JP2001143698A - Negative electrode material for non-aqueous lithium secondary cell and non-aqueous secondary cell using the same - Google Patents

Negative electrode material for non-aqueous lithium secondary cell and non-aqueous secondary cell using the same

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Publication number
JP2001143698A
JP2001143698A JP32514199A JP32514199A JP2001143698A JP 2001143698 A JP2001143698 A JP 2001143698A JP 32514199 A JP32514199 A JP 32514199A JP 32514199 A JP32514199 A JP 32514199A JP 2001143698 A JP2001143698 A JP 2001143698A
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JP
Japan
Prior art keywords
negative electrode
electrode material
graphite
substance
weight
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.)
Granted
Application number
JP32514199A
Other languages
Japanese (ja)
Other versions
JP4416232B2 (en
Inventor
Toru Fuse
亨 布施
Hideji Sato
秀治 佐藤
Keiko Nishioka
圭子 西岡
Shinji Kasamatsu
真治 笠松
Yoshiaki Nitta
芳明 新田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Panasonic Holdings Corp
Original Assignee
Mitsubishi Chemical Corp
Matsushita Electric Industrial Co Ltd
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Filing date
Publication date
Application filed by Mitsubishi Chemical Corp, Matsushita Electric Industrial Co Ltd filed Critical Mitsubishi Chemical Corp
Priority to JP32514199A priority Critical patent/JP4416232B2/en
Priority to US09/712,207 priority patent/US6541156B1/en
Priority to DE60036843T priority patent/DE60036843T2/en
Priority to EP00124323A priority patent/EP1102339B1/en
Publication of JP2001143698A publication Critical patent/JP2001143698A/en
Application granted granted Critical
Publication of JP4416232B2 publication Critical patent/JP4416232B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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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

PROBLEM TO BE SOLVED: To provide a lithium secondary cell using a negative electrode body which has a high capacity, a long cycle life and a low irreversible capacity on primary charging, i.e., is soft to an electrolyte. SOLUTION: The negative electrode material for a non-aqueous lithium secondary cell contains a metallic material M consisting of solid-phases A, B, a graphitic material and a carbonaceous material having a crystalline lower than that of the graphitic material, where the metallic M is a structure coating a portion or front of a circumference of core particle consisting of the solid- phase A with the solid-phase B, the solid-phase A contains at least silicon as a constituent, the solid-phase B is at least one element selected from a group consisting of elements of group 2, transition metal elements, elements of group 12, elements of group 13 and elements of group 14 except for carbon and silicon, solid solution with silicon, or inter-metallic compounds.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、小型、計量の電気
機器や電気自動車の電源として好適な、非水系リチウム
二次電池用負極材並びにこれを用いた非水系リチウム二
次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a negative electrode material for a non-aqueous lithium secondary battery and a non-aqueous lithium secondary battery using the same, which is suitable as a power source for small and weighed electric appliances and electric vehicles.

【０００２】[0002]

【従来の技術】近年、電子機器の小型化に伴い、高容量
の二次電池が求められている。そのため、ニッケル・カ
ドミウム電池、ニッケル・水素電池に比べ、エネルギー
密度の高い非水系リチウム二次電池が注目されている。2. Description of the Related Art In recent years, as electronic devices have become smaller, high-capacity secondary batteries have been demanded. For this reason, non-aqueous lithium secondary batteries having higher energy density than nickel-cadmium batteries and nickel-metal hydride batteries have attracted attention.

【０００３】[0003]

【発明が解決しようとする課題】負極材としては、最初
リチウム金属を用いる事が試みられたが、充放電を繰り
返すうちに、樹枝状のリチウムが析出し、セパレーター
を貫通して正極体にまで達し、この結果短絡を起こす可
能性があることが判明した。At first, the use of lithium metal as the negative electrode material was attempted. However, as charge and discharge were repeated, dendritic lithium was precipitated and penetrated through the separator to reach the positive electrode body. It was found that this could cause a short circuit.

【０００４】また、特開昭５７−２０８０７９号公報に
は、リチウムを負極材とし、電極板として結晶化度が高
い黒鉛を使用することが提案された。しかしながら、黒
鉛は、リチウム吸蔵に黒鉛結晶中へのインターカレーシ
ョンを利用するため、常温、常圧では、その体積理論容
量である８２０mAh/ccを超えるものは得られないという
欠点があった。Japanese Patent Laid-Open Publication No. 57-208079 has proposed that lithium be used as a negative electrode material and graphite having a high degree of crystallinity be used as an electrode plate. However, graphite has a drawback that, at normal temperature and normal pressure, a material exceeding the volume theoretical capacity of 820 mAh / cc cannot be obtained because of the use of intercalation into graphite crystals for lithium occlusion.

【０００５】より高容量を発現できる負極材としては、
Ａｌ、Ｓｉ、Ｓｎ等、リチウムと化合する金属を用いれ
ば良いことが知られているが、これらの材料は充放電サ
イクルに伴い、容量が著しく低下するという問題があっ
た。[0005] As a negative electrode material capable of expressing higher capacity,
It is known that a metal that combines with lithium, such as Al, Si, and Sn, may be used. However, these materials have a problem in that the capacity is significantly reduced with charge / discharge cycles.

【０００６】特開平５−２８６７６３号公報には、Ａｌ
に複数種の炭素質物を添加する事で、充放電サイクルに
伴う容量の低下が抑制されることが開示されているが、
Ａｌを用いると、その体積当たりの容量は、最大でも
２，８３９mAh/ccと制限される。一方、Ｓｉはその体積
当たりの容量が最大４，６４８mAh/ccと大きいが、充放
電時の体積変化も大きく、上述の問題が生じる為、負極
材として実用化に至っていない。[0006] Japanese Patent Application Laid-Open No. Hei 5-286763 discloses that Al
It is disclosed that by adding a plurality of types of carbonaceous materials, a decrease in capacity due to a charge / discharge cycle is suppressed,
When Al is used, its capacity per volume is limited to a maximum of 2839 mAh / cc. On the other hand, Si has a large capacity per volume of 4,648 mAh / cc at the maximum, but has a large change in volume at the time of charge / discharge and causes the above-mentioned problems, and thus has not been put to practical use as a negative electrode material.

【０００７】近年、これらの欠点を解決する方法とし
て、珪化物粉体をＬｉ二次電池用負極材として用いる技
術が、特開平７−２４０２０１号公報に開示されてい
る。これらの化合物は体積容量が比較的大きく、サイク
ル寿命も長いことがわかってきたが、本材料は電導度が
低く、単体で用いるとＬｉと十分に化合できず、理論容
量を発現できない。そこで、特開平８−１５３５１７号
公報には本材料粉体にアセチレンブラックなどの導電剤
を添加して負極材を形成する技術が開示されている。In recent years, as a method of solving these drawbacks, Japanese Patent Application Laid-Open No. 7-240201 discloses a technique using silicide powder as a negative electrode material for a Li secondary battery. It has been found that these compounds have a relatively large volume capacity and a long cycle life, but this material has a low conductivity, and when used alone, cannot be sufficiently combined with Li to exhibit a theoretical capacity. Therefore, Japanese Patent Application Laid-Open No. 8-153517 discloses a technique for forming a negative electrode material by adding a conductive agent such as acetylene black to the material powder.

【０００８】しかし、アセチレンブラックは、一般的に
その粒子径が１μm未満と非常に小さいため、比表面積
が大きく、初回充電時の不可逆容量を増大させると言う
問題がある。However, acetylene black generally has a very small particle size of less than 1 μm, and thus has a problem that the specific surface area is large and the irreversible capacity at the time of the first charge is increased.

【０００９】この様な欠点を解決するため、珪化物とと
もに導電材として結晶性の高い黒鉛粒子を用いること
が、特開平１０−１９９５２７号公報に記載されてい
る。これにより、珪化物単体で使用するよりも、容量は
向上し、サイクル寿命も向上、更に初回充電時の不可逆
容量が低減された。しかしながら、長期にわたる充放電
サイクルを行うと容量の漸次低下が起こる。これは、リ
チウムの充放電に伴う珪化物の体積変化が、黒鉛で導電
化されている負極体構造に変化を及ぼし、充放電サイク
ルに伴いこれを破壊していっているためと考えられる。Japanese Patent Application Laid-Open No. 10-199527 discloses that in order to solve such a drawback, graphite particles having high crystallinity are used as a conductive material together with silicide. As a result, the capacity was improved, the cycle life was improved, and the irreversible capacity at the time of the first charge was reduced as compared with the case of using silicide alone. However, when the charge / discharge cycle is performed for a long time, the capacity gradually decreases. This is presumably because the volume change of the silicide due to the charge and discharge of lithium changes the structure of the negative electrode body made conductive with graphite, and destroys the structure with the charge and discharge cycle.

【００１０】負極体の主負極材が珪化物でなくＳｉ金属
ではあるものの、上述の構造破壊を抑制するために、主
負極材に対し、導電剤である黒鉛質物をより近接させた
構造を得るために、負極材粉体と黒鉛を共に機械処理す
る方法が特開平９−２４９４０７号公報に提案されてい
る。本技術を珪化物に適用すればＳｉの場合と同様、サ
イクル寿命は更に伸びると推察されるが、その一方で、
黒鉛粒子を機械処理することは、黒鉛の比表面積を増加
させることに繋がり、結果として初回充電時の不可逆容
量の増加を招いてしまうことも考えられる。Although the main negative electrode material of the negative electrode body is made of Si metal instead of silicide, a structure in which a graphite material as a conductive agent is brought closer to the main negative electrode material in order to suppress the above-described structural destruction is obtained. Therefore, a method of mechanically processing both the negative electrode material powder and graphite has been proposed in Japanese Patent Application Laid-Open No. 9-249407. If this technology is applied to silicide, the cycle life is expected to be further extended, as in the case of Si.
Mechanical treatment of the graphite particles leads to an increase in the specific surface area of the graphite, which may result in an increase in the irreversible capacity at the time of the first charge.

