JP2003100284A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JP2003100284A JP2003100284A JP2001291043A JP2001291043A JP2003100284A JP 2003100284 A JP2003100284 A JP 2003100284A JP 2001291043 A JP2001291043 A JP 2001291043A JP 2001291043 A JP2001291043 A JP 2001291043A JP 2003100284 A JP2003100284 A JP 2003100284A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- negative electrode
- pores
- carbon
- secondary battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- 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]
【発明の属する技術分野】本発明は、高容量・長寿命の
リチウム二次電池の負極材料を改良したリチウム二次電
池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lithium secondary battery having an improved negative electrode material for a high capacity and long life lithium secondary battery.
【０００２】[0002]
【従来の技術】近年、携帯電話、ラップトップコンピュ
ーター等の移動体通信機器や携帯電子機器が数多く登場
しており、その電源として主にリチウム二次電池が用い
られている。リチウム二次電池は、ニッケルカドミウム
電池等の他の二次電池と比較して、大きなエネルギー密
度をもっているが、移動体通信機器や携帯電子機器のさ
らなる小型軽量化に伴い、そのエネルギー密度やサイク
ル特性の向上が求められている。2. Description of the Related Art In recent years, a large number of mobile communication devices such as mobile phones and laptop computers and mobile electronic devices have appeared, and lithium secondary batteries are mainly used as the power source thereof. Lithium secondary batteries have a larger energy density than other secondary batteries such as nickel-cadmium batteries, but with the further reduction in size and weight of mobile communication devices and portable electronic devices, their energy density and cycle characteristics Is required to improve.
【０００３】現在の一般的なリチウム二次電池では、負
極材料として黒鉛を代表とする炭素材料が用いられてい
る。しかし、黒鉛からなる負極材料では、リチウムがＬ
ｉＣ 6の組成までしか挿入できず、理論容量３７２ｍＡ
ｈ／ｇが限度であり、高容量化への障害になっている。In the current general lithium secondary battery,
Carbon materials such as graphite are used as pole materials.
It However, in the negative electrode material made of graphite, lithium is
iC 6The theoretical capacity is 372mA.
The limit is h / g, which is an obstacle to higher capacity.
【０００４】炭素以外の負極材料として、アルミニウ
ム、ケイ素、スズ等のリチウムと合金化する負極材料の
研究も行われている。これらの負極材料は、炭素材料に
比べて高容量であることが特徴である。特に、ケイ素は
理論容量が４２００ｍＡｈ／ｇであり、黒鉛の理論容量
３７２ｍＡｈ／ｇより遥かに大きく、また、リチウムと
合金化する負極材料の中で最も容量が大きい。しかし、
リチウムと合金化する負極材料は、サイクル劣化が非常
に大きいという欠点を持っていた。As a negative electrode material other than carbon, a negative electrode material alloying with lithium such as aluminum, silicon and tin has also been studied. These negative electrode materials are characterized by having a higher capacity than carbon materials. In particular, silicon has a theoretical capacity of 4200 mAh / g, which is much larger than the theoretical capacity of graphite of 372 mAh / g, and is the highest capacity among the negative electrode materials alloyed with lithium. But,
The negative electrode material that alloys with lithium has a drawback that the cycle deterioration is very large.
【０００５】リチウムと合金化する負極材料を用いる場
合には、リチウムと合金化する負極材料と、炭素材料な
どの導電材、及びポリフッ化ビニリデン（ＰＶＤＦ）な
どの結着剤を混合しスラリー状にしたものを、銅箔など
の集電体上に塗布し、乾燥プレスしたものを負極として
いる。When a negative electrode material that alloys with lithium is used, a negative electrode material that alloys with lithium, a conductive material such as a carbon material, and a binder such as polyvinylidene fluoride (PVDF) are mixed to form a slurry. The obtained product is applied onto a current collector such as a copper foil and dried and pressed to obtain a negative electrode.
【０００６】リチウムと合金化する負極材料を用いた際
のサイクル劣化の原因として、これまで用いられていた
リチウムと合金化する負極材料の粒径は、１０μｍ以上
と大きく比表面積が小さいために、導電材との接触面積
が小さく、十分に導電性が確保できないといった点があ
げられる。As a cause of cycle deterioration when a negative electrode material alloyed with lithium is used, since the particle size of the negative electrode material conventionally alloyed with lithium is as large as 10 μm or more and the specific surface area is small, The contact area with the conductive material is small, and sufficient conductivity cannot be ensured.
【０００７】人造黒鉛のような一般に用いられている導
電材は、塊状であるために、リチウムと合金化する負極
材料との接触が点接触でしかなく、リチウムと合金化す
る負極材料の粒径が大きい場合には、接触面積が小さく
なり十分な導電性が確保できない。Since a commonly used conductive material such as artificial graphite has a lump shape, the contact with the negative electrode material that alloys with lithium is only point contact, and the particle size of the negative electrode material that alloys with lithium is small. Is large, the contact area becomes small and sufficient conductivity cannot be secured.
【０００８】また、もう一つのサイクル劣化の原因とし
て、リチウムのドープ・脱ドープつまり吸蔵・放出に伴
い、リチウムと合金化する負極材料の体積変化が大き
く、微細化が起こることが挙げられる。例えば、リチウ
ムはケイ素にＬｉ4．4Ｓｉの組成までドープ可能である
が、体積はケイ素の約４倍となる。このようにリチウム
のドープ・脱ドープに伴い非常に大きな格子体積の膨張
・収縮が起こり、応力歪が生じて微細化が進むことによ
り、導電材との密着性が低下し、サイクル劣化が起こる
ものである。Another cause of cycle deterioration is that the volume change of the negative electrode material alloyed with lithium is large due to lithium doping / dedoping, that is, occlusion / desorption, and miniaturization occurs. For example, lithium can be converted into silicon by Li 4 . It is possible to dope up to the composition of 4 Si, but the volume is about 4 times that of silicon. In this way, due to the very large lattice volume expansion / contraction with lithium doping / dedoping, stress strain occurs and the miniaturization progresses, which reduces the adhesion to the conductive material and causes cycle deterioration. Is.
