mass can be adopted.
【００１８】非晶性炭素粒子上に結晶性炭素被膜を形成
させる場合としては、上記した非晶性炭素になり得る樹
脂類粉末に易黒鉛化樹脂で被覆し、これを黒鉛化温度ま
で焼成すれば良い。In order to form a crystalline carbon film on the amorphous carbon particles, the above-mentioned resin powder capable of forming amorphous carbon is coated with an easily graphitizable resin, which is fired to a graphitization temperature. Good.
【００１９】[0019]
【実施例】以下に実施例を示し、本発明の特徴とすると
ころを一層明らかにする。EXAMPLES Examples are shown below to further clarify the features of the present invention.
【００２０】実施例１ 平均粒径１５μｍの黒鉛粒子（結晶層間距離：０．６７
１０ｎｍ，結晶子の大きさ：１００ｎｍ以下）をアンモ
ニアを触媒にして合成したレゾールタイプのフェノール
樹脂溶液（樹脂固形分２５ｗｔ％、メタノール７５ｗｔ
％溶液）に浸し、軽く真空脱泡してからロ過して過剰の
フェノール樹脂溶液を取り除いた。次いで２４時間室温
にて放置して風乾した後４０℃の熱風循環式恒温乾燥機
内で２４時間予備硬化した。さらに１５０℃まで１００
時間かけて温度を上昇させて硬化した。Example 1 Graphite particles having an average particle diameter of 15 μm (distance between crystal layers: 0.67)
A resol-type phenol resin solution (resin solid content 25 wt%, methanol 75 wt%) synthesized using ammonia as a catalyst for 10 nm, crystallite size: 100 nm or less.
% Solution), gently vacuum degassed, and filtered to remove excess phenol resin solution. Then, it was left at room temperature for 24 hours and air-dried, and then pre-cured in a hot-air circulation type constant temperature dryer at 40 ° C. for 24 hours. 100 to 150 ° C
The temperature was raised over time to cure.
【００２１】このようにフェノール樹脂で被覆した黒鉛
粒子をアルゴンガス雰囲気下で、室温から７００℃まで
８時間かけて焼成してハイブリッド化した炭素粒子粉末
を得た。これをリチウム電池負極材用充放電測定装置
（（株）ナガノ製ＢＴＳー２００４型。）を用い、電解
液はエチレンカーボネート系で充放電流密度０．１ｍＡ
／ｃｍ2の条件下で充放電特性を調べた。The graphite particles coated with the phenolic resin were fired in an argon gas atmosphere from room temperature to 700 ° C. for 8 hours to obtain hybridized carbon particle powder. This was measured using a charge / discharge measuring device for lithium battery negative electrode material (BTS-2004, manufactured by Nagano Corporation). The electrolyte was an ethylene carbonate system and the charge / discharge current density was 0.1 mA.
The charge / discharge characteristics were examined under the conditions of / cm2.
【００２２】実施例２ 樹脂固形分５０ｗｔ％（メタノール５０ｗｔ％）を使う
以外は実施例１と同様に行った。Example 2 The same procedure as in Example 1 was carried out except that a resin solid content of 50 wt% (methanol 50 wt%) was used.
【００２３】実施例３ 実施例１で用いたものと同様の黒鉛粉末を４００℃の空
気雰囲気下で２４時間酸化処理する以外は実施例１と同
様にして行った。Example 3 The same procedure as in Example 1 was carried out except that the same graphite powder as used in Example 1 was oxidized in an air atmosphere at 400 ° C. for 24 hours.
【００２４】実施例４ 硬化ずみフェノール樹脂粉末をアルゴンガス雰囲気下
で、室温から７００℃まで８時間かけて焼成した非晶性
炭素粉末５０ｗｔ％と実施例２と同様の黒鉛粉末５０ｗ
ｔ％を均一に混合して実施例１と同様に充放電を調べ
た。Example 4 A hardened phenol resin powder was fired from room temperature to 700 ° C. for 8 hours in an argon gas atmosphere for 8 hours, and 50% by weight of amorphous carbon powder and 50 w% of the same graphite powder as in Example 2 were used.