【００１１】我々は、鋭意検討した結果、後述する特定
の構成の材料をリチウム二次電池用負極材として用いる
ことで、高容量、且つ長期にわたる充放電サイクルを行
っても容量劣化が極めて小さく、更に初回充放電時に発
生する不可逆容量も抑制した負極体を作成可能であるこ
とを見いだした。As a result of our intensive studies, we have found that by using a material having a specific structure described below as a negative electrode material for a lithium secondary battery, the capacity deterioration is extremely small even when a high capacity and long charge / discharge cycle is performed. Furthermore, they have found that it is possible to produce a negative electrode body in which the irreversible capacity generated during the initial charge and discharge is suppressed.

【００１２】即ち、本発明の目的は、高容量で、長サイ
クル寿命、且つ初回充電時の不可逆容量が小さく、即ち
電解液に対し優しい負極体を用いたリチウム二次電池を
提供することにある。That is, an object of the present invention is to provide a lithium secondary battery using a negative electrode body having a high capacity, a long cycle life, and a small irreversible capacity at the time of initial charging, that is, an electrolyte-friendly anode body. .

【００１３】[0013]

【課題を解決するための手段】本発明の目的を達するた
め、リチウム二次電池は、正極体、負極体及び非水系溶
媒中に電解質を溶解した電解液から少なくともなる非水
系リチウム二次電池であって、その負極体は、固相Ａ、
Ｂからなる金属質物Ｍ、黒鉛質物、及び当該黒鉛質物よ
り結晶性の低い炭素質物を含有するものであって、該金
属質物Ｍは固相Ａからなる核粒子の周囲の一部又は全面
を、固相Ｂによって被覆した構造であり、前記固相Ａは
構成元素としてケイ素を少なくとも含み、前記固相Ｂは
周期律表の２族元素、遷移金属元素、１２族元素、１３
族元素、並びに炭素とケイ素を除く１４族元素からなる
群から選ばれた少なくとも一種の元素と、ケイ素との固
溶体又は金属間化合物であることを特徴とするものであ
る。In order to achieve the object of the present invention, a lithium secondary battery is a non-aqueous lithium secondary battery comprising at least a positive electrode body, a negative electrode body, and an electrolyte obtained by dissolving an electrolyte in a non-aqueous solvent. Then, the negative electrode body is a solid phase A,
B containing a metal material M, a graphite material, and a carbon material having a lower crystallinity than the graphite material, wherein the metal material M is a part or the entire periphery of core particles made of the solid phase A, It has a structure coated with a solid phase B, wherein the solid phase A contains at least silicon as a constituent element, and the solid phase B is a group 2 element, a transition metal element, a group 12 element,
A solid solution or an intermetallic compound of silicon with at least one element selected from the group consisting of group 14 elements and group 14 elements excluding carbon and silicon.

【００１４】上記金属質物Ｍは、固溶体もしくは金属間
化合物からなるが、これは構成元素を所定の比率で混合
した物を高温で溶融させ、その溶融物を乾式噴霧法、ロ
ール急冷法、及び回転電極法などで、急冷、凝固させる
ことで得られる。その際、必要に応じて、金属状態図に
おける該粒子の構成元素比率での固溶線温度よりも低い
温度で熱処理することにより、好ましい固溶体もしくは
金属間化合物の組織を得ることができる。本方法は溶融
物の急冷、凝固の制御により、上記固相Ａからなる核の
周囲の全面、又は一部に上記固相Ｂを析出させて被覆
し、金属質物Ｍを得る方法であるが、その後の熱処理に
より、更に固相Ａ，Ｂ相の均一性を高めることもでき、
この様な物を金属質物Ｍとして用いても良い。また、急
冷、凝固の方法は上記手法に何ら限定されるものではな
い。The above-mentioned metallic substance M is composed of a solid solution or an intermetallic compound, which is obtained by melting a mixture of the constituent elements at a predetermined ratio at a high temperature, and subjecting the molten substance to a dry spray method, a roll quenching method, and a rotating method. It is obtained by rapid cooling and solidification by an electrode method or the like. At this time, if necessary, a heat treatment is performed at a temperature lower than the solid solution temperature at the constituent element ratio of the particles in the metal phase diagram, whereby a preferable solid solution or intermetallic compound structure can be obtained. This method is a method of obtaining a metallic material M by depositing and coating the solid phase B on the entire surface or a part of the nucleus made of the solid phase A by controlling the quenching and solidification of the melt, The subsequent heat treatment can further enhance the uniformity of the solid phases A and B,
Such a material may be used as the metal material M. In addition, the method of quenching and solidification is not limited to the above method.

【００１５】また、金属質物Ｍは、固相Ａからなる粉末
の表面に固相Ｂの構成元素から固相Ａの構成元素を除い
た元素からなる層を付着させ、それを金属状態図におけ
る金属質物Ｍの固相線温度より低い温度で熱処理して得
ても良い。本熱処理により、固相Ａ中の元素が、付着し
た層に拡散して、その拡散層が固相Ｂの組成となる。前
記付着は、メッキ法、又はメカニカルアロイング法によ
り行うことができる。メカニカルアロイング法は熱処理
をせずに上記金属質物Ｍを得ることが可能な方法の一つ
である。The metallic substance M is formed by attaching a layer made of an element obtained by removing the constituent elements of the solid phase A from the constituent elements of the solid phase B to the surface of the powder made of the solid phase A. The heat treatment may be performed at a temperature lower than the solidus temperature of the substance M. By this heat treatment, the elements in the solid phase A diffuse into the layer to which the solid phase A has adhered, and the diffusion layer has the composition of the solid phase B. The attachment can be performed by a plating method or a mechanical alloying method. The mechanical alloying method is one of the methods capable of obtaining the metal material M without heat treatment.

【００１６】上述した金属質物Ｍと導電性に優れた黒鉛
粒子を炭素質物と混合、被覆することにより、高容量、
長サイクル寿命、且つ初回充電時に生じる不可逆容量を
抑制した材料を作成できる。By mixing and coating the above-described metal material M and graphite particles having excellent conductivity with a carbon material, a high capacity,
A material having a long cycle life and suppressed irreversible capacity generated at the time of initial charging can be produced.

【００１７】[0017]

【発明の実施の形態】次に本発明の詳細を述べる。本発
明の負極材を構成する、金属質物Ｍ、黒鉛、及び黒鉛質
物より結晶性の低い炭素質物の複合の形態としては、例
えば、（１）金属質物Ｍ粉体、黒鉛質物粉体、及び炭素
質物粉体が混合された形態、（２）金属質物Ｍ粉体と、
炭素質物により表面の一部、又は全部が被覆された黒鉛
質物粉体を混合した形態、（３）金属質物Ｍ粉体の表面
の一部又は全部を炭素質物により被覆し、ここに黒鉛質
物粉体、或いは炭素質物により表面の一部又は全部が被
覆された黒鉛質物粉体を混合した形態、（４）金属質物
Ｍ粉体の表面の一部又は全部を、黒鉛質物粉体及び炭素
質物により結合、又は被覆した形態、（５）金属質物Ｍ
粉体の表面の一部又は全部を黒鉛質物粉体により一旦被
覆し、当該被覆物を更に炭素質物により結合、又は被覆
した形態、或いはこれらの形態の一種以上の混成された
形態が挙げられる。Next, the details of the present invention will be described. Examples of the composite form of the metal material M, graphite, and a carbon material having lower crystallinity than the graphite material, which constitute the negative electrode material of the present invention, include (1) a metal material M powder, a graphite material powder, and a carbon material. And (2) a metallic substance M powder,
A form in which a graphite material powder whose surface is partially or wholly coated with a carbonaceous material is mixed. (3) A part or all of the surface of the metallic material M powder is coated with a carbonaceous material, and the graphite material powder is added thereto. (4) A part or all of the surface of the metallic material M powder is mixed with the graphite material powder and the carbonaceous material. Bonded or coated form, (5) metallic material M
A form in which a part or the whole of the surface of the powder is once coated with a graphite substance powder, and the coated substance is further bound or covered with a carbon substance, or a form in which one or more of these forms are mixed.

【００１８】本負極材の上記（３）、（４）又は（５）
の形態は金属質物Ｍの表面を、黒鉛及び／又は黒鉛質物
より結晶性の低い炭素質物が直接覆う形状を作ることが
可能となるので、電解液と金属質物Ｍとの反応性が低減
し、安全性が向上するという面から好ましく、（４）、
（５）の形態は黒鉛質物が金属質物Ｍの近傍に存在し、
導電性を保ちやすい構造を形成し得るという観点から、
更に好ましい。The above (3), (4) or (5) of the present negative electrode material
Can form a shape in which the surface of the metal material M is directly covered with graphite and / or a carbon material having a lower crystallinity than the graphite material, so that the reactivity between the electrolytic solution and the metal material M is reduced, It is preferable from the viewpoint that safety is improved. (4),
In the form (5), the graphite substance exists near the metal substance M,
From the viewpoint that a structure that easily maintains conductivity can be formed,
More preferred.

【００１９】本負極材の平均粒子径としては、レーザー
回折式粒度分布計を用いた場合、８〜２５μmに有るこ
とが望ましい。この粒子径以下であると比表面積が増大
するため、リチウム二次電池用の負極材としたときに、
初回充放電時の不可逆容量が大きくなり、この粒子径以
上であると、後述する様な負極体を作成しにくい。The average particle diameter of the present negative electrode material is preferably 8 to 25 μm when using a laser diffraction type particle size distribution meter. Since the specific surface area increases when the particle size is not more than this, when used as a negative electrode material for a lithium secondary battery,
The irreversible capacity at the time of the first charge / discharge becomes large, and if the irreversible capacity is more than this particle size, it is difficult to form a negative electrode body as described later.