【０００９】リチウムのドープ・脱ドープに伴う体積変
化が起こっても十分に導電性を確保できるようにする方
法として、例えば、特開平２０００−１７３６１２号公
報には、導電材として繊維状炭素を用いることが開示さ
れている。また、特開平１０−３９２０号公報には、炭
素質物層を活物質表面に形成させることにより、また、
特開平６−２７９１１２号公報には、炭素質物で活物質
を包含させることで導電性を向上させることが開示され
ている。As a method for ensuring sufficient conductivity even when a volume change occurs due to lithium doping / dedoping, for example, Japanese Patent Laid-Open No. 2000-173612 uses fibrous carbon as a conductive material. It is disclosed. Further, in JP-A-10-3920, by forming a carbonaceous material layer on the surface of an active material,
Japanese Unexamined Patent Publication No. 6-279112 discloses that the conductivity is improved by including an active material with a carbonaceous material.
【００１０】また、特開平２０００−３５７５１４号公
報には、リチウムと合金化する非炭素材料と、炭素材料
の混合物からなる負極材料のうち、リチウムと合金化す
る非炭素材料の平均粒径をＲM、炭素材料の平均粒径を
ＲCとした時、ＲMとＲCとの比ＲM／ＲCを１以下に規定
することにより、導電性を向上させることが開示されて
いる。Further, in Japanese Unexamined Patent Publication No. 2000-357514, the average particle size of a non-carbon material alloyed with lithium among negative electrode materials made of a mixture of a non-carbon material alloyed with lithium and a carbon material is R. M, when the average particle size of the carbon material was R C, by defining the ratio R M / R C of R M and R C to 1 or less, to improve the conductivity is disclosed.
【００１１】これらの方法では、導電材とリチウムと合
金化する負極材料との接触を多くすることができ、リチ
ウムのドープ・脱ドープに伴う体積変化が起こっても十
分な導電性を保つことができるため、サイクル特性をあ
る程度向上させることができる。According to these methods, it is possible to increase the contact between the conductive material and the negative electrode material which is alloyed with lithium, and it is possible to maintain sufficient conductivity even if the volume change due to doping / dedoping of lithium occurs. Therefore, the cycle characteristics can be improved to some extent.
【００１２】しかし、上記のいずれの方法を用いても、
正極にＬｉＣｏＯ2を用いた電池のサイクル特性は、３
００サイクル後の容量維持率が８０％以下であり、未だ
十分な寿命を得るには至ってない。However, using any of the above methods,
The cycle characteristics of the battery using LiCoO 2 for the positive electrode are 3
The capacity retention rate after 00 cycles is 80% or less, and a sufficient life has not yet been obtained.
【００１３】[0013]
【発明が解決しようとする課題】本発明の目的は、サイ
クル特性を向上させたリチウム二次電池を提供すること
にある。An object of the present invention is to provide a lithium secondary battery having improved cycle characteristics.
【００１４】[0014]
【課題を解決するたの手段】上記の目的を達成するため
に、本発明では、負極には複数の孔を有する活性炭を使
用し、活性炭の表面及び孔内にリチウムイオンを吸蔵・
放出するケイ素化合物を付着させ、活性炭とケイ素化合
物との間の密着性を保つことが出来るようになり、サイ
クル特性を向上させることを特徴とする。In order to achieve the above object, in the present invention, an active carbon having a plurality of pores is used for the negative electrode, and lithium ions are occluded on the surface and in the pores of the activated carbon.
It is characterized in that the silicon compound to be released can be adhered to maintain the adhesion between the activated carbon and the silicon compound, thereby improving the cycle characteristics.
【００１５】[0015]
【発明の実施の形態】一般に、リチウム二次電池は、正
極、負極及びこれを分離するセパレーターを具備し、正
極と負極の間に電解液を介在させたものから構成されて
いる。DESCRIPTION OF THE PREFERRED EMBODIMENTS Generally, a lithium secondary battery comprises a positive electrode, a negative electrode, and a separator for separating the positive electrode, a negative electrode, and an electrolyte solution interposed between the positive electrode and the negative electrode.
【００１６】正極活物質としては、リチウムコバルト酸
化物（ＬｉＣｏＯ2）、リチウムニッケル酸化物（Ｌｉ
ＮｉＯ2）、リチウムマンガン酸化物（ＬｉＭｎ
2Ｏ4）、リチウム含有バナジウム酸化物などを用いる。
これらと、人造黒鉛、アセチレンブラック等の導電材及
びポリフッ化ビニリデン（ＰＶＤＦ）などの結着剤を混
合してスラリー状にしたものを、アルミニウム箔などの
集電体上に塗布し、乾燥プレスすることにより正極とす
る。As the positive electrode active material, lithium cobalt oxide (LiCoO 2 ) and lithium nickel oxide (Li
NiO 2 ), lithium manganese oxide (LiMn
2 O 4 ), lithium-containing vanadium oxide, etc. are used.
A conductive material such as artificial graphite or acetylene black and a binder such as polyvinylidene fluoride (PVDF) are mixed to form a slurry, which is applied onto a current collector such as an aluminum foil and dried and pressed. This makes it a positive electrode.
【００１７】負極活物質としては、一般に、人造黒鉛、
天然黒鉛、非晶質炭素などの、リチウムの挿入・脱離可
能な炭素材料を用いる。これらと、ポリフッ化ビニリデ
ン（ＰＶＤＦ）やポリテトラフルオロエチレン（ＰＴＦ
Ｅ）などの結着剤を混合してスラリー状にしたものを、
銅箔などの集電体上に塗布し、乾燥プレスすることによ
り負極とする。As the negative electrode active material, artificial graphite,
A carbon material such as natural graphite or amorphous carbon capable of inserting and removing lithium is used. In addition to these, polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTF)
E) and other binders are mixed to form a slurry,
It is applied onto a collector such as a copper foil and dried to give a negative electrode.
【００１８】また、正極と負極を分離するセパレーター
としては、ポリエチレン多孔質フィルム、ポリプロピレ
ン多孔質フィルムなどを用いるのが一般的である。As the separator for separating the positive electrode and the negative electrode, it is common to use a polyethylene porous film, a polypropylene porous film, or the like.
【００１９】電解液としては、プロピレンカーボネー
ト、エチレンカーボネート、エチルメチルカーボネー
ト、ジメチルカーボネート、ジエチルカーボネートなど
の混合溶媒に、ＬｉＰＦ6、ＬｉＣｌＯ4などの電解質を
溶解させたものを用いる。As the electrolytic solution, a solution prepared by dissolving an electrolyte such as LiPF 6 or LiClO 4 in a mixed solvent such as propylene carbonate, ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate or diethyl carbonate is used.
