JPH0955200A - Non-aqueous electrolyte battery - Google Patents
Non-aqueous electrolyte batteryInfo
- Publication number
- JPH0955200A JPH0955200A JP7227438A JP22743895A JPH0955200A JP H0955200 A JPH0955200 A JP H0955200A JP 7227438 A JP7227438 A JP 7227438A JP 22743895 A JP22743895 A JP 22743895A JP H0955200 A JPH0955200 A JP H0955200A
- Authority
- JP
- Japan
- Prior art keywords
- electrode active
- active material
- positive electrode
- aqueous electrolyte
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
(57)【要約】
【課題】放電電圧の高い非水電解質電池を提供する。
【解決手段】金属オキサイドを正極活物質６として含
み、アルカリ金属またはアルカリ金属を吸蔵、放出可能
な物質を負極活物質４とし、前記アルカリ金属のイオン
が前記正極活物質及び前記負極活物質と電気化学反応を
するための移動を行い得る物質を電解質物質としたこと
を特徴とする。
【効果】電電圧の高い非水電解質電池を構成することが
でき、様々な分野に利用できるという利点を有する。
(57) Abstract: A non-aqueous electrolyte battery having a high discharge voltage is provided. SOLUTION: A metal oxide is contained as a positive electrode active material 6, and an alkali metal or a material capable of occluding and releasing an alkali metal is used as a negative electrode active material 4, and ions of the alkali metal are electrically connected to the positive electrode active material and the negative electrode active material. It is characterized in that a substance capable of moving for a chemical reaction is an electrolyte substance. [Effect] It is possible to construct a non-aqueous electrolyte battery having a high electric voltage and has an advantage that it can be used in various fields.
Description
【０００１】[0001]
【産業上の利用分野】本発明は非水電解質電池、さらに
詳細には放電電圧の高い非水電解質電池を提供する正極
活物質に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-aqueous electrolyte battery, and more particularly to a positive electrode active material for providing a non-aqueous electrolyte battery having a high discharge voltage.
【０００２】[0002]
【従来の技術及び問題点】従来の非水電解質電池正極活
物質には酸化物、硫化物等が挙げられているが、これら
は例えばリチウム負極に対して２Ｖ程度の電圧しか持た
ず、放電電圧が低いという欠点があった。2. Description of the Related Art Oxides, sulfides, and the like are mentioned as conventional positive electrode active materials for non-aqueous electrolyte batteries, but these have only a voltage of about 2 V with respect to a lithium negative electrode, and therefore have a discharge voltage. It had the drawback of being low.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記のよう
に電池電圧が低いという現状の課題を解決し、放電電圧
の高い非水電解質電池を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to solve the current problem that the battery voltage is low as described above and provide a non-aqueous electrolyte battery having a high discharge voltage.
【０００４】[0004]
【問題点を解決するための手段】かかる目的を達成する
ために本発明の非水電解質電池では、金属オキサイドを
正極活物質として含み、アルカリ金属またはアルカリ金
属を吸蔵、放出可能な物質を負極活物質とし、前記アル
カリ金属のイオンが前記正極活物質及び前記負極活物質
と電気化学反応をするための移動を行い得る物質を電解
質物質としたことを特徴としており、特に金属オキシハ
ライドの金属元素としてＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、
Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、、Ｚｒ、Ｎｂ、Ｍｏ、Ｓｎ、
Ｓｂ、Ｔｅ、Ｈｆ、Ｔａ、Ｗ、Ｐｂ、Ｂｉの中の少なく
とも一種類を含み、ハロゲンとしてフッ素Ｆを含む金属
オキシハライドを正極活物質として含むことを特徴とし
ている。In order to achieve the above object, in the non-aqueous electrolyte battery of the present invention, a metal oxide is contained as a positive electrode active material, and an alkali metal or a substance capable of occluding and releasing an alkali metal is used as a negative electrode active material. As a substance, the alkali metal ion is characterized in that it is a substance that can be moved to perform an electrochemical reaction with the positive electrode active material and the negative electrode active material is an electrolyte substance, especially as a metal element of the metal oxyhalide. Ti, V, Cr, Mn, Fe,
Co, Ni, Cu, Zn, Zr, Nb, Mo, Sn,
It is characterized in that it contains at least one kind of Sb, Te, Hf, Ta, W, Pb, and Bi and contains a metal oxyhalide containing fluorine F as halogen as a positive electrode active material.