【００２０】本負極材のタップ密度は、粉体密度測定器
（（株）セイシン企業社製タップデンサ−ＫＹＴ−３０
００）を用いて測定することができる。この測定器を用
いてストローク長１０mmのタップを１００回行なった場
合、そのタップ密度が１．３g/cm3以上と大きく、リチ
ウム二次電池用の負極材とした時に、黒鉛系負極や非晶
質炭素系の負極材と比べ、体積（cm3）当たり高容量を
発現できるので好ましい。タップ密度が１．５g/cm3以
上、又は１．７g/cm3以上のものは、充填性が良く、容
量を大きくできるので更に好ましい。The tap density of the present negative electrode material was measured using a powder density measuring instrument (Tap Denser KYT-30 manufactured by Seishin Enterprise Co., Ltd.).
00). When a tap having a stroke length of 10 mm is performed 100 times using this measuring instrument, the tap density is as large as 1.3 g / cm 3 or more, and when used as a negative electrode material for a lithium secondary battery, a graphite-based negative electrode or an amorphous This is preferable because a higher capacity per volume (cm 3 ) can be achieved as compared with a carbonaceous negative electrode material. Those having a tap density of 1.5 g / cm 3 or more, or 1.7 g / cm 3 or more are more preferable because they have good filling properties and can increase the capacity.

【００２１】また、上記（３）、（４）、及び（５）の
複合形態に於いては、金属質物Ｍの最表面上に、上記黒
鉛質物、及び／又は炭素質物からなる被覆層が少なくと
も一層以上存在しても良いが、そのような場合、この厚
みは、レーザー回折式粒度分布計にて測定した際得られ
る本発明材料粒子のモード径と、同様に測定した前記金
属質物Ｍ粒子単体のモード径の差から得られる。本発明
材料粒子を負極材として用いるときには、この大きさが
０．０５〜５μmの範囲にあると好ましい。０．１〜４
μmの範囲にあると更に好ましい。In the composite form of the above (3), (4) and (5), at least the coating layer made of the graphite substance and / or the carbon substance is formed on the outermost surface of the metal substance M. More than one layer may be present, but in such a case, the thickness is the same as the mode diameter of the material particles of the present invention obtained when measured by a laser diffraction type particle size distribution analyzer, and the metal substance M particles alone similarly measured. Is obtained from the difference in the mode diameters. When the material particles of the present invention are used as a negative electrode material, the size is preferably in the range of 0.05 to 5 μm. 0.1-4
More preferably, it is in the range of μm.

【００２２】負極材内での金属質物Ｍ、黒鉛質物、及び
炭素質物の割合は、求められる電池の性能によって、そ
れぞれの含有量を任意に変化させれば良いが、粉体全体
を１００重量％としたとき、それぞれ５０〜９５重量
％、４．９〜３０重量％、及び０．１〜２０重量％の範
囲に収めると、高容量で、サイクル寿命が長く、且つ初
回充放電時の不可逆容量が低減される様なものとなるの
で好ましい。上記範囲がそれぞれ８０〜９５重量％、
４．９〜２０重量％、及び０．１〜１０重量％の範囲に
あるものが更に好ましく、８２〜９５重量％、４．９〜
１７重量％、及び０．１〜１０重量％の範囲にあるもの
が最も好ましい。The content of the metallic substance M, the graphite substance, and the carbonaceous substance in the negative electrode material may be arbitrarily changed depending on the required performance of the battery. When they are within the ranges of 50 to 95% by weight, 4.9 to 30% by weight, and 0.1 to 20% by weight, respectively, the capacity is high, the cycle life is long, and the irreversible capacity at the time of the first charge / discharge. Is preferably reduced. 80 to 95% by weight of each of the above ranges,
Those in the range of 4.9 to 20% by weight, and 0.1 to 10% by weight are more preferable, and 82 to 95% by weight, 4.9 to
Most preferred are those in the range of 17% by weight, and 0.1 to 10% by weight.

【００２３】また、上記負極材の波長５１４．３nmのア
ルゴンイオンレーザー光を用いたラマンスペクトル分析
に於いて、１５８０cm-1〜１６２０cm-1の範囲に現れる
ピークの強度をＩＡ、１３５０cm-1〜１３７０cm-1の範
囲に現れるピークの強度をＩＢとしたときのピーク強度
比Ｒ（＝ＩＢ／ＩＡ）が、０．２以上１以下の範囲にあ
るものが好ましく、０．２５以上０．７以下の範囲にあ
るものは更に好ましい。Further, the negative electrode material an argon ion laser beam having a wavelength 514.3nm of In Raman spectrum analysis using an intensity of a peak appearing in the range of 1580cm -1 ~1620cm -1 IA, 1350cm -1 ~1370cm It is preferable that the peak intensity ratio R (= IB / IA) when the intensity of the peak appearing in the range of -1 is IB is in the range of 0.2 to 1, and 0.25 to 0.7. Those in the range are more preferred.

【００２４】窒素ガスにより測定したＢＥＴ比表面積が
０．１〜２０m2/gであると、負極体としたときの初回充
放電時の不可逆容量が低減されるので好ましい。０．１
〜１５m2/gであると更に好ましく、０．１〜６m2/gであ
ると最も好ましい。It is preferable that the BET specific surface area measured with nitrogen gas is 0.1 to 20 m 2 / g, because the irreversible capacity at the time of the first charge / discharge of the negative electrode body is reduced. 0.1
More preferable to be ~15m 2 / g, most preferably a 0.1~6m 2 / g.

【００２５】該負極材の電導度は以下の様に測定した。
四端子電極式電導度測定機（三菱化学製 Loresta-GP
MCP-T600）に、加圧式粉体抵抗測定ユニットオプション
（三菱化学製）を接続し、該活物質粉体を測定セルに投
入後、その空隙率が７５％になる様に該粉体にかかる圧
力を調整した。この時測定された電気伝導度が１×１０
-5S/cm以上であるものは、負極材としたとき、リチウム
の充放電が速やかに行われるので好ましい。この値が、
１×１０-4S/cm以上であるものは更に好ましく、１×１
０-3S/cm以上であるものは最も好ましい。電気伝導度の
上限は通常１×１０4S/cm以下である。The conductivity of the negative electrode material was measured as follows.
Four-terminal electrode conductivity meter (Mitsubishi Chemical's Loresta-GP
MCP-T600), pressurized powder resistance measurement unit option (manufactured by Mitsubishi Chemical Corporation) is connected, and after the active material powder is charged into the measurement cell, the powder is applied to the powder so that the porosity is 75%. The pressure was adjusted. At this time, the measured electric conductivity is 1 × 10
A material having a resistivity of -5 S / cm or more is preferable when used as a negative electrode material because lithium can be rapidly charged and discharged. This value is
More preferably, it is 1 × 10 −4 S / cm or more.
Those having 0 -3 S / cm or more are most preferable. The upper limit of the electric conductivity is usually 1 × 10 4 S / cm or less.

【００２６】また、上述したように形態的には金属質物
Ｍ粒子の周囲を黒鉛質物、及び／又は且つ炭素質物から
なる層が、結着或いは被覆している構造のものが好まし
い。更に、その様な構造を持つ材料の中でも、本発明材
料粉体をエポキシ樹脂中に包埋、硬化後、ミクロトーム
で切断し、現れた切断面をＳＥＭにより観察したとき
に、前記金属質物Ｍの最表面の円周上に、黒鉛質物、及
び／又は炭素質物からなる、厚みを持った被覆層が観察
でき、且つその被覆層の長さが、金属質物Ｍ最表面円周
長の３０〜１００％を占める様な粒子が少なくとも複数
個観察されるものは好ましい。即ち、金属質物Ｍを、そ
のモード径から換算される球体として考えたときに、そ
の球表面を、平均３０〜１００％、黒鉛質物又は／且つ
炭素質物からなる層が被覆しているものが好ましい。９
０％〜１００％被覆しているものは更に好ましく、１０
０％であるものは最も好ましい。As described above, the morphology is preferably a structure in which a layer made of a graphite material and / or a carbon material is bound or covered around the metal material M particles. Furthermore, among materials having such a structure, the material powder of the present invention is embedded in an epoxy resin, cured, cut with a microtome, and the cut surface that appears is observed with a SEM. A thick coating layer made of a graphite substance and / or a carbon substance can be observed on the circumference of the outermost surface, and the length of the coating layer is 30 to 100 of the circumference of the outermost surface of the metal substance M. % Is preferred. That is, when the metallic material M is considered as a sphere converted from its mode diameter, it is preferable that the surface of the sphere is covered with a layer made of a graphite material and / or a carbon material on average 30 to 100%. . 9
More preferably, 0% to 100% is coated.
A value of 0% is most preferred.