【００２０】負極の活物質として、ケイ素やアルミニウ
ムなどのリチウムと合金化するものを用いた場合、リチ
ウムのドープ・脱ドープに伴い非常に大きな格子体積の
膨張・収縮が起こり、応力歪が生じて微細化が進む。こ
のため、活物質と導電材との密着性或いは活物質と集電
体との密着性が低下してサイクル劣化が起こる。When a material such as silicon or aluminum that alloys with lithium is used as the active material of the negative electrode, a very large lattice volume expands and contracts due to lithium doping / dedoping, resulting in stress strain. Miniaturization progresses. For this reason, the adhesion between the active material and the conductive material or the adhesion between the active material and the current collector is reduced, and cycle deterioration occurs.
【００２１】このサイクル劣化を軽減することを目的と
して、本発明は、リチウム二次電池用負極材料が、リチ
ウムをドープ・脱ドープ可能な、炭素以外の無機化合物
を、粒子内部に細孔構造を有する多孔質炭素の表面及び
細孔内に付着させたものから構成されることを特徴とす
るリチウム二次電池を提供するものである。For the purpose of reducing this cycle deterioration, the present invention provides a negative electrode material for a lithium secondary battery, which comprises an inorganic compound other than carbon capable of being doped or dedoped with lithium with a pore structure inside the particles. It is intended to provide a lithium secondary battery characterized in that the lithium secondary battery is composed of the porous carbon which is attached to the surface and inside the pores.
【００２２】本発明では、上記粒子内部に細孔構造を有
する多孔質炭素材料として、カーボンブラック、非晶質
炭素、活性炭等を用いたものである。より好ましくは、
粒径が１〜１００μｍ、比表面積が１００〜３０００ｍ
2／ｇであり、ミクロ孔と呼ばれる直径０．００２μｍ
以下の細孔、メソ孔と呼ばれる直径０．００２〜０．０
５μｍの細孔、及びマクロ孔と呼ばれる直径０．０５μ
ｍ以上の細孔を有する活性炭を用いるものである。In the present invention, carbon black, amorphous carbon, activated carbon or the like is used as the porous carbon material having a pore structure inside the particles. More preferably,
Particle size is 1 to 100 μm, specific surface area is 100 to 3000 m
2 / g, which is called a micropore and has a diameter of 0.002 μm
The following pores, diameters called mesopores 0.002-0.0
5μm pores and 0.05μm diameter called macropores
Activated carbon having pores of m or more is used.
【００２３】また、リチウムをドープ・脱ドープ可能な
炭素以外の無機化合物として、アルミ化合物、スズ化合
物、ケイ素化合物等のリチウムと合金化するものや、Ｌ
ｉ4Ｔｉ5Ｏ12等のリチウムイオンを構造内にインターカ
レーションするものを用いた。より好ましくは、理論容
量の大きいケイ素化合物を用いるものである。Inorganic compounds other than carbon capable of being doped and dedoped with lithium, such as aluminum compounds, tin compounds, and silicon compounds, which are alloyed with lithium, and L
An intercalator of lithium ions such as i 4 Ti 5 O 12 was used in the structure. More preferably, a silicon compound having a large theoretical capacity is used.
【００２４】また、上記炭素材料の平均粒径をＲC、上
記リチウムをドープ・脱ドープ可能なケイ素化合物の平
均粒径をＲSiとする時、ＲSi／ＲC＜０．１であること
が望ましい。また、そのケイ素化合物の粒径は、０．０
０１μｍ〜１０μｍの範囲にあることが望ましい。Further, when the average particle diameter R C of the carbon material, the average particle size of the lithium capable of doping and dedoping silicon compound and R Si, it is R Si / R C <0.1 Is desirable. The particle size of the silicon compound is 0.0
It is desirable to be in the range of 01 μm to 10 μm.
【００２５】リチウムをドープ・脱ドープ可能な、炭素
以外の無機化合物を、炭素材料表面及び細孔内に付着さ
せた負極材料の製造工程を以下に示す。リチウムをドー
プ・脱ドープ可能な、炭素以外の無機化合物源として、
有機金属、或いは無機化合物塩を溶解させた水溶液等の
液体状の物質を用いる。これらの液体状の無機化合物源
と、活性炭などの炭素材料とを混合させて、無機化合物
源を、炭素材料の表面及び細孔内に付着させる。The steps for producing a negative electrode material in which an inorganic compound other than carbon capable of being doped / dedoped with lithium is attached to the surface of the carbon material and the inside of the pores will be described below. As a source of inorganic compounds other than carbon that can be doped and dedoped with lithium,
A liquid substance such as an aqueous solution in which an organic metal or an inorganic compound salt is dissolved is used. These liquid inorganic compound sources are mixed with a carbon material such as activated carbon, and the inorganic compound sources are attached to the surface and pores of the carbon material.
【００２６】その後、ＡｒやＮ2等の不活性ガス雰囲気
中で熱処理し、無機化合物源を熱分解させることで、リ
チウムをドープ・脱ドープ可能な、炭素以外の無機化合
物を、炭素材料表面に分散或いは炭素材料の細孔内に含
有させることができる。この時の熱処理温度としては、
１００℃から、炭素材料の黒鉛化が起こる３５００℃ま
でが望ましい。熱処理時間としては、３０分から１０時
間が望ましい。After that, a heat treatment is performed in an atmosphere of an inert gas such as Ar or N 2 to thermally decompose the inorganic compound source, so that an inorganic compound other than carbon capable of being doped or dedoped with lithium is deposited on the surface of the carbon material. It can be dispersed or contained in the pores of the carbon material. The heat treatment temperature at this time is
It is desirable that the temperature is 100 ° C. to 3500 ° C. where graphitization of the carbon material occurs. The heat treatment time is preferably 30 minutes to 10 hours.
【００２７】リチウムをドープ・脱ドープ可能な、炭素
以外の無機化合物源として、金属アルコキシドを用いた
場合の製造工程を以下に示す。まず、金属アルコキシド
と炭素材料を混合させて、金属アルコキシドを炭素材料
表面に分散或いは炭素材料の細孔内に含有させる。The production process when a metal alkoxide is used as a source of an inorganic compound other than carbon that can be doped and dedoped with lithium will be described below. First, the metal alkoxide and the carbon material are mixed, and the metal alkoxide is dispersed on the surface of the carbon material or contained in the pores of the carbon material.
