JP2007165096A - Positive electrode for lithium secondary battery, and nonaqueous lithium secondary battery using it - Google Patents
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Abstract
Description
本発明は、リチウム二次電池用正極およびそれを用いた非水系リチウム二次電池に関する。 The present invention relates to a positive electrode for a lithium secondary battery and a non-aqueous lithium secondary battery using the same.
従来、非水系リチウム二次電池においては、正極材料として、コバルト酸リチウム、マンガン酸リチウム、およびニッケル酸リチウムが広く用いられている。しかし、これらの正極材料を用いた二次電池の充放電容量は、理論的にも、コバルト酸リチウムで１３７ｍＡｈ／ｇ、マンガン酸リチウムで１４８ｍＡｈ／ｇ、ニッケル酸リチウムで１９３ｍＡｈ／ｇに留まり、２００ｍＡｈ／ｇを超える充放電容量を得ることができなかった。 Conventionally, lithium cobaltate, lithium manganate, and lithium nickelate have been widely used as positive electrode materials in non-aqueous lithium secondary batteries. However, the charge / discharge capacity of the secondary battery using these positive electrode materials theoretically remains 137 mAh / g for lithium cobaltate, 148 mAh / g for lithium manganate, 193 mAh / g for lithium nickelate, and 200 mAh. The charge / discharge capacity exceeding / g could not be obtained.
これに対し、五酸化バナジウム（Ｖ２Ｏ５）系正極材料は、理論的には高い充放電容量が得られるものであり、そのリチウム二次電池への応用研究が盛んに行われている。 On the other hand, a vanadium pentoxide (V 2 O 5 ) -based positive electrode material can theoretically obtain a high charge / discharge capacity, and its application research to lithium secondary batteries has been actively conducted.
例えば、非特許文献１および非特許文献２には、層状化合物である五酸化バナジウムの層間にポリ（３，４−エチレンジオキシチオフェン）（ＰＥＤＯＴ）を挿入した有機・無機ハイブリッド正極が記載されている。また、非特許文献３には、高エネルギー密度を有する２，５−ジメルカプト−１，３，４−チアジアゾール（ＤＭｃＴ）を五酸化バナジウムの層間に挿入した正極材料が記載されている。
しかし、上記非特許文献１〜３に開示された正極のいずれも、非水系リチウム二次電池に組んだ際に、負極にリチウム含有負極材料を用いることが必要である。また、これらのリチウム二次電池は、初期の充放電容量が低い。 However, when any of the positive electrodes disclosed in Non-Patent Documents 1 to 3 is assembled in a non-aqueous lithium secondary battery, it is necessary to use a lithium-containing negative electrode material for the negative electrode. Moreover, these lithium secondary batteries have a low initial charge / discharge capacity.
従って、本発明は、非水系リチウム二次電池に組んだ際に、負極にリチウムを含む負極材料を用いずとも、比較的高い充放電容量を初期段階から安定に示し得る非水系リチウム二次電池用の金属酸化物系正極およびそれを用いた非水系リチウム二次電池を提供することを目的とする。 Therefore, the present invention provides a non-aqueous lithium secondary battery that can stably exhibit a relatively high charge / discharge capacity from the initial stage without using a negative electrode material containing lithium as a negative electrode when assembled in a non-aqueous lithium secondary battery. An object of the present invention is to provide a metal oxide positive electrode and a non-aqueous lithium secondary battery using the same.
本発明の１つの側面によれば、導電性基体と、この導電性基体の表面に形成された正極材料の層を備え、前記正極材料は、活物質として周期律表第Ｖ族元素および第ＶＩ族元素から選ばれる少なくとも１種の元素の酸化物を含み、前記酸化物は結晶構造を有しているとともに、リチウムがドープされていることを特徴とするリチウム二次電池用正極が提供される。 According to one aspect of the present invention, a conductive substrate and a layer of a positive electrode material formed on the surface of the conductive substrate are provided, and the positive electrode material includes a group V element and a group VI element of the periodic table as an active material. There is provided a positive electrode for a lithium secondary battery comprising an oxide of at least one element selected from group elements, wherein the oxide has a crystal structure and is doped with lithium .