【００２７】上記の金属質物Ｍ、黒鉛質物、及び炭素質
物の種類としては、請求項の範囲に有る限り、従来公知
のものを使用することが可能であるが、例えば、金属質
物Ｍとしては前記固相ＡがＳｉからなり、固相ＢがＮｉ
Ｓｉ2、ＣｏＳｉ2、ＶＳｉ2、ＴｉＳｉ2、ＭｎＳ
ｉ1.8、及び／又はＭｇ2Ｓｉからなる金属質物、黒鉛質
物としては、例えば結晶面（００２）の面間隔ｄ002が
０．３３８nm以下である高結晶性の人造黒鉛、天然黒
鉛、これらの高純度精製品、又はこれらのものの混合品
が好ましく、更に炭素質物としては、黒鉛質物よりも結
晶性の低い、例えば、結晶面（００２）の面間隔ｄ002
が０．３４nm以上の有機物由来の焼成炭を用いることが
できる。As the types of the metallic substance M, the graphite substance, and the carbonaceous substance, conventionally known substances can be used as long as they fall within the scope of the claims. The solid phase A is made of Si, and the solid phase B is made of Ni
Si 2 , CoSi 2 , VSi 2 , TiSi 2 , MnS
Examples of the metal material and the graphite material made of i 1.8 and / or Mg 2 Si include, for example, highly crystalline artificial graphite and natural graphite having a spacing d 002 of a crystal plane (002) of 0.338 nm or less. purified product, or preferably mixed products of these things, as a further carbonaceous material, low crystallinity than the graphite pledge, for example, interplanar spacing of the crystal plane (002) d 002
However, calcined charcoal derived from organic matter having a particle size of 0.34 nm or more can be used.

【００２８】次に、本発明材料を負極材とし、これを用
いて負極を構成する方法について説明する。Next, a method for forming a negative electrode using the material of the present invention as a negative electrode material will be described.

【００２９】本発明の負極体は、上記金属質物Ｍ、黒鉛
質物、及び当該黒鉛質物より結晶性の低い炭素質物を使
用する限り、限定無く従来公知の方法が採用可能である
が、例えば、その構成が金属質物Ｍ／黒鉛質物／炭素質
物との重量比が９０／９／１であるような材料を混合、
加熱処理によって作成し、好ましくは８〜２５μm、更
に好ましくは８〜２０μm、最も好ましくは１０〜１５
μmの範囲に粉砕又は解砕し、粉体状とする。これに導
電剤、結着剤、溶媒等を加えて、スラリー状とし、銅
箔、ニッケルメッシュ、又はステンレスメッシュ等の集
電体の基板にスラリーを塗布・乾燥することで電極とす
る。該粒子を結着させる集電体としては、限定無く用い
ることができ、例えば金属円柱、金属コイル、金属板、
炭素板、炭素円柱などを用いることができるが、ニッケ
ル箔やアルミニウム箔などの金属薄膜が好ましい。銅箔
は更に好ましい。更に、これら集電体に負極材となる粒
子を付着させた電極材料をそのままロール成形、圧縮成
形等の方法で任意の形状に成形することもできる。The negative electrode body of the present invention can employ any conventionally known method without limitation, as long as the metal material M, the graphite material, and the carbon material having lower crystallinity than the graphite material are used. A material whose composition is such that the weight ratio of metal material M / graphite material / carbon material is 90/9/1,
Prepared by heat treatment, preferably 8 to 25 μm, more preferably 8 to 20 μm, most preferably 10 to 15 μm
Pulverized or crushed to a range of μm to make a powder. A conductive agent, a binder, a solvent, and the like are added thereto to form a slurry, and the slurry is applied to a current collector substrate such as a copper foil, a nickel mesh, or a stainless steel mesh and dried to form an electrode. The current collector for binding the particles can be used without limitation, for example, a metal cylinder, a metal coil, a metal plate,
Although a carbon plate and a carbon column can be used, a metal thin film such as a nickel foil or an aluminum foil is preferable. Copper foil is more preferred. Further, an electrode material in which particles serving as a negative electrode material are adhered to these current collectors can be directly formed into an arbitrary shape by a method such as roll forming or compression molding.

【００３０】上記の目的で使用できる導電剤としては、
その電導度が１S/cm以上の高結晶性の人造黒鉛、天然黒
鉛、これらの高純度精製品、また、例えば銅、ニッケ
ル、ステンレス、鉄などで、その粒子径が２５μm以
下、好ましくは１５μm以下、更に好ましくは１０μm以
下、通常０．１μm以上の金属微粉、又はこれらのもの
の混合品が挙げられる。Examples of the conductive agent that can be used for the above purpose include:
Highly crystalline artificial graphite having a conductivity of 1 S / cm or more, natural graphite, high-purity refined products thereof, and, for example, copper, nickel, stainless steel, iron, etc., having a particle diameter of 25 μm or less, preferably 15 μm or less. More preferably, metal fine powder of 10 μm or less, usually 0.1 μm or more, or a mixture thereof is used.

【００３１】結着剤としては、溶媒に対して安定な、ポ
リエチレン、ポリプロピレン、ポリエチレンテレフタレ
ート、芳香族ポリアミド、セルロース等の樹脂系高分
子、スチレン・ブタジエンゴム、イソプレンゴム、ブタ
ジエンゴム、エチレン・プロピレンゴム等のゴム状高分
子、スチレン・ブタジエン・スチレンブロック共重合
体、その水素添加物、スチレン・エチレン・ブタジエン
・スチレン共重合体、スチレン・イソプレン・スチレン
ブロック共重合体、その水素添加物等の熱可塑性エラス
トマー状高分子、シンジオタクチック１，２−ポリブタ
ジエン、エチレン・酢酸ビニル共重合体、プロピレン・
α−オレフィン（炭素数２〜１２）共重合体等の軟質樹
脂状高分子、ポリフッ化ビニリデン、ポリテトラフルオ
ロエチレン、ポリテトラフルオロエチレン・エチレン共
重合体等のフッ素系高分子、アルカリ金属イオン、特に
リチウムイオンのイオン伝導性を有する高分子組成物や
上記の結着剤の混合物が挙げられる。Examples of the binder include resin-based polymers such as polyethylene, polypropylene, polyethylene terephthalate, aromatic polyamide, and cellulose, styrene / butadiene rubber, isoprene rubber, butadiene rubber, and ethylene / propylene rubber which are stable to solvents. Heat of rubber-like polymers such as styrene / butadiene / styrene block copolymers, hydrogenated products thereof, styrene / ethylene / butadiene / styrene copolymers, styrene / isoprene / styrene block copolymers, hydrogenated products, etc. Plastic elastomeric polymer, syndiotactic 1,2-polybutadiene, ethylene / vinyl acetate copolymer, propylene /
soft resin-like polymers such as α-olefin (C 2 to C 12) copolymers, fluorine-based polymers such as polyvinylidene fluoride, polytetrafluoroethylene, polytetrafluoroethylene / ethylene copolymers, alkali metal ions, In particular, a polymer composition having lithium ion ionic conductivity and a mixture of the above-mentioned binders are exemplified.

【００３２】上記のイオン伝導性を有する高分子として
は、ポリエチレンオキシド、ポリプロピレンオキシド等
のポリエーテル系高分子化合物、ポリエーテル化合物の
架橋体高分子、ポリエピクロルヒドリン、ポリフォスフ
ァゼン、ポリシロキサン、ポリビニルピロリドン、ポリ
ビニリデンカーボネート、ポリアクリロニトリル等の高
分子化合物に、リチウム塩、又はリチウムを主体とする
アルカリ金属塩を複合させた系、或いはこれにプロピレ
ンカーボネート、エチレンカーボネート、γ−ブチロラ
クトン等の高い誘電率を有する有機化合物を配合した系
を用いることができる。Examples of the polymer having ion conductivity include polyether polymer compounds such as polyethylene oxide and polypropylene oxide, crosslinked polymers of polyether compounds, polyepichlorohydrin, polyphosphazene, polysiloxane, polyvinylpyrrolidone, and the like. Polyvinylidene carbonate, a polymer compound such as polyacrylonitrile, a lithium salt, or a system in which an alkali metal salt mainly composed of lithium is compounded, or propylene carbonate, ethylene carbonate, having a high dielectric constant such as γ-butyrolactone A system containing an organic compound can be used.

【００３３】溶媒としては、上記溶媒の他、水、アセト
ン、ジメチルエーテル、或いはメタノール、エタノー
ル、ブタノール、イソプロパノール等のアルコール、Ｎ
−メチルピロリジノン、ジメチルホルムアミド、ジメチ
ルアセタミド、ヘキサメチルホスフォルアミド、ジメチ
ルスルフォキシド、ベンゼン、トルエン、キシレン、キ
ノリン、ピリジン、メチルナフタレン、ヘキサン等を用
いることができる。Examples of the solvent include water, acetone, dimethyl ether, alcohols such as methanol, ethanol, butanol and isopropanol, N
-Methylpyrrolidinone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, dimethylsulfoxide, benzene, toluene, xylene, quinoline, pyridine, methylnaphthalene, hexane and the like can be used.

【００３４】本発明に用いる上記負極材粒子及び上記結
着剤との混合形式としては、各種の形態をとることがで
きる。即ち、二種の粒子が混合結着した形態、繊維状の
結着剤が上記発明粒子及び導電剤に絡み合う形で混合し
た形態、又は結着剤の層が粒子表面に付着した形態など
が挙げられる。The negative electrode material particles and the binder used in the present invention can be mixed in various forms. That is, a form in which two kinds of particles are mixed and bound, a form in which a fibrous binder is mixed in a form entangled with the above-mentioned invention particles and a conductive agent, or a form in which a layer of a binder is attached to the particle surface, and the like. Can be

【００３５】上記負極材粒子と導電剤の混合割合は、負
極体の構成物質全体を１００重量％とした時、負極材を
少なくとも６０重量％以上、且つ導電剤を１重量％以上
３０重量％以下とすると好ましい。これ以上の量の導電
剤を添加すると、単位体積あたりに電極が発生できる充
放電容量が小さくなり、これ以下の量では導電剤同士の
導電パスが電極内に形成できないなどの理由で添加効果
が十分に発現されない。The mixing ratio of the negative electrode material particles and the conductive agent is such that, when the total constituent materials of the negative electrode body are 100% by weight, the negative electrode material is at least 60% by weight and the conductive agent is 1% by weight to 30% by weight. Is preferable. If the conductive agent is added in an amount greater than this, the charge / discharge capacity that the electrode can generate per unit volume decreases, and if the amount is less than this, the effect of the addition cannot be formed because conductive paths between the conductive agents cannot be formed in the electrode. Not fully expressed.