【００２８】次に、Ｈ2Ｏを加えて金属アルコキシドを
加水分解させる。そして、過剰のＨ2Ｏを空気中６０〜
１００℃で乾燥させる。その後、ＡｒやＮ2等の不活性
ガス雰囲気中で熱処理することにより、リチウムをドー
プ・脱ドープ可能な、炭素以外の無機化合物を、炭素材
料表面に分散或いは炭素材料の細孔内に含有させること
ができる。Next, H 2 O is added to hydrolyze the metal alkoxide. And, excess H 2 O in air is 60-
Dry at 100 ° C. Then, by heat treatment in an atmosphere of an inert gas such as Ar or N 2 , an inorganic compound other than carbon capable of doping and dedoping lithium is dispersed on the surface of the carbon material or contained in the pores of the carbon material. be able to.
【００２９】リチウムをドープ・脱ドープ可能な、炭素
以外の無機化合物源として、無機化合物塩を用いた場合
の製造工程を以下に示す。まず、Ｈ2Ｏ、無機化合物塩
及び炭素材料を混合させる。そして、ｐＨ調整すること
により、炭素材料表面或いは炭素材料の細孔内に、無機
化合物塩を析出させる。The manufacturing process when an inorganic compound salt is used as a source of an inorganic compound other than carbon that can be doped / dedoped with lithium will be described below. First, H 2 O, an inorganic compound salt and a carbon material are mixed. Then, by adjusting the pH, the inorganic compound salt is deposited on the surface of the carbon material or in the pores of the carbon material.
【００３０】そして、Ｈ2Ｏを空気中６０〜１００℃で
乾燥させる。その後、ＡｒやＮ2等の不活性ガス雰囲気
中で熱処理することにより、リチウムをドープ・脱ドー
プ可能な、炭素以外の無機化合物を、炭素材料表面に分
散或いは炭素材料の細孔内に含有させることができる。Then, H 2 O is dried in air at 60 to 100 ° C. Then, by heat treatment in an atmosphere of an inert gas such as Ar or N 2 , an inorganic compound other than carbon capable of doping and dedoping lithium is dispersed on the surface of the carbon material or contained in the pores of the carbon material. be able to.
【００３１】リチウムをドープ・脱ドープ可能な、炭素
以外の無機化合物の中で、最も大きな容量を示すのがケ
イ素である。以下に、ケイ素を炭素材料表面及び細孔内
に付着させた負極材料の製造工程を詳しく示す。Among inorganic compounds other than carbon that can be doped and dedoped with lithium, silicon has the largest capacity. The manufacturing process of the negative electrode material in which silicon is attached to the surface of the carbon material and the inside of the pores will be described in detail below.
【００３２】ケイ素源としての、液体状のケイ素化合物
は、Ｓｉ（ＯＣＨ3）4やＳｉ（ＯＣ 2Ｈ5）4のような金
属アルコキシドや、Ｃ3Ｈ3Ｎ2−ＣＨ2ＣＨ（ＯＨ）ＣＨ
2Ｏ（ＣＨ2）3Ｓｉ（ＯＣＨ3）3などのようなポリシラ
ン等を用いることができる。Liquid Silicon Compound as Silicon Source
Is Si (OCH3)FourAnd Si (OC 2HFive)FourLike gold
Genus alkoxide, C3H3N2-CH2CH (OH) CH
2O (CH2)3Si (OCH3)3Polysila such as
Can be used.
【００３３】炭素材料は、粒径が１〜１００μｍ、比表
面積が１００〜３０００ｍ2／ｇであり、ミクロ孔と呼
ばれる直径０．００２μｍ以下の細孔、メソ孔と呼ばれ
る直径０．００２〜０．０５μｍの細孔、及びマクロ孔
と呼ばれる直径０．０５μｍ以上の細孔を有する活性炭
を用いることができる。The carbon material has a particle size of 1 to 100 μm, a specific surface area of 100 to 3000 m 2 / g, micropores having a diameter of 0.002 μm or less, and mesopores having a diameter of 0.002 to 0. Activated carbon having pores with a diameter of 0.05 μm and macro pores having a diameter of 0.05 μm or more can be used.
【００３４】まず、上記液体状のケイ素化合物及び上記
活性炭を混合させ、ケイ素化合物を、活性炭の表面及び
細孔内に分散付着させる。First, the liquid silicon compound and the activated carbon are mixed, and the silicon compound is dispersed and adhered to the surface and the pores of the activated carbon.
【００３５】次にＨ2Ｏを加えて、ケイ素化合物を加水
分解して、活性炭の表面に分散或いは活性炭の細孔内に
含有したＳｉ（ＯＨ）4を得る。Next, H 2 O is added to hydrolyze the silicon compound to obtain Si (OH) 4 dispersed on the surface of the activated carbon or contained in the pores of the activated carbon.
【００３６】そして、過剰のＨ2Ｏ及び加水分解による
副生成物を空気中で乾燥させる。その時の乾燥温度は、
６０〜１００℃、乾燥時間は、２時間〜１２時間が望ま
しい。Then, excess H 2 O and the hydrolysis by-product are dried in air. The drying temperature at that time is
The drying time is preferably 60 to 100 ° C. and 2 to 12 hours.
【００３７】次に、ＡｒやＮ2等の不活性ガス気流中
で、活性炭の表面に分散或いは活性炭の細孔内に含有し
たＳｉ（ＯＨ）4を熱処理することにより、ＯＨ基を脱
離させて、活性炭の表面に分散或いは活性炭の細孔内に
含有させたケイ素を得ることができる。この時の熱処理
温度としては、１００℃から、活性炭の黒鉛化が起こる
３５００℃までが望ましい。熱処理時間としては、３０
分から１０時間が望ましい。Then, Si (OH) 4 dispersed on the surface of the activated carbon or contained in the pores of the activated carbon is heat-treated in a stream of an inert gas such as Ar or N 2 to remove the OH group. Thus, silicon dispersed on the surface of activated carbon or contained in the pores of activated carbon can be obtained. The heat treatment temperature at this time is preferably 100 ° C. to 3500 ° C. at which graphitization of activated carbon occurs. The heat treatment time is 30
Minutes to 10 hours is desirable.
