JP2002151067A - Negative electrode alloy material for lithium secondary battery, and its manufacturing method - Google Patents
Negative electrode alloy material for lithium secondary battery, and its manufacturing methodInfo
- Publication number
- JP2002151067A JP2002151067A JP2000348256A JP2000348256A JP2002151067A JP 2002151067 A JP2002151067 A JP 2002151067A JP 2000348256 A JP2000348256 A JP 2000348256A JP 2000348256 A JP2000348256 A JP 2000348256A JP 2002151067 A JP2002151067 A JP 2002151067A
- Authority
- JP
- Japan
- Prior art keywords
- negative electrode
- lithium secondary
- alloy
- secondary battery
- alloy material
- 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.)
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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、リチウム二次電池
用負極合金材料及びその製造方法に関する。The present invention relates to a negative electrode alloy material for a lithium secondary battery and a method for producing the same.
【０００２】[0002]
【従来技術】リチウム二次電池は、携帯電話、ノート型
パソコン等のバッテリーとして幅広く利用されている。
近年、これら製品の小型化に伴ってリチウム二次電池の
小型化も進んでいる。このリチウム二次電池の負極材料
としては、炭素系材料のほか、Ａｌ、Ｓｉ、Ｓｎ等が使
用されている。2. Description of the Related Art Lithium secondary batteries are widely used as batteries for mobile phones, notebook computers and the like.
In recent years, with the miniaturization of these products, the miniaturization of lithium secondary batteries has been progressing. As a negative electrode material of this lithium secondary battery, Al, Si, Sn, or the like is used in addition to a carbon-based material.
【０００３】しかしながら、従来のリチウム二次電池に
使用されている炭素系負極は軽量で嵩高いことから、電
池自体を小型化するには限界がある。炭素系材料はＬｉ
Ｃ6の組成までしかＬｉを吸蔵できないため、Ｌｉ吸蔵
放出の体積容量（単位体積当たりの容量）は理論的に８
３７Ａｈ／リットルが最大であり、体積容量については
さらなる改善が必要である。However, since the carbon-based negative electrode used in the conventional lithium secondary battery is lightweight and bulky, there is a limit in reducing the size of the battery itself. The carbon-based material is Li
Since Li can be stored only up to the composition of C 6 , the volume capacity (capacity per unit volume) of Li storage and release is theoretically 8
The maximum is 37 Ah / liter, and the volume capacity needs further improvement.
【０００４】一方、Ｓｎ負極では７２００Ａｈ／リット
ルの最大理論容量を有し、炭素系負極のそれよりもはる
かに大きな値を示すものの、Ｌｉ吸蔵時の体積膨張が大
きい。このため、負極材料の微粉化が起こり、この場合
にはサイクル寿命が非常に短くなるという問題がある。On the other hand, the Sn negative electrode has a maximum theoretical capacity of 7200 Ah / liter, and shows a much larger value than that of the carbon-based negative electrode, but has a large volume expansion during Li occlusion. For this reason, the anode material is pulverized, and in this case, there is a problem that the cycle life becomes very short.
【０００５】[0005]
【発明が解決しようとする課題】従って、本発明の主な
目的は、高い放電容量とともに優れたサイクル特性を発
揮できるリチウム二次電池用負極材料を提供することに
ある。SUMMARY OF THE INVENTION Accordingly, it is a primary object of the present invention to provide a negative electrode material for a lithium secondary battery which can exhibit high cycle capacity and excellent cycle characteristics.
【０００６】[0006]
【課題を解決するための手段】本発明者は、かかる従来
技術の問題に鑑みて鋭意研究を重ねた結果、特定組成の
合金をリチウム二次電池用負極材料として用いることに
よって上記目的を達成できることを見出し、本発明を完
成するに至った。Means for Solving the Problems The present inventor has conducted intensive studies in view of the problems of the prior art, and as a result, has found that the above object can be achieved by using an alloy having a specific composition as a negative electrode material for a lithium secondary battery. And completed the present invention.
【０００７】すなわち、本発明は、下記のリチウム二次
電池用負極合金材料及びその製造方法に係るものであ
る。That is, the present invention relates to the following negative electrode alloy material for a lithium secondary battery and a method for producing the same.
【０００８】１．Ｖ−Ｓｎ系合金を用いたリチウム二次
電池用負極合金材料。[0008] 1. A negative electrode alloy material for a lithium secondary battery using a V-Sn-based alloy.
【０００９】２．Ｖ−Ｓｎ系合金が、合金組成（酸素を
除く。）Ｖ1-xＳｎaＭx（但し、ＭはＡｌ、Ｆｅ、Ｍ
ｎ、Ｃｕ、Ｃｏ、Ｃｒ、Ｎｉ及びＣの少なくとも１種、
０≦ｘ≦０．５、１≦ａ≦２を示す。）を有する項１記
載のリチウム二次電池用負極合金材料。[0009] 2. V-Sn based alloy has an alloy composition (excluding oxygen) V 1-x Sn a M x (where M is Al, Fe, M
at least one of n, Cu, Co, Cr, Ni and C;
0 ≦ x ≦ 0.5 and 1 ≦ a ≦ 2. Item 7. The negative electrode alloy material for a lithium secondary battery according to Item 1, comprising:
【００１０】３．酸素含有量が合金材料中０．１重量％
以上である項１又は２に記載のリチウム二次電池用負極
合金材料。[0010] 3. Oxygen content is 0.1% by weight in alloy material
Item 3. The negative electrode alloy material for a lithium secondary battery according to item 1 or 2 above.