【００３６】上記結着剤の上記負極材粒子及び導電剤と
の混合割合は、負極材粒子と導電剤の合計の重量に対
し、好ましくは０．１〜３０重量％、より好ましくは、
０．５〜５重量％である。これ以上の量の結着剤を添加
すると、電極の内部抵抗が大きくなり、好ましくなく、
これ以下の量では集電体と電極粉体の結着性に劣る。The mixing ratio of the binder to the negative electrode material particles and the conductive agent is preferably 0.1 to 30% by weight, more preferably 0.1 to 30% by weight, based on the total weight of the negative electrode material particles and the conductive agent.
0.5 to 5% by weight. If the binder is added in an amount larger than this, the internal resistance of the electrode increases, which is not preferable.
If the amount is less than this, the binding property between the current collector and the electrode powder is inferior.

【００３７】この負極体を用いて電池を作製する場合を
以下に説明する。電解液、正極体を、その他の公知の電
池構成要素であるセパレータ、ガスケット、集電体、封
口板、セルケース等と組み合わせて非水系リチウム二次
電池を構成する。作成可能な電池は筒型、角型、コイン
型等特に限定されるものではないが、基本的にはセル床
板上に集電体と負極体を乗せ、その上に電解液とセパレ
ータを、更に負極と対向するように正極を乗せ、ガスケ
ット、封口板と共にかしめて二次電池とする。A case where a battery is manufactured using this negative electrode body will be described below. The nonaqueous lithium secondary battery is formed by combining the electrolyte solution and the positive electrode body with other known battery components such as a separator, a gasket, a current collector, a sealing plate, and a cell case. The batteries that can be created are not particularly limited, such as a cylindrical type, a square type, a coin type, but basically, a current collector and a negative electrode body are placed on a cell floor plate, and an electrolytic solution and a separator are further placed thereon. A positive electrode is placed so as to face the negative electrode, and caulked together with a gasket and a sealing plate to form a secondary battery.

【００３８】電解液用に使用できる非水溶媒としては、
プロピレンカーボネート、エチレンカーボネート、ジエ
チルカーボネート、ジメチルカーボネート、エチルメチ
ルカーボネート、１，２−ジメトキシエタン、γ−ブチ
ロラクトン、テトラヒドロフラン、２−メチルテトラヒ
ドロフラン、スルホラン、１，３−ジオキソラン、ジメ
チルスルフィド、プロピレンサルファイド、エチレンサ
ルファイド、ビニレンカーボネート等の有機溶媒、ポリ
エピクロルヒドリン、ポリフォスファゼン、ポリシロキ
サン、ポリビニルピロリドン、ポリビニリデンカーボネ
ート、ポリアクリロニトリル等の高分子化合物に、リチ
ウム塩、又はリチウムを主体とするアルカリ金属塩を複
合させた系、或いはこれに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高い誘電
率やイオン−双極子相互作用力を有する有機化合物の単
独、又は二種類以上を混合したものを用いることができ
る。Non-aqueous solvents that can be used for the electrolyte include:
Propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, γ-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, sulfolane, 1,3-dioxolan, dimethyl sulfide, propylene sulfide, ethylene sulfide An organic solvent such as vinylene carbonate, polyepichlorohydrin, polyphosphazene, polysiloxane, polyvinylpyrrolidone, polyvinylidene carbonate, a polymer compound such as polyacrylonitrile, a lithium salt, or an alkali metal salt mainly composed of lithium was compounded. System or high dielectric constants such as propylene carbonate, ethylene carbonate, γ-butyrolactone, and ion-dipole Organic compounds having an interaction force can be used alone or in combination of two or more.

【００３９】これらの溶媒に０．５〜２．０Ｍ程度のＬ
ｉＣｌＯ4、ＬｉＰＦ6、ＬｉＢＦ4、ＬｉＣＦ3ＳＯ3、
ＬｉＡｓＦ6、ＬｉＣｌ、ＬｉＢｒ、Ｌｉトリフルオロ
スルフォンイミド、Ｌｉビス（テトラフルオロメタンス
ルフォニル）イミド等の電解質を溶解して電解液とす
る。In these solvents, L of about 0.5 to 2.0 M is added.
iClO 4 , LiPF 6 , LiBF 4 , LiCF 3 SO 3 ,
An electrolyte such as LiAsF 6 , LiCl, LiBr, Li trifluorosulfonimide, or Li bis (tetrafluoromethanesulfonyl) imide is dissolved to form an electrolyte.

【００４０】また、リチウムイオン等のアルカリ金属カ
チオンの導電体であるポリエチレンオキシドやポリプロ
ピレンオキシド、ポリ（メタクロイルエチレンオキシ
ド）等のポリエーテル系高分子化合物、ポリエーテル化
合物の架橋体高分子、またこれらのものの構造末端の水
素基がメチル基、或いはエチル基等のアルキル基に交換
されたポリエチレンオキシドジメチルエーテル等のω−
アルキル基化ポリエーテル、ポリアクリロニトリルやけ
ん化度が高いポリビニルアルコールを上記有機溶媒と上
記電解質を混合したゲル電解質を用いることもできる。Further, polyether polymer compounds such as polyethylene oxide, polypropylene oxide and poly (methacryloyl ethylene oxide) which are conductors of alkali metal cations such as lithium ions, cross-linked polymers of polyether compounds, Ω- such as polyethylene oxide dimethyl ether in which the hydrogen group at the structural end has been replaced by an alkyl group such as a methyl group or an ethyl group
It is also possible to use a gel electrolyte in which the above organic solvent and the above electrolyte are mixed with an alkylated polyether, polyacrylonitrile, or polyvinyl alcohol having a high degree of saponification.

【００４１】正極材としては、従来から知られているい
ずれも使用でき、特に限定されるものではない。具体的
には、ＬｉＦｅＯ2、ＬｉＣｏＯ2、ＬｉＮｉＯ2、Ｌｉ
Ｍｎ2Ｏ4及びこれらの非定比化合物、ＭｎＯ2、Ｔｉ
Ｓ2、ＦｅＳ2、Ｎｂ3Ｓ4、Ｍｏ3Ｓ4、ＣｏＳ2、Ｖ
2Ｏ5、Ｐ2Ｏ5、ＣｒＯ3、Ｖ3Ｏ3、ＴｅＯ2、ＧｅＯ2等
を用いることができる。As the positive electrode material, any conventionally known one can be used, and it is not particularly limited. Specifically, LiFeO 2 , LiCoO 2 , LiNiO 2 , Li
Mn 2 O 4 and their non-stoichiometric compounds, MnO 2 , Ti
S 2 , FeS 2 , Nb 3 S 4 , Mo 3 S 4 , CoS 2 , V
2 O 5 , P 2 O 5 , CrO 3 , V 3 O 3 , TeO 2 , GeO 2 and the like can be used.

【００４２】正極体は、例えば、上記正極材に、アセチ
レンブラック、黒鉛等の導電剤を添加し、テトラフルオ
ロエチレン等を結着剤として混合後、アルミ箔上に塗布
し、成形、乾燥することによって得ることができる。The positive electrode body is prepared, for example, by adding a conductive agent such as acetylene black or graphite to the above-mentioned positive electrode material, mixing tetrafluoroethylene or the like as a binder, applying the mixture on an aluminum foil, molding and drying. Can be obtained by

【００４３】[0043]

【実施例】次に実施例により本発明を更に詳細に説明す
るが、本発明はこれらの例によってなんら限定されるも
のではない。Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention.

【００４４】電極材料の評価方法 すべての評価は以下の如く行った。本発明の負極材と結
着剤を用い、銅箔集電体上に塗布、結着した後、ペレッ
ト状に成形した。これをセパレーター、電解液と共に、
対極をリチウム金属とした半電池とし、２０１６コイン
セル中に組み立てた。充放電容量は充放電試験機を用
い、上述の様なセルで評価したが、正極体とともに組ん
だリチウムイオン電池でも同様な効果が期待できる。Evaluation Method for Electrode Materials All evaluations were performed as follows. The negative electrode material of the present invention and a binder were applied and bound on a copper foil current collector, and then formed into a pellet. This together with the separator and electrolyte,
A half-cell with a lithium metal counter electrode was assembled in 2016 coin cells. The charge / discharge capacity was evaluated using a cell as described above using a charge / discharge tester. Similar effects can be expected with a lithium ion battery assembled with a positive electrode body.