【００３８】以上の方法により製造したケイ素を炭素材
料表面或いは炭素材料の細孔内に付着させた負極材料の
表面及び細孔部分の概略図を図１に示す。ケイ素を炭素
材料表面或いは炭素材料の細孔内に含有させることによ
り、ケイ素と炭素材料との密着性を向上させることがで
きる。FIG. 1 is a schematic view of the surface and pores of the negative electrode material in which the silicon produced by the above method is attached to the surface of the carbon material or the pores of the carbon material. By containing silicon on the surface of the carbon material or in the pores of the carbon material, the adhesion between the silicon and the carbon material can be improved.
【００３９】リチウムをドープ・脱ドープ可能な、炭素
以外の無機化合物を、炭素材料表面に分散及び炭素材料
の細孔内に付着させることにより、リチウムをドープ・
脱ドープ可能な、炭素以外の無機化合物と炭素材料との
密着性を高めることができるため、サイクル特性を向上
させることが可能である。An inorganic compound other than carbon, which is capable of being doped or dedoped with lithium, is dispersed on the surface of the carbon material and adhered in the pores of the carbon material to dope lithium.
Since it is possible to improve the adhesion between the carbon material and the inorganic compound other than carbon that can be dedoped, it is possible to improve the cycle characteristics.
【００４０】以下、本発明について実施例を用いて詳細
に説明する。尚、本発明は下記実施例に限定されるもの
ではない。
（実施例１）本実施例においては、ケイ素源として、Ｓ
ｉ（ＯＣ2Ｈ5）4で表されるテトラエトキシシリコンを
用い、多孔質炭素材料として、平均粒径が１μｍ、比表
面積が１２７０ｍ2／ｇである活性炭を用いた。The present invention will be described in detail below with reference to examples. The present invention is not limited to the examples below. (Example 1) In this example, S was used as a silicon source.
Tetraethoxy silicon represented by i (OC 2 H 5 ) 4 was used, and activated carbon having an average particle size of 1 μm and a specific surface area of 1270 m 2 / g was used as a porous carbon material.
【００４１】５ｍｌのテトラエトキシシリコンを磁製容
器に入れ、かき混ぜながら１ｇの活性炭を投入し、テト
ラエトキシシリコンを、活性炭の表面及び細孔内に付着
させた。その後、磁製容器内に水を投入し、テトラエト
キシシリコンを加水分解させ、Ｓｉ（ＯＨ）4で表され
る水酸化シリコンを活性炭の表面及び細孔内に分散付着
させた。5 ml of tetraethoxy silicon was placed in a porcelain container, and 1 g of activated carbon was charged with stirring to deposit tetraethoxy silicon on the surface and pores of the activated carbon. Then, water was charged into the porcelain container to hydrolyze the tetraethoxysilicone, and silicon hydroxide represented by Si (OH) 4 was dispersed and adhered to the surface and the pores of the activated carbon.
【００４２】そして、空気中８０℃で１２時間乾燥し、
過剰の水及び加水分解で生じたＣ2Ｈ5ＯＨを取り除い
た。その後、Ａｒガス気流中１０００℃で８時間焼成し
て、水酸基を脱離させて、図１に示すケイ素を炭素材料
表面或いは炭素材料の細孔内に含有させることにより、
ケイ素と炭素材料との密着性を向上させることができ
る。Then, it is dried in air at 80 ° C. for 12 hours,
Excess water and C 2 H 5 OH formed by hydrolysis were removed. Then, by firing at 1000 ° C. for 8 hours in an Ar gas stream to eliminate the hydroxyl groups, and to contain the silicon shown in FIG. 1 on the surface of the carbon material or in the pores of the carbon material,
The adhesion between silicon and the carbon material can be improved.
【００４３】図１において、炭素材料は例えば活性炭１
０には複数の多孔を形成しており、この多孔にはマクロ
孔１とマクロ孔１の径より小さい枝状にメソ孔２を有
し、メソ孔２の先端にミクロ孔３を有する。これらの孔
内及び活性炭１０の表面にはケイ素粒子４を加水分解に
より付着している。ＳＥＭ、ＴＥＭ観察等により、活性
炭１０の平均粒径ＲCとケイ素４の平均粒径ＲSiの比
は、ＲSi／ＲC＜０．１であった。In FIG. 1, the carbon material is, for example, activated carbon 1.
In FIG. 0, a plurality of pores are formed, and the pores have macropores 1 and mesopores 2 in a branch shape smaller than the diameter of the macropores 1, and micropores 3 at the tips of the mesopores 2. Silicon particles 4 are attached to these pores and the surface of the activated carbon 10 by hydrolysis. From the SEM and TEM observations, the ratio of the average particle size R C of the activated carbon 10 and the average particle size R Si of the silicon 4 was R Si / R C <0.1.
【００４４】電極特性を調べるために、以下のように電
極を作製した。ケイ素を含有させた活性炭と結着剤とし
てのポリフッ化ビニリデン（ＰＶＤＦ）を、９５：５の
重量比で混合した後、Ｎ−メチル−２−ピロリドンに分
散させてスラリー状とした。このスラリーを、負極集電
体である銅箔上に均一に塗布し、８０℃で２時間乾燥
後、油圧プレス機でプレスした。それを直径１５ｍｍの
円形状に打ち抜いたものを電極とした。In order to examine the electrode characteristics, electrodes were prepared as follows. Activated carbon containing silicon and polyvinylidene fluoride (PVDF) as a binder were mixed at a weight ratio of 95: 5 and then dispersed in N-methyl-2-pyrrolidone to form a slurry. This slurry was uniformly applied on a copper foil as a negative electrode current collector, dried at 80 ° C. for 2 hours, and then pressed by a hydraulic press machine. An electrode was formed by punching it out into a circular shape having a diameter of 15 mm.
【００４５】電極特性は、対極、参照極に金属リチウム
を用いた３極式セルを用いて測定した。電解液は、エチ
レンカーボネートとジメチルカーボネートを１：２で混
合した溶液にＬｉＰＦ6を１．０Ｍ溶解させたものを用
いた。充放電は、０．５ｍＡ／ｃｍ2の定電流で、２．
０〜０．０１Ｖの範囲でおこなった。The electrode characteristics were measured using a three-electrode cell using metallic lithium for the counter electrode and the reference electrode. As the electrolytic solution, a solution obtained by dissolving LiPF 6 at 1.0 M in a solution in which ethylene carbonate and dimethyl carbonate were mixed at a ratio of 1: 2 was used. Charge / discharge was performed with a constant current of 0.5 mA / cm 2 , 2.
It was performed in the range of 0 to 0.01V.