【００１１】４．Ｖ及びＳｎを含む原料粉末を加圧成形
した後、得られた成形体を不活性ガス雰囲気下６００〜
９００℃で焼成することを特徴とするリチウム二次電池
用負極合金材料の製造方法。4. After pressure-molding the raw material powder containing V and Sn, the obtained molded body is subjected to an inert gas atmosphere at 600 to
A method for producing a negative electrode alloy material for a lithium secondary battery, characterized by firing at 900 ° C.
【００１２】５．酸化バナジウム、スズ及びアルミニウ
ムを含む原料粉末をテルミット反応させることを特徴と
するリチウム二次電池用負極合金材料の製造方法。5. A method for producing a negative electrode alloy material for a lithium secondary battery, comprising subjecting a raw material powder containing vanadium oxide, tin and aluminum to a thermit reaction.
【００１３】６．さらに、不活性ガス雰囲気下４００〜
１０００℃で熱処理する項５記載の製造方法。6. Further, under an inert gas atmosphere,
Item 6. The production method according to Item 5, wherein the heat treatment is performed at 1000 ° C.
【００１４】７．項１〜３のいずれかに記載のリチウム
二次電池用負極合金材料を用いたリチウム二次電池用負
極。7. Item 7. A negative electrode for a lithium secondary battery using the negative electrode alloy material for a lithium secondary battery according to any one of Items 1 to 3.
【００１５】８．項７記載の負極を用いたリチウム二次
電池。[8] Item 7. A lithium secondary battery using the negative electrode according to Item 7.
【００１６】[0016]
【発明の実施の形態】１．リチウム二次電池用負極材料 本発明のリチウム二次電池用負極合金材料は、Ｖ−Ｓｎ
系合金を用いることに特徴を有する。上記Ｖ−Ｓｎ系合
金は、Ｖ及びＳｎからなる２成分系合金のほか、第三成
分を含む合金であっても良い。なお、本発明における
「合金」は「金属間化合物」も含む。BEST MODE FOR CARRYING OUT THE INVENTION Negative electrode material for lithium secondary battery The negative electrode alloy material for a lithium secondary battery of the present invention is V-Sn
It is characterized by using a system alloy. The V-Sn-based alloy may be an alloy containing a third component in addition to a binary alloy composed of V and Sn. In the present invention, “alloy” includes “intermetallic compound”.
【００１７】上記合金としては、合金組成（酸素を除
く。）Ｖ1-xＳｎaＭx（但し、Ｍ（第三成分）はＡｌ、
Ｆｅ、Ｍｎ、Ｃｕ、Ｃｏ、Ｃｒ、Ｎｉ及びＣの少なくと
も１種、０≦ｘ≦０．５、１≦ａ≦２を示す。）を有す
る合金が好ましい。As the above alloy, alloy composition (excluding oxygen) V 1-x Sn a M x (where M (third component) is Al,
At least one of Fe, Mn, Cu, Co, Cr, Ni and C represents 0 ≦ x ≦ 0.5 and 1 ≦ a ≦ 2. ) Are preferred.
【００１８】上記一般式において、第三成分としてのＭ
はＣｏ、Ａｌ及びＣｕの少なくとも１種が好ましい。ま
た、ｘの値は０≦ｘ≦０．２が好ましい。ａの値は、
１．２≦ａ≦１．５が好ましい。より具体的には、２成
分系合金であるＶ2Ｓｎ3等を好適に用いることができ
る。In the above general formula, M as the third component
Is preferably at least one of Co, Al and Cu. The value of x is preferably 0 ≦ x ≦ 0.2. The value of a is
1.2 ≦ a ≦ 1.5 is preferred. More specifically, a two-component alloy such as V 2 Sn 3 can be suitably used.
【００１９】また、本発明合金材料の酸素含有量は限定
的ではないが、通常は合金材料中０．１重量％以上、特
に０．３重量％以上とすることが望ましい。なお、酸素
含有量の上限値は、通常は１重量％程度とすれば良い。
上記所定量の酸素を含有することにより、反応性をいっ
そう高めることができる。 ２．リチウム二次電池用負極材料の製造方法 本発明の製造方法は、Ｖ及びＳｎを含む原料粉末を加圧
成形した後、得られた成形体を不活性ガス雰囲気下６０
０〜９００℃で焼成することを特徴とする（第一方
法）。Although the oxygen content of the alloy material of the present invention is not limited, it is generally desirable that the oxygen content be 0.1% by weight or more, especially 0.3% by weight or more in the alloy material. In addition, the upper limit of the oxygen content may be usually about 1% by weight.
By containing the predetermined amount of oxygen, the reactivity can be further increased. 2. Method for Producing Negative Electrode Material for Lithium Secondary Battery According to the production method of the present invention, after the raw material powder containing V and Sn is subjected to pressure molding,
It is characterized by firing at 0 to 900 ° C (first method).
