JP2003048706A - Raw material for carbon material and carbon material obtained by using the same - Google Patents
Raw material for carbon material and carbon material obtained by using the sameInfo
- Publication number
- JP2003048706A JP2003048706A JP2001235214A JP2001235214A JP2003048706A JP 2003048706 A JP2003048706 A JP 2003048706A JP 2001235214 A JP2001235214 A JP 2001235214A JP 2001235214 A JP2001235214 A JP 2001235214A JP 2003048706 A JP2003048706 A JP 2003048706A
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- Japan
- Prior art keywords
- silicon
- carbon
- carbon material
- secondary battery
- raw material
- Prior art date
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Classifications
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- 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]
【発明の属する技術分野】本発明は、炭素材用原料、炭
素材およびそれを用いた二次電池負極材、リチウム二次
電池に関する。TECHNICAL FIELD The present invention relates to a raw material for a carbon material, a carbon material, a negative electrode material for a secondary battery using the same, and a lithium secondary battery.
【０００２】[0002]
【従来の技術】近年、ビデオカメラやノート型パソコン
などのポータブル機器の普及に伴い、移動用電源として
小型高容量の二次電池に対する需要が高まり、リチウム
二次電池の使用が拡大されてきた。上記に示したリチウ
ム二次電池の負極材用炭素材としては、特開平５−７４
４５７号公報記載の黒鉛を使用しているものが挙げられ
る。黒鉛は、サイクル性が非常によいことが特長である
が、理論充放電容量が３７２ｍＡｈ／ｇであるため、こ
れ以上の充放電容量は望めないという欠点がある。ま
た、黒鉛材料以外では、特開平５−２８９９６号公報、
特開平７−７３８６８号公報に示されるピッチコークス
を使用した負極材が挙げられる。この材料は易黒鉛化炭
素材であるが、焼成温度が２０００℃を超える領域では
黒鉛化が進行する。黒鉛になってしまうと充放電容量が
決定されてしまう。また黒鉛化される前の温度域（１０
００〜１８００℃）においては充放電容量の高い炭素材
が得られている。しかしながら、サイクル性が乏しく、
ピッチコークスは不純物を多く含んでおり、電池特性に
悪影響を及ぼす。2. Description of the Related Art In recent years, with the widespread use of portable devices such as video cameras and notebook computers, the demand for small high-capacity secondary batteries as mobile power sources has increased, and the use of lithium secondary batteries has expanded. As the carbon material for the negative electrode material of the lithium secondary battery described above, there is disclosed in Japanese Patent Laid-Open No. 5-74
An example is one using the graphite described in Japanese Patent No. 457. Graphite has a feature that it has very good cycleability, but since it has a theoretical charge / discharge capacity of 372 mAh / g, it has a drawback that a charge / discharge capacity higher than that cannot be expected. In addition to graphite materials, JP-A-5-28996 discloses
A negative electrode material using pitch coke disclosed in JP-A-7-73868 can be used. This material is a graphitizable carbon material, but graphitization proceeds in the region where the firing temperature exceeds 2000 ° C. If it becomes graphite, the charge / discharge capacity will be determined. The temperature range before graphitization (10
(00 to 1800 ° C.), a carbon material having a high charge / discharge capacity is obtained. However, the cycleability is poor,
Pitch coke contains a large amount of impurities and adversely affects the battery characteristics.
【０００３】また、熱処理温度が５００℃〜７００℃程
度の低温で処理された炭素負極は、次世代の高容量型炭
素負極の有力候補の一つである。可逆容量で８５０ｍＡ
ｈ／ｇと、重量あたりの容量で黒鉛をこえる。また、低
温処理であるため、エネルギーメリットも高い。しかし
ながら、電位が高く、充放電での電位のヒステリシスが
大きいのが難点である。炭素以外のリチウムイオン負極
材として注目されているのが特開平５−１６６５３６号
公報に示される金属酸化物含有炭素材、及び特開平６−
２９０７８２号公報に示される窒素含有炭素材である。
しかしながら、これらの炭素材では充放電容量８００ｍ
Ａｈ／ｇと非常に大容量ではあるが、瞬間放電量が非常
に高いことからその制御が困難であるとされている。A carbon negative electrode treated at a low heat treatment temperature of about 500 ° C. to 700 ° C. is one of the promising candidates for the next-generation high-capacity carbon negative electrode. 850mA with reversible capacity
The graphite exceeds h / g and the capacity per weight. Further, since it is a low temperature treatment, it has a high energy merit. However, it has a drawback that the potential is high and the hysteresis of the potential during charge and discharge is large. As a lithium ion negative electrode material other than carbon, attention is paid to a metal oxide-containing carbon material disclosed in JP-A-5-166536 and JP-A-6-
It is a nitrogen-containing carbon material disclosed in Japanese Patent No. 290782.
However, these carbon materials have a charge / discharge capacity of 800 m.
Although it has a very large capacity of Ah / g, it is said that its control is difficult because the instantaneous discharge amount is very high.
