JP2001332256A - Material for electrode, its manufacturing method and cell therewith - Google Patents
Material for electrode, its manufacturing method and cell therewithInfo
- Publication number
- JP2001332256A JP2001332256A JP2000149780A JP2000149780A JP2001332256A JP 2001332256 A JP2001332256 A JP 2001332256A JP 2000149780 A JP2000149780 A JP 2000149780A JP 2000149780 A JP2000149780 A JP 2000149780A JP 2001332256 A JP2001332256 A JP 2001332256A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- manganese dioxide
- battery
- sample
- electrode
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電極材料、その製造方法
及びその電極材料を正極活物質として含む電池、さらに
詳細には良好なサイクル特性を持つ電池を提供する技術
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode material, a method for producing the same, and a battery containing the electrode material as a positive electrode active material, and more particularly to a technique for providing a battery having good cycle characteristics.
【０００２】[0002]
【従来の技術及び問題点】一般式ＭXＭｎＯ2-δ・ｎＨ2
Ｏ（Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含む１種
類以上の元素、０．１≦Ｘ≦０．５、−０．２≦δ≦
０．２、０．５≦ｎ≦１．０）で表される層状二酸化マ
ンガンは現行のリチウムイオン電池の正極活物質である
ＬｉＣｏＯ2に代わる、安価で熱安定性の高い材料とし
て提案されている。しかし、一般式Ｍ XＭｎＯ2-δ・ｎ
Ｈ2Ｏ（Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含
む１種類以上の元素、０．１≦Ｘ≦０．５、−０．２≦
δ≦０．２、０．５≦ｎ≦１．０）で表される層状二酸
化マンガンは水分子を含んでおり、充放電時にこの水が
電解液中に抜け出し、負極と反応し、サイクル特性が悪
いという欠点があった。2. Description of the Related Art General formula MXMnO2-δ・ NHTwo
O (M = Li, Na, K, Rb, Cs, Mg, Ca, S
One containing any of r, Ba, Al, Ni, La, and Bi
Or more elements, 0.1 ≦ X ≦ 0.5, −0.2 ≦ δ ≦
0.2, 0.5 ≦ n ≦ 1.0)
Ngan is the cathode active material of current lithium-ion batteries
LiCoOTwoInexpensive and highly heat-stable material
It has been proposed. However, the general formula M XMnO2-δ・ N
HTwoO (M = Li, Na, K, Rb, Cs, Mg, C
a, Sr, Ba, Al, Ni, La, Bi
One or more elements, 0.1 ≦ X ≦ 0.5, −0.2 ≦
δ ≦ 0.2, 0.5 ≦ n ≦ 1.0)
Manganese oxide contains water molecules.
It escapes into the electrolyte and reacts with the negative electrode, resulting in poor cycle characteristics.
There was a disadvantage that.
【０００３】また、加熱脱水を行った場合には、構造変
化が生じ、サイクル特性の悪い構造に変化するという問
題があった。In addition, when heat dehydration is performed, there is a problem that a structural change occurs, and the structure changes to a structure having poor cycle characteristics.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記のよう
な現状の課題を解決し、上述のような層状二酸化マンガ
ンで、かつ良好なサイクル特性を有する電極材料、その
製造方法、及びその電極材料の層状二酸化マンガンを正
極活物質として含む電池を提供することにある。SUMMARY OF THE INVENTION The present invention solves the above-mentioned current problems and provides an electrode material having the above-mentioned layered manganese dioxide and good cycle characteristics, a method for producing the same, and an electrode for the same. An object of the present invention is to provide a battery including a layered manganese dioxide material as a positive electrode active material.
【０００５】[0005]
【問題を解決するための手段】かかる目的を達成するた
めに本発明による電極材料は、脱水した下記の一般式で
表される層状二酸化マンガンであることを特徴とする。 一般式 ＭXＭｎＯ2-δ・ｎＨ2Ｏ （Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含む１種
類以上の元素、０．１≦Ｘ≦０．５、−０．２≦δ≦
０．２、０．５≦ｎ≦１．０） また本発明による電極材料の製造方法は、下記の一般式
で表される層状二酸化マンガンを、有機溶媒中にアルカ
リ金属、アルカリ土類金属、モレキュラシーブス、活性
アルミナの内１種類以上と、同時に浸すことを特徴とす
る。In order to achieve the above object, an electrode material according to the present invention is characterized in that it is a dehydrated layered manganese dioxide represented by the following general formula. Formula M X MnO 2-δ · nH 2 O (M = Li, Na, K, Rb, Cs, Mg, Ca, S
one or more elements including any of r, Ba, Al, Ni, La and Bi, 0.1 ≦ X ≦ 0.5, −0.2 ≦ δ ≦
0.2, 0.5 ≦ n ≦ 1.0) In addition, the method for producing an electrode material according to the present invention comprises the steps of: forming a layered manganese dioxide represented by the following general formula into an organic solvent with an alkali metal, an alkaline earth metal, It is characterized by being simultaneously soaked with at least one of molecular sieves and activated alumina.