【００２０】また、本発明の製造方法は、酸化バナジウ
ム、スズ及びアルミニウムを含む原料粉末をテルミット
反応させることを特徴とする（第二方法）。 （１）第一方法 第一方法では、まずＶ及びＳｎを含む原料粉末を加圧成
形する。原料粉末は、Ｖ及びＳｎを含むものであれば限
定的でない。より具体的には、本発明合金材料の好まし
いＶ−Ｓｎ系合金の組成となるように調合することが望
ましい。例えば、Ｖ粉末とＳｎ粉末との割合を調整した
上、両者を公知の方法により混合すれば良い。また、第
三成分を含む合金材料を製造する場合は、前記組成とな
るように第三成分の供給材料（例えば、第三成分の単独
粉末（金属粉末）、第三成分の２種以上を含む合金粉末
等）を添加すれば良い。原料粉末の粒度は限定的ではな
いが、通常は０．１ｍｍ以下とすれば良い。The production method of the present invention is characterized in that a raw material powder containing vanadium oxide, tin and aluminum is subjected to a thermite reaction (second method). (1) First Method In the first method, first, a raw material powder containing V and Sn is subjected to pressure molding. The raw material powder is not limited as long as it contains V and Sn. More specifically, it is desirable to formulate the alloy material of the present invention so as to have a preferable composition of the V-Sn alloy. For example, after adjusting the ratio of the V powder and the Sn powder, both may be mixed by a known method. When an alloy material containing the third component is produced, a supply material of the third component (for example, a single powder of the third component (metal powder) or a mixture of two or more of the third component) so that the above composition is obtained. Alloy powder or the like). The particle size of the raw material powder is not limited, but may be usually 0.1 mm or less.
【００２１】加圧成形する方法は特に限定されず、公知
の成形方法に従って実施すれば良い。例えば、プレス成
形法、冷間静水圧成形法（ＣＩＰ）、熱間静水圧成形法
（ＨＩＰ）等を採用することができる。成形圧は、原料
粉末の粒度、最終製品の用途等によって適宜設定できる
が、通常は１００ｋｇｆ／ｃｍ2以上とすれば良い。ま
た、成形体の形状も限定的でなく、最終製品の使用目的
等に応じて適宜決定すれば良い。The method of pressure molding is not particularly limited, and may be carried out according to a known molding method. For example, press molding, cold isostatic pressing (CIP), hot isostatic pressing (HIP) and the like can be employed. The molding pressure can be appropriately set depending on the particle size of the raw material powder, the use of the final product, and the like, but is usually 100 kgf / cm 2 or more. In addition, the shape of the molded body is not limited, and may be appropriately determined according to the purpose of use of the final product.
【００２２】次いで、得られた成形体を不活性ガス雰囲
気下６００〜９００℃で焼成する。不活性ガスとして
は、例えばアルゴンガス、ヘリウムガス、窒素ガス等を
採用することができる。雰囲気圧力は限定的ではない
が、通常は０．５ＭＰａ以上が好ましく、特に０．７〜
１ＭＰａがより好ましい。焼成温度は通常６００〜９０
０℃の範囲で良いが、特に７００〜９００℃とすること
が好ましい。焼成時間は焼成温度等によって適宜設定す
れば良いが、通常は１０〜５０時間程度である。 （２）第二方法 第二方法で用いる酸化バナジウム、スズ及びアルミニウ
ムを含む原料粉末は、本発明合金材料の好ましいＶ−Ｓ
ｎ系合金の組成となるように調合することが望ましい。
例えば、酸化バナジウム粉末（五酸化バナジウム：Ｖ2
Ｏ5）、スズ粉末及びアルミニウム粉末を用いて原料粉
末を調合すれば良い。原料粉末の一部として合金粉末を
用いても良い。還元剤としてのアルミニウム粉末の使用
量は、酸化バナジウム量等に応じて適宜設定すれば良
い。また、第三成分を含む合金材料を製造する場合は、
前記組成となるように第三成分の供給材料（例えば、第
三成分の単独粉末、第三成分の酸化物粉末等）を添加す
れば良い。原料粉末の粒度は限定的ではないが、通常は
０．５ｍｍ以下、好ましくは０．３〜０．５μｍとすれ
ば良い。Next, the obtained molded body is fired at 600 to 900 ° C. in an inert gas atmosphere. As the inert gas, for example, argon gas, helium gas, nitrogen gas, or the like can be used. The atmospheric pressure is not limited, but is usually preferably 0.5 MPa or more, particularly 0.7 to 0.7 MPa.
1 MPa is more preferable. The firing temperature is usually 600 to 90
The temperature may be in the range of 0 ° C., but is particularly preferably 700 to 900 ° C. The firing time may be appropriately set depending on the firing temperature and the like, but is usually about 10 to 50 hours. (2) Second method The raw material powder containing vanadium oxide, tin and aluminum used in the second method is preferably a VS of the alloy material of the present invention.
It is desirable to prepare the composition so as to have the composition of the n-type alloy.
