JP2001283852A - Positive active material for nonaqueous electrolyte secondary battery - Google Patents
Positive active material for nonaqueous electrolyte secondary batteryInfo
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- JP2001283852A JP2001283852A JP2000101063A JP2000101063A JP2001283852A JP 2001283852 A JP2001283852 A JP 2001283852A JP 2000101063 A JP2000101063 A JP 2000101063A JP 2000101063 A JP2000101063 A JP 2000101063A JP 2001283852 A JP2001283852 A JP 2001283852A
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- positive electrode
- active material
- present
- nafeo
- secondary battery
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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
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、非水電解質二次電
池用正極活物質に関する。The present invention relates to a positive electrode active material for a non-aqueous electrolyte secondary battery.
【０００２】[0002]
【従来の技術】近年、携帯用電話、ビデオカメラ等の小
型電源および電気自動車、電力平準化用の大型電源とし
て、高エネルギー密度、高出力密度を有する二次電池、
特にリチウム二次電池が大きな注目を受けている。この
リチウム二次電池に用いられる材料として、正極にはリ
チウム遷移金属酸化物が、負極には黒鉛、低温焼成炭
素、酸化物、リチウム合金およびリチウム金属が提案さ
れている。2. Description of the Related Art In recent years, secondary batteries having a high energy density and a high output density have been used as small power sources such as portable telephones and video cameras and large power sources for electric vehicles and power leveling.
In particular, lithium secondary batteries have received great attention. As a material used for this lithium secondary battery, a lithium transition metal oxide has been proposed for the positive electrode, and graphite, low-temperature fired carbon, oxide, lithium alloy and lithium metal have been proposed for the negative electrode.
【０００３】現在、正極活物質として使われているコバ
ルト酸リチウム（ＬｉＣｏＯ2）は高価であり、将来予
測されるリチウム二次電池の大量消費に対応するために
は、より安価で埋蔵量が豊富な正極活物質の開発が重要
である。現在、マンガンやニッケル、鉄を含む酸化物が
リチウム二次電池用正極活物質として精力的に研究され
ている。中でも鉄は最も安価で環境負荷の小さい材料で
あるため、鉄を主体として含む酸化物は次世代リチウム
二次電池用正極活物質として大変魅力的である。[0003] Lithium cobalt oxide (LiCoO 2 ) currently used as a positive electrode active material is expensive, and in order to cope with the mass consumption of lithium secondary batteries expected in the future, it is cheaper and has abundant reserves. It is important to develop a positive electrode active material. At present, oxides containing manganese, nickel, and iron are being vigorously studied as positive electrode active materials for lithium secondary batteries. Among them, iron is the cheapest and has a low environmental load, and thus an oxide mainly containing iron is very attractive as a positive electrode active material for a next-generation lithium secondary battery.
【０００４】鉄を主体として含むリチウム二次電池用正
極活物質として、これまで種々のリチウム含有鉄酸化物
が提案されてきた。例えば、トンネル構造または層状ジ
グザグ構造を有するリチウム鉄複合酸化物（ＬｉＦｅＯ
2）（例えばＪ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，
１４３，２４３５（１９９６））、オリビン型ＬｉＦｅ
ＰＯ4（Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，１４
４，１６０９（１９９７））、さらに、六方晶層状岩塩
型構造を有するＬｉＦｅＯ2（例えば特開平１０―６７
５１９）等が挙げられる。Various lithium-containing iron oxides have been proposed as positive electrode active materials for lithium secondary batteries containing iron as a main component. For example, a lithium iron composite oxide having a tunnel structure or a layered zigzag structure (LiFeO
2 ) (for example, J. Electrochem. Soc.,
143 , 2435 (1996)), olivine type LiFe
PO 4 (J. Electrochem. Soc., 14
4 , 1609 (1997)), and LiFeO 2 having a hexagonal layered rock salt type structure (for example, see JP-A-10-67).
519).