【０００５】本発明をさらに詳しく説明する。The present invention will be described in more detail.
【０００６】発明者は放電電圧の高い非水電解質電池材
料を鋭意探索した結果、上述のように金属オキシハライ
ド、特に金属元素としてＴｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、
Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｎｂ、Ｍｏ、Ｓｎ、Ｓｂ、Ｔ
ｅ、Ｈｆ、Ｔａ、Ｗ、Ｐｂ、Ｂｉの中の少なくとも一種
類を含み、組成式ＭＸn（Ｍは金属元素、Ｘはハロゲ
ン、ｎは３以上の正数）で表され、ハロゲンとしてフッ
素Ｆを含む金属オキシハライドを正極活物質として含む
ことにより、従来の電池より放電電圧の高い電池を構成
できることを確かめ、その認識の下に本発明を完成し
た。As a result of earnest search for a non-aqueous electrolyte battery material having a high discharge voltage, the inventor has found that metal oxyhalides, particularly Ti, V, Cr, Mn, Fe as metal elements, as described above, are obtained.
Co, Ni, Cu, Zn, Nb, Mo, Sn, Sb, T
e, Hf, Ta, W, Pb, and Bi, and is represented by the composition formula MX n (M is a metal element, X is a halogen, and n is a positive number of 3 or more), and fluorine F is used as a halogen. It was confirmed that a battery having a higher discharge voltage than that of a conventional battery can be formed by including a metal oxyhalide containing a compound as a positive electrode active material, and the present invention has been completed based on this recognition.
【０００７】本発明の非水電解質電池が従来の酸化物、
硫化物を正極活物質とする電池に比べて放電電圧が高い
理由は、次のように考えられる。即ち、電気陰性度が強
いハロゲンＸを有すると、金属Ｍとハロゲン間の電子は
強くハロゲンＸに引きつけられるため、同じ金属Ｍの同
じ価数を持つ化合物で比較しても、オキシハライドの金
属Ｍは酸化物、硫化物の金属Ｍに比べて強く陽電荷を帯
び、高電圧になると考えられる。The non-aqueous electrolyte battery of the present invention is a conventional oxide,
The reason why the discharge voltage is higher than that of the battery using sulfide as the positive electrode active material is considered as follows. That is, when the halogen X having a strong electronegativity is present, the electrons between the metal M and the halogen are strongly attracted to the halogen X, and therefore, even when the compounds having the same valence of the same metal M are compared, the metal M of the oxyhalide is Is considered to have a higher positive voltage and a higher voltage than the oxide or sulfide metal M.
【０００８】またオキシハライドは分子量が低いため、
重量エネルギー密度が高くなるという利点を有する。Since oxyhalide has a low molecular weight,
It has the advantage that the weight energy density is high.
【０００９】また、ハロゲンとしてフッ素Ｆを含む場
合、フッ素が最も電気陰性度が高い元素であるため、高
電圧が期待できる。また、フッ素は他のハロゲンよりも
分子量が低いため、この観点からは重量エネルギー密度
が非常に高くなるという利点を有する。When fluorine F is contained as halogen, high voltage can be expected because fluorine is the element with the highest electronegativity. Further, since fluorine has a lower molecular weight than other halogens, it has an advantage that the weight energy density becomes very high from this viewpoint.
【００１０】また、アルカリ金属を正極活物質中に吸
蔵、放出させることにより、二次電池として用いること
もできる。Further, it can be used as a secondary battery by inserting and extracting an alkali metal in the positive electrode active material.