For example, vanadium oxide powder (vanadium pentoxide: V 2
The raw material powder may be prepared using O 5 ), tin powder and aluminum powder. An alloy powder may be used as a part of the raw material powder. The amount of the aluminum powder used as the reducing agent may be appropriately set according to the amount of vanadium oxide and the like. When manufacturing an alloy material containing the third component,
A supply material of the third component (for example, a single powder of the third component, an oxide powder of the third component, etc.) may be added so as to have the above composition. Although the particle size of the raw material powder is not limited, it is usually 0.5 mm or less, preferably 0.3 to 0.5 μm.
【００２３】上記原料粉末を用いてテルミット反応させ
る。テルミット反応の方法自体は、公知の方法に従えば
良い。例えば、原料粉末を反応容器中に装填し、必要に
応じてマグネシウム粉、過酸化バリウム等の着火剤を用
い、原料粉末に着火させる。反応容器は公知のものが使
用でき、例えばアルミナ耐火物でライニング加工された
反応容器を好適に使用することができる。A thermite reaction is carried out using the above raw material powder. The method of thermite reaction itself may be in accordance with a known method. For example, the raw material powder is charged into a reaction vessel, and the raw material powder is ignited using an igniting agent such as magnesium powder or barium peroxide as necessary. A well-known reaction vessel can be used. For example, a reaction vessel lined with an alumina refractory can be suitably used.
【００２４】本発明において、テルミット反応は通常数
秒程度で終了し、反応熱によって２０００℃以上の温度
に達する。反応終了時には高温のために合金とスラグ
（主にアルミナ）は液体状態となっており、比重の差に
よって合金とスラグは上下に分離する。分離した状態で
そのまま冷却した後、合金とスラグをその界面で分離す
ることによって合金を得ることができる。In the present invention, the thermite reaction is usually completed within about several seconds, and reaches a temperature of 2000 ° C. or more by the heat of the reaction. At the end of the reaction, the alloy and the slag (mainly alumina) are in a liquid state due to the high temperature, and the alloy and the slag are separated vertically by a difference in specific gravity. After cooling as it is in the separated state, the alloy can be obtained by separating the alloy and the slag at the interface.
【００２５】テルミット反応により得られた合金は、必
要に応じて、不活性ガス雰囲気下４００〜１０００℃で
熱処理しても良い。これによって、合金の均質化をより
促進させることができる。不活性ガスは前記と同様のも
のを挙げることができる。熱処理時間は熱処理温度等に
よって異なるが、通常は１０〜４０時間程度とすれば良
い。 ３．負極及びリチウム二次電池の製造 本発明では、前記（１）（２）の方法で製造された合金
材料を用いるほかは、公知の材料及び方法で負極を製造
することができる。The alloy obtained by the thermit reaction may be heat-treated at 400 to 1000 ° C. in an inert gas atmosphere, if necessary. Thereby, homogenization of the alloy can be further promoted. The inert gas may be the same as described above. The heat treatment time varies depending on the heat treatment temperature and the like, but is usually set to about 10 to 40 hours. 3. Manufacture of Negative Electrode and Lithium Secondary Battery In the present invention, a negative electrode can be manufactured by known materials and methods other than using the alloy materials manufactured by the methods (1) and (2).
【００２６】まず、本発明合金材料を必要に応じて公知
の方法に従って粉砕し、さらに分級する。粉砕方法は限
定的でなく、例えば乳鉢、ボールミル、振動ミル、ロッ
ドミル、ハンマーミル、ジョークラッシャー等の公知の
粉砕装置を使用して行えば良い。また、分級方法も特に
制限されず、例えば篩い、振動機、遠心分離機等を使用
して実施すれば良い。合金粉末の粒度は限定的ではない
が、通常は平均粒径２５μｍ以下、好ましくは１〜１０
μｍに調整すれば良い。First, the alloy material of the present invention is pulverized according to a known method, if necessary, and further classified. The crushing method is not limited, and may be performed using a known crusher such as a mortar, a ball mill, a vibration mill, a rod mill, a hammer mill, a jaw crusher, and the like. In addition, the classification method is not particularly limited, and may be performed using, for example, a sieve, a vibrator, a centrifuge, or the like. The particle size of the alloy powder is not limited, but is usually 25 μm or less in average particle size, preferably 1 to 10 μm.
It may be adjusted to μm.
【００２７】次いで、上記合金材料（粉末）に対し、導
電助剤、結着剤等の添加剤を適宜配合し、さら有機溶媒
を配合してスラリー化し、このスラリーを銅箔等の電極
支持基板に塗布し、乾燥すれば良い。さらに、必要に応
じて圧延ロール等による圧延又はプレス加工を施しても
良い。前記の導電助剤、結着剤、有機溶媒等は、公知の
もの又は市販品を使用できる。具体的には、導電助剤と
して、例えば黒鉛、ケッチェンブラック等が使用でき
る。結着剤として、例えばポリフッ化ビニリデン等を用
いることができる。有機溶媒として、例えばＮ−メチル
ピロリドン等を使用できる。Next, additives such as a conductive auxiliary agent and a binder are appropriately added to the alloy material (powder), and an organic solvent is further added to form a slurry. And dried. Further, rolling or press working with a rolling roll or the like may be performed as necessary. As the conductive aid, the binder, the organic solvent and the like, known or commercially available products can be used. Specifically, for example, graphite, Ketjen black, or the like can be used as the conductive assistant. As the binder, for example, polyvinylidene fluoride can be used. As the organic solvent, for example, N-methylpyrrolidone or the like can be used.