また、本発明の別の側面によれば、正極と、負極と、前記正極と負極の間に配置された電解質層を備え、前記正極が、本発明のリチウム電池用正極からなることを特徴とする二次電池が提供される。 According to another aspect of the present invention, a positive electrode, a negative electrode, and an electrolyte layer disposed between the positive electrode and the negative electrode are provided, and the positive electrode includes the positive electrode for a lithium battery according to the present invention. A secondary battery is provided.
本発明によれば、非水系リチウム二次電池に組んだ際に、負極にリチウムを含む負極材料を用いずとも、比較的高い充放電容量を初期段階から安定に示し得るリチウム二次電池用の金属酸化物系正極およびそれを用いた非水系リチウム二次電池を提供することができる。 According to the present invention, when assembled in a non-aqueous lithium secondary battery, the lithium secondary battery can stably exhibit a relatively high charge / discharge capacity from the initial stage without using a negative electrode material containing lithium for the negative electrode. A metal oxide positive electrode and a non-aqueous lithium secondary battery using the same can be provided.
以下、本発明をより詳しく説明する。 Hereinafter, the present invention will be described in more detail.
本発明のリチウム電池用正極は、導電性基体と、この導電性基体の表面に形成された正極材料の層を備える。正極材料は活物質として、周期律表第Ｖ族元素および第ＶＩ族元素から選ばれる少なくとも１種の元素の酸化物を含む。本発明ではこれら元素のうち、金属元素を用いる。この金属元素の酸化物を以下、金属酸化物という。金属酸化物は、酸化バナジウムおよび酸化ニオブであることが好ましく、五酸化バナジウムであることが特に好ましい。金属酸化物は、結晶構造を有している。このことは、本発明のリチウム電池用正極の活物質に含まれる金属酸化物が、Ｘ線回折パターンにおいて、回折角２θで、結晶構造に特有の１８〜２０°の範囲にピークを有することを意味する。 The positive electrode for a lithium battery of the present invention includes a conductive substrate and a layer of a positive electrode material formed on the surface of the conductive substrate. The positive electrode material contains an oxide of at least one element selected from Group V elements and Group VI elements of the periodic table as an active material. In the present invention, among these elements, metal elements are used. Hereinafter, the oxide of the metal element is referred to as a metal oxide. The metal oxide is preferably vanadium oxide and niobium oxide, and particularly preferably vanadium pentoxide. The metal oxide has a crystal structure. This means that the metal oxide contained in the active material of the positive electrode for a lithium battery of the present invention has a peak in the range of 18 to 20 ° peculiar to the crystal structure at a diffraction angle of 2θ in the X-ray diffraction pattern. means.
本発明において、上記結晶性金属酸化物にはリチウムがドープされている。リチウムは、例えば、バナジウム金属に対して当モル量以下の量でドープされていることが好ましい。リチウムのドープ量がバナジウム金属に対して当モル量を超えると、五酸化バナジウムの結晶系が変化する傾向を示す。 In the present invention, the crystalline metal oxide is doped with lithium. Lithium is preferably doped, for example, in an amount equal to or less than that of vanadium metal. When the doping amount of lithium exceeds an equimolar amount with respect to the vanadium metal, the crystal system of vanadium pentoxide tends to change.
本発明によれば、上記活物質は、結晶構造を有する（従って層状構造を有する）金属酸化物を、非水系溶媒中、リチウム源の存在下で加熱するという簡単な方法により得ることができる。より具体的には、例えば、金属酸化物とリチウム源を非水系溶媒に入れ、還流下に、例えば１２時間以上加熱することができる。 According to the present invention, the active material can be obtained by a simple method of heating a metal oxide having a crystal structure (and thus a layered structure) in a non-aqueous solvent in the presence of a lithium source. More specifically, for example, a metal oxide and a lithium source can be placed in a non-aqueous solvent and heated under reflux, for example, for 12 hours or more.