【００１１】負極活物質としては、アルカリ金属または
アルカリ金属を吸蔵、放出可能な物質を用いることによ
り、還元性の強い負極活物質とすることができ、電池電
圧が高くなるという利点を有する。この中には、リチウ
ム、ナトリウム、カリウム、ルビジウム、セシウム等の
アルカリ金属、及びそれらの金属合金、リチウムを吸
蔵、放出可能な炭素材料、等が挙げられる。The use of an alkali metal or a substance capable of occluding and releasing an alkali metal as the negative electrode active material makes it possible to obtain a negative electrode active material having a strong reducing property, which has the advantage of increasing the battery voltage. Among these, alkali metals such as lithium, sodium, potassium, rubidium, and cesium, metal alloys thereof, carbon materials capable of inserting and extracting lithium, and the like can be given.
【００１２】この正極活物質を用いて正極を形成するに
は、前記化合物粉末とポリテトラフルオロエチレンのご
とき結着剤粉末との混合物をステンレス等の支持体上に
圧着成形する、あるいは、かかる混合物粉末に導電性を
付与するためアセチレンブラックのような導電性粉末を
混合し、これにさらにポリテトラフルオロエチレンのよ
うな結着剤粉末を所要に応じて加え、この混合物を金属
容器にいれる、あるいは前述の混合物をステンレスなど
の支持体に圧着成形する、あるいは前述の混合物を有機
溶剤等の溶媒中に分散してスラリー状にして金属基板上
に塗布する、等の手段によって形成される。To form a positive electrode using this positive electrode active material, a mixture of the compound powder and a binder powder such as polytetrafluoroethylene is pressure-molded on a support such as stainless steel, or such a mixture is formed. A conductive powder such as acetylene black is mixed to impart conductivity to the powder, and a binder powder such as polytetrafluoroethylene is further added to the powder as needed, and the mixture is put in a metal container, or It is formed by means such as press-molding the above mixture on a support such as stainless steel, or dispersing the above mixture in a solvent such as an organic solvent to form a slurry and coating it on a metal substrate.
【００１３】負極活物質は一般の電池のそれと同様にシ
ート上にして、またそのシートをニッケル、ステンレス
等の導電体網に圧着して負極として形成される。The negative electrode active material is formed on a sheet as in the case of a general battery, and the sheet is pressure-bonded to a conductor network of nickel, stainless steel or the like to form a negative electrode.
【００１４】電解液としては、有機溶媒としては例えば
ジメトキシエタン、２−メチルテトラヒドロフラン、エ
チレンカーボネート、メチルホルメート、ジメチルスル
ホキシド、プロピレンカーボネート、アセトニトリル、
ブチロラクトン、ジメチルホルムアミド、ジメチルカー
ボネート、ジエチルカーボネート、スルホラン、エチル
メチルカーボネート等に、アルカリ金属イオンを含むル
イス酸を溶解した非水電解質溶媒、あるいは固体電解質
等が使用できる。Examples of the electrolytic solution include organic solvents such as dimethoxyethane, 2-methyltetrahydrofuran, ethylene carbonate, methyl formate, dimethyl sulfoxide, propylene carbonate, acetonitrile,
A non-aqueous electrolyte solvent in which a Lewis acid containing an alkali metal ion is dissolved in butyrolactone, dimethylformamide, dimethyl carbonate, diethyl carbonate, sulfolane, ethylmethyl carbonate, or the like, or a solid electrolyte can be used.
【００１５】さらに、セパレータ、電池ケース等の構造
材料等の他の要素についても従来公知の各種材料が使用
でき、特に制限はない。Furthermore, various conventionally known materials can be used for other elements such as structural materials such as a separator and a battery case, and there is no particular limitation.
【００１６】[0016]
【実施例】以下実施例によって本発明の方法をさらに具
体的に説明するが、本発明はこれらによりなんら制限さ
れるものではない。なお、実施例において電池の作成及
び測定はアルゴン雰囲気下のドライボックス内で行っ
た。EXAMPLES The method of the present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the examples, preparation and measurement of the battery were performed in a dry box under an argon atmosphere.
