JP2003086179A - Electrode material, its method of manufacture, and battery using the same - Google Patents
Electrode material, its method of manufacture, and battery using the sameInfo
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- JP2003086179A JP2003086179A JP2001273327A JP2001273327A JP2003086179A JP 2003086179 A JP2003086179 A JP 2003086179A JP 2001273327 A JP2001273327 A JP 2001273327A JP 2001273327 A JP2001273327 A JP 2001273327A JP 2003086179 A JP2003086179 A JP 2003086179A
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- electrode material
- lithium
- battery
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- electrode
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Classifications
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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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電極材料、その製造
方法及びそれを用いた電池に関するものである。TECHNICAL FIELD The present invention relates to an electrode material, a method for producing the same, and a battery using the same.
【０００２】[0002]
【従来の技術】二酸化マンガン類と一般に称される化合
物は、マンガンの見かけ上の価数が３価から４価までの
酸化物を広く含んでおり、またマンガンと酸素以外に種
々のカチオンや水のような中性分子が構造中に存在する
ものも含んでおり、非常に広範囲の組成や構造を持つ化
合物が知られている。2. Description of the Related Art Compounds generally referred to as manganese dioxides include a wide range of oxides having an apparent valence of manganese from 3 to 4 and, in addition to manganese and oxygen, various cations and water. Compounds having a very wide range of compositions and structures are known, including those in which a neutral molecule such as is present in the structure.
【０００３】マンガンの酸化還元対が比較的高い電位を
持つことから、これら二酸化マンガン類は乾電池を始め
とする水溶液系の電池、並びにリチウムイオン電池を始
めとする非水溶液系の電池の正極材料として、研究・開
発されている。Since the redox couple of manganese has a relatively high potential, these manganese dioxides are used as a positive electrode material for aqueous batteries such as dry batteries and non-aqueous batteries such as lithium ion batteries. , Researched and developed.
【０００４】これらの二酸化マンガン類では、マンガン
の周りに６つの酸素が配位した八面体を形成単位とし
て、その八面体が面や稜や頂点を共有して連なった構造
をとる化合物が、多く知られている。その中には、（２
×２）トンネル構造を持つ化合物があり、図１に示すよ
うに、上記の形成単位が２つ連なった４つの辺で囲まれ
たトンネルを有している。なお、図１では、トンネル内
にカチオンＡ＋が含まれる場合を示している。In many of these manganese dioxides, many compounds have an octahedron in which six oxygen atoms are coordinated around manganese as a forming unit, and the octahedron has a structure in which faces, edges and vertices are shared and connected. Are known. Among them, (2
X2) There is a compound having a tunnel structure, and as shown in FIG. 1, it has a tunnel surrounded by four sides in which the above-mentioned two forming units are connected. Note that FIG. 1 shows a case where the cation A + is contained in the tunnel.
【０００５】これらの（２×２）トンネル構造を持つ化
合物は、トンネルをイオン移動パスとして利用できるた
め、電極材料として有望であり、実際にリチウム電池用
などの電極材料としての利用が提案されている。These compounds having a (2 × 2) tunnel structure are promising as an electrode material because the tunnel can be used as an ion transfer path, and their use as an electrode material for lithium batteries has been proposed. There is.
【０００６】[0006]
【発明が解決しようとする課題】しかし、これらの（２
×２）トンネル構造を持つ化合物は、従来、水を用いる
湿式工程によって得られる含水化合物を用いて製造され
ているため、電極としての放電容量が小さいという欠点
があった。この原因は、製造工程中に（２×２）トンネ
ル中に入った水分子は非常に安定であり、この化合物に
脱水処理を施しても、完全には脱水できず、その残存水
分子あるいは残存プロトンが電極特性に悪影響を及ぼす
ためと考えられる。However, these (2
X2) Since a compound having a tunnel structure has been conventionally produced using a hydrated compound obtained by a wet process using water, it has a drawback that the discharge capacity as an electrode is small. The reason for this is that the water molecules that entered the (2 × 2) tunnel during the manufacturing process are very stable, and even if this compound is dehydrated, it cannot be completely dehydrated, and the residual water molecules or residual water molecules remain. It is considered that protons adversely affect the electrode characteristics.
【０００７】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（２×２）トンネル構造を有する二酸
化マンガン類であって、大きな放電容量を有する電極材
料、その製造方法及びその電極材料を用いた電池を提供
することにある。The present invention solves the above-mentioned problems of the present situation, and is an electrode material which is a manganese dioxide having a (2 × 2) tunnel structure as described above and which has a large discharge capacity, a manufacturing method thereof, and It is to provide a battery using the electrode material.