【０００６】一般式 ＭXＭｎＯ2-δ・ｎＨ2Ｏ （Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含む１種
類以上の元素、０．１≦Ｘ≦０．５、−０．２≦δ≦
０．２、０．５≦ｎ≦１．０） また本発明の電池は、前記に記載された層状二酸化マン
ガンを、電池用正極活物質とした正極を有し、リチウ
ム、ナトリウム、カリウム、マグネシウム、カルシウ
ム、ストロンチウム、アルミニウム、銅、銀の何れかを
含む物質またはこの元素を可逆的に挿入・脱離あるいは
吸蔵・脱離できる物質を含む負極を有し、前記元素のイ
オンが前記正極および前記負極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て含むことを
特徴としている。[0006] formula M X MnO 2-δ · nH 2 O (M = Li, Na, K, Rb, Cs, Mg, Ca, S
one or more elements including any of r, Ba, Al, Ni, La and Bi, 0.1 ≦ X ≦ 0.5, −0.2 ≦ δ ≦
0.2, 0.5 ≦ n ≦ 1.0) Further, the battery of the present invention has a positive electrode using the layered manganese dioxide described above as a positive electrode active material for a battery, and includes lithium, sodium, potassium, and magnesium. Having a negative electrode containing a substance containing any of calcium, strontium, aluminum, copper and silver or a substance capable of reversibly inserting / desorbing or occluding / desorbing this element, wherein ions of the element are present in the positive electrode and the positive electrode. It is characterized in that a substance capable of performing a transfer for performing an electrochemical reaction with the negative electrode is contained as an electrolyte substance.
【０００７】本発明をさらに詳しく説明する。発明者は
層状二酸化マンガンに良好なサイクル特性を持たせる製
造方法、及びその方法により脱水された層状二酸化マン
ガンを正極活物質として含む電池を鋭意探索した結果、
前記の層状二酸化マンガンの製造方法により脱水された
層状二酸化マンガンを正極活物質として含む電池によ
り、従来よりも良好なサイクル特性を持つ電池を製造、
実現できることを確かめ、その認識の下に本発明を完成
した。The present invention will be described in more detail. The inventor has conducted a diligent search for a production method for providing layered manganese dioxide with good cycle characteristics, and a battery containing layered manganese dioxide dehydrated by the method as a positive electrode active material,
By using a battery containing the layered manganese dioxide dehydrated by the method for producing a layered manganese dioxide as a positive electrode active material, to produce a battery having better cycle characteristics than before,
The present inventors have confirmed that the present invention can be realized and completed the present invention based on the recognition.
【０００８】本発明の電極材料は、一般式ＭXＭｎＯ
2-δ・ｎＨ2Ｏ（Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍ
ｇ、Ｃａ、Ｓｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れ
かを含む１種類以上の元素、０．１≦Ｘ≦０．５、−
０．２≦δ≦０．２、０．５≦ｎ≦１．０）で表される
層状二酸化マンガンを脱水したものである。The electrode material of the present invention has the general formula M x MnO
2-δ · nH 2 O (M = Li, Na, K, Rb, Cs, M
g, one or more elements including Ca, Sr, Ba, Al, Ni, La, Bi, 0.1 ≦ X ≦ 0.5, −
(0.2 ≦ δ ≦ 0.2, 0.5 ≦ n ≦ 1.0) obtained by dehydrating layered manganese dioxide.
【０００９】上記一般式中、Ｘおよびδは、それぞれ
０．１≦Ｘ≦０．５、−０．２≦δ≦０．２であるが、
これらはＭの種類および合成法により変化する。またｎ
は０．５≦ｎ≦１．０で、これもＭの種類および合成法
により変化する。In the above general formula, X and δ are 0.1 ≦ X ≦ 0.5 and −0.2 ≦ δ ≦ 0.2, respectively.
These vary depending on the type of M and the synthesis method. And n
Is 0.5 ≦ n ≦ 1.0, which also varies depending on the type of M and the synthesis method.
【００１０】本発明による電極材料の製造方法によれ
ば、アルカリ金属、アルカリ土類金属、モレキュラシー
ブス、活性アルミナの内１種類以上を前記層状二酸化マ
ンガンと同時に有機溶媒中に浸すことにより、前記層状
二酸化マンガンを脱水する。According to the method for producing an electrode material of the present invention, at least one of an alkali metal, an alkaline earth metal, molecular sieves and activated alumina is immersed in an organic solvent at the same time as the layered manganese dioxide. Dehydrate manganese dioxide.