【０００４】また、リチウムイオンのインターカレーシ
ョン能が非常に高い材料としてケイ素元素があり、それ
を用いたケイ素含有炭素材として、特開平０５−１４４
７４公報，特開平７−３１５８２２公報，再表９８／０
２４１３５公報，特開平０８−２３１２７３公報等があ
る。これらにおいて、有機ケイ素化合物、無機ケイ素化
合物を使用している場合、ケイ素と結合している有機又
は無機元素の影響を受けケイ素元素が持っている充放電
容量が十分に活かされていない。また、ケイ素元素を使
用している場合でも、易黒鉛化炭素前駆体，難黒鉛化炭
素前駆体又は炭素材にケイ素元素を混合し炭化処理して
いる。この場合、ケイ素の炭素材への分散性は良い。し
かし、炭素材表面へのケイ素元素の露出により容量は高
いが、充放電効率が悪い。あるいは、ケイ素元素の炭素
材表面への露出は少ないが、ケイ素元素へのリチウムイ
オンのインターカレーションによるケイ素元素の膨張に
よる炭素材の破損を押える事が困難で、充放電効率を低
下させる傾向にある。Further, there is silicon element as a material having a very high intercalation ability of lithium ions, and as a silicon-containing carbon material using the element, there is disclosed in Japanese Patent Laid-Open No. 05-144.
74 publication, JP-A-7-315822 publication, re-list 98/0.
24135, JP-A-08-231273 and the like. In these cases, when an organic silicon compound or an inorganic silicon compound is used, the charge / discharge capacity of the silicon element is not fully utilized due to the influence of the organic or inorganic element bonded to silicon. Further, even when the silicon element is used, the carbon element is carbonized by mixing the graphitizable carbon precursor, the non-graphitizable carbon precursor or the carbon material with the silicon element. In this case, the dispersibility of silicon in the carbon material is good. However, although the capacity is high due to the exposure of silicon element to the surface of the carbon material, the charge / discharge efficiency is poor. Alternatively, although the exposure of the silicon element to the surface of the carbon material is small, it is difficult to suppress the damage of the carbon material due to the expansion of the silicon element due to the intercalation of lithium ions into the silicon element, which tends to reduce the charge / discharge efficiency. is there.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、高充
放電容量を発揮することができる炭素材用原料、炭素
材、二次電池負極材およびリチウム二次電池を提供する
ことである。SUMMARY OF THE INVENTION An object of the present invention is to provide a carbon material raw material, a carbon material, a secondary battery negative electrode material and a lithium secondary battery which can exhibit a high charge / discharge capacity.
【０００６】[0006]
【課題を解決するための手段】このような目的は、下記
（１）〜（１０）の本発明により達成される。
（１）ケイ素含有炭素前駆体および炭素質小球体を含む
ことを特徴とする炭素材用原料、（２）前記ケイ素含有
炭素前駆体は、ケイ素粉末とピッチとの混合物から構成
される前記（１）に記載の炭素材用原料、（３）前記ケ
イ素含有炭素前駆体は、ケイ素粉末、アルミナ粉末およ
びピッチとの混合物から構成される前記（１）に記載の
炭素材用原料、（４）前記ケイ素粉末は、前記ケイ素含
有炭素前駆体全体の１５〜６０重量％である前記（１）
ないし（３）に記載の炭素材用原料、（５）前記ケイ素
含有炭素前駆体は、炭素材用原料全体の２０〜６０重量
％である前記（１）ないし（４）のいずれかに記載の炭
素材用原料、（６）前記炭素質小球体は、メソカーボン
マイクロビーズである前記（１）ないし（５）のいずれ
かに記載の炭素材用原料、（７）前記炭素質小球体は、
平均粒子径１〜５０μｍである前記（１）ないし（６）
のいずれかに記載の炭素材用原料、（８）前記（１）な
いし（７）のいずれかに記載の炭素材用原料を炭化処理
してなる炭素材、（９）前記（８）に記載の炭素材を含
有する二次電池負極材、（１０）前記（９）に記載の二
次電池負極材を用いたリチウム二次電池。The above objects are achieved by the present invention described in (1) to (10) below. (1) A raw material for a carbon material characterized by containing a silicon-containing carbon precursor and carbonaceous microspheres, (2) the silicon-containing carbon precursor is composed of a mixture of a silicon powder and a pitch. (3) The carbon material raw material, (3) The silicon-containing carbon precursor is composed of a mixture of silicon powder, alumina powder and pitch, and the carbon material raw material according to (1), (4) above. The silicon powder accounts for 15 to 60% by weight of the whole silicon-containing carbon precursor (1).
To (3), the carbon material raw material (5), wherein the silicon-containing carbon precursor is 20 to 60% by weight of the total carbon material raw material, (1) to (4) Raw material for carbon material, (6) The carbonaceous microspheres are mesocarbon microbeads. Raw material for carbonaceous material according to any one of (1) to (5), (7) The carbonaceous microspheres are:
The above (1) to (6) having an average particle diameter of 1 to 50 μm
(8) The carbon material raw material, (8) the carbon material obtained by carbonizing the carbon material raw material according to any one of (1) to (7), (9) the above (8) (10) A lithium secondary battery using the secondary battery negative electrode material according to (9) above, which contains the carbonaceous material.