【０００８】[0008]
【課題を解決するための手段】前記課題を解決するため
に、本発明は、請求項１に記載のように、組成式Ｎａｘ
ＭｎＯ２＋δで表され、（２×２）トンネル構造を有す
る電極材料であって、前記ｘ及びδが不等式０＜ｘ≦
０．４及び−０．２≦δ≦０．２を満足することを特徴
とする電極材料を構成する。In order to solve the above problems, the present invention provides a composition formula Na x as defined in claim 1.
An electrode material represented by MnO 2 + δ and having a (2 × 2) tunnel structure, in which x and δ are inequality 0 <x ≦
An electrode material is characterized by satisfying 0.4 and -0.2≤δ≤0.2.
【０００９】また、本発明は、請求項２に記載のよう
に、請求項１記載の電極材料を、ナトリウム化合物及び
マンガン化合物を出発原料とし、水を用いない乾式工程
により製造することを特徴とする電極材料の製造方法を
構成する。Further, according to the present invention, as described in claim 2, the electrode material according to claim 1 is produced by a dry process using a sodium compound and a manganese compound as starting materials and not using water. And a method for manufacturing an electrode material to be used.
【００１０】また、本発明は、請求項３に記載のよう
に、組成式ＬｉｙＮａｚＭｎＯ２＋δで表され、（２×
２）トンネル構造を有する電極材料であって、前記ｙ、
ｚ及びδが不等式０＜ｙ≦０．４、０≦ｚ＜０．４、ｙ
＋ｚ≦０．４及び−０．２≦δ≦０．２を満足すること
を特徴とする電極材料を構成する。Further, the present invention is represented by the composition formula Li y Na z MnO 2 + δ , and (2 ×
2) An electrode material having a tunnel structure, wherein the y,
z and δ are inequalities 0 <y ≦ 0.4, 0 ≦ z <0.4, y
An electrode material is characterized by satisfying + z ≦ 0.4 and −0.2 ≦ δ ≦ 0.2.
【００１１】また、本発明は、請求項４に記載のよう
に、請求項１記載の電極材料に含有されるナトリウムの
一部又は全部を、イオン交換処理によって、リチウムに
置換することにより、請求項３記載の電極材料を得るこ
とを特徴とする電極材料の製造方法を構成する。Further, according to the present invention, as described in claim 4, a part or all of sodium contained in the electrode material according to claim 1 is replaced with lithium by an ion exchange treatment. An electrode material manufacturing method is characterized in that the electrode material according to item 3 is obtained.
【００１２】また、本発明は、請求項５に記載のよう
に、請求項４記載の電極材料の製造方法において、前記
イオン交換処理を、リチウム化合物を含有する溶融塩
中、又はリチウム化合物を溶解した有機溶剤中において
行うことを特徴とする電極材料の製造方法を構成する。Further, according to the present invention, as in claim 5, in the method for producing an electrode material according to claim 4, the ion exchange treatment is carried out in a molten salt containing a lithium compound or by dissolving the lithium compound. The method for producing an electrode material is characterized in that the method is carried out in the above organic solvent.
【００１３】また、本発明は、請求項６に記載のよう
に、正極、負極及び電解質物質を有する電池において、
前記正極は請求項１又は請求項３記載の電極材料を用い
て構成されることを特徴とする電池を構成する。Further, the present invention provides a battery having a positive electrode, a negative electrode and an electrolyte substance as described in claim 6,
The positive electrode is configured by using the electrode material according to claim 1 or 3, thereby forming a battery.
【００１４】また、本発明は、請求項７に記載のよう
に、請求項６記載の電池において、前記負極はリチウ
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、銅及び銀のうちの
何れかの元素を含む物質、又は、前記元素を可逆的に挿
入・脱離あるいは吸蔵・放出できる物質を含有し、前記
電解質物質は、前記元素のイオンの前記電解質物質中で
の移動を可能とする物質を含有することを特徴とする電
池を構成する。According to a seventh aspect of the present invention, in the battery according to the sixth aspect, the negative electrode is any one of lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, copper and silver. A substance containing the element, or a substance capable of reversibly inserting / desorbing or occluding / releasing the element, and the electrolyte substance enables migration of ions of the element in the electrolyte substance. A battery is characterized by containing a substance.