【００４５】（実施例１）ＳｉをＮｉＳｉ2の表面及び
内部に包含する平均粒子径１２．５μmの金属質物４０
ｇと、ｄ002が０．３３６nm、ラマンスペクトルから得
られたＲ値が０．２である平均粒子径１．６μmの人造
黒鉛２ｇを、ＭＲＫ製モルダーグラインダーにて大気中
で２分間均一に混合した。この混合物にＨ／Ｃが約１．
０、芳香族性指数ｆａが約０．５のタールピッチ５ｇを
添加し、更に混合した。これを焼成炉中でアルゴン雰囲
気下、昇温速度８℃／min.で９００℃まで昇温させ、１
時間保持した。室温付近まで冷却後、焼成したものを瑪
瑙乳鉢で解砕し、目開き４５μmの篩で分級し、平均粒
子径１４．１μmに整粒してサンプルとした。焼成時の
収率及び元素分析から得られたこの粒子の金属質物Ｍ、
黒鉛質物、及び炭素質物の割合は、粒子全体を１００重
量％とした時、９４重量％、５重量％、及び１重量％で
あった。また、ＳＥＭにより該サンプル粒子を観察した
ところ、金属質物Ｍ粒子の表面を、黒鉛と炭素質物の混
合物が被覆した構造が観察された。該粒子の窒素ガスに
よるＢＥＴ法から求められた比表面積の値は１m2/g、１
００回タップしたときのタップ密度は２．１g/cc、ラマ
ンスペクトルから得られたＲ値は０．４、更に空隙率７
５％の時の電導度は８×１０-4S/cmであった。このサン
プル粒子６ｇに対し導電剤としてｄ002が０．３３６nm
である平均粒子径１．６μmの人造黒鉛１ｇを、結着剤
として前記粒子１００重量％に対し、カルボキシメチル
セルロース（ＣＭＣ）及びスチレンブタジエンゴム（Ｓ
ＢＲ）合計２．４６重量％と、共に混合し、厚み１９μ
mの銅箔上に塗布後、８０℃で予備乾燥した。更に、直
径１２．５mmの円盤状に打ち抜き１１０℃で一昼夜加熱
減圧乾燥して電極とした。得られた電極に対し、電解液
を含浸させたポリエチレン性セパレーターを挟み、リチ
ウム金属電極に対向させたコイン型セルを作成し、充放
電試験を行った。電解液には、エチレンカーボネート
（ＥＣ）とエチルメチルカーボネート（ＥＭＣ）を容量
比で１：３比率で混合した溶媒に、リチウムヘキサフル
オロフォスフェート（ＬｉＰＦ６）を１．２５mol/Lの
割合で溶解させたものを用いた。基準充放電試験は、電
流密度０．３２mA/cm2で極間電位差が０Ｖになるまでド
ープを行い、同じ電流密度で１．５Ｖになるまで脱ドー
プを行った。容量値は、コイン型セル３個について各々
充放電試験を行い、第１回目充放電サイクル時の脱ドー
プ容量の平均、同サイクルのドープ容量から脱ドープ容
量を差し引いた不可逆容量の平均、及び第２０回目の放
電容量を第１回目の放電容量で割った値の百分率（容量
維持率／％）で評価した。(Example 1) Metallic material 40 containing Si at the surface and inside of NiSi 2 and having an average particle diameter of 12.5 μm
g and, d 002 is 0.336 nm, artificial graphite 2g having an average particle diameter of 1.6μm is R value of 0.2 was obtained from the Raman spectra, 2 minutes uniformly mixed in air at MRK made Mulder Grinder did. The mixture has an H / C of about 1.
0 and 5 g of tar pitch having an aromaticity index fa of about 0.5 were added and further mixed. This was heated to 900 ° C. at a rate of 8 ° C./min.
Hold for hours. After cooling to around room temperature, the fired product was crushed in an agate mortar, classified with a sieve having openings of 45 μm, and sized to an average particle size of 14.1 μm to obtain a sample. The metallic material M of the particles obtained from the yield at the time of firing and elemental analysis,
The proportions of the graphite substance and the carbonaceous substance were 94% by weight, 5% by weight, and 1% by weight, assuming that the whole particles were 100% by weight. When the sample particles were observed by SEM, a structure in which the surface of the metallic substance M particles was coated with a mixture of graphite and carbonaceous substance was observed. The specific surface area of the particles determined by the BET method using nitrogen gas is 1 m 2 / g,
The tap density after tapping 00 times is 2.1 g / cc, the R value obtained from the Raman spectrum is 0.4, and the porosity is 7
The conductivity at 5% was 8 × 10 −4 S / cm. D 002 is 0.336 nm as a conductive agent for 6 g of the sample particles.
Carboxymethylcellulose (CMC) and styrene-butadiene rubber (S) were used in an amount of 1 g of artificial graphite having an average particle size of 1.6 μm as a binder.
BR) 2.46% by weight in total and mixed together to a thickness of 19 μ
It was pre-dried at 80 ° C. after coating on a copper foil of m. Further, a disc having a diameter of 12.5 mm was punched out and dried by heating under reduced pressure at 110 ° C. for 24 hours to form an electrode. With respect to the obtained electrode, a coin type cell in which a polyethylene separator impregnated with an electrolytic solution was sandwiched and opposed to a lithium metal electrode was prepared, and a charge / discharge test was performed. In the electrolytic solution, lithium hexafluorophosphate (LiPF6) was dissolved at a ratio of 1.25 mol / L in a solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed at a volume ratio of 1: 3. Was used. In the reference charge / discharge test, doping was performed at a current density of 0.32 mA / cm 2 until the potential difference between the electrodes became 0 V, and undoping was performed at the same current density until the voltage reached 1.5 V. The capacity value was obtained by conducting a charge / discharge test on each of the three coin-type cells, and averaging the undoped capacity in the first charge / discharge cycle, the irreversible capacity obtained by subtracting the undoped capacity from the dope capacity in the same cycle, and Evaluation was made as a percentage (capacity retention /%) of a value obtained by dividing the twentieth discharge capacity by the first discharge capacity.

【００４６】[0046]

【数１】 (Equation 1)

【００４７】なお、負極材の比重には、リチウムドープ
前の該サンプルの真比重を用いた。As the specific gravity of the negative electrode material, the true specific gravity of the sample before lithium doping was used.

【００４８】（実施例２）実施例１の金属質物Ｍ、人造
黒鉛、及びタールピッチをそれぞれ４０ｇ、３ｇ、及び
７ｇ使用し、実施例１と同様の方法で混合、焼成した。
室温付近まで冷却後、瑪瑙乳鉢で解砕し、目開き４５μ
mの篩で分級し、平均粒子径１４．１μmに整粒してサン
プルとした。焼成時の収率及び元素分析から得られたこ
の粒子の金属質物Ｍ、黒鉛質物、及び炭素質物の割合
は、粒子全体を１００重量％としたとき、９１重量％、
７重量％、及び２重量％であった。また、ＳＥＭにより
サンプル粒子を観察したところ、金属質物Ｍ粒子の表面
に炭素質物が被覆した構造が観察された。該粒子の窒素
ガスによるＢＥＴ法から求められた比表面積の値は１m2
/g、１００回タップしたときのタップ密度は１．９g/c
c、ラマンスペクトルから得られたＲ値は０．４、更に
空隙率７５％の時の電導度は９×１０-3S/cmであった。
このサンプル粒子６ｇに対し、導電剤としてｄ002が
０．３３６nmである平均粒子径３．７μmの人造黒鉛
０．９ｇを、結着剤として前記粒子１００重量％に対
し、カルボキシメチルセルロース（ＣＭＣ）及びスチレ
ンブタジエンゴム（ＳＢＲ）合計２．４６重量％と、共
に混合し、実施例１と同様に電極を作製し、充放電試験
を行った。(Example 2) Using 40 g, 3 g and 7 g of the metallic substance M, artificial graphite and tar pitch of Example 1, respectively, were mixed and fired in the same manner as in Example 1.
After cooling to around room temperature, crush it in an agate mortar and open 45μ
The particles were classified with a sieve having a particle size of m and sized to an average particle diameter of 14.1 μm to obtain a sample. The ratio of the metallic substance M, the graphite substance, and the carbonaceous substance of the particles obtained from the yield at the time of firing and the elemental analysis was 91% by weight, when the whole particles were 100% by weight.
7% by weight and 2% by weight. When the sample particles were observed by SEM, a structure in which the surface of the metal material M particles was coated with the carbon material was observed. The specific surface area of the particles determined by the BET method using nitrogen gas is 1 m 2.
/ g, tap density after tapping 100 times is 1.9g / c
c, the R value obtained from the Raman spectrum was 0.4, and the conductivity at a porosity of 75% was 9 × 10 −3 S / cm.
To 6 g of the sample particles, 0.9 g of artificial graphite having an average particle diameter of 3.7 μm having a d 002 of 0.336 nm as a conductive agent, and carboxymethyl cellulose (CMC) and A total of 2.46% by weight of styrene butadiene rubber (SBR) was mixed together to prepare an electrode in the same manner as in Example 1, and a charge / discharge test was performed.

【００４９】（実施例３）実施例１の金属質物Ｍ、人造
黒鉛、及びタールピッチをそれぞれ４０ｇ、４ｇ、及び
１５ｇ使用し、実施例１と同様の方法で混合、焼成し
た。室温付近まで冷却後、ハンマーミルで解砕し、目開
き３８μmの篩で分級し、平均粒子径１４．１μmに整粒
してサンプルとした。焼成時の収率及び元素分析から得
られたこの粒子の金属質物Ｍ、黒鉛質物、及び炭素質物
の割合は、粒子全体を１００重量％としたとき、８７重
量％、９重量％、及び４重量％であった。また、ＳＥＭ
によりサンプル粒子を観察したところ、金属質物Ｍ粒子
の表面に炭素質物が被覆した構造が観察された。該粒子
の窒素ガスによるＢＥＴ法から求められた比表面積の値
は２m2/g、１００回タップしたときのタップ密度は１．
７g/cc、ラマンスペクトルから得られたＲ値は０．４、
更に空隙率７５％の時の電導度は５×１０-3S/cmであっ
た。このサンプル粒子６ｇに対し、導電剤としてｄ002
が０．３３６nmである平均粒子径３．７μmの人造黒鉛
０．６ｇを、結着剤として前記粒子１００重量％に対し
カルボキシメチルセルロース（ＣＭＣ）及びスチレンブ
タジエンゴム（ＳＢＲ）合計２．４６重量％と、共に混
合し、実施例１と同様に電極を作製し、充放電試験を行
った。(Example 3) Using 40 g, 4 g and 15 g of the metallic substance M, artificial graphite and tar pitch of Example 1, respectively, mixing and firing were performed in the same manner as in Example 1. After cooling to around room temperature, the mixture was crushed with a hammer mill, classified with a sieve having openings of 38 μm, and sized to an average particle diameter of 14.1 μm to obtain a sample. The ratio of the metallic substance M, the graphite substance, and the carbonaceous substance of the particles obtained from the yield at the time of calcination and the elemental analysis was 87% by weight, 9% by weight, and 4% by weight when the whole particles were 100% by weight. %Met. Also, SEM
As a result, the structure in which the surface of the metal material M particles was covered with the carbon material was observed. The value of the specific surface area of the particles determined by the BET method using nitrogen gas was 2 m 2 / g, and the tap density after tapping 100 times was 1.
7 g / cc, R value obtained from Raman spectrum is 0.4,
Further, the conductivity at a porosity of 75% was 5 × 10 −3 S / cm. To 6 g of the sample particles, d 002 was used as a conductive agent.
Is 0.336 nm, and 0.6 g of artificial graphite having an average particle diameter of 3.7 μm is used as a binder. The total amount of carboxymethyl cellulose (CMC) and styrene butadiene rubber (SBR) is 2.46% by weight based on 100% by weight of the particles. Were mixed together to form an electrode in the same manner as in Example 1, and a charge / discharge test was performed.