【００１１】これにより有機溶媒中に抜け出した水はア
ルカリ金属、アルカリ土類金属と反応、またはモレキュ
ラシーブス、活性アルミナに吸水され、層状二酸化マン
ガンからの脱水が連続的に進行する。本発明の方法を用
いることで、室温で効率よく十分に脱水させることがで
き、良好なサイクル特性を持つ電池を構成することがで
きる。As a result, the water that has escaped into the organic solvent reacts with the alkali metal or alkaline earth metal, or is absorbed by molecular sieves or activated alumina, and the dehydration from the layered manganese dioxide proceeds continuously. By using the method of the present invention, dehydration can be performed efficiently and sufficiently at room temperature, and a battery having good cycle characteristics can be formed.
【００１２】また、本発明の電極材料の製造方法は、構
造変化を起こさせることなく脱水できる利点を持つ。Further, the method for producing an electrode material of the present invention has an advantage that dehydration can be performed without causing a structural change.
【００１３】脱水に用いる有機溶媒は、脱水に用いるア
ルカリ金属、アルカリ土類金属、モレキュラシーブス、
活性アルミナと反応せず、一般式ＭXＭｎＯ2-δ・ｎＨ2
Ｏ（Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含む１種
類以上の元素、０．１≦Ｘ≦０．５、−０．２≦δ≦
０．２、０．５≦ｎ≦１．０）で表される層状二酸化マ
ンガンとも反応しないものであれば、特に制限はなく、
例えば、脱水に金属リチウムを用いた場合、ジメチルカ
ーボネート、ジエチルカーボネート、プロピレンカーボ
ネート、エチレンカーボネート等を用いることができ
る。The organic solvent used for dehydration includes alkali metals, alkaline earth metals, molecular sieves,
Does not react with activated alumina, the general formula M X MnO 2-δ · nH 2
O (M = Li, Na, K, Rb, Cs, Mg, Ca, S
one or more elements including any of r, Ba, Al, Ni, La and Bi, 0.1 ≦ X ≦ 0.5, −0.2 ≦ δ ≦
0.2, 0.5 ≦ n ≦ 1.0), as long as it does not react with the layered manganese dioxide represented by the formula:
For example, when lithium metal is used for dehydration, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, or the like can be used.
【００１４】本発明の脱水された層状二酸化マンガンの
電極材料を正極活物質に用いて電池正極を形成するに
は、前記層状二酸化マンガン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。或いは、かかる活物質粉末
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、これを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
合物を金属容器に入れる、あるいはステンレス等の支持
体上に圧着成形する、あるいは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 battery positive electrode using the dehydrated layered manganese dioxide electrode material of the present invention as a positive electrode active material, a mixture of the layered manganese dioxide powder and a binder powder such as polytetrafluoroethylene is used. Press molding on a support such as stainless steel. Alternatively, a conductive powder such as acetylene black is mixed to impart conductivity to the active material powder, and a binder powder such as polytetrafluoroethylene is further added as necessary, and the mixture is mixed with a metal. It is formed by means such as placing in a container, press-molding on a support such as stainless steel, or dispersing in a solvent such as an organic solvent to form a slurry and applying the slurry on a metal substrate.
【００１５】前記層状二酸化マンガンを正極活物質に用
いる電池では、リチウム、ナトリウム、カリウム、マグ
ネシウム、カルシウム、ストロンチウム、アルミニウ
ム、銅、銀の何れかを含む物質またはその元素を可逆的
に挿入・脱離あるいは吸蔵・脱離できる物質を含む負極
を有し、前記元素のイオンが前記正極および前記負極と
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
物質として有することにより、元素のイオンが正極と負
極の間を行き来する電池となる。例えば、リチウムを含
む物質としては、リチウム金属、リチウム−アルミニウ
ム合金、リチウム−炭素化合物、リチウム含有窒化物な
ど、従来公知の材料を用いることができる。In the battery using the layered manganese dioxide as a positive electrode active material, a material containing any of lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, copper, and silver or a reversible insertion / desorption of the element is used. Alternatively, a negative electrode containing a substance that can be inserted and extracted can be used, and the element ions can be transferred to the positive electrode and the negative electrode by electrochemical reaction with the positive electrode and the negative electrode. And the battery that moves between the negative electrode. For example, as the substance containing lithium, conventionally known materials such as lithium metal, lithium-aluminum alloy, lithium-carbon compound, and lithium-containing nitride can be used.
【００１６】前記層状二酸化マンガンを正極活物質に用
いる電池では、電解液として、例えばメトキシエタン、
ジエトキシエタン、２−メチルテトラヒドロフラン、エ
チレンカーボネート、プロピレンカーボネート、メチル
ホルメート、ジメチルスルホキシド、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の有機溶媒に、アルカリ金属、ア
ルカリ土類金属等の塩を溶解した非水電解質溶媒、或い
は固体電解質、高分子電解質、前記有機溶媒を担持させ
た高分子電解質等が使用できる。In a battery using the layered manganese dioxide as a positive electrode active material, for example, methoxyethane,
Diethoxyethane, 2-methyltetrahydrofuran, ethylene carbonate, propylene carbonate, methyl formate, dimethyl sulfoxide, acetonitrile,
Butyrolactone, dimethylformamide, dimethyl carbonate, diethyl carbonate, sulfolane, non-aqueous electrolyte solvent in which a salt such as alkaline earth metal is dissolved in an organic solvent such as ethyl methyl carbonate, or a solid electrolyte, a polymer electrolyte, the organic A polymer electrolyte carrying a solvent or the like can be used.