【００１５】[0015]
【発明の実施の形態】かかる目的を達成するために本発
明に係る電極材料は、（２×２）トンネル構造を有す
る、組成式ＮａｘＭｎＯ２＋δ（０＜ｘ≦０．４、−
０．２≦δ≦０．２）で表される化合物、また、（２×
２）トンネル構造を有する、組成式ＬｉｙＮａｚＭｎＯ
２＋δ（０＜ｙ≦０．４、０≦ｚ＜０．４、ｙ＋ｚ≦
０．４、−０．２≦δ≦０．２）で表される化合物であ
ることを特徴としている。BEST MODE FOR CARRYING OUT THE INVENTION In order to achieve such an object, an electrode material according to the present invention has a composition formula of Na x MnO 2 + δ (0 <x ≦ 0.4, − having a (2 × 2) tunnel structure.
0.2 ≦ δ ≦ 0.2), or (2 ×
2) Compositional formula Li y Na z MnO having a tunnel structure
2 + δ (0 <y ≦ 0.4, 0 ≦ z <0.4, y + z ≦
0.4, -0.2 ≤ δ ≤ 0.2).
【００１６】また本発明に係る電極材料の製造方法とし
ては、ナトリウム化合物及びマンガン化合物を出発原料
とし、水を用いない乾式工程により前記組成式ＮａｘＭ
ｎＯ ２＋δ（０＜ｘ≦０．４、−０．２≦δ≦０．２）
で表される化合物を製造すること、前記組成式ＮａｘＭ
ｎＯ２＋δ（０＜ｘ≦０．４、−０．２≦δ≦０．２）
で表される化合物にイオン交換処理を施すことにより、
前記ＬｉｙＮａｚＭｎＯ２＋δ（０＜ｙ≦０．４、０≦
ｚ＜０．４、ｙ＋ｚ≦０．４、−０．２≦δ≦０．２）
で表される化合物を製造すること、及び、リチウム含有
化合物を含む溶融塩中、又はリチウム含有化合物を溶解
した有機溶剤中において、前記イオン交換処理を施すこ
とを特徴としている。Further, as a method for producing an electrode material according to the present invention,
, Sodium compounds and manganese compounds as starting materials
And the composition formula Na by a dry process using no water.xM
nO 2 + δ(0 <x ≦ 0.4, −0.2 ≦ δ ≦ 0.2)
The compound of formula NaxM
nO2 + δ(0 <x ≦ 0.4, −0.2 ≦ δ ≦ 0.2)
By subjecting the compound represented by
The LiyNazMnO2 + δ(0 <y ≦ 0.4, 0 ≦
z <0.4, y + z ≦ 0.4, −0.2 ≦ δ ≦ 0.2)
Producing a compound represented by, and containing lithium
In molten salt containing compound or dissolving lithium-containing compound
Do not perform the ion exchange treatment in the organic solvent
It is characterized by.
【００１７】また、本発明に係る電池は、正極、負極及
び電解質物質を有しており、前記正極に前記本発明に係
る電極材料を含むことを特徴としており、また、前記負
極は、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又はこれらの元素を可逆的に挿入
・脱離あるいは吸蔵・放出できる物質を含み、前記電解
質物質は前記元素のイオンが前記正極及び前記負極と電
気化学反応をするための移動を行い得る物質を含むこと
を特徴としている。The battery according to the present invention has a positive electrode, a negative electrode and an electrolyte substance, and the positive electrode contains the electrode material according to the present invention, and the negative electrode is lithium, Sodium, potassium, magnesium, calcium, strontium, aluminum, copper,
A substance containing any of silver or a substance capable of reversibly inserting / desorbing or occluding / releasing these elements, and the electrolyte substance is used for electrochemical reaction of ions of the element with the positive electrode and the negative electrode. It is characterized in that it contains a substance capable of moving.
【００１８】本発明をさらに詳しく説明する。The present invention will be described in more detail.
【００１９】本願発明者は、（２×２）トンネル構造を
有する二酸化マンガン類で、かつ放電容量の大きい電極
材料を鋭意探索した結果、前述の電極材料を用いること
により従来よりも電池の放電容量が大きくなることを見
出し、また前述の電極材料の製造方法が放電容量増大に
有効であることを見出し、さらにそれを用いた電池の放
電容量が大きくなることを確かめ、その認識の下に本発
明を完成した。The inventor of the present application has made an earnest search for an electrode material of manganese dioxide having a (2 × 2) tunnel structure and having a large discharge capacity. It was found that the above-mentioned method for producing an electrode material is effective for increasing the discharge capacity, and it was confirmed that the discharge capacity of a battery using the same is increased. Was completed.