上記非水系溶媒は、結晶性の金属酸化物を溶かさずに、一方でリチウム源を溶かすものである。例えば、アルコールが好ましく、特にエタノールが好ましい。 The non-aqueous solvent dissolves the lithium source while not dissolving the crystalline metal oxide. For example, alcohol is preferable, and ethanol is particularly preferable.
リチウム源は酸素と反応して水を副生しない無機リチウム化合物であり、リチウムカルコゲニドであることが好ましい。リチウムカルコゲニドの好ましい例を挙げると、硫化リチウム、セレン化リチウム、テルル化リチウムであり、硫化リチウムが特に好ましい。 The lithium source is an inorganic lithium compound that does not by-produce water by reacting with oxygen, and is preferably lithium chalcogenide. Preferable examples of lithium chalcogenides are lithium sulfide, lithium selenide, and lithium telluride, and lithium sulfide is particularly preferable.
本発明の方法により金属酸化物とリチウムカルコゲニドを加熱すると、金属酸化物の酸化力によりカルコゲンが酸化析出し、遊離したリチウムイオンが金属酸化物に取り込まれ、金属酸化物へのリチウムドープが達成される。リチウム源として用いるリチウムカルコゲニドは、水に溶けてアルカリ性を呈するものであり、他方、金属酸化物はアルカリに溶けるものである。従って、反応に用いる溶媒（反応媒体）が水系であると、金属酸化物は当該反応系中で溶けて、その結晶構造を維持することができない。また、用いるリチウム源が水酸化リチウムのように、酸素と反応して水を生成するものであれば、やはり金属酸化物は当該反応系中で溶けてしまう。この反応で析出したカルコゲンは、得られる活物質中に残存する。カルコゲンは活物質中に０．４重量％以上、好ましくは０．４〜５重量％の割合で含まれ得る。 When metal oxide and lithium chalcogenide are heated by the method of the present invention, chalcogen is oxidized and precipitated by the oxidizing power of the metal oxide, liberated lithium ions are taken into the metal oxide, and lithium doping to the metal oxide is achieved. The Lithium chalcogenide used as a lithium source is soluble in water and exhibits alkalinity, while metal oxide is soluble in alkali. Therefore, when the solvent (reaction medium) used in the reaction is aqueous, the metal oxide is dissolved in the reaction system and the crystal structure cannot be maintained. In addition, if the lithium source to be used is one that reacts with oxygen to produce water, such as lithium hydroxide, the metal oxide is dissolved in the reaction system. The chalcogen precipitated by this reaction remains in the obtained active material. Chalcogen can be contained in the active material in an amount of 0.4% by weight or more, preferably 0.4 to 5% by weight.
本発明の方法は、金属酸化物とリチウム源を還流下で加熱するという簡便な方法であるために、活物質の製造に特殊な設備を必要とすることなく、従来通常用いられる設備を用いることができる。 Since the method of the present invention is a simple method in which the metal oxide and the lithium source are heated under reflux, conventionally used equipment is used without requiring special equipment for the production of the active material. Can do.
本発明の正極材料は、上記活物質に加えて、導電性粒子を含むことが好ましい。 The positive electrode material of the present invention preferably contains conductive particles in addition to the active material.
導電性粒子は、本発明の非水系リチウム二次電池用正極材料の導電性を向上させる。導電性粒子の例を挙げると、導電性カーボン（ケッチェンブラック等の導電性カーボン等）、銅、鉄、銀、ニッケル、パラジウム、金、白金、インジウム、タングステン等の金属、酸化インジウム、酸化スズ等の導電性金属酸化物等である。これら導電性粒子は、上記金属酸化物の重量の１〜３０％の割合で含まれることが好ましい。 The conductive particles improve the conductivity of the positive electrode material for a non-aqueous lithium secondary battery of the present invention. Examples of conductive particles include conductive carbon (conductive carbon such as ketjen black), copper, iron, silver, nickel, palladium, gold, platinum, indium, tungsten and other metals, indium oxide, tin oxide Conductive metal oxides and the like. These conductive particles are preferably contained in a proportion of 1 to 30% of the weight of the metal oxide.