【００５０】（実施例４）実施例１使用の金属質物１５
０ｇに、ｄ002が０．３３６nm、ラマンスペクトルのＲ
値が０．１である平均粒子径１．６μmの人造黒鉛１２
ｇを、ホソカワミクロン製メカノフュージョンにて常
温、窒素雰囲気下で実１５分間処理した。この混合物１
００ｇに実施例１で用いたタールピッチ１８ｇを添加
し、更に大気中で混合した。これを実施例１と同様の方
法で焼成、ハンマーミルで解砕し、目開き３８μmの篩
で分級し、平均粒子径１４．１μmに整粒してサンプル
とした。焼成時の収率及び元素分析から得られたこの粒
子の金属質物Ｍ、黒鉛質物、及び炭素質物の割合は、粒
粒子全体を１００重量％としたとき、９０重量％、８重
量％、及び２重量％であった。また、ＳＥＭにより該サ
ンプル粒子を観察したところ、金属質物Ｍ粒子の表面
を、黒鉛と炭素質物の混合物が被覆した構造が観察され
た。該粒子の窒素ガスによるＢＥＴ法から求められた比
表面積の値は３m2/g、１００回タップしたときのタップ
密度は２．２g/cc、ラマンスペクトルから得られたＲ値
は０．２、更に空隙率７５％の時の電導度は３×１０-3
S/cmであった。このサンプル粒子に６ｇに対し、導電剤
としてｄ002が０．３３６nmある平均粒子径３．７μmの
人造黒鉛０．８ｇを、結着剤として前記粒子１００重量
％に対しカルボキシメチルセルロース（ＣＭＣ）及びス
チレンブタジエンゴム（ＳＢＲ）合計２．４６重量％
と、共に混合し、実施例１と同様に電極を作製し、充放
電試験を行った。Example 4 Metallic object 15 used in Example 1
0g, d 002 is 0.336 nm, R of Raman spectrum
Artificial graphite 12 having an average particle size of 1.6 μm having a value of 0.1
g was treated with Mesofusion manufactured by Hosokawa Micron at room temperature under a nitrogen atmosphere for 15 minutes. This mixture 1
18 g of the tar pitch used in Example 1 was added to 00 g, and further mixed in the air. This was fired in the same manner as in Example 1, crushed with a hammer mill, classified with a sieve having an opening of 38 μm, and sized to an average particle diameter of 14.1 μm to obtain a sample. The ratio of the metallic substance M, the graphite substance, and the carbonaceous substance of the particles obtained from the yield at the time of calcination and the elemental analysis was 90% by weight, 8% by weight, and 2% by weight, assuming that all the particles were 100% by weight. % By weight. When the sample particles were observed by SEM, a structure in which the surface of the metallic substance M particles was coated with a mixture of graphite and carbonaceous substance was observed. The value of the specific surface area of the particles determined by the BET method using nitrogen gas was 3 m 2 / g, the tap density after tapping 100 times was 2.2 g / cc, the R value obtained from the Raman spectrum was 0.2, Further, the conductivity at a porosity of 75% is 3 × 10 -3.
It was S / cm. 0.8 g of artificial graphite having an average particle diameter of 3.7 μm having a d 002 of 0.336 nm as a conductive agent was added to 6 g of the sample particles. 2.46% by weight of butadiene rubber (SBR)
Were mixed together to form an electrode in the same manner as in Example 1, and a charge / discharge test was performed.

【００５１】（実施例５）実施例１で使用した金属質物
８０ｇと、ｄ002が０．３３６nm、ラマンスペクトルの
Ｒ値が０．２である平均粒子径１．６μmの人造黒鉛５
ｇを奈良機械製ハイブリダイザーにて常温、アルゴン雰
囲気下で３分間処理した。この混合物４０ｇに実施例１
で用いたタールピッチ８ｇを添加し、更に大気中で混合
した。これを実施例１と同様な方法で焼成、瑪瑙乳鉢で
解砕し、目開き４５μmの篩で分級し、整粒された平均
粒子径１４．１μmのサンプルを得た。焼成時の収率及
び元素分析から、得られたこの粒子の金属質物Ｍ、黒鉛
質物、及び炭素質物の割合は、粒粒子全体を１００重量
％としたとき、９２重量％、６重量％、及び２重量％で
あった。また、ＳＥＭにより該サンプル粒子を観察した
ところ、金属質物Ｍ粒子の表面を、黒鉛と炭素質物の混
合物が被覆した構造が観察された。該粒子の窒素ガスに
よるＢＥＴ法から求められた比表面積の値は２m2/g、１
００回タップしたときのタップ密度は２．２g/cc、ラマ
ンスペクトルから得られたＲ値は０．９、更に空隙率７
５％の時の電導度２×１０-3S/cmであった。このサンプ
ル粒子に６ｇに対し、導電剤としてｄ002が０．３３６n
mある平均粒子径１．６μmの人造黒鉛０．９ｇを、結着
剤として前記粒子１００重量％に対しカルボキシメチル
セルロース（ＣＭＣ）及びスチレンブタジエンゴム（Ｓ
ＢＲ）合計２．４６重量％と、共に混合し、実施例１と
同様に電極を作製し、充放電試験を行った。[0051] (Example 5) and the metal pledge 80g used in Example 1, d 002 is 0.336 nm, the average particle diameter of 1.6 [mu] m R value is 0.2 in the Raman spectrum artificial graphite 5
g was treated with a hybridizer manufactured by Nara Machinery Co., Ltd. for 3 minutes at room temperature under an argon atmosphere. Example 1 was added to 40 g of this mixture.
8 g of the tar pitch used in the above was added and further mixed in the atmosphere. This was fired in the same manner as in Example 1, crushed with an agate mortar, and classified with a sieve having an opening of 45 μm to obtain a sized sample having an average particle diameter of 14.1 μm. From the yield and the elemental analysis at the time of calcination, the ratios of the metal material M, the graphite material, and the carbonaceous material in the obtained particles were 92% by weight, 6% by weight, and 100% by weight of the whole particle. It was 2% by weight. When the sample particles were observed by SEM, a structure in which the surface of the metallic substance M particles was coated with a mixture of graphite and carbonaceous substance was observed. The specific surface area of the particles determined by the BET method using nitrogen gas is 2 m 2 / g, 1
The tap density after tapping 00 times is 2.2 g / cc, the R value obtained from the Raman spectrum is 0.9, and the porosity is 7
The conductivity at 5% was 2 × 10 −3 S / cm. With respect to 6 g of the sample particles, 0.336 n of d 002 was used as a conductive agent.
0.9 g of artificial graphite having an average particle diameter of 1.6 μm is used as a binder, and carboxymethyl cellulose (CMC) and styrene butadiene rubber (S
BR) and a total of 2.46% by weight, and mixed together to produce an electrode in the same manner as in Example 1, and a charge / discharge test was performed.

【００５２】（比較例１）ｄ002が０．３３６nm、ラマ
ンスペクトルのＲ値が０．１、窒素ガスによるＢＥＴ法
から求められた比表面積の値が２１m2/g、１００回タッ
プしたときのタップ密度が０．２g/cc、更に空隙率７５
％の時の電導度５S/cmである平均粒子径３．７μmの人
造黒鉛を、結着剤であるカルボキシメチルセルロース
（ＣＭＣ）及びスチレンブタジエンゴム（ＳＢＲ）合計
２．４６重量％と共に混合し、実施例１と同様に電極を
作製し、充放電試験を行った。Comparative Example 1 d 002 was 0.336 nm, R value of Raman spectrum was 0.1, value of specific surface area determined by BET method using nitrogen gas was 21 m 2 / g, and tapping was performed 100 times. Tap density 0.2g / cc, porosity 75
% Of artificial graphite having an average particle size of 3.7 μm having an electric conductivity of 5 S / cm at the time of mixing with carboxymethylcellulose (CMC) as a binder and 2.46% by weight of styrene-butadiene rubber (SBR) in total. An electrode was prepared in the same manner as in Example 1, and a charge / discharge test was performed.

【００５３】（比較例２）実施例１で用いた、比表面積
の値が０．３m2/g、１００回タップした時のタップ密度
が２．３g/cc、空隙率７５％の時の電導度が６×１０-7
S/cmである金属物質Ｍを、結着剤であるカルボキシメチ
ルセルロース（ＣＭＣ）及びスチレンブタジエンゴム
（ＳＢＲ）合計２．４６重量％と共に混合し、実施例１
と同様に電極を作製し、充放電試験を行った。(Comparative Example 2) Conductivity when the value of the specific surface area used in Example 1 was 0.3 m 2 / g, the tap density after tapping 100 times was 2.3 g / cc, and the porosity was 75%. Degree 6 × 10 -7
Example 1 A metal substance M of S / cm was mixed with carboxymethyl cellulose (CMC) as a binder and 2.46% by weight of styrene butadiene rubber (SBR) in total.
An electrode was prepared in the same manner as described above, and a charge / discharge test was performed.