【０００７】以下、本発明の炭素材用原料、炭素材、二
次電池負極材およびリチウム二次電池について、詳細に
説明する。本発明の炭素材用原料は、ケイ素含有炭素前
駆体および炭素質小球体を含むものである。また、本発
明の炭素材は前記炭素材用原料を炭素化処理したもので
あり、二次電池負極材は前記炭素材を含むものであり、
リチウム二次電池は前記二次電池負極材を用いたもので
ある。The raw material for carbon material, the carbon material, the negative electrode material for the secondary battery and the lithium secondary battery of the present invention will be described in detail below. The raw material for carbon material of the present invention contains a silicon-containing carbon precursor and carbonaceous microspheres. Further, the carbon material of the present invention is obtained by carbonizing the raw material for carbon material, and the secondary battery negative electrode material contains the carbon material.
The lithium secondary battery uses the negative electrode material for the secondary battery.
【０００８】本発明で用いるケイ素含有炭素前駆体とし
ては、例えば、シロキサン，シラザン等の有機ケイ素化
合物、有機ケイ素化合物と石油ピッチ，石炭ピッチ等の
易黒鉛化炭素前駆体、又はかかる易黒鉛化炭素前駆体と
フェノール樹脂，フラン樹脂，エポキシ樹脂等の難黒鉛
化炭素前駆体との混合物、又はケイ素又はケイ素酸化
物，ケイ素炭化物等の無機ケイ素化合物と前記易黒鉛化
炭素前駆体又は難黒鉛化炭素前駆体との混合物等が挙げ
られる。これらの中でもケイ素粉末と易黒鉛化炭素前駆
体又は難黒鉛化炭素前駆体との混合物が好ましい。これ
により、二次電池に用いた場合に高充放電容量を発揮す
ることができる。さらには、前記ケイ素含有炭素前駆体
は、特に限定されないが、ケイ素粉末とピッチとの混合
物であることが好ましい。これにより酸素含有量が少な
く、炭素化率を上がることができるので、上記の効果に
加え、二次電池に用いた場合に放電容量保持率を向上す
ることができる。また、前記ケイ素粉末の配合量は、前
記ケイ素含有炭素前駆体の１５〜６０重量％が好まし
く、特に２０〜５０重量％が好ましい。前記ケイ素粉末
が前記範囲内であると、ケイ素の特性を損なうことなく
二次電池に用いた場合に高充放電容量を発揮することが
できる。Examples of the silicon-containing carbon precursor used in the present invention include organosilicon compounds such as siloxane and silazane, graphitizable carbon precursors such as organosilicon compounds and petroleum pitch, coal pitch, or such graphitizable carbon. A mixture of a precursor and a non-graphitizable carbon precursor such as a phenol resin, a furan resin or an epoxy resin, or an inorganic silicon compound such as silicon or silicon oxide or silicon carbide and the above-mentioned graphitizable carbon precursor or non-graphitizable carbon Examples thereof include a mixture with a precursor. Among these, a mixture of silicon powder and a graphitizable carbon precursor or a non-graphitizable carbon precursor is preferable. Thereby, when used in a secondary battery, a high charge / discharge capacity can be exhibited. Furthermore, the silicon-containing carbon precursor is not particularly limited, but is preferably a mixture of silicon powder and pitch. As a result, the oxygen content is small and the carbonization rate can be increased. Therefore, in addition to the above effects, the discharge capacity retention rate can be improved when used in a secondary battery. Further, the blending amount of the silicon powder is preferably 15 to 60% by weight of the silicon-containing carbon precursor, and particularly preferably 20 to 50% by weight. When the silicon powder is in the above range, a high charge / discharge capacity can be exhibited when used in a secondary battery without impairing the characteristics of silicon.
【０００９】また、前記ケイ素含有炭素前駆体は、特に
限定されないが、ケイ素粉末、アルミナ粉末およびピッ
チとの混合物であることが好ましい。これにより、二次
電池に用いた場合に充放電効率の低下を抑制し、充放電
効率を更に向上することができる。この場合、前記ケイ
素粉末及びアルミナ粉末の配合量については、特に限定
されないが、ケイ素粉末は、前記ケイ素含有炭素前駆体
の１５〜６０重量％が好ましく、特に２０〜５０重量％
が好ましく、ケイ素粉末とアルミナ粉末の合計量は、前
記ケイ素含有炭素前駆体の１６〜８０重量％が好まし
く、特に２５〜７０重量％が好ましい。前記範囲内であ
ると二次電池に用いた場合に高充放電容量を保持したま
ま、充放電効率が向上することができる。前記ケイ素含
有炭素前駆体は、特に限定されないが、炭素材用原料の
２０〜６０重量％で有ることが好ましく、特に３０〜５
０重量％が好ましい。前記ケイ素含有炭素前駆体が前記
範囲内であると上記効果に加え、二次電池に用いた場合
に放電容量保持率を向上することができる。The silicon-containing carbon precursor is not particularly limited, but is preferably a mixture of silicon powder, alumina powder and pitch. As a result, it is possible to suppress a decrease in charge / discharge efficiency when used in a secondary battery and further improve the charge / discharge efficiency. In this case, the blending amounts of the silicon powder and the alumina powder are not particularly limited, but the silicon powder is preferably 15 to 60% by weight of the silicon-containing carbon precursor, and particularly 20 to 50% by weight.