【０００５】[0005]
【発明が解決しようとする課題】上記トンネル構造また
は層状ジグザグ構造を有するＬｉＦｅＯ2は、初期にＬ
ｉＣｏＯ2を凌ぐ高い充放電容量（１５０ｍＡｈ／ｇ以
上）を有するが、１０サイクルの寿命試験で放電容量が
初期容量の８０％以下に低下し、充放電サイクル特性が
低い問題点がある．オリビン型ＬｉＦｅＰＯ4の放電容
量は１４０ｍＡｈ／ｇ以下であり、電池活物質として不
十分である。一方、六方晶層状岩塩型構造を有するＬｉ
ＦｅＯ2は、Ｊ．Ｅｌｅｃｔｒｏｃｈｅｍ．Ｓｏｃ．，
１４４，Ｌ１７７（１９９７）で示されているように、
充放電容量が極めて低く（１０ｍＡｈ／ｇ以下）、さら
に充放電サイクル特性が低い課題がある。The LiFeO 2 having the tunnel structure or the layered zigzag structure is initially L
Although it has a higher charge / discharge capacity (150 mAh / g or more) than iCoO 2 , the discharge capacity is reduced to 80% or less of the initial capacity in a 10-cycle life test, and the charge / discharge cycle characteristics are low. The discharge capacity of the olivine type LiFePO 4 is 140 mAh / g or less, which is insufficient as a battery active material. On the other hand, Li having a hexagonal layered rock salt type structure
FeO 2 is described in J. Electrochem. Soc. ,
144 , L177 (1997),
There is a problem that the charge / discharge capacity is extremely low (10 mAh / g or less) and the charge / discharge cycle characteristics are low.
【０００６】従って、これまで１５０ｍＡｈ／ｇ以上の
高い放電容量を有し、なおかつ充放電サイクル特性に優
れたリチウム鉄複合酸化物は得られていない。Therefore, a lithium iron composite oxide having a high discharge capacity of 150 mAh / g or more and excellent in charge / discharge cycle characteristics has not been obtained.
【０００７】一方、アルカリ電池正極活物質であるＭｎ
Ｏ2の利用率向上に、Ｂｉ2Ｏ3およびＰｂＯ等の金属酸
化物を混合することが有効であることが知られている
（Ｈ．Ｓ．Ｗｒｏｂｌｏｗａ ａｎｄ Ｎ． Ｇｕｐｔ
ａ，Ｊ．Ｅｌｅｃｔｒｏａｎａｌ． Ｃｈｅｍ．，２３
８，９３（１９８７））。金属酸化物の作用として、近
年、触媒性が指摘されている（ＤｅＹａｎＧ Ｑｕ，
Ｊ．Ａｐｐｌ．Ｅｌｅｃｔｒｏｃｈｅｍ．，２９，５１
１（１９９９））。マンガンにはＢｉ2Ｏ3およびＰｂＯ
との混合が有効であるのに対し、他の遷移金属、例えば
鉄にいかなる金属酸化物が良好な作用をもたらすかは明
らかになっていない。On the other hand, Mn, which is an alkaline battery positive electrode active material,
It is known that it is effective to mix metal oxides such as Bi 2 O 3 and PbO to improve the utilization of O 2 (HS Wroblowa and N. Gupt).
a, J. et al. Electroanal. Chem. , 23
8 , 93 (1987)). In recent years, catalytic properties have been pointed out as a function of metal oxides (DeYanG Qu,
J. Appl. Electrochem. , 29 , 51
1 (1999)). Manganese includes Bi 2 O 3 and PbO
It is not clear which metal oxides have a good effect on other transition metals, for example iron, while the mixing with is effective.
【０００８】本発明はかかる金属酸化物の添加効果に注
目したものであり、その目的とするところは、高い充放
電容量を持ち、さらに良好な充放電サイクル特性を持つ
非水電解質二次用鉄含有正極活物質を提供することにあ
る。The present invention focuses on the effect of the addition of such a metal oxide. The object of the present invention is to provide a non-aqueous electrolyte secondary iron having a high charge / discharge capacity and good charge / discharge cycle characteristics. It is to provide a contained positive electrode active material.
【０００９】[0009]
【課題を解決するための手段】本発明の非水電解質二次
電池用正極活物質は、六方晶層状岩塩型構造を有するア
ルカリ金属含有鉄酸化物とバナジウム酸化物とが混合さ
れ、前記アルカリ金属含有鉄酸化物の表面の少なくとも
一部に前記バナジウム酸化物が担持されていることを特
徴とする。The positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention is obtained by mixing an alkali metal-containing iron oxide having a hexagonal layered rock salt type structure and vanadium oxide, The vanadium oxide is supported on at least a part of the surface of the contained iron oxide.