The charge and discharge were examined in the same manner as in Example 1 by uniformly mixing t%.
【００２５】実施例５ 実施例４における非晶性炭素粉末を２５ｗｔ％、黒鉛粉
末７５ｗｔ％とする以外は実施例４と同様にして行っ
た。Example 5 The procedure of Example 4 was repeated except that the amorphous carbon powder was 25 wt% and the graphite powder was 75 wt%.
【００２６】実施例６ 実施例４における非晶性炭素粉末を７５ｗｔ％、黒鉛粉
末２５ｗｔ％とする以外は実施例４と同様にして行っ
た。Example 6 The procedure of Example 4 was repeated except that the amorphous carbon powder was 75 wt% and the graphite powder was 25 wt%.
【００２７】実施例７ 硬化ずみフェノール樹脂粉末５０ｗｔ％および実施例２
の黒鉛粉末５０ｗｔ％を均一に混合し、アルゴンガス雰
囲気下で、室温から７００℃まで８時間かけて焼成して
実施例１と同様に充放電を測定した。Example 7 50% by weight of cured phenol resin powder and Example 2
Of graphite powder was uniformly mixed and fired in an argon gas atmosphere from room temperature to 700 ° C. for 8 hours, and charge and discharge were measured in the same manner as in Example 1.
【００２８】実施例８ 硬化ずみフェノール樹脂粉末７５ｗｔ％および実施例２
の黒鉛粉末２５ｗｔ％とする以外は実施例７と同様にし
て行った。Example 8 75% by weight of cured phenol resin powder and Example 2
Except that the graphite powder was 25 wt%.
【００２９】実施例９ 硬化ずみフェノール樹脂粉末２５ｗｔ％および実施例２
の黒鉛粉末７５ｗｔ％とする以外は実施例７と同様にし
て行った。Example 9 25% by weight of cured phenol resin powder and Example 2
Except that the graphite powder was 75 wt%.
【００３０】実施例１０ 実施例２と同様の黒鉛粉末にプロパンガス５０ｖｏｌ％
およびアルゴンガス５０ｖｏｌ％になるように混合ガス
を流し、パルスＣＶＩ装置（フルテック（株）製ＦＴ−
ＣＶＩ １２００型）を用いて８００℃の温度で１００
０パルスになるまでパルス処理を行ってハイブリッド化
した炭素粉末を得て実施例１と同様に充放電を測定し
た。Example 10 The same graphite powder as in Example 2 was mixed with 50% by volume of propane gas.
And a mixed gas of 50 vol% of argon gas, and a pulse CVI device (FT-FFT, manufactured by Flutec Co., Ltd.).
CVI 1200) at 800 ° C.
Pulse processing was performed until the number of pulses became 0, and a hybridized carbon powder was obtained. The charge and discharge were measured in the same manner as in Example 1.