本発明において、正極材料の層を支持する基体（集電体）は、少なくとも本発明の正極材料と接する表面において導電性を示す導電性基体である。この基体は、金属、導電性金属酸化物、導電性カーボン等の導電性材料で形成することができるが、銅、金、アルミニウムもしくはそれらの合金または導電性カーボンで形成することが好ましい。あるいは、基体は非導電性材料で形成された基体本体をこれら導電性材料で被覆することによっても形成することができる。 In the present invention, the substrate (current collector) that supports the layer of the positive electrode material is a conductive substrate that exhibits conductivity at least on the surface in contact with the positive electrode material of the present invention. The substrate can be formed of a conductive material such as metal, conductive metal oxide, or conductive carbon, but is preferably formed of copper, gold, aluminum, an alloy thereof, or conductive carbon. Alternatively, the substrate can also be formed by coating a substrate body formed of a nonconductive material with these conductive materials.
本発明において、正極材料の層は、１０〜１００μｍの厚さを有することが好ましい。 In the present invention, the positive electrode material layer preferably has a thickness of 10 to 100 μm.
本発明の正極は、上記正極材料にポリフッ化ビニリデン（ＰＶＤＦ）等のバインダを加え、これを適当な溶媒によりスラリーとし、このスラリーを導電性基体上に塗布、乾燥することによって得ることができる。 The positive electrode of the present invention can be obtained by adding a binder such as polyvinylidene fluoride (PVDF) to the positive electrode material, making this a slurry with an appropriate solvent, and applying and drying this slurry on a conductive substrate.
本発明の非水系リチウム二次電池は、上記正極と、負極と、前記正極と負極の間に配置された電解質層を備える。 The non-aqueous lithium secondary battery of this invention is equipped with the said positive electrode, a negative electrode, and the electrolyte layer arrange | positioned between the said positive electrode and negative electrode.
本発明の非水系リチウム二次電池において、負極は、通常使用されているリチウム系材料で形成することができる。このようなリチウム系材料としては、金属リチウムやリチウム合金（例えばＬｉ−Ａｌ合金）のようなリチウム系金属材料、スズやケイ素のような金属とリチウムとの金属間化合物材料、窒化リチウムのようなリチウム化合物、またはリチウムインターカレーション炭素材料を例示することができる。しかしながら、本発明のリチウム二次電池用正極材料は、予め（電池としての使用前から）リチウムが層状の金属酸化物にドープされているために、負極にリチウムを含む負極材料を用いずとも、初期段階から安定した充放電容量を示すことができる。そのような非リチウム系負極材料としては、カーボンが好適である。非リチウム系負極材料を用いると、デントライト状リチウムの析出を有効に回避することができる。 In the nonaqueous lithium secondary battery of the present invention, the negative electrode can be formed of a commonly used lithium material. Examples of such lithium-based materials include lithium-based metal materials such as metallic lithium and lithium alloys (for example, Li-Al alloys), intermetallic compound materials of metals and lithium such as tin and silicon, and lithium nitride. A lithium compound or a lithium intercalation carbon material can be exemplified. However, the positive electrode material for a lithium secondary battery of the present invention is preliminarily doped with a layered metal oxide (before use as a battery), so even without using a negative electrode material containing lithium in the negative electrode, A stable charge / discharge capacity can be exhibited from the initial stage. Carbon is suitable as such a non-lithium negative electrode material. If a non-lithium negative electrode material is used, precipitation of dentlite-like lithium can be effectively avoided.