【００４６】このように、実施例１によれば、ケイ素化
合物であるテトラエトキシシリコンを容器に入れ、かき
混ぜながら活性炭を投入し、その後、容器内に水を投入
し、ケイ素化合物を加水分解させ、Ｓｉ（ＯＨ）4で表
される水酸化シリコンを活性炭の表面及び細孔内に分散
付着させた後、乾燥し、水分を蒸発してケイ素化合物を
活性炭の表面及び細孔内に効率良く分散付着させること
ができるようになった。As described above, according to Example 1, tetraethoxysilicon, which is a silicon compound, was placed in a container, activated carbon was added while stirring, and then water was placed in the container to hydrolyze the silicon compound, Silicon hydroxide represented by Si (OH) 4 is dispersed and adhered on the surface and pores of activated carbon, then dried and water is evaporated to efficiently disperse silicon compounds on the surface and pores of activated carbon. I was able to let you.
【００４７】またリチウムイオンの吸蔵・放出に伴いケ
イ素化合物が膨張・収縮にしても、ケイ素化合物が活性
炭の表面及び細孔内に密着して剥離しにくいので、活性
炭とケイ素化合物との間の接触抵抗が増加せず、導電性
が良くなり、図２及び図３に示す放電容量特性図及び充
電容量特性図を得た。Further, even if the silicon compound expands or contracts due to the occlusion / release of lithium ions, the silicon compound adheres to the surface and pores of the activated carbon and is difficult to be peeled off. Therefore, contact between the activated carbon and the silicon compound occurs. The resistance was not increased and the conductivity was improved, and the discharge capacity characteristic chart and the charge capacity characteristic chart shown in FIGS. 2 and 3 were obtained.
【００４８】図２に本発明の充電容量特性Ａ・放電容量
特性Ｂを示す。この特性図によれば、初充電容量は１８
９０ｍＡｈ／ｇ、初放電容量は１６５０ｍＡｈ／ｇであ
り、不可逆容量は２４０ｍＡｈ／ｇであった。平均放電
電圧は０．５Ｖであった。FIG. 2 shows the charge capacity characteristic A and the discharge capacity characteristic B of the present invention. According to this characteristic diagram, the initial charge capacity is 18
The discharge capacity was 90 mAh / g, the initial discharge capacity was 1650 mAh / g, and the irreversible capacity was 240 mAh / g. The average discharge voltage was 0.5V.
【００４９】図３にサイクル特性図を示す。３００サイ
クル後の容量は１４７０ｍＡｈ／ｇであり、容量維持率
は９０％であった。本発明の放電容量特性Ｂにおける初
放電容量は１６５０ｍＡｈ／ｇであるが、２回以降のサ
イクル特性は一定値を維持している。これに対して、従
来技術の放電容量特性Ａ１における初放電容量は大きい
が、２回目以降の放電容量であるサイクル特性は一定値
を維持できないで、減少して行く。FIG. 3 shows a cycle characteristic diagram. The capacity after 300 cycles was 1470 mAh / g, and the capacity retention rate was 90%. In the discharge capacity characteristic B of the present invention, the initial discharge capacity is 1650 mAh / g, but the cycle characteristics after two times maintain a constant value. On the other hand, although the initial discharge capacity in the discharge capacity characteristic A1 of the prior art is large, the cycle characteristic, which is the discharge capacity after the second time, cannot maintain a constant value and decreases.
【００５０】更に、ケイ素化合物の粒径が、０．００１
μｍ〜１０μｍの範囲を使用するとよい。それはケイ素
化合物の粒径が、１０μｍ以上になると、粒径が大きく
なり、多孔質炭素とケイ素化合物との間の密着性が悪く
なり、接触抵抗が増し、導電性が低下し、サイクル特性
を向上することができないからである。又０．００１μ
ｍ以下になると、製造しにくくなり、コスト高となり、
使用できないからである。
（実施例２）本実施例においては、ケイ素源として、Ｓ
ｉ（ＯＣ2Ｈ5）4で表されるテトラエトキシシリコンを
用い、多孔質炭素材料として、平均粒径が１０μｍ、比
表面積が７００ｍ2／ｇである活性炭を用いた。実施例
１と同様の方法で、ケイ素を活性炭の表面及び細孔内に
分散付着させた。ＳＥＭ、ＴＥＭ観察等により、活性炭
の平均粒径ＲCとケイ素の平均粒径ＲSiの比は、ＲSi／
ＲC＜０．１であった。Further, the particle size of the silicon compound is 0.001.
A range of μm to 10 μm may be used. When the particle size of the silicon compound is 10 μm or more, the particle size becomes large, the adhesion between the porous carbon and the silicon compound deteriorates, contact resistance increases, conductivity decreases, and cycle characteristics improve. Because you cannot do it. Also 0.001μ
If it is less than m, it will be difficult to manufacture and the cost will increase,
This is because it cannot be used. (Example 2) In this example, S was used as a silicon source.
Tetraethoxysilicone represented by i (OC 2 H 5 ) 4 was used, and activated carbon having an average particle diameter of 10 μm and a specific surface area of 700 m 2 / g was used as the porous carbon material. In the same manner as in Example 1, silicon was dispersed and adhered on the surface and pores of activated carbon. The ratio of the average particle size R C of activated carbon to the average particle size R Si of silicon is R Si /
R C <0.1.
【００５１】実施例１と同様の方法で、電極を作製し、
電極特性を調べた。初充電容量は、１０４５ｍＡｈ／
ｇ、初放電容量は８４５ｍＡｈ／ｇであり、不可逆容量
は２００ｍＡｈ／ｇであった。３００サイクル後の放電
容量は７８６ｍＡｈ／ｇであり、容量維持率は９３％で
あった。
（比較例１）本比較例においては、負極活物質として平
均粒径１０μｍからなるケイ素を用い、導電材として平
均粒径２０μｍからなる人造黒鉛を用いた。ケイ素と人
造黒鉛、及び結着剤としてのポリフッ化ビニリデン（Ｐ
ＶＤＦ）を混合後、Ｎ−メチル−２−ピロリドンに分散
させてスラリー状とした。An electrode was prepared in the same manner as in Example 1,
The electrode characteristics were investigated. The initial charge capacity is 1045 mAh /
g, the initial discharge capacity was 845 mAh / g, and the irreversible capacity was 200 mAh / g. The discharge capacity after 300 cycles was 786 mAh / g, and the capacity retention rate was 93%. Comparative Example 1 In this comparative example, silicon having an average particle size of 10 μm was used as the negative electrode active material, and artificial graphite having an average particle size of 20 μm was used as the conductive material. Silicon and artificial graphite, and polyvinylidene fluoride (P
VDF) was mixed and then dispersed in N-methyl-2-pyrrolidone to form a slurry.