【００１０】さらに、本発明の非水電解質二次電池用正
極活物質では、前記アルカリ金属含有鉄酸化物がα−Ｎ
ａＦｅＯ2であることを特徴とする。Further, in the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention, the alkali metal-containing iron oxide is α-N
aFeO 2 .
【００１１】[0011]
【発明の実施の形態】本発明では、六方晶層状岩塩型構
造を有するアルカリ金属含有鉄酸化物の表面の少なくと
も一部にバナジウム酸化物を担持させることにより、ア
ルカリ金属含有鉄酸化物の非水電解質二次電池用正極活
物質としての利用率を大幅に増加させ、サイクル特性を
良好にすることができる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, vanadium oxide is supported on at least a part of the surface of an alkali metal-containing iron oxide having a hexagonal layered rock-salt structure, so that non-aqueous The utilization factor as a positive electrode active material for an electrolyte secondary battery can be greatly increased, and the cycle characteristics can be improved.
【００１２】本発明のアルカリ金属含有鉄酸化物には、
ＬｉＦｅＯ2、a−ＮａＦｅＯ2を用いることができ、Ｎ
ａを一部Ｌｉで置換したＬｉ1-xＮａxＦｅＯ2（０＜ｘ
＜１）、および鉄の一部を他の遷移金属元素で置換した
ＬｉＭ1- yＦｅyＯ2（Ｍ＝Ｃｏ，Ｍｎ，Ｎｉ）（０＜ｙ
＜１）も用いることができる。ただし、いずれも六方晶
層状岩塩型構造を有することを特徴とする。[0012] The alkali metal-containing iron oxide of the present invention includes:
LiFeO 2 or a-NaFeO 2 can be used.
a 1-x Na x FeO 2 (0 <x
<1) and LiM 1- y Fe y O 2 (M = Co, Mn, Ni) (0 <y
<1) can also be used. However, each of them is characterized by having a hexagonal layered rock salt type structure.
【００１３】本発明で用いられるバナジウム酸化物に
は、Ｖ2Ｏ3、Ｖ2Ｏ4、Ｖ2Ｏ5を用いることが可能であ
る。As the vanadium oxide used in the present invention, V 2 O 3 , V 2 O 4 and V 2 O 5 can be used.
【００１４】[0014]
【実施例】以下に本発明なる非水電解質二次電池用正極
活物質の実施例を説明する。しかし、本発明は以下の実
施例に限定されるものではない。EXAMPLES Examples of the positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention will be described below. However, the present invention is not limited to the following examples.
【００１５】［実施例１］酸化第二鉄（a−Ｆｅ2Ｏ3）
および過酸化ナトリウム（Ｎａ2Ｏ2）をそれぞれ０．０
３モル秤量し、乳鉢で混合し、ペレット化した後、酸素
雰囲気下、５５０℃で２０時間焼成した。つづいて、試
料を粉砕し、再度５５０℃で２０時間焼成することによ
り、六方晶層状岩塩型構造を有するa−ＮａＦｅＯ2を得
た。試料の秤量、乳鉢での混合はすべてアルゴン雰囲気
下のグローブボックス内で行った。Example 1 Ferric oxide (a-Fe 2 O 3 )
And sodium peroxide (Na 2 O 2 )
After weighing 3 mol, mixing in a mortar, and pelletizing, the mixture was baked at 550 ° C. for 20 hours in an oxygen atmosphere. Subsequently, the sample was pulverized and fired again at 550 ° C. for 20 hours to obtain a-NaFeO 2 having a hexagonal layered rock salt type structure. All the samples were weighed and mixed in a mortar in a glove box under an argon atmosphere.
【００１６】つぎに、上記で得られたa−ＮａＦｅＯ2と
Ｖ2Ｏ5をモル比が４０：１になるようにメタノール中で
湿式混合し、８０℃で乾燥することによって、a−Ｎａ
ＦｅＯ2の表面にバナジウム酸化物が担持された正極活
物質を作製した。正極活物質としてのa−ＮａＦｅＯ2と
Ｖ2Ｏ5の混合物７５重量部に、導電剤としてのアセチレ
ンブラック２０重量部と、結着剤としてのポリフッカビ
ニリデン（ＰＶＤＦ）５重量部を加え、溶剤であるＮ―
メチルー２ピロリドンと湿式混合してスラリーにした。
このスラリーを集電体であるアルミニウムメッシュの両
面に塗付した後、１ｔ／ｃｍ2で加圧成形し、真空下に
て２３０℃で乾燥し、大きさ１５ｍｍ×１５ｍｍ×０．
５ｍｍの本発明正極板（Ａ１）を作製した。Next, the a-NaFeO 2 and V 2 O 5 obtained above were wet-mixed in methanol so that the molar ratio became 40: 1, and dried at 80 ° C. to obtain a-NaFeO 2.