【００１７】また前記電池の放電・充電を繰り返し行う
ことで、これを二次電池として用いることもできる。By repeatedly discharging and charging the battery, the battery can be used as a secondary battery.
【００１８】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。As for other elements such as a structural material such as a separator and a battery case, various conventionally known materials can be used, and there is no particular limitation.
【００１９】[0019]
【実施例】以下実施例によって本発明を具体的に説明す
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。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００２０】[0020]
【実施例１】図１は本発明による電極材料の層状二酸化
マンガンを、正極活物質に用い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 using a layered manganese dioxide as an electrode material according to the present invention as a positive electrode active material, wherein 1 is a sealing plate, and 2 is a gasket. Reference numeral 3 denotes a positive electrode case, 4 denotes a negative electrode, 5 denotes a separator, and 6 denotes a positive electrode mixture pellet.
【００２１】正極活物質は、次のようにして試料ａを製
造し、この試料ａを脱水した試料ｂを用いた。まずアル
ゴンガスを通じて酸素を脱気した水に塩化マンガンを溶
解させ、アルゴン雰囲気中でよく攪拌した後、水酸化ナ
トリウム溶液を、原子比でＭｎ：Ｎａ＝１：５０になる
よう混合し、生じた沈殿が均一になるようにさらに攪拌
した。次にここに酸素を通じて十分酸化させ、固形分を
溶液から濾別して取り出し、さらに水洗して過剰のアル
カリ分を除去し、乾燥させることにより、層状二酸化マ
ンガンＮａ0.28ＭｎＯ2・０．７Ｈ2Ｏを得た。この試料
をａとする。このようにして製造した試料ａを、ジメチ
ルカーボネート中に、試料と接触しないよう配置した金
属リチウムとともに浸し、２４時間放置し脱水した。そ
の後金属リチウムを取り出した後、ジメチルカーボネー
トから試料を濾別して取り出し、室温で乾燥させた。Ｘ
線回折によりこの試料は、試料ａと同様な構造を持つこ
とが判明した。この試料をｂとする。As the positive electrode active material, a sample a was manufactured as follows, and a sample b obtained by dehydrating the sample a was used. First, manganese chloride was dissolved in water from which oxygen was degassed through an argon gas, and the mixture was stirred well in an argon atmosphere. Then, a sodium hydroxide solution was mixed at an atomic ratio of Mn: Na = 1: 50 to form a mixture. The mixture was further stirred so that the precipitate became uniform. Next, it is sufficiently oxidized with oxygen, the solid content is filtered out of the solution, taken out, and further washed with water to remove the excess alkali content, and dried to obtain layered manganese dioxide Na 0.28 MnO 2 .0.7H 2 O. Obtained. This sample is designated as a. The sample a thus produced was immersed in dimethyl carbonate together with lithium metal arranged so as not to come into contact with the sample, and left to stand for 24 hours to dehydrate. Then, after taking out the metallic lithium, a sample was taken out from the dimethyl carbonate by filtration and dried at room temperature. X
Line diffraction revealed that this sample had a structure similar to that of sample a. This sample is designated as b.
【００２２】この試料ｂの粉末を導電剤（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。The powder of the sample b was mixed with a conductive agent (acetylene black) and a binder (polytetrafluoroethylene), and then roll-formed, and then mixed with a positive electrode mixture pellet 6 (thickness 0.5 mm, diameter 15 mm). did.
【００２３】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等容積混合溶媒に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 is placed under pressure on a sealing plate 1 made of stainless steel, is inserted into a concave portion of a gasket 2 made of polypropylene, and a separator 5 made of polypropylene and made of polypropylene is placed on the negative electrode 4. After arranging the positive electrode mixture pellets 6 in this order, injecting and impregnating an appropriate amount of a 1 N solution of LiPF 6 dissolved in an equal volume mixed solvent of ethylene carbonate and dimethyl carbonate as an electrolytic solution,
A coin-type battery having a thickness of 2 mm and a diameter of 23 mm was produced by covering and swaging a stainless steel positive electrode case 3.
【００２４】このようにして製造し、脱水を行った試料
ｂを正極活物質とする電池を、０．１ｍＡ／ｃｍ2の電
流密度で、２．０Ｖまでの放電と４．０Ｖまでの充電を
繰り返し行った。すると、第１０回目まで安定してサイ
クルし、第１０回目の放電容量は第１回目の放電容量の
８０％に達した。従って、この製造方法で層状二酸化マ
ンガンを脱水することにより、良好なサイクル特性を持
つ電池を実現できる。A battery using the thus prepared and dehydrated sample b as a positive electrode active material was discharged to 2.0 V and charged to 4.0 V at a current density of 0.1 mA / cm 2. Repeated. Then, the cycle was stably performed until the tenth discharge, and the tenth discharge capacity reached 80% of the first discharge capacity. Therefore, by dehydrating the layered manganese dioxide by this manufacturing method, a battery having good cycle characteristics can be realized.