Is preferable, and the total amount of the silicon powder and the alumina powder is preferably 16 to 80% by weight of the silicon-containing carbon precursor, and particularly preferably 25 to 70% by weight. Within the above range, when used in a secondary battery, the charge / discharge efficiency can be improved while maintaining a high charge / discharge capacity. The silicon-containing carbon precursor is not particularly limited, but is preferably 20 to 60% by weight of the carbonaceous material, and particularly 30 to 5%.
0% by weight is preferred. When the silicon-containing carbon precursor is within the above range, in addition to the above effects, the discharge capacity retention rate can be improved when used in a secondary battery.
【００１０】本発明で用いる炭素質小球体は、炭素材と
して、あるいは炭化処理して炭素材となる球体又は曲面
を有する形状の粉末をいう。例えば、球状のフェノール
樹脂、メラミン樹脂、ポリイミド，メソフェーズ小球体
等、あるいはこれらを炭化処理し得られる炭素質小球体
等の易黒鉛化炭素前駆体や難黒鉛化炭素前駆体、あるい
は前記易黒鉛化炭素前駆体や難黒鉛化炭素前駆体を炭化
処理した後、機械的に球体近い形状に粉砕処理した粉
末、又は紡糸し繊維化したものを炭化処理し粉砕した粉
末等が挙げられる。これらの中でもメソフェーズ小球
体、これを炭化処理して得られるメソフェーズ含有炭素
質小球体、あるいは黒鉛化処理して得られるメソカーボ
ンマイクロビーズが好ましく、この中でも特にメソカー
ボンマイクロビーズが好ましい。これにより、ケイ素の
リチウムとの反応による膨張収縮力を球体の曲面で分散
させることにより、二次電池に用いた場合に高い充放電
効率を発揮することができる。前記炭素質小球体は、特
に限定されないが、炭素材用原料全体の４０〜８０重量
％が好ましく、特に５０〜７０重量％が好ましい。前記
炭素質小球体が前記範囲内であるとケイ素の高容量特性
を維持しながら、二次電池に用いた場合に高充放電効率
を発揮することができる。The carbonaceous small spheres used in the present invention mean powders having a spherical shape or a curved surface as a carbon material or carbonized to become a carbon material. For example, a graphitizable carbon precursor or a non-graphitizable carbon precursor such as spherical phenol resin, melamine resin, polyimide, mesophase spheres, or carbonaceous spheres obtained by carbonizing these, or the above-mentioned graphitizable carbon Examples include powders obtained by carbonizing a carbon precursor or a non-graphitizable carbon precursor and then mechanically pulverizing it into a shape close to a sphere, or powders obtained by spinning and fiberizing carbonized and pulverized. Among these, mesophase microspheres, mesophase-containing carbonaceous microspheres obtained by carbonizing the same, or mesocarbon microbeads obtained by graphitizing treatment are preferable, and among them, mesocarbon microbeads are particularly preferable. As a result, by dispersing the expansion / contraction force due to the reaction of silicon with lithium on the curved surface of the sphere, it is possible to exhibit high charge / discharge efficiency when used in a secondary battery. The carbonaceous microspheres are not particularly limited, but are preferably 40 to 80% by weight, and particularly preferably 50 to 70% by weight of the total carbonaceous material. When the carbonaceous microspheres are within the above range, high charge / discharge efficiency can be exhibited when used in a secondary battery while maintaining the high capacity characteristics of silicon.
【００１１】また、前記炭素質小球体は、特に限定され
ないが、平均粒径１〜５０μｍが好ましく、特に５〜３
０μｍが好ましい。前記炭素質小球体の粒径が前記範囲
内であると上述の効果に加え、負極材作製時の取り扱い
性が良く、また、作製後の負極材塗布面が平滑となる。The carbonaceous spheres are not particularly limited, but preferably have an average particle size of 1 to 50 μm, and particularly 5 to 3
0 μm is preferable. When the particle size of the carbonaceous spheres is within the above range, in addition to the above-mentioned effects, the handleability during the production of the negative electrode material is good, and the negative electrode material coated surface after the production becomes smooth.
【００１２】本発明では、前記炭素材用原料を炭化処理
して炭素材を得ることができる。炭化処理は特に限定さ
れないが、例えば、前記ケイ素含有炭素前駆体と炭素質
小球体を粉砕または溶融混合した後、窒素雰囲気下で５
０〜２００℃／時間で昇温し、４００〜６００℃で１〜
５時間保持し冷却後、１００μｍ以下まで粉砕する。粉
砕処理品を更に窒素雰囲気下で１０〜１５０℃／時間で
昇温し８００〜１２００℃にて１〜１０時間保持し室温
まで冷却し、前記炭素材を得ることができる。In the present invention, the carbon material can be obtained by carbonizing the raw material for carbon material. The carbonization treatment is not particularly limited. For example, after the silicon-containing carbon precursor and the carbonaceous spheres are pulverized or melt-mixed, the carbonization is performed under a nitrogen atmosphere at 5
The temperature is raised at 0 to 200 ° C / hour, and at 1 to 400 ° C to 600 ° C.
After being kept for 5 hours and cooled, it is ground to 100 μm or less. The crushed product is further heated in a nitrogen atmosphere at 10 to 150 ° C./hour, kept at 800 to 1200 ° C. for 1 to 10 hours, and cooled to room temperature to obtain the carbon material.