A positive electrode active material in which vanadium oxide was supported on the surface of FeO 2 was produced. To 75 parts by weight of a mixture of a-NaFeO 2 and V 2 O 5 as a positive electrode active material, 20 parts by weight of acetylene black as a conductive agent, and 5 parts by weight of polyfukkavinylidene (PVDF) as a binder were added. N-
Slurry was obtained by wet mixing with methyl-2-pyrrolidone.
This slurry was applied to both sides of an aluminum mesh as a current collector, then molded under pressure at 1 t / cm 2 , dried at 230 ° C. under vacuum, and sized 15 mm × 15 mm × 0.
A 5 mm positive electrode plate (A1) of the present invention was produced.
【００１７】［実施例２］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：２になるよう
に混合し、正極活物質としたこと以外は実施例１と同様
にして、本発明正極板（Ａ２）を作製した。[Embodiment 2] a obtained based on Embodiment 1
-NaFeO 2 and V 2 O 5 molar ratio of 40 were mixed at 2, except that a cathode active material in the same manner as in Example 1 to prepare a present invention positive electrode plate (A2).
【００１８】［実施例３］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：４になるよう
に混合し、正極活物質としたこと以外は実施例１と同様
にして、本発明正極板（Ａ３）を作製した。[Embodiment 3] a obtained based on Embodiment 1
-NaFeO 2 and V 2 O 5 molar ratio of 40 were mixed so that the 4, except that a cathode active material in the same manner as in Example 1 to prepare a present invention positive electrode plate (A3).
【００１９】［実施例４］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：１０になるよ
うに混合し、正極活物質としたこと以外は実施例１と同
様にして、本発明正極板（Ａ４）を作製した。[Embodiment 4] a obtained based on Embodiment 1
A positive electrode plate (A4) of the present invention was produced in the same manner as in Example 1 except that -NaFeO 2 and V 2 O 5 were mixed at a molar ratio of 40:10 to obtain a positive electrode active material.
【００２０】［実施例５］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：２０になるよ
うに混合し、正極活物質としたこと以外は実施例１と同
様にして、本発明正極板（Ａ５）を作製した。[Embodiment 5] a obtained based on Embodiment 1
A positive electrode plate (A5) of the present invention was produced in the same manner as in Example 1, except that -NaFeO 2 and V 2 O 5 were mixed at a molar ratio of 40:20 to prepare a positive electrode active material.
【００２１】［実施例６］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：４０になるよ
うに混合し、正極活物質としたこと以外は実施例１と同
様にして、本発明正極板（Ａ６）を作製した。[Embodiment 6] a obtained based on Embodiment 1
-NaFeO 2 and V 2 O 5 molar ratio were mixed so that the 40:40, except that a cathode active material in the same manner as in Example 1 to prepare a present invention positive electrode plate (A6).
【００２２】［実施例７］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：６０になるよ
うに混合し、正極活物質としたこと以外は実施例１と同
様にして、本発明正極板（Ａ７）を作製した。[Embodiment 7] a obtained based on Embodiment 1
-NaFeO 2 and V 2 O 5 molar ratio were mixed so that the 40:60, except that a cathode active material in the same manner as in Example 1 to prepare a present invention positive electrode plate (A7).
【００２３】［実施例８］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：８０になるよ
うに混合し、正極活物質としたこと以外は実施例１と同
様にして、本発明正極板（Ａ８）を作製した。[Embodiment 8] a obtained based on Embodiment 1
-NaFeO 2 and V 2 O 5 molar ratio were mixed so that the 40:80, except that a cathode active material in the same manner as in Example 1 to prepare a present invention positive electrode plate (A8).