【００２５】[0025]
【実施例２】実施例２では、試料ａを次のようにして脱
水した試料ｃを用いる他は、実施例１と同様にしてリチ
ウム電池を作製した。まず試料ａを、プロピレンカーボ
ネート中に、試料と接触しないよう配置した金属リチウ
ムとともに浸し、２４時間放置し脱水した。その後金属
リチウムを取り出した後、プロピレンカーボネートから
試料を濾別して取り出し、室温で乾燥させた。Ｘ線回折
によりこの試料は、試料ａと同様な構造を持つことが判
明した、この試料をｃとする。Example 2 In Example 2, a lithium battery was produced in the same manner as in Example 1, except that Sample c was used in which Sample a was dehydrated as follows. First, sample a was immersed in propylene carbonate together with lithium metal arranged so as not to come into contact with the sample, and left for 24 hours to dehydrate. Then, after removing metallic lithium, a sample was removed by filtration from propylene carbonate and dried at room temperature. X-ray diffraction revealed that this sample had a structure similar to that of sample a, and this sample is referred to as c.
【００２６】このようにして製造し、脱水を行った試料
ｃを正極活物質とする電池を、０．１ｍＡ／ｃｍ2の電
流密度で、２．０Ｖまでの放電と４．０Ｖまでの充電を
繰り返し行った。すると、第１０回目まで安定してサイ
クルし、第１０回目の放電容量は第１回目の放電容量の
８０％に達した。従って、この製造方法で層状二酸化マ
ンガンを脱水することにより、良好なサイクル特性を持
つ電池を実現できる。A battery using the thus prepared and dehydrated sample c as a positive electrode active material was discharged to 2.0 V and charged to 4.0 V at a current density of 0.1 mA / cm 2. Repeated. Then, the cycle was stably performed until the tenth discharge, and the tenth discharge capacity reached 80% of the first discharge capacity. Therefore, by dehydrating the layered manganese dioxide by this manufacturing method, a battery having good cycle characteristics can be realized.
【００２７】[0027]
【実施例３】実施例３では、次のようにして試料ｄを製
造し、この試料ｄを脱水した試料ｅを用いる他は、実施
例１と同様にしてリチウム電池を作製した。まず試料ａ
の粉末を、塩化リチウム溶液中に分散させ、２４時間放
置し、その後濾別、乾燥した。同様の作業を２回繰り返
した後、試料を溶液から濾別して取り出し、さらに水洗
して塩化リチウムを除去し、乾燥させることにより、層
状二酸化マンガンＬｉ 0.28ＭｎＯ2・０．９Ｈ2Ｏを得
た。この試料をｄとする。Embodiment 3 In Embodiment 3, a sample d was manufactured as follows.
Except that a sample e obtained by dehydrating this sample d was used.
A lithium battery was produced in the same manner as in Example 1. First, sample a
Is dispersed in a lithium chloride solution, and released for 24 hours.
And then filtered off and dried. Repeat the same work twice
After that, remove the sample from the solution by filtration and wash with water.
To remove lithium chloride and dry the layer.
Manganese dioxide Li 0.28MnOTwo・ 0.9HTwoGet O
Was. This sample is referred to as d.
【００２８】このようにして製造した試料ｄを、ジメチ
ルカーボネート中に、試料と接触しないよう配置した金
属リチウムとともに浸し、２４時間放置し脱水した。そ
の後金属リチウムを取り出した後、ジメチルカーボネー
トから試料を濾別して取り出し、室温で乾燥させた。Ｘ
線回折によりこの試料は、試料ｄと同様な構造を持つこ
とが判明した。この試料をｅとする。The sample d thus produced was immersed in dimethyl carbonate together with lithium metal arranged so as not to come into contact with the sample, and left to stand for 24 hours to dehydrate. Then, after taking out metallic lithium, a sample was taken out from dimethyl carbonate by filtration and dried at room temperature. X
Line diffraction revealed that this sample had a structure similar to that of sample d. This sample is referred to as e.
【００２９】このようにして製造し、脱水を行った試料
ｅを正極活物質とする電池を、０．１ｍＡ／ｃｍ2の電
流密度で、２．０Ｖまでの放電と４．０Ｖまでの充電を
繰り返し行った。すると、第１０回目まで安定してサイ
クルし、第１０回目の放電容量は第１回目の放電容量の
９０％に達した。従って、この製造方法で層状二酸化マ
ンガンを脱水することにより、良好なサイクル特性を持
つ電池を実現できる。A battery using the thus prepared and dehydrated sample e as a positive electrode active material was discharged to 2.0 V and charged to 4.0 V at a current density of 0.1 mA / cm 2. Repeated. Then, the cycle was stably performed until the tenth discharge, and the tenth discharge capacity reached 90% of the first discharge capacity. Therefore, by dehydrating the layered manganese dioxide by this manufacturing method, a battery having good cycle characteristics can be realized.