電解質としては、ＣＦ３ＳＯ３Ｌｉ、Ｃ４Ｆ９ＳＯ８Ｌｉ、（ＣＦ３ＳＯ２）２ＮＬｉ、（ＣＦ３ＳＯ２）３ＣＬｉ、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＣｌＯ４等のリチウム塩を使用することができる。これら電解質を溶解する溶媒は非水系溶媒である。非水系溶媒には、鎖状カーボネート、環状カーボネート、環状エステル、ニトリル化合物、酸無水物、アミド化合物、ホスフェート化合物、アミン化合物等が含まれる。非水系溶媒の具体例を挙げると、エチレンカーボネート、ジエチルカーボネート（ＤＥＣ）、プロピレンカーボネート、ジメトキシエタン、γ−ブチロラクトン、ｎ−メチルピロリジノン、Ｎ，Ｎ’−ジメチルアセトアミド、アセトニトリル、あるいはプロピレンカーボネートとジメトキシエタンとの混合物、スルホランとテトラヒドロフランとの混合物等である。正極と負極との間に介挿される電解質層としては、上記電解質の非水系溶媒中の溶液であってもよいし、この電解質溶液を含むポリマーゲル（ポリマーゲル電解質）であってもよい。 As an electrolyte, lithium salts such as CF 3 SO 3 Li, C 4 F 9 SO 8 Li, (CF 3 SO 2 ) 2 NLi, (CF 3 SO 2 ) 3 CLi, LiBF 4 , LiPF 6 , LiClO 4 are used. can do. The solvent that dissolves these electrolytes is a non-aqueous solvent. Non-aqueous solvents include chain carbonates, cyclic carbonates, cyclic esters, nitrile compounds, acid anhydrides, amide compounds, phosphate compounds, amine compounds, and the like. Specific examples of the non-aqueous solvent include ethylene carbonate, diethyl carbonate (DEC), propylene carbonate, dimethoxyethane, γ-butyrolactone, n-methylpyrrolidinone, N, N′-dimethylacetamide, acetonitrile, or propylene carbonate and dimethoxyethane. And a mixture of sulfolane and tetrahydrofuran. The electrolyte layer interposed between the positive electrode and the negative electrode may be a solution of the electrolyte in a non-aqueous solvent or a polymer gel (polymer gel electrolyte) containing the electrolyte solution.
以下、本発明を実施例により説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
実施例１〜４
２ｇの五酸化バナジウム（Ｖ２Ｏ５）と、この五酸化バナジウムに対して０．５〜３．６モル当量（表１参照）の硫化リチウム（Ｌｉ２Ｓ）とをエタノール５０ｍｌ中に入れ、還流下に１２時間加熱を行い、緑色〜黒色の沈殿物を得た。この沈殿物をろ過し、１００℃で終夜真空乾燥することにより目的の活物質を得た。この活物質のＬｉおよびＶについてＩＣＰ分析を行い、Ｌｉ／Ｖモル比を算出した。結果を表１に示す。
2 g of vanadium pentoxide (V 2 O 5 ) and 0.5 to 3.6 molar equivalents (see Table 1) of lithium sulfide (Li 2 S) with respect to the vanadium pentoxide were placed in 50 ml of ethanol, Heating was performed for 12 hours under reflux to obtain a green to black precipitate. The precipitate was filtered and vacuum dried at 100 ° C. overnight to obtain the target active material. ICP analysis was performed on Li and V of this active material, and the Li / V molar ratio was calculated. The results are shown in Table 1.
表１からわかるように、仕込みモル比Ｌｉ／Ｖが０．５である場合は仕込みモル比通りにリチウムが五酸化バナジウムにドープされて、ＬｉＶ２Ｏ５が生成していた。仕込みモル比Ｌｉ／Ｖが１以上になると、リチウムは五酸化バナジウムに仕込みモル比通りにドープされなかったが、五酸化バナジウム１モルに対して少なくともリチウムが１原子ドープされていることが確認された。また、得られた活物質の硫黄分析を行った。結果を表１に併記する。全ての活物質に硫黄が０．４重量％以上含まれていることが確認された。 As can be seen from Table 1, when the charged molar ratio Li / V was 0.5, lithium was doped into vanadium pentoxide according to the charged molar ratio, and LiV 2 O 5 was generated. When the charged molar ratio Li / V was 1 or more, lithium was not doped in the vanadium pentoxide according to the charged molar ratio, but it was confirmed that at least one atom of lithium was doped per mole of vanadium pentoxide. It was. The obtained active material was analyzed for sulfur. The results are also shown in Table 1. It was confirmed that all active materials contained 0.4% by weight or more of sulfur.