【００５４】（比較例３）実施例１で用いた金属質物Ｍ
４．８ｇに対し、比較例１で用いた人造黒鉛を１．２ｇ
添加し、均一に混合した。該混合物の窒素ガスによるＢ
ＥＴ法から求められた比表面積の値は４m2/g、１００回
タップしたときのタップ密度は０．８g/cc、ラマンスペ
クトルから得られたＲ値は０．１、更に空隙率７５％の
時の電導度は１×１０-7S/cm以上であった。この混合物
１００重量％に対し、結着剤であるカルボキシメチルセ
ルロース（ＣＭＣ）及びスチレンブタジエンゴム（ＳＢ
Ｒ）合計２．４６重量％を共に混合し、実施例１と同様
に電極を作製し、充放電試験を行った。(Comparative Example 3) Metallic object M used in Example 1
1.2 g of the artificial graphite used in Comparative Example 1 with respect to 4.8 g
Add and mix homogeneously. B of the mixture with nitrogen gas
The value of the specific surface area determined by the ET method was 4 m 2 / g, the tap density after tapping 100 times was 0.8 g / cc, the R value obtained from the Raman spectrum was 0.1, and the porosity was 75%. The conductivity at that time was 1 × 10 −7 S / cm or more. With respect to 100% by weight of this mixture, carboxymethylcellulose (CMC) as a binder and styrene-butadiene rubber (SB) were used.
R) A total of 2.46% by weight was mixed together to prepare an electrode in the same manner as in Example 1, and a charge / discharge test was performed.

【００５５】以下、本発明によって作製したリチウム二
次電池を具体的に充放電した実施例１から５及び比較例
１から３との比較検討を示す。表１に実施例１から５及
び比較例１から３のリチウム二次電池の脱ドープ容量、
不可逆容量、容量維持率をまとめた。The following is a comparison study between Examples 1 to 5 and Comparative Examples 1 to 3 in which the lithium secondary battery manufactured according to the present invention was specifically charged and discharged. Table 1 shows the undoping capacity of the lithium secondary batteries of Examples 1 to 5 and Comparative Examples 1 to 3,
The irreversible capacity and capacity maintenance rate are summarized.

【００５６】[0056]

【表１】 [Table 1]

【００５７】[0057]

【発明の効果】本発明の負極材を用いることにより、高
容量で、長期サイクルでの容量劣化が小さく、更に初回
充電時に発生する不可逆容量が小さいリチウム二次電池
を提供することができる。By using the negative electrode material of the present invention, it is possible to provide a lithium secondary battery having a high capacity, a small capacity deterioration in a long-term cycle, and a small irreversible capacity generated at the time of initial charging.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 秀治 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 (72)発明者 西岡 圭子 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 (72)発明者 笠松 真治 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 (72)発明者 新田 芳明 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 Ｆターム(参考） 5H003 AA02 AA04 BB02 BB15 BC01 BC05 BD00 BD03 BD04 BD05 5H014 AA02 EE05 EE07 HH01 HH02 HH04 HH08 5H029 AJ03 AJ05 AK02 AK03 AK05 AL11 AM03 AM04 AM05 AM07 BJ02 BJ03 HJ01 HJ07 HJ08 HJ13 HJ20  ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideharu Sato 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Inside the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Keiko Nishioka 8-chome, Ami-cho, Inashiki-gun, Ibaraki Prefecture No. 3-1 Mitsubishi Chemical Corporation Tsukuba Research Laboratory (72) Inventor Shinji Kasamatsu 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Inventor Yoshiaki Nitta 1006 Odaka Kadoma Kadoma, Osaka Matsushita Electric F-term (reference) in Sangyo Co., Ltd.

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 固相Ａ、Ｂからなる金属質物Ｍ、黒鉛質
物、及び当該黒鉛質物より結晶性の低い炭素質物を含有
する非水系リチウム二次電池用負極材であって、該金属
質物Ｍは固相Ａからなる核粒子の周囲の一部又は全面
を、固相Ｂによって被覆した構造であり、前記固相Ａは
構成元素としてケイ素を少なくとも含み、前記固相Ｂは
周期律表の２族元素、遷移金属元素、１２族元素、１３
族元素、並びに炭素とケイ素を除く１４族元素からなる
群から選ばれた少なくとも一種の元素と、ケイ素との固
溶体又は金属間化合物であることを特徴とする、前記負
極材。1. A negative electrode material for a non-aqueous lithium secondary battery, comprising a metal substance M composed of solid phases A and B, a graphite substance, and a carbon substance having a lower crystallinity than the graphite substance. Has a structure in which a part or the entire surface of a core particle composed of a solid phase A is covered with a solid phase B. The solid phase A contains at least silicon as a constituent element. Group element, transition metal element, group 12 element, 13
The negative electrode material, characterized in that the negative electrode material is a solid solution or an intermetallic compound of silicon with a group IV element and at least one element selected from the group consisting of group 14 elements excluding carbon and silicon. 【請求項２】 金属質物Ｍが、その表面の一部又は全部
を、予め黒鉛質物及び当該黒鉛質物より結晶性の低い炭
素質物で被覆したものである請求項１記載の負極材。2. The negative electrode material according to claim 1, wherein the metal material M is obtained by coating a part or all of the surface thereof in advance with a graphite material and a carbon material having a lower crystallinity than the graphite material. 【請求項３】 １００回タップしたときのタップ密度が
１．３g/cm3以上である請求項１又は２記載の負極材。3. The negative electrode material according to claim 1, wherein the tap density after tapping 100 times is 1.3 g / cm 3 or more. 【請求項４】 前記金属質物Ｍ、黒鉛、及び炭素質物の
割合が、それぞれ５０〜９５重量％、４．９〜３０重量
％、及び０．１〜２０重量％である請求項１乃至３のい
ずれか１に記載の負極材。4. The method according to claim 1, wherein the proportions of the metallic substance M, graphite and carbonaceous substance are 50 to 95% by weight, 4.9 to 30% by weight, and 0.1 to 20% by weight, respectively. The negative electrode material according to any one of the above. 【請求項５】 波長５１４．３nmのアルゴンイオンレー
ザー光を用いたラマンスペクトル分析に於いて、１５８
０cm-1〜１６２０cm-1の範囲に現れるピークの強度をＩ
Ａ、１３５０cm-1〜１３７０cm-1の範囲に現れるピーク
の強度をＩＢとしたときのピーク強度比Ｒ（＝ＩＢ／Ｉ
Ａ）が、０．２以上１以下である請求項１乃至４のいず
れか１に記載の負極材。5. In Raman spectrum analysis using argon ion laser light having a wavelength of 514.3 nm, 158
The intensity of the peak appearing in the range of 0cm -1 ~1620cm -1 I
A, peak intensity ratio R (= IB / I) where IB is the peak intensity appearing in the range of 1350 cm -1 to 1370 cm -1
The negative electrode material according to any one of claims 1 to 4, wherein A) is 0.2 or more and 1 or less. 【請求項６】 窒素ガスにより測定したＢＥＴ比表面積
が０．１〜２０m2/gである請求項１乃至５のいずれか１
に記載の負極材。6. The method according to claim 1, wherein the BET specific surface area measured with nitrogen gas is 0.1 to 20 m 2 / g.
The negative electrode material according to 1. 【請求項７】 空隙率が７５％である時に電気伝導度が
１ｘ１０-5S/cm以上である請求項１乃至６のいずれか１
に記載の負極材。7. The method according to claim 1, wherein the electric conductivity is 1 × 10 −5 S / cm or more when the porosity is 75%.
The negative electrode material according to 1. 【請求項８】 ＳＥＭから観察される前記金属質物Ｍの
表面を被覆する黒鉛質物又は炭素質物の被覆割合が、金
属質物Ｍの全表面の３０〜１００％を占める請求項２乃
至７のいずれか１に記載の負極材。8. The metal material M covered by a graphite or carbon material covering 30% to 100% of the entire surface of the metal material M as observed from an SEM. 2. The negative electrode material according to 1. 【請求項９】 正極体、負極体及び非水系溶媒中に電解
質を溶解した電解液から少なくともなる非水系リチウム
二次電池であって、請求項１乃至８のいずれか１に記載
の負極材を負極体に含むことを特徴とする非水系リチウ
ム二次電池。9. A non-aqueous lithium secondary battery comprising at least a positive electrode body, a negative electrode body, and an electrolytic solution obtained by dissolving an electrolyte in a non-aqueous solvent, wherein the negative electrode material according to claim 1 is used. A non-aqueous lithium secondary battery, which is included in a negative electrode body. 【請求項１０】 負極体が、負極体の材料全体を１００
重量％とした時、負極材を少なくとも６０重量％以上、
且つ導電剤として黒鉛質物を１重量％以上３０重量％以
下含む請求項９記載のリチウム二次電池。10. The negative electrode body contains 100% of the whole material of the negative electrode body.
Wt%, the negative electrode material is at least 60 wt% or more,
The lithium secondary battery according to claim 9, further comprising a graphite substance as a conductive agent in an amount of 1% by weight to 30% by weight.
JP32514199A 1999-11-16 1999-11-16 Anode material for non-aqueous lithium secondary battery and non-aqueous lithium secondary battery using the same Expired - Fee Related JP4416232B2 (en)

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