【００３０】[0030]
【比較例１】比較例１では、本発明の製造方法で脱水を
行わない層状二酸化マンガンとして試料ａを用いる他
は、実施例１と同様にしてリチウム電池を作製した。Comparative Example 1 In Comparative Example 1, a lithium battery was produced in the same manner as in Example 1, except that Sample a was used as the layered manganese dioxide not subjected to dehydration in the production method of the present invention.
【００３１】この電池を、０．１ｍＡ／ｃｍ2の電流密
度で、２．０Ｖまでの放電と４．０Ｖまでの充電を繰り
返し行った。すると、第２回目の放電容量は第１回目の
放電容量の１５％であった。この電池と比較すると、本
発明の実施例で脱水された試料を正極活物質として含む
電池は、より良好なサイクル特性を持つことが分かる。This battery was repeatedly discharged at a current density of 0.1 mA / cm 2 to 2.0 V and charged to 4.0 V repeatedly. Then, the second discharge capacity was 15% of the first discharge capacity. Compared with this battery, it is found that the battery including the sample dehydrated in the example of the present invention as the positive electrode active material has better cycle characteristics.
【００３２】[0032]
【比較例２】比較例２では、試料ａに次のようにして熱
処理を行った試料ｆを用いる他は、実施例１と同様にし
てリチウム電池を作製した。まず試料ａの粉末を、大気
中で２００℃で２４時間熱処理した。Ｘ線回折により得
られたパターンは、試料ａと異なっており、構造変化が
生じていることが判明した。Comparative Example 2 In Comparative Example 2, a lithium battery was fabricated in the same manner as in Example 1, except that Sample a, which was heat-treated as follows, was used for Sample a. First, the powder of the sample a was heat-treated at 200 ° C. for 24 hours in the air. The pattern obtained by X-ray diffraction was different from that of Sample a, and it was found that a structural change had occurred.
【００３３】このようにして製造し、熱処理を行った試
料ｆを正極活物質とする電池を、０．１ｍＡ／ｃｍ2の
電流密度で、２．０Ｖまでの放電と４．０Ｖまでの充電
を繰り返し行った。すると、第１０回目の放電容量は第
１回目の放電容量の６５％であった。この電池と比較す
ると、本発明の実施例で脱水された試料を正極活物質と
して含む電池は、より良好なサイクル特性を持つことが
分かる。The battery manufactured and heat-treated using the sample f as the positive electrode active material was discharged to 2.0 V and charged to 4.0 V at a current density of 0.1 mA / cm 2. Repeated. Then, the tenth discharge capacity was 65% of the first discharge capacity. Compared with this battery, it is found that the battery including the sample dehydrated in the example of the present invention as the positive electrode active material has better cycle characteristics.
【００３４】[0034]
【比較例３】比較例３では、本発明の製造方法で脱水を
行わない層状二酸化マンガンとして試料ｄを用いる他
は、実施例１と同様にしてリチウム電池を作製した。Comparative Example 3 In Comparative Example 3, a lithium battery was produced in the same manner as in Example 1, except that Sample d was used as the layered manganese dioxide not subjected to dehydration in the production method of the present invention.
【００３５】この電池を、０．１ｍＡ／ｃｍ2の電流密
度で、２．０Ｖまでの放電と４．０Ｖまでの充電を繰り
返し行った。すると、第２回目の放電容量は第１回目の
放電容量の１５％であった。この電池と比較すると、本
発明の実施例で脱水された試料を正極活物質として含む
電池は、より良好なサイクル特性を持つことが分かる。The battery was repeatedly discharged to 2.0 V and charged to 4.0 V at a current density of 0.1 mA / cm 2 . Then, the second discharge capacity was 15% of the first discharge capacity. Compared with this battery, it is found that the battery including the sample dehydrated in the example of the present invention as the positive electrode active material has better cycle characteristics.
【００３６】[0036]
【発明の効果】以上説明したように、本発明による層状
二酸化マンガンの製造方法、及びその方法により製造さ
れた層状二酸化マンガンを正極活物質として含む電池に
よれば、良好なサイクル特性を持つ電池を実現すること
ができ、種々の電子機器の電源を始め、様々な分野に利
用できるという点を有する。As described above, according to the method for producing layered manganese dioxide according to the present invention and the battery containing the layered manganese dioxide produced by the method as a positive electrode active material, a battery having good cycle characteristics can be obtained. It can be realized and can be used in various fields including power supply of various electronic devices.