【００５２】このスラリーを、負極集電体である銅箔上
に均一に塗布し、８０℃で２時間乾燥後、油圧プレス機
でプレスした。それを直径１５ｍｍの円形状に打ち抜い
たものを電極とした。電極特性は、対極、参照極に金属
リチウムを用いた３極式セルを用いて測定した。This slurry was uniformly applied on a copper foil as a negative electrode current collector, dried at 80 ° C. for 2 hours and then pressed by a hydraulic press machine. An electrode was formed by punching it out into a circular shape having a diameter of 15 mm. The electrode characteristics were measured using a three-electrode cell using metallic lithium for the counter electrode and the reference electrode.
【００５３】電解液は、エチレンカーボネートとジメチ
ルカーボネートを１：２で混合した溶液にＬｉＰＦ6を
１．０Ｍ溶解させたものを用いた。充放電は、０．５ｍ
Ａ／ｃｍ2の定電流で、２．０〜０．０１Ｖの範囲でお
こなった。The electrolytic solution used was a solution of ethylene carbonate and dimethyl carbonate mixed in a ratio of 1: 2, in which 1.0 M of LiPF 6 was dissolved. Charge / discharge is 0.5m
It was carried out at a constant current of A / cm 2 in the range of 2.0 to 0.01V.
【００５４】初期放電容量は、２２００ｍＡｈ／ｇだっ
たものの、３００サイクル後の容量は、４８ｍＡｈ／ｇ
であり、容量維持率は２％であった。Although the initial discharge capacity was 2200 mAh / g, the capacity after 300 cycles was 48 mAh / g.
And the capacity retention rate was 2%.
【００５５】[0055]
【表１】
表１に示すように、実施例１や実施例２のようにケイ素
を活性炭の表面及び細孔内に分散付着させた負極材料に
比べて、比較例１のように製造した負極材料では、１サ
イクル目の放電容量は大きくなるものの、３００サイク
ル後の放電容量維持率は遥かに低いものとなった。
（実施例３）実施例１、実施例２、比較例１に記載した
方法で製造した負極を用いて、図４に示すような円筒型
リチウム二次電池を作製した。図４の円筒型リチウム二
次電池は、帯状正極４１と帯状負極４２を、セパレータ
ー４３を挟んで重ねあわせて、渦巻き状に捲回した渦巻
き状電極を電池缶４４に収容した構成である。電池缶４
４内には、電解液が注入されている。また、渦巻き状電
極の上下には、電池缶４４との間に絶縁板４５が配置さ
れている。帯状負極４２としては実施例１の負極材料を
使用した。[Table 1] As shown in Table 1, as compared with the negative electrode material obtained by dispersing and depositing silicon on the surface and the pores of activated carbon as in Example 1 and Example 2, the negative electrode material manufactured as in Comparative Example 1 has 1 Although the discharge capacity at the cycle increased, the discharge capacity retention rate after 300 cycles was much lower. (Example 3) Using the negative electrode manufactured by the method described in Example 1, Example 2 and Comparative Example 1, a cylindrical lithium secondary battery as shown in FIG. 4 was manufactured. The cylindrical lithium secondary battery of FIG. 4 has a structure in which a band-shaped positive electrode 41 and a band-shaped negative electrode 42 are superposed with a separator 43 interposed therebetween, and a spirally wound electrode is housed in a battery can 44. Battery can 4
An electrolyte solution is injected into the inside of 4. In addition, insulating plates 45 are arranged above and below the spiral electrode between the spiral can electrode and the battery can 44. The negative electrode material of Example 1 was used as the strip negative electrode 42.
【００５６】正極活物質にはＬｉＣｏＯ2を用いた。正
極は、ＬｉＣｏＯ2と、導電材としての人造黒鉛、及び
結着剤としてのポリフッ化ビニリデン（ＰＶＤＦ）を、
８０：１３：７の重量比で混合した後、Ｎ−メチル−２
−ピロリドンに分散させてスラリー状とした。このスラ
リーを、正極集電体であるアルミニウム箔上に均一に塗
布し、８０℃で２時間乾燥後、油圧プレス機でプレスし
たものを正極とした。LiCoO 2 was used as the positive electrode active material. The positive electrode comprises LiCoO 2 , artificial graphite as a conductive material, and polyvinylidene fluoride (PVDF) as a binder,
After mixing in a weight ratio of 80: 13: 7, N-methyl-2
-Dispersed in pyrrolidone to form a slurry. This slurry was uniformly applied onto an aluminum foil as a positive electrode current collector, dried at 80 ° C. for 2 hours, and then pressed with a hydraulic press machine to obtain a positive electrode.
【００５７】電解液は、エチレンカーボネートとジメチ
ルカーボネートを１：２で混合した溶液にＬｉＰＦ6を
１．０Ｍ溶解させたものを用いた。セパレーターには、
ポリエチレン多孔質フィルムを用いた。The electrolyte used was a solution of ethylene carbonate and dimethyl carbonate mixed in a ratio of 1: 2, in which 1.0 M of LiPF 6 was dissolved. For the separator,
A polyethylene porous film was used.
【００５８】各電池に対して、充電を１Ａの定電流で
４．２Ｖまで行い、放電を０．５Ａの定電流で２．５Ｖ
まで行った。以上の工程を１サイクルとして、３００サ
イクルまで行った。Each battery was charged to 4.2 V at a constant current of 1 A and discharged to 2.5 V at a constant current of 0.5 A.
I went up to. The above process was set as one cycle and was repeated up to 300 cycles.
【００５９】[0059]
【表２】
表２に示すように、比較例１により製造した負極を用い
た電池と比較して、実施例１、実施例２により製造した
負極を用いた電池では、放電容量維持率が飛躍的に向上
した。[Table 2] As shown in Table 2, as compared with the battery using the negative electrode manufactured according to Comparative Example 1, the batteries using the negative electrode manufactured according to Example 1 and Example 2 had a dramatically improved discharge capacity retention rate. .
【００６０】[0060]
【発明の効果】以上のように、本発明によれば、充電及
び放電を繰り返しても導電性の確保ができる容量を有
し、サイクル特性を向上させることが可能である。As described above, according to the present invention, it is possible to improve the cycle characteristics by having a capacity capable of ensuring conductivity even if charging and discharging are repeated.