【００２８】このようにして得られた負極は、さらに公
知のリチウム二次電池の構成要素を用いてリチウム二次
電池を組み立てることができる。The negative electrode thus obtained can be used to assemble a lithium secondary battery using known lithium secondary battery components.
【００２９】例えば、正極としてはＬｉを含有する、Ｔ
ｉ、Ｍｏ、Ｗ、Ｎｂ、Ｖ、Ｍｎ、Ｆｅ、Ｃｒ、Ｃｏ等の
遷移金属の複合酸化物、複合硫化物等の１種又は２種以
上を含む材料を用いることができる。セパレータとして
は、例えばポリプロピレン、ポリエチレン等のポリオレ
フィン系の多孔性ポリマーフィルムが使用できる。電解
液としては、有機溶媒にリチウム塩を溶解させた非水電
解液、ポリマー電解質、無機固体電解質等が使用でき
る。このうち、上記非水電解液における溶媒としては、
例えばエチレンカーボネート、プロピレンカーボネー
ト、ジメチルカーボネート、ジエチルカーボネート、メ
チルエチルカーボネート等の鎖状エステル類、１，２−
ジメトキシエタン、１，２−ジエトキシエタン等の鎖状
エーテル類等が使用できる。また、非水電解液の溶質と
しては、ＬｉＡｓＦ6、ＬｉＢＦ6、ＬｉＰＦ6、ＬｉＡ
ｌＣｌ4、ＬｉＣｌＯ4等のリチウム塩又はこれらの混合
物が挙げられる。For example, as the positive electrode, T containing T
A material containing one or more of composite oxides and composite sulfides of transition metals such as i, Mo, W, Nb, V, Mn, Fe, Cr, and Co can be used. As the separator, for example, a polyolefin-based porous polymer film such as polypropylene and polyethylene can be used. As the electrolyte, a non-aqueous electrolyte in which a lithium salt is dissolved in an organic solvent, a polymer electrolyte, an inorganic solid electrolyte, or the like can be used. Among them, as the solvent in the non-aqueous electrolyte,
For example, chain esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate;
Chain ethers such as dimethoxyethane and 1,2-diethoxyethane can be used. The solutes of the non-aqueous electrolyte include LiAsF 6 , LiBF 6 , LiPF 6 , LiA
Examples thereof include lithium salts such as lCl 4 and LiClO 4 or a mixture thereof.
【００３０】[0030]
【発明の効果】本発明の合金材料はＶ−Ｓｎ系合金を電
極活物質（負極活物質）として用いることから、従来の
炭素系材料を用いた負極よりも高い容量（体積容量）を
発揮することができる。Since the alloy material of the present invention uses a V-Sn-based alloy as an electrode active material (negative electrode active material), it exhibits a higher capacity (volume capacity) than a conventional negative electrode using a carbon-based material. be able to.
【００３１】また、Ｖ及びＳｎの合金化によってＬｉの
吸蔵・放出に伴う微粉化が起こりにくくなる結果、サイ
クル寿命特性の向上を図ることができる。これにより、
従来の炭素系材料を用いた負極と同程度又はそれ以上の
サイクル寿命特性を得ることができる。Further, alloying of V and Sn makes it difficult for pulverization accompanying occlusion and release of Li to occur, thereby improving cycle life characteristics. This allows
It is possible to obtain a cycle life characteristic equal to or better than that of a negative electrode using a conventional carbon-based material.
【００３２】さらに、Ｖ−Ｓｎ系合金中に所定量の酸素
が含まれる場合には、電池の充放電による合金中のＳｎ
の吸着・脱離を円滑にし、合金中においてＶとＳｎのた
めのバインダー的な役割を果たす。このＶ−Ｏ−Ｓｎ結
合状態は、Ｌｉを可逆的に吸蔵・放出する反応性を高め
ることができる。Further, when a predetermined amount of oxygen is contained in the V-Sn-based alloy, Sn-
Plays a role as a binder for V and Sn in the alloy. This VO-Sn bonding state can enhance the reactivity of reversibly occluding and releasing Li.
【００３３】このような特長をもつ本発明負極材料は、
リチウム二次電池に好適に用いることができる。The negative electrode material of the present invention having such features is as follows:
It can be suitably used for a lithium secondary battery.
【００３４】[0034]
【実施例】以下に実施例及び比較例を示し、本発明の特
徴をより詳細に説明する。但し、本発明の範囲は、これ
ら実施例に限定されるものではない。EXAMPLES Examples and comparative examples will be shown below to explain the features of the present invention in more detail. However, the scope of the present invention is not limited to these examples.