【００３１】実施例１１ ３、５ジメチルフェノール１モルに対し、ホルマリン
１．５モルおよびアンモニア０．００２ｗｔ％から合成
したレゾールタイプの３、５ジメチルフェノール樹脂の
メタノール溶液（樹脂固形分２５ｗｔ％、メタノール７
５ｗｔ％）中に２００メッシュパス硬化ずみフェノール
樹脂粉末を入れ、よくかき混ぜた後、軽く真空脱泡して
硬化ずみフェノール樹脂粉末表面上に３、５ジメチルフ
ェノール樹脂を被覆した。次にこれをロ過し、過剰の
３、５ジメチルフェノール樹脂溶液を取り除いた後３、
５ジメチルフェノール樹脂を被覆した硬化ずみフェノー
ル樹脂粉末を室温にて２４時間風乾した。さらに４０℃
の熱風循環式恒温乾燥機内で２４時間予備硬化した後１
５０℃まで１０時間かけて温度を上昇させて硬化ずみフ
ェノール樹脂粉末表面の３、５ジメチルフェノール樹脂
硬化させた。これをアルゴンガス雰囲気下で１２時間か
けて１２００℃まで温度を上昇させて炭素化した。さら
に超高温炉にてアルゴンガス雰囲気下で室温から２５０
０℃まで１０時間で上昇させ、この温度で１時間保持し
た。このような黒鉛化処理を行って難黒鉛化炭素粉末表
面に易黒鉛化炭素被膜を形成させたハイブリッド化した
炭素粉末を得て実施例１と同様に充放電を測定した。Example 11 A methanol solution of resole type 3,5 dimethylphenol resin synthesized from 1.5 mol of formalin and 0.002 wt% of ammonia per 1 mol of 3,5 dimethylphenol (resin solid content 25 wt%, methanol 7
(5 wt%), a 200-mesh pass cured phenol resin powder was added, mixed well, and then gently vacuum degassed to coat 3,5 dimethylphenol resin on the surface of the cured phenol resin powder. Next, this was filtered, and after removing the excess 3,5 dimethylphenol resin solution,
The cured phenol resin powder coated with 5-dimethylphenol resin was air-dried at room temperature for 24 hours. 40 ° C
After pre-curing for 24 hours in a hot air circulation type constant temperature dryer
The temperature was raised to 50 ° C. over 10 hours to cure 3,5 dimethylphenol resin on the surface of the cured phenol resin powder. This was carbonized by raising the temperature to 1200 ° C. over 12 hours in an argon gas atmosphere. Further, the temperature is increased from room temperature to 250
The temperature was raised to 0 ° C. in 10 hours and maintained at this temperature for 1 hour. By performing such a graphitization treatment, a hybridized carbon powder having a non-graphitizable carbon powder formed on the surface of the non-graphitizable carbon powder was obtained, and charge and discharge were measured in the same manner as in Example 1.
【００３２】比較例１ 実施例１で用いたと同様の黒鉛粉末を何も処理せずに実
施例１と同様に充放電を測定した。Comparative Example 1 The same graphite powder as that used in Example 1 was subjected to the same measurement as in Example 1 without any treatment.
【００３３】比較例２ 硬化ずみフェノール樹脂粉末をアルゴンガス雰囲気下
で、室温から７００℃まで８時間かけて焼成した非晶性
炭素粉末を実施例１と同様に充放電を測定した。Comparative Example 2 Amorphous carbon powder obtained by calcining a cured phenol resin powder from room temperature to 700 ° C. for 8 hours in an argon gas atmosphere was measured for charge and discharge in the same manner as in Example 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【発明の効果】本発明によるリチウムイオン二次電池用
負極材は、サイクル特性に優れているが、放電容量に劣
る黒鉛粒子および放電容量は大きいがサイクル特性に劣
る非晶製炭素粒子の欠点を補完するものである。The negative electrode material for a lithium ion secondary battery according to the present invention has the disadvantages of graphite particles having excellent cycle characteristics but poor discharge capacity and amorphous carbon particles having large discharge capacity but poor cycle characteristics. It complements.