【図１】本発明の実施例として示した活性炭の表面及び
細孔内にケイ素を付着させた負極材料の概略図。FIG. 1 is a schematic view of a negative electrode material in which silicon is attached to the surface and pores of activated carbon shown as an example of the present invention.
【図２】図１の負極材料の初回充電及び放電特性図。FIG. 2 is a characteristic diagram of initial charge and discharge of the negative electrode material of FIG.
【図３】図１の負極材料におけるサイクル特性図。FIG. 3 is a cycle characteristic diagram of the negative electrode material of FIG.
【図４】図１の負極材料を使用したリチウム二次電池の
構成を示す断面図。FIG. 4 is a cross-sectional view showing the configuration of a lithium secondary battery using the negative electrode material of FIG.
１…活性炭細孔（マクロ孔）、２…活性炭細孔（メソ
孔）、３…活性炭細孔（ミクロ孔）、４…ケイ素粒子、
１０…活性炭、４１…帯状正極、４２…帯状負極、４３
…セパレーター、４４…電池缶、４５…絶縁板、４６…
電流引き出し用タブ。1 ... Activated carbon pores (macro pores), 2 ... Activated carbon pores (meso pores), 3 ... Activated carbon pores (micro pores), 4 ... Silicon particles,
10 ... Activated carbon, 41 ... Strip positive electrode, 42 ... Strip negative electrode, 43
... Separator, 44 ... Battery can, 45 ... Insulation plate, 46 ...
Current drawing tab.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 本棒 英利 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 Ｆターム(参考） 5H029 AJ05 AK03 AL01 AL02 AL03 AL06 AL08 AM03 AM05 AM07 BJ02 BJ14 CJ22 HJ05 5H050 AA07 BA17 CA08 CA09 CB01 CB02 CB03 CB07 CB09 DA19 FA05 GA22 HA05 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Honri 7-1-1, Omika-cho, Hitachi-shi, Ibaraki Prefecture Inside the Hitachi Research Laboratory, Hitachi Ltd. F term (reference) 5H029 AJ05 AK03 AL01 AL02 AL03 AL06 AL08 AM03 AM05 AM07 BJ02 BJ14 CJ22 HJ05 5H050 AA07 BA17 CA08 CA09 CB01 CB02 CB03 CB07 CB09 DA19 FA05 GA22 HA05
Claims (7)
リチウムイオンを吸蔵・放出する負極と、前記正極と負
極との間に介在させた電解液とを備えたリチウム二次電
池において、前記負極に多孔質炭素を使用し、前記多孔
質炭素の表面及び孔内に前記リチウムイオンを吸蔵・放
出する無機化合物（但し炭素を省く）を付着させること
を特徴とするリチウム二次電池。1. A positive electrode containing a lithium composite oxide,
In a lithium secondary battery comprising a negative electrode that absorbs and releases lithium ions, and an electrolytic solution interposed between the positive electrode and the negative electrode, porous carbon is used for the negative electrode, and the surface of the porous carbon and A lithium secondary battery, wherein an inorganic compound (excluding carbon) that absorbs and releases the lithium ions is attached to the inside of the pores.
用することを特徴とする請求項１に記載のリチウム二次
電池。2. The lithium secondary battery according to claim 1, wherein a silicon compound is used as the inorganic compound.
リチウムイオンを吸蔵・放出する負極と、前記正極と負
極との間に介在させた電解液とを備えたリチウム二次電
池において、前記負極に多孔質炭素を使用し、前記多孔
質炭素の表面及び孔内に前記リチウムイオンを吸蔵・放
出するケイ素化合物を付着させ、そのケイ素化合物の粒
径が、０．００１μｍ〜１０μｍの範囲にあることを特
徴とするリチウム二次電池。3. A positive electrode containing a lithium composite oxide,
In a lithium secondary battery comprising a negative electrode that absorbs and releases lithium ions, and an electrolytic solution interposed between the positive electrode and the negative electrode, porous carbon is used for the negative electrode, and the surface of the porous carbon and A lithium secondary battery, characterized in that a silicon compound which occludes / desorbs the lithium ion is attached to the inside of the pores, and the particle size of the silicon compound is in the range of 0.001 μm to 10 μm.
用することを特徴とする請求項１に記載のリチウム二次
電池。4. The lithium secondary battery according to claim 1, wherein a silicon compound is used as the inorganic compound.
リチウムを吸蔵・放出するケイ素化合物の平均粒径をＲ
Siとする時、ＲSi／ＲC＜０．１であることを特徴とす
る請求項１又は２に記載のリチウム二次電池。5. The average particle size of the porous carbon is R C , and the average particle size of the silicon compound that absorbs and releases lithium is R.
The lithium secondary battery according to claim 1 or 2, wherein when Si is used, R Si / R C <0.1.
することを特徴とする請求項１から４のいずれか１項に
記載のリチウム二次電池。6. The lithium secondary battery according to claim 1, further comprising a separator disposed between the positive electrode and the negative electrode.
リチウムイオンを吸蔵・放出する負極と、前記正極と負
極との間に介在させた電解液とを備えたリチウム二次電
池において、前記負極として複数の孔を有する活性炭と
リチウムイオンを吸蔵・放出する液体状のケイ素化合物
を混合させることにより、前記活性炭表面及び孔内にケ
イ素化合物を付着させたものを用いることを特徴とする
リチウム二次電池。7. A positive electrode containing a lithium composite oxide,
In a lithium secondary battery including a negative electrode that stores and releases lithium ions, and an electrolyte solution that is interposed between the positive electrode and the negative electrode, activated carbon having a plurality of holes as the negative electrode and stores and releases lithium ions. A lithium secondary battery characterized in that a silicon compound is adhered to the surface and inside the pores of the activated carbon by mixing a liquid silicon compound.
Priority Applications (1)
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|---|---|---|---|
| JP2001291043A JP2003100284A (en) | 2001-09-25 | 2001-09-25 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001291043A JP2003100284A (en) | 2001-09-25 | 2001-09-25 | Lithium secondary battery |
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| Publication Number | Publication Date |
|---|---|
| JP2003100284A true JP2003100284A (en) | 2003-04-04 |
Family
ID=19113250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001291043A Pending JP2003100284A (en) | 2001-09-25 | 2001-09-25 | Lithium secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP2003100284A (en) |
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