【００２４】［実施例９］実施例１に基づき得られるa
−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：１００になる
ように混合し、正極活物質としたこと以外は実施例１と
同様にして、本発明正極板（Ａ９）を作製した。[Embodiment 9] a obtained based on Embodiment 1
-NaFeO 2 and V 2 O 5 molar ratio of 40 were mixed so that the 100, except that the positive electrode active material in the same manner as in Example 1 to prepare a present invention positive electrode plate (A9).
【００２５】［実施例１０］実施例１に基づき得られる
a−ＮａＦｅＯ2とＶ2Ｏ5をモル比が４０：１２０になる
ように混合し、正極活物質としたこと以外は実施例１と
同様にして、本発明正極板（Ａ１０）を作製した。[Embodiment 10] Obtained based on Embodiment 1.
A positive electrode plate (A10) of the present invention was produced in the same manner as in Example 1 except that a-NaFeO 2 and V 2 O 5 were mixed at a molar ratio of 40: 120 to obtain a positive electrode active material.
【００２６】［比較例１］正極活物質としてa−ＮａＦ
ｅＯ2を単独で用いたこと以外は実施例１と同様にし
て、比較正極板（Ｂ１）を作製した。Comparative Example 1 a-NaF as a positive electrode active material
A comparative positive electrode plate (B1) was produced in the same manner as in Example 1 except that eO 2 was used alone.
【００２７】［充放電特性］本発明正極板（Ａ１）〜
（Ａ１０）および比較正極板（Ｂ１）をそれぞれ試験極
基材とし、実験用セルを構成した。対極および参照極に
リチウム金属、非水電解液に１ｍｏｌ／l の過塩素酸リ
チウムを溶解させたエチレンカーボネートとジエチルカ
ーボネートの体積比１：１の混合溶液を用いた。[Charge / Discharge Characteristics] The positive electrode plate (A1) of the present invention
(A10) and the comparative positive electrode plate (B1) were each used as a test electrode base material to constitute an experimental cell. A mixed solution of ethylene carbonate and diethyl carbonate in which 1 mol / l of lithium perchlorate was dissolved in a non-aqueous electrolyte at a volume ratio of 1: 1 was used.
【００２８】上記実験用セルを用いて、正極充放電特性
を調べた。本発明正極板（Ａ１）〜（Ａ１０）、および
比較正極板（Ｂ１）について、電流密度２ｍＡ／ｇで
１．５Ｖまで放電した後、折り返し２ｍＡ／ｇで３．５
Ｖまで充電した。放電容量をＣ１、充電容量をＣ２とお
くとき、充放電サイクル効率を以下の式から算出した。
充放電サイクル効率（％）＝（Ｃ２／Ｃ１）×１００な
お、充放電試験は放電（リチウム挿入）から開始した。The charge / discharge characteristics of the positive electrode were examined using the above experimental cell. The positive electrode plates (A1) to (A10) of the present invention and the comparative positive electrode plate (B1) were discharged to 1.5 V at a current density of 2 mA / g, and then turned back to 3.5 at 2 mA / g.
Charged to V When the discharge capacity is C1 and the charge capacity is C2, the charge / discharge cycle efficiency was calculated from the following equation.
Charge / discharge cycle efficiency (%) = (C2 / C1) × 100 The charge / discharge test was started from discharge (lithium insertion).