【００１３】また、本発明では前記炭素材を含む二次電
池負極材を得ることができる。二次電池負極材に適用す
る場合、例えば、前記炭素材１００重量部に対しポリエ
チレン，ポリプロピレン等を含むフッ素系高分子、ブチ
ルゴム，ブタジエンゴム等のゴム状高分子等の有機高分
子結着剤１〜３０重量部及び適量のＮ−メチル−２−ピ
ロリドン，ジメチルホルムアミド等の粘度調整用溶剤を
混練し、ペースト状にした混合物を圧縮成形，ロール成
形等によりシート状、ペレット状等に成形し得ることが
できる。また、粘度調整用溶剤量を調整、スラリー状に
した混合物を銅箔、ニッケル箔等の集電体に塗布成形し
得ることもできる。Further, according to the present invention, a secondary battery negative electrode material containing the above carbon material can be obtained. When applied to a secondary battery negative electrode material, for example, an organic polymer binder 1 such as a fluoropolymer containing polyethylene, polypropylene or the like, or a rubber-like polymer such as butyl rubber or butadiene rubber based on 100 parts by weight of the carbon material 1 -30 parts by weight and an appropriate amount of a solvent for adjusting viscosity such as N-methyl-2-pyrrolidone and dimethylformamide are kneaded, and a paste-like mixture can be formed into a sheet, a pellet or the like by compression molding, roll molding or the like. be able to. It is also possible to adjust the amount of the solvent for adjusting the viscosity and apply the slurry mixture to a current collector such as a copper foil or a nickel foil for molding.
【００１４】また、本発明では前記二次電池用負極材を
用いたリチウム二次電池を得ることができる。リチウム
二次電池に前記二次電池用負極材を適用する場合、例え
ば、前記二次電池用負極材はセパレータを介して正極材
と対抗して配置され、電解液を用いリチウム二次電池が
得られる。正極材としては特に限定されないが、リチウ
ムコバルト酸化物、リチウムニッケル酸化物，リチウム
マンガン酸化物等の複合酸化物やポリアニリン，ポリピ
ロール等の導電性高分子等を用いることができる。セパ
レータとしては特に限定されないが、ポリエチレン，ポ
リプロピレン等の微多孔質、不織布等を用いることがで
きる。電解液としては特に限定されないが、非水系溶媒
に電解質となるリチウム塩を溶解したものを用いる。電
解質としてはＬｉＣｌＯ4，ＬｉＰＦ6等のリチウム金属
塩、テトラアルキルアンモニウム塩等を用いることがで
きる。非水系溶媒としては、プロピレンカーボネート、
エチレンカーボネート、γ−ブチロラクトン等の環状エ
ステル類、ジエチルカーボネート等の鎖状エステル類、
ジメトキシエタン等のエーテル類等の混合物等を用いる
ことができる。また、上記塩類をポリエチレンオキサイ
ド、ポリアクリロニトリル等に混合された固体電解質を
用いることもできる。Further, according to the present invention, a lithium secondary battery using the negative electrode material for secondary battery can be obtained. When the negative electrode material for a secondary battery is applied to a lithium secondary battery, for example, the negative electrode material for a secondary battery is arranged to face the positive electrode material via a separator, and a lithium secondary battery is obtained using an electrolytic solution. To be The positive electrode material is not particularly limited, but composite oxides such as lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, and conductive polymers such as polyaniline and polypyrrole can be used. The separator is not particularly limited, but a microporous material such as polyethylene or polypropylene, a non-woven fabric, or the like can be used. The electrolytic solution is not particularly limited, but a nonaqueous solvent in which a lithium salt serving as an electrolyte is dissolved is used. As the electrolyte, a lithium metal salt such as LiClO 4 or LiPF 6 or a tetraalkylammonium salt can be used. As the non-aqueous solvent, propylene carbonate,
Cyclic esters such as ethylene carbonate and γ-butyrolactone, chain esters such as diethyl carbonate,
A mixture of ethers such as dimethoxyethane can be used. It is also possible to use a solid electrolyte prepared by mixing the above salts with polyethylene oxide, polyacrylonitrile, or the like.