【００３６】本発明による結晶性炭素と非晶性炭素のハ
イブリッド炭素材料は、黒鉛粒子上に非晶性炭素薄膜の
形成、および／または非晶性炭素粒子上に黒鉛層を少な
くとも一層形成させること、および／または黒鉛粒子と
非晶性炭素粒子を均一混合する３法から成る。これら３
法の何れも、結晶性炭素である黒鉛粒子のみからなるリ
チウムイオン二次電池用負極材よりも放電容量を大きく
することが可能となった。同時にポリアセンのような非
晶質系炭素のみからなるリチウムイオン二次電池用負極
材よりもサイクル特性に優れ、充放電効率を高めること
が可能となった。The hybrid carbon material of crystalline carbon and amorphous carbon according to the present invention comprises forming an amorphous carbon thin film on graphite particles and / or forming at least one graphite layer on amorphous carbon particles. And / or three methods of uniformly mixing graphite particles and amorphous carbon particles. These three
In any of the methods, the discharge capacity can be made larger than that of a negative electrode material for a lithium ion secondary battery comprising only graphite particles as crystalline carbon. At the same time, it has more excellent cycle characteristics than a negative electrode material for a lithium ion secondary battery made of only amorphous carbon such as polyacene, and it has become possible to increase the charge / discharge efficiency.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮本大樹 奈良県奈良市西千代ケ丘１丁目23ー17 (72)発明者 長谷川省治 大阪府枚方市香里ケ丘12丁目28ー37 (72)発明者 田村貞隆 大阪府豊中市南桜塚３ー６ー13ー305 (72)発明者 三木亮太郎 大阪府大阪市住之江区平林北２丁目８ー59 (72)発明者 野瀬初穂 大阪府大阪市住吉区杉本２丁目９ー27 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Daiki Miyamoto 1-23-17 Nishichiyogaoka, Nara City, Nara Prefecture (72) Inventor Shoji Hasegawa 12-28-37, Karikagaoka, Hirakata City, Osaka Prefecture (72) Inventor Sadataka Tamura Osaka Minami-Sakurazuka, Toyonaka, 3-3-13-305 (72) Inventor, Ryotaro Miki 2-59, Hirabayashikita, Suminoe-ku, Osaka, Osaka (72) Inventor, Hatsune Nose 2--9, Sugimoto, Sumiyoshi-ku, Osaka, Osakaー 27
Claims (14)
末粒子表面にこれと結晶構造の違う炭素の薄膜を均一
に、少なくとも一層被覆してなるリチウムイオン二次電
池用負極材。1. A negative electrode material for a lithium ion secondary battery comprising a carbon powder particle used as a component of a negative electrode, and a carbon thin film having a different crystal structure from the surface of the carbon powder particle uniformly coated at least one layer.
に付着させ、これを焼成することにより非晶質炭素薄膜
を形成してなる請求項１に記載のリチウムイオン二次電
池用負極材。2. The negative electrode material for a lithium ion secondary battery according to claim 1, wherein the surface of the graphite powder particles is uniformly adhered to a liquid resin, and the resultant is fired to form an amorphous carbon thin film.
より液状樹脂の付着性を改善してなる請求項２に記載の
リチウムイオン二次電池用負極材。3. The negative electrode material for a lithium ion secondary battery according to claim 2, wherein the surface of the graphite powder particles is surface-treated to improve the adhesion of the liquid resin.
性樹脂を被覆し、これを黒鉛化温度まで焼成して得られ
る請求項１に記載のリチウムイオン二次電池用負極材。4. The negative electrode material for a lithium ion secondary battery according to claim 1, obtained by coating the surface of the non-graphitizable resin powder particles with a graphitizable resin and firing the resin to a graphitization temperature.
を均一に混合してなるリチウムイオン二次電池用負極
材。5. A negative electrode material for a lithium ion secondary battery obtained by uniformly mixing graphite powder particles and amorphous carbon powder particles.
粒子を均一に混合し、これを焼成して樹脂分を炭素化し
てなるリチウムイオン二次電池用負極材。6. A negative electrode material for a lithium ion secondary battery obtained by uniformly mixing graphite powder particles and non-graphitizable resin powder particles, and baking the mixture to carbonize the resin component.
より表面処理することにより非晶質炭素薄膜を形成して
なる請求項１に記載のリチウムイオン二次電池用負極
材。7. The negative electrode material for a lithium ion secondary battery according to claim 1, wherein the surface of the graphite powder particles is subjected to a surface treatment by a chemical vapor impregnation method to form an amorphous carbon thin film.
末粒子表面にこれと結晶構造の違う炭素の薄膜を均一
に、少なくとも一層被覆してなるリチウムイオン二次電
池用負極材の製造方法。8. A method for producing a negative electrode material for a lithium ion secondary battery, comprising uniformly and at least one layer of a carbon thin film having a different crystal structure from the surface of carbon powder particles used as a component of a negative electrode.