【００２９】a−ＮａＦｅＯ2とＶ2Ｏ5のモル比をｘ、ｙ
とするとき、本発明正極板（Ａ１）〜（Ａ１０）および
比較正極板（Ｂ１）の（ｙ／ｘ）の値と各サイクルにお
ける充電容量との関係を表１に示す。また、本発明正極
板（Ａ１）〜（Ａ１０）および比較正極板（Ｂ１）の各
サイクルにおけるサイクル効率を表２に示す。さらに、
本発明正極板（Ａ６）と比較正極板（Ｂ１）の３サイク
ル目における充放電曲線をそれぞれ図１、図２に示す。The molar ratio between a-NaFeO 2 and V 2 O 5 is x, y
Table 1 shows the relationship between the (y / x) value of the positive electrode plates (A1) to (A10) of the present invention and the comparative positive electrode plate (B1) and the charge capacity in each cycle. Table 2 shows the cycle efficiency in each cycle of the positive electrode plates (A1) to (A10) of the present invention and the comparative positive electrode plate (B1). further,
The charge and discharge curves of the positive electrode plate of the present invention (A6) and the comparative positive electrode plate (B1) in the third cycle are shown in FIGS. 1 and 2, respectively.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】図１、図２から、a−ＮａＦｅＯ2とＶ2Ｏ5
の混合物（Ａ６）ではa−ＮａＦｅＯ2（Ｂ１）と比較
し、その充放電曲線が大きく異なることが分かる。すな
わち、a−ＮａＦｅＯ2（Ｂ１）では電位がなだらかに変
化したのに対し、a−ＮａＦｅＯ2とＶ2Ｏ5の混合物（Ａ
６）では約２Ｖに電位の平坦性が確認された。約２Ｖの
電位の平坦性はＶ2Ｏ5を活物質とした場合の初期サイク
ルにおいても同様にして現れるが、以後のサイクルで
は、構造がアモルファス化し、電位がなだらかに変化す
ることが報告されている（小柴ら，ＤＥＮＫＩ ＫＡＧ
ＡＫＵ，３３２（１９９４））。また、本発明正極板に
おいてＶ2Ｏ5のみ反応に寄与していると仮定し、初期サ
イクル放電過程における容量（２．１Ｖ〜１．５Ｖ）を
比較すると、本発明正極板（Ａ４）では２４０ｍＡｈ／
ｇとなるのに対し、Ｖ2Ｏ5では約２００ｍＡｈ／ｇとな
る（小柴ら，ＤＥＮＫＩ ＫＡＧＡＫＵ，３３２ （１９
９４））。FIGS. 1 and 2 show that a-NaFeO 2 and V 2 O 5
It can be seen that the charge-discharge curve of the mixture (A6) is significantly different from that of a-NaFeO 2 (B1). That is, while the potential of a-NaFeO 2 (B1) gradually changed, a mixture of a-NaFeO 2 and V 2 O 5 (A
In 6), the flatness of the potential was confirmed at about 2 V. The flatness of the potential of about 2 V appears similarly in the initial cycle when V 2 O 5 is used as the active material, but it is reported that in the subsequent cycles, the structure becomes amorphous and the potential changes gradually. (Koshiba et al., DENKI KAG
AKU, 332 (1994)). Further, assuming that only V 2 O 5 contributes to the reaction in the positive electrode plate of the present invention, and comparing the capacities (2.1 V to 1.5 V) in the initial cycle discharge process, the positive electrode plate of the present invention (A4) has a capacity of 240 mAh. /
g, whereas for V 2 O 5 it is about 200 mAh / g (Koshiba et al., DENKI KAGAKU, 332 (19).
94)).
【００３３】以上の結果、本発明正極板では、Ｖ2Ｏ5単
独の特性が現れているのでなく、a−ＮａＦｅＯ2が充放
電反応に大きく寄与していると考えられる。Ｖ2Ｏ5との
混合により、比較正極板（Ｂ１）と比べて本発明正極板
の容量が増加したのは、a−ＮａＦｅＯ2の利用率の向上
に起因すると考えられる。As a result, it is considered that, in the positive electrode plate of the present invention, the characteristics of V 2 O 5 alone do not appear, and a-NaFeO 2 greatly contributes to the charge / discharge reaction. The increase in the capacity of the positive electrode plate of the present invention as compared with the comparative positive electrode plate (B1) due to the mixing with V 2 O 5 is considered to be due to the improvement in the utilization of a-NaFeO 2 .
【００３４】Ｆｅの２価／３価の酸化還元反応は約２Ｖ
でおこることが報告されている（Ｋ．Ａｍｉｎｅ ｅ
ｔ．ａｌ．，Ｊ．Ｐｏｗｅｒ．Ｓｏｕｒｃｅｓ，８１−
８２，２２１（１９９９））。従って、本発明正極板で
出現した約２Ｖの電位の平坦性（図１）は、a−ＮａＦ
ｅＯ2へのリチウムの挿入・脱離にともなうＦｅの２価
／３価の酸化還元反応に起因し、a−ＮａＦｅＯ2の利用
率の向上によってもたらされたと考えられる。The divalent / trivalent redox reaction of Fe is about 2 V
(K. Amine e)
t. al. , J. et al. Power. Sources, 81-
82 , 221 (1999)). Therefore, the flatness of the potential of about 2 V that appeared in the positive electrode plate of the present invention (FIG. 1) is a-NaF
Due to the bivalent / trivalent redox reaction of Fe with the insertion and extraction of lithium into eO 2, it is believed to have been brought about by improving the utilization of a-NaFeO 2.