【００１５】以下、本発明を実施例及び比較例により詳
細に説明するが、本発明はこれに限定されるものではな
い。Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
【００１６】実施例１
＜炭素材の製造＞
ケイ素含有炭素前駆体の作製
軟化点１２０℃のピッチ５００重量部を１Ｌのフラスコ
入れ、１８０〜２４０℃でピッ チを溶解した。溶解し
たピッチにケイ素粉末１５０重量部、アルミナ粉末２５
重量部を 徐々に逐添し、添加終了後、更に１時間攪拌
した後、室温まで冷却し、粗砕しケイ素含 有炭素前駆
体Ａを得た。
炭素材用原料の混合
上記にて得られたケイ素含有炭素前駆体を全体の４０
重量％使用し、炭素質小球体としてメソカーボンマイク
ロビーズであるＫＭＦＣ（川崎製鉄（株）製）を全体の
６０重量％使用し、Ｖ型ブレンダーを用いて３０分間混
合した。次いで、衝撃式粉砕機でスクリーン１ｍｍφで
１００μｍ以下に粉砕した。
不融化処理および整粒
上記粉砕品を窒素雰囲気下で１００℃／時間で５５０℃
まで昇温して１．５時間保持した。その後、冷却して振
動ボールミルを用いて４５μｍ以下まで粉砕した。
炭化処理
上記粉砕品を１００℃／時間で１０００℃まで昇温して
３時間保持した。その後、冷却して４５μｍ篩で篩い、
炭素材を得た。Example 1 <Production of carbon material> Preparation of silicon-containing carbon precursor 500 parts by weight of a pitch having a softening point of 120 ° C. was put into a 1 L flask and the pitch was dissolved at 180 to 240 ° C. 150 parts by weight of silicon powder and 25 alumina powder in the melted pitch
By weight, the parts were gradually added, and after the addition was completed, the mixture was stirred for another 1 hour, cooled to room temperature, and crushed to obtain a silicon-containing carbon precursor A. Mixing of raw materials for carbon material 40% of the silicon-containing carbon precursor obtained above
By weight, KMFC (manufactured by Kawasaki Steel Co., Ltd.), which is mesocarbon microbeads, was used as carbonaceous microspheres in an amount of 60% by weight based on the total amount, and mixed for 30 minutes using a V-type blender. Then, it was crushed to 100 μm or less with a screen 1 mmφ by an impact crusher. Infusibilization and sizing The crushed product was 550 ° C at 100 ° C / hour in a nitrogen atmosphere.
The temperature was raised to and held for 1.5 hours. Then, it was cooled and pulverized to 45 μm or less using a vibrating ball mill. Carbonization treatment The pulverized product was heated to 1000 ° C at 100 ° C / hour and held for 3 hours. Then, cool and sieve with a 45 μm sieve,
A carbon material was obtained.
【００１７】＜二次電池の製造＞
上述の炭素材に結合剤としてポリフッ化ビニリデン１
０重量％、アセチレンブラック３重量％を添加し、希釈
溶媒としてＮ−メチル−２−ピロリドンを適量加え混合
し、スラリー状の負極混合物を調整した。調整した負極
スラリー状混合物を１０μｍの銅箔の両面に塗布し、そ
の後、１１０℃で１時間真空乾燥した。真空乾燥後、ロ
ールプレスによって電極を加圧成形した。これを幅４０
ｍｍで長さ２９０ｍｍの大きさに切り出し負極を作製し
た。但し、負極両端１０ｍｍの部分は銅箔が露出してお
り、この一方に負極タブを圧着した。
正極は正極活物質をＬｉＣｏＯ2３００重量部、アセ
チレンブラック１５重量部、ポリフッ化ビニリデン１５
重量部を添加し、希釈溶媒としてＮ−メチル−２−ピロ
リドンを適量加え混合し、スラリー状の正極混合物を調
整した。調整した正極スラリー状混合物を２５μｍのア
ルミ箔の両面に塗布し、その後、１１０℃で１時間真空
乾燥した。真空乾燥後、ロールプレスによって電極を加
圧成形した。これを幅４０ｍｍで長さ２８０ｍｍの大き
さに切り出し正極を作製した。但し、正極両端１０ｍｍ
の部分はアルミ箔が露出しており、この一方に正極タブ
を圧着した。
前記正極、セパレータ（ポリプロピレン製多孔質フィ
ルム：幅４５ｍｍ、厚さ２５μｍ）、前記負極、セパレ
ータ、前記正極…の順で前記負極が外側になるよう渦巻
き状に捲回して電極を作製した。作製した電極を単三型
の電池缶に挿入し負極タブを缶底と溶接する。電解液と
して体積比が１：１のエチレンカーボネートとジエチレ
ンカーボネートの混合液に６フッ化リン酸リチウムを１
モル／リットル溶解させたものを電池缶に注入した後、
正極タブを正極蓋に溶接し、正極蓋をかしめ付けて二次
電池を作製した。<Manufacture of Secondary Battery> Polyvinylidene fluoride 1 as a binder in the above carbon material.
0% by weight and 3% by weight of acetylene black were added, and an appropriate amount of N-methyl-2-pyrrolidone was added as a diluent solvent and mixed to prepare a slurry-like negative electrode mixture. The prepared negative electrode slurry-like mixture was applied to both surfaces of a 10 μm copper foil, and then vacuum dried at 110 ° C. for 1 hour. After vacuum drying, the electrode was pressure-molded by a roll press. Width 40
A negative electrode was prepared by cutting it out into a size of 290 mm and a length of 290 mm. However, the copper foil was exposed at the portion of 10 mm on both ends of the negative electrode, and a negative electrode tab was pressure-bonded to this one. For the positive electrode, the positive electrode active material was 300 parts by weight of LiCoO 2 , 15 parts by weight of acetylene black, and 15 parts of polyvinylidene fluoride.