【図面の簡単な説明】[Brief description of the drawings]
【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 material pellet
───────────────────────────────────────────────────── フロントページの続き (72)発明者 櫻井 庸司 東京都千代田区大手町二丁目３番１号 日 本電信電話株式会社内 Ｆターム(参考） 4G048 AA04 AA05 AC06 AE05 5H029 AJ05 AK03 AL06 AL11 AL12 AM03 AM05 AM07 BJ03 BJ16 CJ13 DJ16 DJ17 HJ02 5H050 AA07 BA17 CA09 CB07 CB12 DA09 EA02 EA10 EA24 FA17 FA18 GA13 HA02 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoji Sakurai 2-3-1 Otemachi, Chiyoda-ku, Tokyo Nippon Telegraph and Telephone Corporation F-term (reference) 4G048 AA04 AA05 AC06 AE05 5H029 AJ05 AK03 AL06 AL11 AL12 AL03 AM05 AM07 BJ03 BJ16 CJ13 DJ16 DJ17 HJ02 5H050 AA07 BA17 CA09 CB07 CB12 DA09 EA02 EA10 EA24 FA17 FA18 GA13 HA02
Claims (3)
酸化マンガンであることを特徴とする電極材料。 一般式 ＭXＭｎＯ2-δ・ｎＨ2Ｏ （Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含む１種
類以上の元素、０．１≦Ｘ≦０．５、−０．２≦δ≦
０．２、０．５≦ｎ≦１．０）An electrode material comprising dehydrated layered manganese dioxide represented by the following general formula: Formula M X MnO 2-δ · nH 2 O (M = Li, Na, K, Rb, Cs, Mg, Ca, S
one or more elements including any of r, Ba, Al, Ni, La and Bi, 0.1 ≦ X ≦ 0.5, −0.2 ≦ δ ≦
0.2, 0.5 ≦ n ≦ 1.0)
ガンを、有機溶媒中にアルカリ金属、アルカリ土類金
属、モレキュラシーブス、活性アルミナの内１種類以上
と、同時に浸すことを特徴とする電極材料の製造方法。 一般式 ＭXＭｎＯ2-δ・ｎＨ2Ｏ （Ｍ＝Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａ、Ａｌ、Ｎｉ、Ｌａ、Ｂｉの何れかを含む１種
類以上の元素、０．１≦Ｘ≦０．５、−０．２≦δ≦
０．２、０．５≦ｎ≦１．０）2. An electrode characterized in that a layered manganese dioxide represented by the following general formula is simultaneously immersed in an organic solvent with at least one of an alkali metal, an alkaline earth metal, molecular sieves and activated alumina. Material manufacturing method. Formula M X MnO 2-δ · nH 2 O (M = Li, Na, K, Rb, Cs, Mg, Ca, S
one or more elements including any of r, Ba, Al, Ni, La and Bi, 0.1 ≦ X ≦ 0.5, −0.2 ≦ δ ≦
0.2, 0.5 ≦ n ≦ 1.0)
極活物質として含む正極を有し、リチウム、ナトリウ
ム、カリウム、マグネシウム、カルシウム、ストロンチ
ウム、アルミニウム、銅、銀の何れかを含む物質または
この元素を可逆的に挿入・脱離あるいは吸蔵・脱離でき
る物質を含む負極を有し、前記元素のイオンが前記正極
および前記負極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て含むことを特徴とする電
池。3. A substance having a positive electrode containing the layered manganese dioxide according to claim 1 as a positive electrode active material, and containing any one of lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, copper, and silver, or an element thereof. Having a negative electrode containing a substance capable of reversibly inserting / desorbing or occluding / desorbing, and including, as an electrolyte substance, a substance capable of performing an ion reaction of the element for the electrochemical reaction with the positive electrode and the negative electrode A battery comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000149780A JP2001332256A (en) | 2000-05-22 | 2000-05-22 | Material for electrode, its manufacturing method and cell therewith |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000149780A JP2001332256A (en) | 2000-05-22 | 2000-05-22 | Material for electrode, its manufacturing method and cell therewith |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001332256A true JP2001332256A (en) | 2001-11-30 |
Family
ID=18655584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000149780A Pending JP2001332256A (en) | 2000-05-22 | 2000-05-22 | Material for electrode, its manufacturing method and cell therewith |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001332256A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006082719A1 (en) * | 2005-02-07 | 2006-08-10 | Sanyo Electric Co., Ltd. | Positive electrode and nonaqueous electrolyte secondary battery |
| JP2006216508A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2006216509A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Positive electrode and nonaqueous electrolyte secondary battery using the same |
| JP2006216511A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2006216510A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Positive electrode and nonaqueous electrolyte secondary battery using the same |
| US8411414B2 (en) | 2009-09-16 | 2013-04-02 | Samsung Electro-Mechanics Co., Ltd. | Metal oxide electrode material, and electrochemical capacitor using the same and manufacturing process for producing the same |
| WO2013129831A1 (en) * | 2012-02-27 | 2013-09-06 | Sk Innovation Co.,Ltd. | Turbostratic na birnessite and method for preparing the same |
| US10615452B2 (en) | 2011-06-22 | 2020-04-07 | Toyota Motor Engineering & Manufacturing North America, Inc. | High voltage rechargeable magnesium cell |