に付着させ、これを焼成することにより非晶質炭素薄膜
を形成してなる請求項１に記載のリチウムイオン二次電
池用負極材の製造方法。9. The method for producing a negative electrode material for a lithium ion secondary battery according to claim 1, wherein the surface of the graphite powder particles is uniformly adhered to a liquid resin, and the resultant is baked to form an amorphous carbon thin film. Method.
により液状樹脂の付着性を改善してなる請求項２に記載
のリチウムイオン二次電池用負極材の製造方法。10. The method for producing a negative electrode material for a lithium ion secondary battery according to claim 2, wherein the adhesion of the liquid resin is improved by treating the surface of the graphite powder particles.
化性樹脂を被覆し、これを黒鉛化温度まで焼成して得ら
れる請求項１に記載のリチウムイオン二次電池用負極材
の製造方法。11. The production of a negative electrode material for a lithium ion secondary battery according to claim 1, wherein the surface of the non-graphitizable resin powder particles is coated with a graphitizable resin, and the resultant is fired to a graphitization temperature. Method.
子を均一に混合してなるリチウムイオン二次電池用負極
材の製造方法。12. A method for producing a negative electrode material for a lithium ion secondary battery, comprising uniformly mixing graphite powder particles and amorphous carbon powder particles.
末粒子を均一に混合し、これを焼成して樹脂分を炭素化
してなるリチウムイオン二次電池用負極材の製造方法。13. A method for producing a negative electrode material for a lithium ion secondary battery, wherein graphite powder particles and non-graphitizable resin powder particles are uniformly mixed and fired to carbonize the resin component.
により表面処理することにより非晶質炭素薄膜を形成し
てなる請求項１に記載のリチウムイオン二次電池用負極
材の製造方法。14. The method for producing a negative electrode material for a lithium ion secondary battery according to claim 1, wherein the surface of the graphite powder particles is subjected to a surface treatment by a chemical vapor impregnation method to form an amorphous carbon thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10137698A JPH11317228A (en) | 1998-04-30 | 1998-04-30 | Negative electrode material for lithium ion secondary battery and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10137698A JPH11317228A (en) | 1998-04-30 | 1998-04-30 | Negative electrode material for lithium ion secondary battery and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11317228A true JPH11317228A (en) | 1999-11-16 |
Family
ID=15204731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10137698A Pending JPH11317228A (en) | 1998-04-30 | 1998-04-30 | Negative electrode material for lithium ion secondary battery and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11317228A (en) |
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| JP2006338977A (en) * | 2005-06-01 | 2006-12-14 | Shin Kobe Electric Mach Co Ltd | Lithium secondary battery |
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| US6764791B2 (en) | 2000-07-19 | 2004-07-20 | Sanyo Electric Co., Ltd. | Rechargeable lithium battery |
| US7273503B2 (en) * | 2000-09-29 | 2007-09-25 | Sharp Corporation | Lithium polymer secondary battery and method for manufacturing the same |
| US7192675B2 (en) * | 2000-09-29 | 2007-03-20 | Sharp Kabushiki Kaisha | Lithium polymer secondary battery |
| US7270914B2 (en) * | 2000-09-29 | 2007-09-18 | Sharp Corporation | Lithium secondary cell |
| JP2006338977A (en) * | 2005-06-01 | 2006-12-14 | Shin Kobe Electric Mach Co Ltd | Lithium secondary battery |
| JP4595931B2 (en) * | 2006-12-08 | 2010-12-08 | 三菱化学株式会社 | Negative electrode material for lithium secondary battery and negative electrode sheet produced therefrom |
| JP2007103382A (en) * | 2006-12-08 | 2007-04-19 | Mitsubishi Chemicals Corp | Negative electrode material for lithium secondary battery and negative electrode sheet manufactured of this |
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| JPWO2012039477A1 (en) * | 2010-09-24 | 2014-02-03 | 日立化成株式会社 | Lithium ion battery and battery module using the same |
| JP6003648B2 (en) * | 2010-09-24 | 2016-10-05 | 日立化成株式会社 | Negative electrode active material, lithium ion battery, and battery module using the same |
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