A weight part was added, and an appropriate amount of N-methyl-2-pyrrolidone was added as a diluent solvent and mixed to prepare a slurry-like positive electrode mixture. The prepared positive electrode slurry-like mixture was applied on both sides of a 25 μm aluminum foil, and then vacuum dried at 110 ° C. for 1 hour. After vacuum drying, the electrode was pressure-molded by a roll press. This was cut into a size of 40 mm in width and 280 mm in length to prepare a positive electrode. However, both ends of the positive electrode are 10 mm
The aluminum foil was exposed at the portion of, and the positive electrode tab was pressure-bonded to this one side. An electrode was manufactured by spirally winding the positive electrode, the separator (porous film made of polypropylene: width 45 mm, thickness 25 μm), the negative electrode, the separator, the positive electrode in this order so that the negative electrode is on the outside. The prepared electrode is inserted into an AA battery can and the negative electrode tab is welded to the can bottom. As an electrolytic solution, 1 volume of lithium hexafluorophosphate is added to a mixed solution of ethylene carbonate and diethylene carbonate having a volume ratio of 1: 1.
After injecting the dissolved mol / l into the battery can,
The positive electrode tab was welded to the positive electrode lid, and the positive electrode lid was caulked to manufacture a secondary battery.
【００１８】実施例２
実施例１で得たケイ素含有炭素前駆体Ａの使用量を全体
の３０重量％とし、ＫＭＦＣの使用量を全体の７０重量
％とした以外は、実施例１と同様にした。Example 2 The same as Example 1 except that the silicon-containing carbon precursor A obtained in Example 1 was used in an amount of 30% by weight and the KMFC was used in an amount of 70% by weight. did.
【００１９】実施例３
実施例１において、アルミナ粉末の添加量をケイ素含有
炭素前駆体全体に対して１０重量％としたケイ素含有炭
素前駆体Ｂを使用した以外は、実施例１と同様にした。Example 3 The same as Example 1 except that the silicon-containing carbon precursor B was used in which the amount of alumina powder added was 10% by weight based on the whole silicon-containing carbon precursor. .
【００２０】実施例４
実施例１で得たケイ素含有炭素前駆体Ａの使用量を全体
の１５重量％とし、ＫＭＦＣの使用量を全体の８５重量
％とした以外は実施例１と同様にした。Example 4 Same as Example 1 except that the silicon-containing carbon precursor A obtained in Example 1 was used in an amount of 15% by weight and the KMFC was used in an amount of 85% by weight. .
【００２１】実施例５
実施例１で得たケイ素含有炭素前駆体Ａの使用量を全体
の７０重量％とし、ＫＭＦＣの使用量を全体の３０重量
％とした以外は実施例１と同様にした。Example 5 The same procedure was performed as in Example 1 except that the silicon-containing carbon precursor A obtained in Example 1 was used in an amount of 70% by weight and the KMFC was used in an amount of 30% by weight. .
【００２２】実施例６
実施例１において、アルミナ粉末を添加していないケイ
素含有炭素前駆体Ｃを使用した以外は、実施例１と同様
にした。Example 6 The procedure of Example 1 was repeated, except that the silicon-containing carbon precursor C to which no alumina powder was added was used.
【００２３】実施例７
炭素質小球体として、球状フェノール樹脂（住友ベーク
ライト製ＰＲ−ＡＣＳ−７Ｐ）を用いた以外は、実施例
１と同様にした。Example 7 The procedure of Example 1 was repeated except that a spherical phenol resin (PR-ACS-7P manufactured by Sumitomo Bakelite) was used as the carbonaceous microspheres.
【００２４】比較例１
炭素質小球体を使用しない以外は、実施例１と同様にし
た。Comparative Example 1 The procedure of Example 1 was repeated except that carbonaceous microspheres were not used.
【００２５】比較例２
ケイ素含有炭素前駆体Ａを使用しない以外は、実施例１
と同様にした。Comparative Example 2 Example 1 except that the silicon-containing carbon precursor A was not used.
Same as.
【００２６】比較例３
ケイ素を含有しない炭素前駆体（大阪化成（株）製ＴＧ
Ｐ）を用いた以外は、実施例１と同様にした。Comparative Example 3 Carbon precursor containing no silicon (TG manufactured by Osaka Kasei Co., Ltd.)
Same as Example 1 except that P) was used.
【００２７】上述の実施例および比較例により得られた
結果を表１に示す。なお、比表面積は、炭素材製造後に
ユアサアイオニクス社製ＮＯＶＡ１２００を用いて、窒
素ガスＢＥＴ３点法で測定した。２．５Ｖ放電容量、初
回充放電効率および放電容量保持率については、二次電
池製造後に測定した。充電条件は、電流２５ｍＡ／ｇの
低電流で１ｍＶになるまで保持し、その後、１．２５ｍ
Ａｈ／ｇ以下に電流が減衰するまでとした。また、放電
条件のカットオフ電位は２．５Ｖとした。放電容量保持
率は初回放電容量に対する３００サイクル後の放電容量
の保持率とした。Table 1 shows the results obtained by the above-mentioned Examples and Comparative Examples. The specific surface area was measured by the nitrogen gas BET three-point method using NOVA1200 manufactured by Yuasa Ionics Inc. after the carbon material was manufactured. The 2.5 V discharge capacity, the initial charge / discharge efficiency and the discharge capacity retention rate were measured after the secondary battery was manufactured. The charging conditions are as follows: a low current of 25 mA / g is maintained until it reaches 1 mV, then 1.25 m
It was set until the current decreased to Ah / g or less. The cut-off potential of the discharge condition was 2.5V. The discharge capacity retention rate was defined as the retention rate of the discharge capacity after 300 cycles with respect to the initial discharge capacity.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１に示すように、実施例１〜７は、ケイ
素含有炭素前駆体を使用しているため放電容量に優れ
る。特に実施例１と３は、適量のアルミナ粉末を配合し
ていることから充放電効率に優れる。また、特に実施例
１〜４は、ケイ素を含有したピッチからなるケイ素含有
炭素前駆体及びメソフェーズ含有炭素質小球体の混合物
を炭化処理して使用しているため放電容量保持率も優れ
る。As shown in Table 1, Examples 1 to 7 are excellent in discharge capacity because they use the silicon-containing carbon precursor. In particular, Examples 1 and 3 are excellent in charge / discharge efficiency because they contain a proper amount of alumina powder. Further, particularly in Examples 1 to 4, since the mixture of the silicon-containing carbon precursor composed of the pitch containing silicon and the mesophase-containing carbonaceous small spheres was carbonized and used, the discharge capacity retention rate was also excellent.