| CN115000394A (en) * | 2022-05-18 | 2022-09-02 | 安徽信息工程学院 | Electrochemical material and preparation method and application thereof |
-
2000
- 2000-05-22 JP JP2000149780A patent/JP2001332256A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4739769B2 (en) * | 2005-02-07 | 2011-08-03 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| WO2006082719A1 (en) * | 2005-02-07 | 2006-08-10 | Sanyo Electric Co., Ltd. | Positive electrode and nonaqueous electrolyte secondary battery |
| JP2006216509A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Positive electrode and nonaqueous electrolyte secondary battery using the same |
| JP2006216511A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2006216510A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Positive electrode and nonaqueous electrolyte secondary battery using the same |
| JP4739770B2 (en) * | 2005-02-07 | 2011-08-03 | 三洋電機株式会社 | Nonaqueous electrolyte secondary battery |
| JP2006216508A (en) * | 2005-02-07 | 2006-08-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| US8815449B2 (en) | 2005-02-07 | 2014-08-26 | Sanyo Electric Co., Ltd. | Positive electrode and non-aqueous electrolyte secondary battery |
| US8411414B2 (en) | 2009-09-16 | 2013-04-02 | Samsung Electro-Mechanics Co., Ltd. | Metal oxide electrode material, and electrochemical capacitor using the same and manufacturing process for producing the same |
| US10615452B2 (en) | 2011-06-22 | 2020-04-07 | Toyota Motor Engineering & Manufacturing North America, Inc. | High voltage rechargeable magnesium cell |
| KR102058460B1 (en) * | 2012-02-27 | 2019-12-23 | 에스케이이노베이션 주식회사 | Turbostratic Na birnessite and the Fabrication Method Thereof |
| WO2013129831A1 (en) * | 2012-02-27 | 2013-09-06 | Sk Innovation Co.,Ltd. | Turbostratic na birnessite and method for preparing the same |
| CN115000394A (en) * | 2022-05-18 | 2022-09-02 | 安徽信息工程学院 | Electrochemical material and preparation method and application thereof |
| CN115000394B (en) * | 2022-05-18 | 2024-04-12 | 安徽信息工程学院 | Electrochemical material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3875053B2 (en) | ELECTRODE MATERIAL, ITS MANUFACTURING METHOD, AND BATTERY USING THE SAME | |
| JP4152618B2 (en) | Method for producing positive electrode active material for layered oxide battery | |
| JPH0982359A (en) | Lithium secondary battery | |
| JP2000149942A (en) | Lithium-manganese composite oxide and lithium secondary battery using it as positive electrode active material | |
| WO2018176063A2 (en) | A stabilized birnessite cathode for high power and high energy density applications | |
| JP3403569B2 (en) | Lithium nickel composite oxide, its production method and its use | |
| JP3819940B2 (en) | Nonaqueous electrolyte secondary battery | |
| JPH06283207A (en) | Nonaqueous electrolyte battery | |
| US7378189B2 (en) | Electrode material for lithium secondary battery, electrode structure employing electrode material, and lithium secondary battery having electrode structure | |
| JP3647758B2 (en) | Non-aqueous battery positive electrode material, method for producing the same, and battery using the same | |
| JP2001332256A (en) | Material for electrode, its manufacturing method and cell therewith | |
| JP3532139B2 (en) | Method for producing nickel-containing oxide electrode material and battery using the electrode material | |
| JPH10134812A (en) | Nonaqueous electrolyte lithium secondary cell and manufacture of its positive electrode material | |
| JP4339741B2 (en) | Layered oxide electrode material and battery using the same | |
| JP2000182616A (en) | Manufacture of positive electrode active material for nonaqueous electrolyte secondary battery | |
| JPH08287914A (en) | Lithium battery | |
| JPH09259879A (en) | Manufacture of positive electrode active material for lithium battery | |
| JP3625629B2 (en) | Nickel oxide cathode material manufacturing method and battery using nickel oxide manufactured by the method | |
| JP3289256B2 (en) | Method for producing positive electrode active material for lithium battery | |
| KR20070018293A (en) | Cathode active material coated with aluminium or their alloy and electrochemical device using the same | |
| JP2000149943A (en) | Process for lithium manganese compound oxide for lithium secondary battery positive active material | |
| JP3403568B2 (en) | Lithium nickel composite oxide, its production method and its use | |
| JP3301026B2 (en) | Lithium battery | |
| JP3436292B2 (en) | Positive electrode material for lithium battery, method for producing the same, and lithium battery using the same | |
| JPH113707A (en) | Lithium secondary battery |