さらに、得られた活物質のＸ線回折分析も行った。Ｘ線回折パターンを図１に示す。実施例１のＸ線回折パターンを線ａ、実施例２のＸ線回折パターンを線ｂ、実施例３のＸ線回折パターンを線ｃ、実施例４のＸ線回折パターンを線ｄで示す。三角印は、ＬｉＶ２Ｏ５の代表的なピーク位置を示す。図１によれば、実施例１〜４のリチウムドープ五酸化バナジウムのＸ線回折パターンは、全て、回折角２θで、五酸化バナジウムの結晶構造に特有の１８〜２０°の範囲にピークを有するために、全ての五酸化バナジウムが結晶構造を有していることが立証された。とりわけ、線ａおよび線ｂで示されるリチウムドープ五酸化バナジウムは、１８°に高いピークを有する。また、活物質中のＬｉ／Ｖモル比が１．０以上である線ｃおよびｄで示される活物質のＸ線回折パターンによれば、リチウムドープ五酸化バナジウムの結晶系が変化していることがわかった。 Furthermore, X-ray diffraction analysis of the obtained active material was also performed. The X-ray diffraction pattern is shown in FIG. The X-ray diffraction pattern of Example 1 is indicated by line a, the X-ray diffraction pattern of Example 2 by line b, the X-ray diffraction pattern of Example 3 by line c, and the X-ray diffraction pattern of Example 4 by line d. Triangles, shows the typical peak position of LiV 2 O 5. According to FIG. 1, the X-ray diffraction patterns of the lithium-doped vanadium pentoxides of Examples 1 to 4 all have a diffraction angle of 2θ and have a peak in the range of 18 to 20 ° characteristic of the crystal structure of vanadium pentoxide. Therefore, it was proved that all vanadium pentoxide has a crystal structure. In particular, lithium-doped vanadium pentoxide represented by lines a and b has a high peak at 18 °. In addition, according to the X-ray diffraction pattern of the active material indicated by lines c and d in which the Li / V molar ratio in the active material is 1.0 or more, the crystal system of lithium-doped vanadium pentoxide is changed. I understood.
比較例１
エタノールの代わりに水を用いたこと以外は実施例１〜４と同様の操作を行った。しかし、五酸化バナジウムが水に溶解してしまったため、結晶性の五酸化バナジウムを含む本発明の活物質を得ることができなかった。
Comparative Example 1
The same operation as in Examples 1 to 4 was performed except that water was used instead of ethanol. However, since vanadium pentoxide was dissolved in water, the active material of the present invention containing crystalline vanadium pentoxide could not be obtained.
比較例２
リチウム源として、硫化リチウムの代わりに水酸化リチウムを用いたこと以外は実施例１〜４と同様の操作を行った。本比較例でも五酸化バナジウムが溶媒中に溶解してしまったために、結晶性の五酸化バナジウムを含む本発明の活物質を得ることができなかった。
Comparative Example 2
The same operation as in Examples 1 to 4 was performed except that lithium hydroxide was used instead of lithium sulfide as the lithium source. Also in this comparative example, since the vanadium pentoxide was dissolved in the solvent, the active material of the present invention containing crystalline vanadium pentoxide could not be obtained.