【００３５】実施例１ （１）焼成体の製造 粒径４５μｍ以下の金属バナジウム粉末０．５０３ｇと
粒径５０μｍ以下の金属スズ粉末１．５００ｇとをそれ
ぞれ秤量し、乳鉢上で十分に混合した。この混合粉末を
加圧力１５０ｋｇｆ／ｃｍ2の圧力で加圧成形すること
により、直径１０ｍｍ及び厚さ約６ｍｍの円筒状の加圧
成形体を得た。この加圧成形体をアルゴンガス０．７Ｍ
Ｐａの雰囲気下において、昇温速度２．５℃／分で室温
から７５０℃まで昇温した後、７５０℃で１０時間保持
することによって焼成した。焼成により得られたＶ−Ｓ
ｎ合金の化学分析値を表１に示す。Example 1 (1) Production of fired body 0.503 g of metal vanadium powder having a particle size of 45 μm or less and 1.500 g of metal tin powder having a particle size of 50 μm or less were weighed and thoroughly mixed in a mortar. This mixed powder was pressed under a pressure of 150 kgf / cm 2 to obtain a cylindrical pressed body having a diameter of 10 mm and a thickness of about 6 mm. This press-formed body was treated with 0.7M argon gas.
In a Pa atmosphere, the temperature was raised from room temperature to 750 ° C. at a rate of 2.5 ° C./min, followed by firing at 750 ° C. for 10 hours. VS obtained by firing
Table 1 shows the chemical analysis values of the n alloy.
【００３６】[0036]
【表１】 [Table 1]
【００３７】（２）電極評価用試験セルの作製 上記Ｖ−Ｓｎ合金を振動ミルで粉砕し、分級して粒径２
５μｍ以下の粉末に粒度調整した。この合金粉末８０重
量部に対し、導電助剤としてケッチェンブラック１０重
量部、結着剤としてポリフッ化ビニリデン１０重量部を
加え、これらを溶媒（Ｎ−メチルピロリドン）約５ｍｌ
中で混合し、スラリーを得た。得られたスラリーを銅箔
（厚さ１８μｍ）にドクターブレード法で塗布し、仮乾
燥後、ロール圧延により圧密化させた後、真空中１２０
℃で１６時間乾燥した。次いで、乾燥したシート状物を
打ち抜いて直径１１ｍｍの円板を得た。これを電極（作
用極）として用いた。(2) Preparation of Test Cell for Evaluating Electrode The above V-Sn alloy was pulverized with a vibration mill and classified to obtain a particle size of 2
The particle size was adjusted to a powder of 5 μm or less. To 80 parts by weight of this alloy powder, 10 parts by weight of Ketjen black as a conductive aid and 10 parts by weight of polyvinylidene fluoride as a binder were added, and these were added in a solvent (N-methylpyrrolidone) of about 5 ml.
And a slurry was obtained. The obtained slurry was applied to a copper foil (thickness: 18 μm) by a doctor blade method, temporarily dried, and then consolidated by roll rolling.
Dry at 16 ° C. for 16 hours. Next, the dried sheet was punched to obtain a disk having a diameter of 11 mm. This was used as an electrode (working electrode).
【００３８】この作用極を用いて電極評価用試験セルを
作製した。まず、対極としてＬｉ金属箔を直径１６ｍｍ
に打ち抜いた円板を用い、セパレータとしてポリプロピ
レン多孔質フィルムを用いた。また、電解液としては、
エチレンカーボネート：ジメチルカーボネート＝１：２
（体積比）の混合液にＬｉＰＦ6を１Ｍ濃度で溶解させ
た溶液を使用した。次に、電解液をセパレータに含浸さ
せ、このセパレータを作用極と対極との間に挟んでステ
ンレス鋼製ケースに収納した後、ケースをかしめにより
封止して電極評価用試験セルとした。 （３）電池試験 上記セルを用いて電池試験を行った。充電については、
０．２５ｍＡの電流で、作用極に対する対極の電位差が
０Ｖになるまで充電した。放電については、０．２５ｍ
Ａの電流で、作用極に対する対極の電位差が１．５Ｖと
なるまで放電した。なお、上記試験セルでは、対極のＬ
ｉ金属の方が負極となり、充電・放電が上記とは逆にな
るが、この電池試験は本発明の合金を負極材料として評
価するものであるため、Ｌｉを放出する方を「放電」と
定義した。Using this working electrode, a test cell for electrode evaluation was prepared. First, a Li metal foil having a diameter of 16 mm was used as a counter electrode.
Was used, and a porous polypropylene film was used as a separator. Also, as the electrolyte,
Ethylene carbonate: dimethyl carbonate = 1: 2
A solution obtained by dissolving LiPF 6 at a concentration of 1 M in a mixed solution (volume ratio) was used. Next, the separator was impregnated with the electrolytic solution, the separator was sandwiched between the working electrode and the counter electrode, and stored in a stainless steel case, and the case was sealed by caulking to obtain a test cell for electrode evaluation. (3) Battery test A battery test was performed using the above cell. For charging,
The battery was charged with a current of 0.25 mA until the potential difference between the working electrode and the counter electrode became 0V. 0.25m for discharge
The current A was discharged until the potential difference between the counter electrode and the working electrode became 1.5 V. In the above test cell, the counter electrode L
The i-metal is the negative electrode, and charging and discharging are opposite to the above, but since this battery test evaluates the alloy of the present invention as a negative electrode material, the one that releases Li is defined as "discharge". did.