【００３０】[0030]
【発明の効果】本発明によれば、二次電池の高充放電容
量を発揮することができる。また、ケイ素含有ピッチと
メソカーボンマイクロビーズからなる組成物を炭化処理
した炭素材を用いる場合、特に二次電池の放電容量保持
率を保持及び充放電効率を向上することができる。According to the present invention, the high charge / discharge capacity of the secondary battery can be exhibited. When a carbon material obtained by carbonizing a composition containing silicon-containing pitch and mesocarbon microbeads is used, the discharge capacity retention rate of the secondary battery can be maintained and the charge / discharge efficiency can be improved.
フロントページの続き Ｆターム(参考） 4G046 CA00 CA07 CB09 CC01 4H058 DA13 DA22 DA24 EA12 FA03 GA16 HA03 HA13 5H029 AJ03 AK03 AK16 AL06 AM03 AM04 AM05 AM07 DJ16 HJ01 HJ05 5H050 AA08 BA17 CA08 CA09 CB07 FA17 GA10 HA01 HA05 Continued front page F-term (reference) 4G046 CA00 CA07 CB09 CC01 4H058 DA13 DA22 DA24 EA12 FA03 GA16 HA03 HA13 5H029 AJ03 AK03 AK16 AL06 AM03 AM04 AM05 AM07 DJ16 HJ01 HJ05 5H050 AA08 BA17 CA08 CA09 CB07 FA17 GA10 HA01 HA05
Claims (10)
体を含むことを特徴とする炭素材用原料。1. A raw material for a carbonaceous material, comprising a silicon-containing carbon precursor and carbonaceous microspheres.
末とピッチとの混合物から構成される請求項１に記載の
炭素材用原料。2. The raw material for carbon material according to claim 1, wherein the silicon-containing carbon precursor is composed of a mixture of silicon powder and pitch.
末、アルミナ粉末およびピッチとの混合物から構成され
る請求項１に記載の炭素材用原料。3. The raw material for a carbon material according to claim 1, wherein the silicon-containing carbon precursor is composed of a mixture of silicon powder, alumina powder and pitch.
前駆体全体の１５〜６０重量％である請求項２または３
に記載の炭素材用原料。4. The silicon powder accounts for 15 to 60% by weight of the total silicon-containing carbon precursor.
The raw material for carbon material described in.
原料全体の２０〜６０重量％である請求項１ないし４の
いずれかに記載の炭素材用原料。5. The raw material for carbon material according to claim 1, wherein the silicon-containing carbon precursor is 20 to 60% by weight of the total raw material for carbon material.
クロビーズである請求項１ないし５のいずれかに記載の
炭素材用原料。6. The raw material for carbon material according to claim 1, wherein the carbonaceous microspheres are mesocarbon microbeads.
０μｍである請求項１ないし６のいずれかに記載の炭素
材用原料。7. The carbonaceous spheres have an average particle size of 1 to 5
The carbon material raw material according to claim 1, which has a thickness of 0 μm.
素材用原料を炭化処理してなる炭素材。8. A carbon material obtained by carbonizing the carbon material raw material according to claim 1.
電池負極材。9. A secondary battery negative electrode material containing the carbon material according to claim 8.
いたリチウム二次電池。10. A lithium secondary battery using the secondary battery negative electrode material according to claim 9.
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| KR100830612B1 (en) | 2006-05-23 | 2008-05-21 | 강원대학교산학협력단 | Negative active material for lithium secondary battery, method of preparing same, and lithium secondary battery comprising same |
| KR101072068B1 (en) | 2007-12-13 | 2011-10-10 | 주식회사 엘지화학 | Secondary battery |
| JP2015090748A (en) * | 2013-11-05 | 2015-05-11 | エム・ティー・カーボン株式会社 | Silicon-containing amorphous carbon material, manufacturing method thereof, and lithium ion secondary battery |
| JP2018081923A (en) * | 2017-12-25 | 2018-05-24 | 戸田工業株式会社 | Silicon-containing amorphous carbon material and lithium ion secondary battery |
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| JP2018081923A (en) * | 2017-12-25 | 2018-05-24 | 戸田工業株式会社 | Silicon-containing amorphous carbon material and lithium ion secondary battery |
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