【００３５】表１から、（ｙ／ｘ）の値が１〜３．０で
ある本発明正極活物質は大きな放電容量（１３０〜２０
０ｍＡｈ／ｇ）を有することが分かる。また、表２か
ら、（ｙ／ｘ）の値が０〜２．５である本発明正極活物
質は、比較正極板と比べてサイクル特性が優れているこ
とが分かる。従って、（ｙ／ｘ）の値が１〜２．５であ
るa−ＮａＦｅＯ2とＶ2Ｏ5の混合物を用いることが、高
容量で、良好なサイクル特性を有する非水電解質正極活
物質を得る上で好ましいことが分かる。From Table 1, it can be seen that the cathode active material of the present invention in which the value of (y / x) is 1 to 3.0 has a large discharge capacity (130 to 20).
0 mAh / g). In addition, Table 2 shows that the positive electrode active material of the present invention in which the value of (y / x) is 0 to 2.5 has excellent cycle characteristics as compared with the comparative positive electrode plate. Therefore, using a mixture of a-NaFeO 2 and V 2 O 5 having a value of (y / x) of 1 to 2.5 makes it possible to obtain a nonaqueous electrolyte positive electrode active material having high capacity and good cycle characteristics. It turns out that it is preferable in obtaining.
【００３６】本実施例では、アルカリ金属含有鉄酸化物
にa−ＮａＦｅＯ2、バナジウム酸化物にＶ2Ｏ5を選んで
説明したが、a−ＮａＦｅＯ2にＶ2Ｏ3、Ｖ2Ｏ4を混合し
た活物質や、ＬｉＦｅＯ2、ＦｅＯＯＨにＶ2Ｏ3、Ｖ2Ｏ
4、Ｖ2Ｏ5を混合した活物質においても同様にして、高
容量で、良好なサイクル特性が得られた。In this embodiment, a-NaFeO 2 was selected as the alkali metal-containing iron oxide and V 2 O 5 was selected as the vanadium oxide. However, V 2 O 3 and V 2 O 4 were selected as the a-NaFeO 2. V 2 O 3 , V 2 O on mixed active material, LiFeO 2 , FeOOH
4. Similarly, a high capacity and good cycle characteristics were obtained in the active material mixed with V 2 O 5 .
【００３７】本発明により、高容量で充放電特性に優れ
たアルカリ金属含有鉄酸化物を得ることに初めて成功
し、安価で環境負荷の小さい非水電解質二次電池用正極
活物質の開発に大きく寄与するものである。According to the present invention, an alkali metal-containing iron oxide having high capacity and excellent charge / discharge characteristics was successfully obtained for the first time, and has been greatly developed for the development of a positive electrode active material for a nonaqueous electrolyte secondary battery which is inexpensive and has a small environmental load. It will contribute.
【００３８】[0038]
【発明の効果】本発明の非水電解質二次電池用正極活物
質は、アルカリ金属含有鉄酸化物の表面の少なくとも一
部にバナジウム酸化物を担持したことを特徴とし、アル
カリ金属含有鉄酸化物にa−ＮａＦｅＯ2を、バナジウム
酸化物にＶ2Ｏ5を用いた場合、a−ＮａＦｅＯ2とＶ2Ｏ5
のモル比をｘ、ｙとすると、０＜（ｙ／ｘ）＜３、さら
に好ましくは１＜（ｙ／ｘ）＜２．５とした時に、高容
量で、サイクル特性が特に良好となる。The positive electrode active material for a non-aqueous electrolyte secondary battery according to the present invention is characterized in that vanadium oxide is supported on at least a part of the surface of an alkali metal-containing iron oxide. If the a-NaFeO 2, with V 2 O 5 in the vanadium oxide, a-NaFeO 2 and V 2 O 5
Assuming that the molar ratio of x and y is 0 <(y / x) <3, more preferably 1 <(y / x) <2.5, the capacity is high and the cycle characteristics are particularly good.
【図１】本発明正極板（Ａ６）の３サイクル目における
充放電特性を示す図である。FIG. 1 is a diagram showing charge / discharge characteristics of a positive electrode plate (A6) of the present invention in a third cycle.