【００３９】上記の充電・放電の条件にて１回放電する
ことを１サイクルとし、１サイクル目、１０サイクル
目、２０サイクル目及び３０サイクル目の放電容量をそ
れぞれ測定した。その結果を表２に示す。また、サイク
ル−放電容量カーブを図２に示す。One cycle was defined as discharging once under the above-described charge / discharge conditions, and the discharge capacities at the first cycle, the tenth cycle, the twentieth cycle and the thirty cycle were measured. Table 2 shows the results. FIG. 2 shows a cycle-discharge capacity curve.
【００４０】実施例２ テルミット反応によりＶ−Ｓｎ合金を製造した。まず、
原料であるＶ2Ｏ5９３６ｇ、粒状Ｓｎ１６３８ｇ及びＡ
ｌ粉末４５１ｇを適当量の着火剤とともに図１に示す反
応容器内に入れ、着火剤に点火してテルミット反応させ
た。反応終了後、冷却し、生成した合金を取り出した。
得られた合金の化学分析値を表１に示す。また、この合
金の粉末Ｘ線回折パターンの結果より、その主成分がＶ
2Ｓｎ3であることが判明した。Example 2 A V-Sn alloy was produced by a thermite reaction. First,
936 g of V 2 O 5 as raw materials, 1638 g of granular Sn and A
451 g of the powder was placed in the reaction vessel shown in FIG. 1 together with an appropriate amount of the igniting agent, and the igniting agent was ignited to cause a thermite reaction. After the completion of the reaction, the resultant was cooled and the produced alloy was taken out.
Table 1 shows the chemical analysis values of the obtained alloy. Also, from the result of the powder X-ray diffraction pattern of this alloy, the main component was V
It was found to be 2 Sn 3 .
【００４１】次いで、この合金を用いて実施例１の
（２）と同様にして電極評価用試験セルを作製した。さ
らに、このセルを用い実施例１の（３）と同様にして電
池試験を行った。その結果を表２に示す。Next, a test cell for electrode evaluation was prepared using this alloy in the same manner as in (2) of Example 1. Further, a battery test was performed using this cell in the same manner as in (3) of Example 1. Table 2 shows the results.
【００４２】[0042]
【表２】 [Table 2]
【００４３】実施例３ 実施例２で得られたＶ−Ｓｎ合金をさらにアルゴンガス
０．７ＭＰａの雰囲気下において、昇温速度２．５℃／
分で室温から７５０℃まで昇温した後、７５０℃で１０
時間保持することによって焼成した。Example 3 The V-Sn alloy obtained in Example 2 was further heated at a rate of 2.5 ° C./2.5° C. in an atmosphere of 0.7 MPa of argon gas.
After raising the temperature from room temperature to 750 ° C. in
It was fired by holding for a time.
【００４４】焼成された合金を用いて実施例１の（２）
と同様にして電極評価用試験セルを作製した。さらに、
このセルを用い実施例１の（３）と同様にして電池試験
を行った。その結果を表２に示す。Using the fired alloy in Example 1 (2)
In the same manner as in the above, a test cell for electrode evaluation was produced. further,
Using this cell, a battery test was performed in the same manner as in Example 1, (3). Table 2 shows the results.
【００４５】比較例１ Ｖ−Ｓｎ合金粉末８０重量部の代わりにＳｎ粉末８０重
量部を用いたほかは、実施例１の（２）と同様にして電
極評価用試験セルを作製した。さらに、このセルを用い
実施例１の（３）と同様にして電池試験を行った。その
結果を表３に示す。また、サイクル−放電容量カーブを
図３に示す。Comparative Example 1 A test cell for electrode evaluation was prepared in the same manner as in (2) of Example 1, except that 80 parts by weight of Sn powder was used instead of 80 parts by weight of V-Sn alloy powder. Further, a battery test was performed using this cell in the same manner as in (3) of Example 1. Table 3 shows the results. FIG. 3 shows a cycle-discharge capacity curve.
【００４６】[0046]
【表３】 [Table 3]
【００４７】比較例２ 粒径１５０μｍ以下の金属バナジウム２．８６２ｇと粒
径２０μｍ以下の金属スズ粉末１０ｇとをステンレス鋼
製ボール１９０ｇとともにステンレス鋼製ポットに入
れ、これを遊星ボールミルにて７５Ｇの重力加速度にお
いて１０時間粉砕を行った。Comparative Example 2 2.862 g of metal vanadium having a particle size of 150 μm or less and 10 g of metal tin powder having a particle size of 20 μm or less were placed in a stainless steel pot together with 190 g of stainless steel balls, and this was placed in a planetary ball mill at a gravity of 75 G. Grinding was performed at an acceleration for 10 hours.
【００４８】得られた混合粉末を用いて実施例１の
（２）と同様にして電極評価用試験セルを作製した。さ
らに、このセルを用い実施例１の（３）と同様にして電
池試験を行った。その結果を表３に示す。Using the obtained mixed powder, a test cell for electrode evaluation was prepared in the same manner as in (2) of Example 1. Further, a battery test was performed using this cell in the same manner as in (3) of Example 1. Table 3 shows the results.