【００１７】[0017]
【実施例１】図１は本発明による電池の一具体例である
コイン型電池の断面図であり、図中１は封口板、２はガ
スケット、３は正極ケース、４は負極、５はセパレー
タ、６は正極合剤ペレットを示す。Embodiment 1 FIG. 1 is a cross-sectional view of a coin-type battery which is a specific example of a battery according to the present invention, wherein 1 is a sealing plate, 2 is a gasket, 3 is a positive electrode case, 4 is a negative electrode, and 5 is a separator. And 6 indicate positive electrode material mixture pellets.
【００１８】正極活物質には、ＦｅＯＦを用いた。この
試料をａとする。FeOF was used as the positive electrode active material. This sample is designated as a.
【００１９】この試料ａを粉砕して粉末とし、導電剤
（アセチレンブラック）、結着剤（ポリテトラフルオロ
エチレン）と共に混合の上、ロール成形し、正極合剤ペ
レット６（厚さ０．５ｍｍ、直径１５ｍｍ）とした。This sample a was crushed into powder, mixed with a conductive agent (acetylene black) and a binder (polytetrafluoroethylene), and then roll-molded to form a positive electrode mixture pellet 6 (thickness 0.5 mm, The diameter was 15 mm).
【００２０】次にステンレス製の封口板１上に金属リチ
ウムの負極4を加圧配置したものをポリプロピレン製ガ
スケット２の凹部に挿入し、負極4の上にポリプロピレ
ン製で微孔性のセパレータ５、正極合剤ペレット６をこ
の順序に配置し、電解液としてエチレンカーボネートと
ジメチルカーボネートの混合溶媒にＬｉＰＦ6を溶解さ
せた１規定溶液を適量注入して含浸させた後に、ステン
レス製の正極ケース３を被せてかしめることにより、厚
さ２ｍｍ、直径２３ｍｍのコイン型電池を作製した。Next, a negative electrode 4 made of metallic lithium, which was placed under pressure on a stainless steel sealing plate 1, was inserted into a recess of a polypropylene gasket 2, and a polypropylene microporous separator 5 was placed on the negative electrode 4. After arranging the positive electrode material mixture pellets 6 in this order and injecting an appropriate amount of a 1N solution of LiPF 6 dissolved in a mixed solvent of ethylene carbonate and dimethyl carbonate as an electrolytic solution for impregnation, the positive electrode case 3 made of stainless steel is placed. By covering and caulking, a coin-type battery having a thickness of 2 mm and a diameter of 23 mm was produced.
【００２１】このようにして作製した試料ａを正極活物
質とする電池を、０．５ｍＡ／ｃｍ2の電流密度で２．
０Ｖまで放電させた際の放電容量を表１に示す。放電電
圧が高いため２．０Ｖまでの容量が大きく、高エネルギ
ー密度電池として利用できる利点を有している。[0021] The batteries of the sample a prepared in this manner and the positive electrode active material, at a current density of 0.5mA / cm 2 2.
Table 1 shows the discharge capacities when discharged to 0V. Since the discharge voltage is high, the capacity up to 2.0 V is large, and it has an advantage that it can be used as a high energy density battery.
【００２２】[0022]
【比較例１】比較例１では、正極活物質には酸化物Ｆｅ
2Ｏ3を用いる他は実施例１と同様にして電池を作製し
た。この試料をｂとする。Comparative Example 1 In Comparative Example 1, an oxide Fe was used as the positive electrode active material.
A battery was made in the same manner as in Example 1 except that 2 O 3 was used. This sample is designated as b.
【００２３】このようにして作製した試料ｂを正極活物
質とする電池を、０．５ｍＡ／ｃｍ2の電流密度で、
２．０Ｖまで放電させた際の放電容量を表１に示す。こ
の電池と比較すると、本発明の実施例で作製した電池
は、放電エネルギーが大きいことがわかる。A battery using the thus prepared sample b as a positive electrode active material was tested at a current density of 0.5 mA / cm 2 .
Table 1 shows the discharge capacity when discharged to 2.0 V. Compared with this battery, it can be seen that the batteries produced in the examples of the present invention have higher discharge energy.