【００２０】本発明に係る電極材料である、（２×２）
トンネル構造を有する、組成式Ｎａ ｘＭｎＯ２＋δ（０
＜ｘ≦０．４、−０．２≦δ≦０．２）で表される化合
物のトンネル内には、少量のマンガンを含む場合もある
が、多くの場合にナトリウムのみを含んでおり、水やプ
ロトンが存在していないのが特徴である。The electrode material according to the present invention is (2 × 2)
Composition formula Na having a tunnel structure xMnO2 + δ(0
<X ≦ 0.4, −0.2 ≦ δ ≦ 0.2)
A small amount of manganese may be contained in the material tunnel.
However, it often contains only sodium,
The feature is that there is no roton.
【００２１】また、本発明に係る電極材料である、（２
×２）トンネル構造を有する、組成式ＬｉｙＮａｚＭｎ
Ｏ２＋δ（０＜ｙ≦０．４、０≦ｚ＜０．４、ｙ＋ｚ≦
０．４、−０．２≦δ≦０．２）で表される化合物のト
ンネル内には、少量のマンガンを含む場合もあるが、多
くの場合にナトリウムとリチウムのみを含んでおり、水
やプロトンが存在していないのが特徴である。The electrode material according to the present invention (2
X2) Compositional formula Li y Na z Mn having a tunnel structure
O 2 + δ (0 <y ≦ 0.4, 0 ≦ z <0.4, y + z ≦
0.4, -0.2 ≤ δ ≤ 0.2) may contain a small amount of manganese in the tunnel of the compound, but in many cases, it contains only sodium and lithium, It is characterized by the absence of or protons.
【００２２】これらの化合物を電極材料に用いた場合、
電池特性に悪影響を及ぼす水分子やプロトンが存在しな
いため、大きな放電容量が得られるものと考えられる。
またナトリウム、リチウム以外のイオンや分子がトンネ
ル間に存在しないため、分子量が比較的小さく、重量あ
たりのエネルギー密度が大きくなるという利点もある。
また他の二酸化マンガン類に比べて密度（比重）が高い
ため、体積当たりのエネルギー密度も大きいという利点
がある。When these compounds are used as electrode materials,
It is considered that a large discharge capacity can be obtained because there are no water molecules or protons that adversely affect the battery characteristics.
Further, since ions and molecules other than sodium and lithium do not exist between the tunnels, the molecular weight is relatively small and the energy density per weight is large.
Further, since it has a higher density (specific gravity) than other manganese dioxides, there is an advantage that the energy density per volume is also large.
【００２３】本発明に係る前記組成式ＮａｘＭｎＯ
２＋δ（０＜ｘ≦０．４、−０．２≦δ≦０．２）で表
される化合物である電極材料を製造する場合には、ナト
リウム化合物とマンガン化合物とを出発原料とし、これ
らの原料を混合して焼成するなどの、水を用いない乾式
工程により製造することができる。このような乾式工程
によりこの化合物を製造すれば、化合物中の（２×２）
トンネル内への水の混入を避けることができ、電池特性
に悪影響を及ぼす水分子やプロトンの混入を避けること
ができるという利点を有する。例えば、上記の化合物
は、炭酸ナトリウムとβ二酸化マンガン（鉱物名：パイ
ロルサイト）を混合して、酸素中で反応させることによ
り製造することができる。望ましくは酸素分圧が１気圧
を越える雰囲気で、４００℃〜７００℃の温度で、この
化合物を製造することが好ましい。According to the present invention, the composition formula Na x MnO
When producing an electrode material which is a compound represented by 2 + δ (0 <x ≦ 0.4, −0.2 ≦ δ ≦ 0.2), a sodium compound and a manganese compound are used as starting materials, and It can be produced by a dry process that does not use water, such as mixing raw materials and firing. If this compound is prepared by such a dry process, (2 × 2)
This has the advantage that water can be prevented from entering the tunnel and water molecules and protons that adversely affect the battery characteristics can be avoided. For example, the above compound can be produced by mixing sodium carbonate and β-manganese dioxide (mineral name: pyrolsite) and reacting them in oxygen. It is preferable to produce this compound at a temperature of 400 ° C. to 700 ° C. in an atmosphere having an oxygen partial pressure of more than 1 atm.