実施例５〜８、比較例３
実施例１〜４で得られた活物質に、活物質の２５重量％に相当する量の導電性カーボンブラックおよび５重量％に相当する量のポリフッ化ビニリデン（ＰＶＤＦ）（バインダ）とを混合し、溶媒としてＮ−メチルピロリドン（ＮＭＰ）を用いてスラリーとした後、アルミニウム箔上にドクターブレード法によってコーティングし、乾燥して正極を作製した。この正極を用い、電解質液として、エチレンカーボネート（ＥＣ）とジエチルカーボネート（ＤＥＣ）との体積比１：３の混合溶媒中に１Ｍ濃度でＬｉＢＦ４を含有する溶液を用い、負極としてカーボンを用いて非水系リチウム二次電池を組み立て、０．１Ｃ放電にて充放電評価を行った。なお、活物質として、リチウムがドープされていない五酸化バナジウムを用いた以外は同様に作製した非水系リチウム二次電池（比較例３）についても充放電評価を行った。各電池について、活物質１グラム当たりの初期充電容量を表２に示す。ここで、初期充電容量は、０．１Ｃの電流量を用いて、開放電位から４．２Ｖまで変化させた際の容量である。
The active material obtained in Examples 1 to 4 was mixed with conductive carbon black in an amount corresponding to 25% by weight of the active material and polyvinylidene fluoride (PVDF) (binder) in an amount corresponding to 5% by weight. A slurry was prepared using N-methylpyrrolidone (NMP) as a solvent, and then coated on an aluminum foil by a doctor blade method and dried to prepare a positive electrode. Using this positive electrode, as the electrolyte solution, using a solution containing LiBF 4 at a concentration of 1M in a mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1: 3, and using carbon as the negative electrode A non-aqueous lithium secondary battery was assembled, and charge / discharge evaluation was performed at 0.1 C discharge. In addition, charge / discharge evaluation was performed also about the non-aqueous lithium secondary battery (comparative example 3) produced similarly except having used vanadium pentoxide which is not doped with lithium as an active material. Table 2 shows the initial charge capacity per gram of active material for each battery. Here, the initial charge capacity is a capacity when changing from an open potential to 4.2 V using a current amount of 0.1 C.
本発明の非水系リチウム二次電池は、比較例と比べて、初期充電容量が有意に増加した。特に、活物質中のＬｉ／Ｖモル比が１．０以下である場合に高い初期充電容量が得られた。中でもＬｉ／Ｖモル比が１．０である実施例７において２００ｍＡｈ／ｇを超える初期充電容量が得られた。 In the nonaqueous lithium secondary battery of the present invention, the initial charge capacity was significantly increased as compared with the comparative example. In particular, a high initial charge capacity was obtained when the Li / V molar ratio in the active material was 1.0 or less. In particular, in Example 7 where the Li / V molar ratio was 1.0, an initial charge capacity exceeding 200 mAh / g was obtained.
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| JPH04269467A (en) * | 1991-02-25 | 1992-09-25 | Seiko Electronic Components Ltd | Nonaqueous electrolyte secondary battery |
| JPH04363874A (en) * | 1989-12-11 | 1992-12-16 | Saft (Soc Accumulateurs Fixes Traction) Sa | Rechargeable electrochemical battery including cathode of vanadium oxide base |
| JPH06295743A (en) * | 1993-04-02 | 1994-10-21 | Shin Kobe Electric Mach Co Ltd | Lithium solid electrolyte battery |
| JPH10302769A (en) * | 1997-04-24 | 1998-11-13 | Ricoh Co Ltd | Secondary battery electrode and secondary battery using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH04363874A (en) * | 1989-12-11 | 1992-12-16 | Saft (Soc Accumulateurs Fixes Traction) Sa | Rechargeable electrochemical battery including cathode of vanadium oxide base |
| JPH04269467A (en) * | 1991-02-25 | 1992-09-25 | Seiko Electronic Components Ltd | Nonaqueous electrolyte secondary battery |
| JPH06295743A (en) * | 1993-04-02 | 1994-10-21 | Shin Kobe Electric Mach Co Ltd | Lithium solid electrolyte battery |
| JPH10302769A (en) * | 1997-04-24 | 1998-11-13 | Ricoh Co Ltd | Secondary battery electrode and secondary battery using the same |
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