【００２４】 [0024]
【００２５】[0025]
【発明の効果】以上説明したように、本発明によれば、
放電電圧の高い非水電解質電池を構成することができ、
様々な分野に利用できるという利点を有する。As described above, according to the present invention,
A non-aqueous electrolyte battery with a high discharge voltage can be constructed,
It has the advantage that it can be used in various fields.
【図１】本発明の実施例におけるコイン型電池の構成例
を示す断面図。FIG. 1 is a sectional view showing a configuration example of a coin-type battery according to an embodiment of the present invention.
１ 封口板 ２ ガスケット ３ 正極ケース ４ 負極 ５ セパレータ ６ 正極合剤ペレット DESCRIPTION OF SYMBOLS 1 Sealing plate 2 Gasket 3 Positive electrode case 4 Negative electrode 5 Separator 6 Positive electrode mixture pellet
フロントページの続き (72)発明者 山木 準一 東京都千代田区内幸町１丁目１番６号 日 本電信電話株式会社内Front page continuation (72) Inventor Junichi Yamaki 1-1-6 Uchisaiwaicho, Chiyoda-ku, Tokyo Nihon Telegraph and Telephone Corporation
Claims (3)
含みアルカリ金属またはアルカリ金属を吸蔵、放出可能
な物質を負極活物質とし、前記アルカリ金属のイオンが
前記正極活物質及び前記負極活物質と電気化学反応をす
るための移動を行い得る物質を電解質物質としたことを
特徴とする非水電解質電池。1. A negative electrode active material comprising a metal oxyhalide as a positive electrode active material and capable of occluding and releasing an alkali metal or an alkali metal, wherein ions of the alkali metal are electrically connected to the positive electrode active material and the negative electrode active material. A non-aqueous electrolyte battery, wherein an electrolyte material is used as a substance that can move for a chemical reaction.
Ｔｉ、Ｖ、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚ
ｎ、、Ｚｒ、Ｎｂ、Ｍｏ、Ｓｎ、Ｓｂ、Ｔｅ、Ｈｆ、Ｔ
ａ、Ｗ、Ｐｂ、Ｂｉの中の少なくとも一種類を含んで構
成される物質であることを特徴とする請求項１の非水電
解質電池。2. The metal oxyhalide as a metal element is Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Z.
n, Zr, Nb, Mo, Sn, Sb, Te, Hf, T
The non-aqueous electrolyte battery according to claim 1, which is a substance containing at least one of a, W, Pb, and Bi.
フッ素Ｆを含むことを特徴とする請求項２の非水電解質
電池。3. The non-aqueous electrolyte battery according to claim 2, wherein the metal oxyhalide contains fluorine F as halogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7227438A JPH0955200A (en) | 1995-08-11 | 1995-08-11 | Non-aqueous electrolyte battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7227438A JPH0955200A (en) | 1995-08-11 | 1995-08-11 | Non-aqueous electrolyte battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0955200A true JPH0955200A (en) | 1997-02-25 |
Family
ID=16860871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7227438A Pending JPH0955200A (en) | 1995-08-11 | 1995-08-11 | Non-aqueous electrolyte battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0955200A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011523171A (en) * | 2008-05-23 | 2011-08-04 | ラトガーズ ザ ステイト ユニバーシティ | Iron oxyfluoride electrode for electrochemical energy storage |
| WO2012176907A1 (en) * | 2011-06-22 | 2012-12-27 | 国立大学法人九州大学 | Method for producing iron oxyfluoride positive electrode active substance and iron oxyfluoride positive electrode active substance |
-
1995
- 1995-08-11 JP JP7227438A patent/JPH0955200A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011523171A (en) * | 2008-05-23 | 2011-08-04 | ラトガーズ ザ ステイト ユニバーシティ | Iron oxyfluoride electrode for electrochemical energy storage |
| WO2012176907A1 (en) * | 2011-06-22 | 2012-12-27 | 国立大学法人九州大学 | Method for producing iron oxyfluoride positive electrode active substance and iron oxyfluoride positive electrode active substance |
| US9312538B2 (en) | 2011-06-22 | 2016-04-12 | Kyushu University, National University Corporation | Method for producing iron oxyfluoride positive electrode active substance and iron oxyflouride positive electrode active substance |
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