【図２】比較正極板（Ｂ１）の３サイクル目における充
放電特性を示す図である。FIG. 2 is a diagram showing charge / discharge characteristics of a comparative positive electrode plate (B1) in a third cycle.
Claims (2)
属含有鉄酸化物とバナジウム酸化物とが混合され、前記
アルカリ金属含有鉄酸化物の表面の少なくとも一部に前
記バナジウム酸化物が担持されていることを特徴とする
非水電解質二次電池用正極活物質。An alkali metal-containing iron oxide having a hexagonal layered rock salt type structure and a vanadium oxide are mixed, and the vanadium oxide is supported on at least a part of the surface of the alkali metal-containing iron oxide. A positive electrode active material for a non-aqueous electrolyte secondary battery.
ＦｅＯ2であることを特徴とする非水電解質二次電池用
正極活物質。2. The method according to claim 1, wherein the alkali metal-containing iron oxide is α-Na
A positive electrode active material for a non-aqueous electrolyte secondary battery, which is FeO 2 .
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005096415A1 (en) * | 2004-03-31 | 2005-10-13 | Sumitomo Chemical Company, Limited | Positive electrode active material for non-aqueous electrolyte secondary cell |
| JP2005317511A (en) * | 2004-03-31 | 2005-11-10 | Junichi Yamaki | Anode active material for non-aqueous electrolyte secondary battery |
| US7045250B2 (en) | 2000-11-13 | 2006-05-16 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte battery |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0487152A (en) * | 1990-07-27 | 1992-03-19 | Sanyo Electric Co Ltd | Nonaqueous battery |
| JPH06275273A (en) * | 1993-03-17 | 1994-09-30 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
| JPH08250120A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JPH09293508A (en) * | 1996-04-25 | 1997-11-11 | Sony Corp | Positive electrode material for lithium secondary battery, its manufacture and nonaqueous electrolyte secondary battery using it |
| JPH09330719A (en) * | 1996-06-11 | 1997-12-22 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JPH1067519A (en) * | 1996-08-27 | 1998-03-10 | Agency Of Ind Science & Technol | Production of laminar rock salt type lithium ferrite by solvothermal ion exchange method |
| JPH10241667A (en) * | 1997-02-26 | 1998-09-11 | Toyota Central Res & Dev Lab Inc | Electrode active substance for nonaqueous battery |
| JPH1140156A (en) * | 1997-07-16 | 1999-02-12 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
-
2000
- 2000-04-03 JP JP2000101063A patent/JP4765137B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0487152A (en) * | 1990-07-27 | 1992-03-19 | Sanyo Electric Co Ltd | Nonaqueous battery |
| JPH06275273A (en) * | 1993-03-17 | 1994-09-30 | Sanyo Electric Co Ltd | Nonaqueous secondary battery |
| JPH08250120A (en) * | 1995-03-08 | 1996-09-27 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JPH09293508A (en) * | 1996-04-25 | 1997-11-11 | Sony Corp | Positive electrode material for lithium secondary battery, its manufacture and nonaqueous electrolyte secondary battery using it |
| JPH09330719A (en) * | 1996-06-11 | 1997-12-22 | Sanyo Electric Co Ltd | Lithium secondary battery |
| JPH1067519A (en) * | 1996-08-27 | 1998-03-10 | Agency Of Ind Science & Technol | Production of laminar rock salt type lithium ferrite by solvothermal ion exchange method |
| JPH10241667A (en) * | 1997-02-26 | 1998-09-11 | Toyota Central Res & Dev Lab Inc | Electrode active substance for nonaqueous battery |
| JPH1140156A (en) * | 1997-07-16 | 1999-02-12 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045250B2 (en) | 2000-11-13 | 2006-05-16 | Sanyo Electric Co., Ltd. | Non-aqueous electrolyte battery |
| WO2005096415A1 (en) * | 2004-03-31 | 2005-10-13 | Sumitomo Chemical Company, Limited | Positive electrode active material for non-aqueous electrolyte secondary cell |
| JP2005317511A (en) * | 2004-03-31 | 2005-11-10 | Junichi Yamaki | Anode active material for non-aqueous electrolyte secondary battery |
| US7794879B2 (en) | 2004-03-31 | 2010-09-14 | Jun-ichi Yamaki | Positive electrode active material for non-aqueous electrolyte secondary cell |
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| JP4765137B2 (en) | 2011-09-07 |
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