【００４９】以上の結果より、本発明の電極材料では、
３０サイクル後でも比較的高い放電容量を維持できるこ
とがわかる。また、実施例の中で最も容量の低い実施例
２の体積容量（３０サイクル後）は１４７４Ａｈ／リッ
トルであることから、本発明品は最大容量８３７Ａｈ／
リットルである炭素系材料負極よりも優れていることが
わかる。From the above results, in the electrode material of the present invention,
It can be seen that a relatively high discharge capacity can be maintained even after 30 cycles. Further, since the volume capacity (after 30 cycles) of Example 2, which has the lowest capacity among the examples, is 1474 Ah / liter, the product of the present invention has a maximum capacity of 837 Ah / liter.
It turns out that it is superior to the carbon-based material negative electrode which is liter.
【図１】実施例で用いたテルミット反応の反応方法の概
要を示す図（断面図）である。FIG. 1 is a diagram (cross-sectional view) showing an outline of a reaction method of a thermite reaction used in Examples.
【図２】実施例１〜３の電池試験におけるサイクル−放
電容量カーブを示す図である。FIG. 2 is a diagram showing a cycle-discharge capacity curve in the battery tests of Examples 1 to 3.
【図３】比較例１〜２の電池試験におけるサイクル−放
電容量カーブを示す図である。FIG. 3 is a diagram showing a cycle-discharge capacity curve in battery tests of Comparative Examples 1 and 2.
１…アルミナ耐火物製反応容器 ２…原料 ３…着火剤 1. Reactor container made of alumina refractory 2. Raw material 3. Ignition agent
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水谷 肇 兵庫県赤穂市中広字東沖1603番１号 太陽 鉱工株式会社内 (72)発明者 境 哲男 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 (72)発明者 夏 永姚 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 (72)発明者 藤枝 卓也 大阪府池田市緑丘１丁目８番31号 工業技 術院大阪工業技術研究所内 Ｆターム(参考） 5H029 AJ03 AJ05 AK03 AK05 AL12 AM03 AM05 AM07 CJ01 CJ02 CJ03 CJ06 CJ28 HJ01 HJ02 HJ14 5H050 AA07 AA08 BA17 CA07 CA11 CB11 GA01 GA02 GA03 GA08 GA27 HA01 HA02 HA14 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hajime Mizutani 1603-1 No.1, Higashi-oki, Nakahirohiro, Ako-shi, Hyogo Taiyo Mining Co., Ltd. No. 72, Industrial Technology Institute, Osaka Industrial Technology Research Institute (72) Inventor Natsu Yongya, 8-3-131 Midorioka, Ikeda-shi, Osaka Prefecture, Japan Industrial Technology Institute Osaka Industrial Technology Research Institute (72) Inventor, Takuya Fujieda Midorioka, Ikeda-shi, Osaka Prefecture 1-8-31 F Term in Osaka Institute of Industrial Technology, Industrial Technology Institute (Reference) HA02 HA14
Claims (8)
用負極合金材料。A negative electrode alloy material for a lithium secondary battery using a V-Sn alloy.
く。）Ｖ1-xＳｎaＭx（但し、ＭはＡｌ、Ｆｅ、Ｍｎ、
Ｃｕ、Ｃｏ、Ｃｒ、Ｎｉ及びＣの少なくとも１種、０≦
ｘ≦０．５、１≦ａ≦２を示す。）を有する請求項１記
載のリチウム二次電池用負極合金材料。2. A V-Sn based alloy comprising an alloy composition (excluding oxygen) V 1-x Sn a M x (where M is Al, Fe, Mn,
At least one of Cu, Co, Cr, Ni and C, 0 ≦
x ≦ 0.5 and 1 ≦ a ≦ 2. The negative electrode alloy material for a lithium secondary battery according to claim 1, comprising:
である請求項１又は２に記載のリチウム二次電池用負極
合金材料。3. The negative electrode alloy material for a lithium secondary battery according to claim 1, wherein the oxygen content is 0.1% by weight or more in the alloy material.
後、得られた成形体を不活性ガス雰囲気下６００〜９０
０℃で焼成することを特徴とするリチウム二次電池用負
極合金材料の製造方法。4. After pressure-forming a raw material powder containing V and Sn, the obtained compact is subjected to 600 to 90 under an inert gas atmosphere.
A method for producing a negative electrode alloy material for a lithium secondary battery, characterized by firing at 0 ° C.
含む原料粉末をテルミット反応させることを特徴とする
リチウム二次電池用負極合金材料の製造方法。5. A method for producing a negative electrode alloy material for a lithium secondary battery, wherein a raw material powder containing vanadium oxide, tin and aluminum is subjected to a thermite reaction.
００℃で熱処理する請求項５記載の製造方法。6. The method according to claim 1, further comprising the steps of:
The method according to claim 5, wherein the heat treatment is performed at 00C.
二次電池用負極合金材料を用いたリチウム二次電池用負
極。7. A negative electrode for a lithium secondary battery using the negative electrode alloy material for a lithium secondary battery according to claim 1.
電池。8. A lithium secondary battery using the negative electrode according to claim 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11102699A (en) * | 1997-09-26 | 1999-04-13 | Asahi Chem Ind Co Ltd | Lithium secondary battery and negative electrode used therefor |
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