【００２４】また本発明に係る前記組成式ＬｉｙＮａｚ
ＭｎＯ２＋δ（０＜ｙ≦０．４、０≦ｚ＜０．４、ｙ＋
ｚ≦０．４、−０．２≦δ≦０．２）で表される化合物
である電極材料は、前記組成式ＮａｘＭｎＯ２＋δ（０
＜ｘ≦０．４、−０．２≦δ≦０．２）で表される化合
物に、イオン交換処理を施すことにより、製造すること
ができる。すなわち、イオン交換処理により、前記組成
式ＮａｘＭｎＯ２＋δ中のナトリウムが、部分的ないし
全てリチウムに置換され、前記組成式ＬｉｙＮａｚＭｎ
Ｏ２＋δ（０＜ｙ≦０．４、０≦ｚ＜０．４、ｙ＋ｚ≦
０．４、−０．２≦δ≦０．２）で表される化合物が得
られる。The composition formula Li y Na z according to the present invention is also
MnO 2 + δ (0 <y ≦ 0.4, 0 ≦ z <0.4, y +
The electrode material which is a compound represented by z ≦ 0.4, −0.2 ≦ δ ≦ 0.2) has the composition formula Na x MnO 2 + δ (0
It can be produced by subjecting the compound represented by <x ≦ 0.4, −0.2 ≦ δ ≦ 0.2) to an ion exchange treatment. That is, by the ion exchange treatment, the sodium in the composition formula Na x MnO 2 + δ is partially or entirely replaced with lithium, and the composition formula Li y Na z Mn.
O 2 + δ (0 <y ≦ 0.4, 0 ≦ z <0.4, y + z ≦
0.4, −0.2 ≦ δ ≦ 0.2) is obtained.
【００２５】この場合に、リチウム含有化合物を含む溶
融塩中、又はリチウム含有化合物を溶解した有機溶剤中
において、イオン交換処理を施すことが好適である。前
記電極材料が水を吸収しやすい特性を考えれば、これら
の非水環境中でイオン交換を行うことが望ましい。溶融
塩としては硝酸リチウム、塩化リチウム、臭化リチウ
ム、ヨウ化リチウムの何れか１種類以上を含む溶融塩を
用いることができる。また塩化リチウム、臭化リチウム
などのリチウム含有化合物を溶解した有機溶剤中でイオ
ン交換を行うこともできる。イオン交換においては、交
換できるイオン種が多量に存在するほどイオン交換速度
が高いので、リチウム化合物を直接溶融した溶融塩を用
いることが特に好ましい。また、高温で行うほど交換速
度が高いので、ナトリウムをできるだけ多くのリチウム
に短時間で交換するには、高温でイオン交換することが
好ましい。但し温度が必要以上に高いと、生成した化合
物が分解する可能性があるので、４００℃以下の温度で
行うことが好ましい。溶融塩を用いる場合、反応温度は
溶融塩の融点以上の温度が必要であることは言うまでも
ない。有機溶剤中でイオン交換を行う場合は、イオン交
換速度を高めるため、有機溶剤の沸点付近で、溶剤を還
流させながら、イオン交換させることが好ましい。In this case, it is preferable to perform the ion exchange treatment in a molten salt containing the lithium-containing compound or in an organic solvent in which the lithium-containing compound is dissolved. Considering the characteristic that the electrode material easily absorbs water, it is desirable to perform ion exchange in these non-aqueous environments. As the molten salt, a molten salt containing one or more of lithium nitrate, lithium chloride, lithium bromide and lithium iodide can be used. Ion exchange can also be performed in an organic solvent in which a lithium-containing compound such as lithium chloride or lithium bromide is dissolved. In ion exchange, it is particularly preferable to use a molten salt obtained by directly melting a lithium compound, because the ion exchange rate becomes higher as the amount of ion species that can be exchanged increases. Further, the higher the temperature, the higher the exchange rate. Therefore, in order to exchange sodium for as much lithium as possible in a short time, it is preferable to perform ion exchange at a high temperature. However, if the temperature is unnecessarily high, the produced compound may be decomposed. Therefore, it is preferable to perform the temperature at 400 ° C. or lower. Needless to say, when a molten salt is used, the reaction temperature needs to be at least the melting point of the molten salt. When performing ion exchange in an organic solvent, it is preferable to perform ion exchange while refluxing the solvent near the boiling point of the organic solvent in order to increase the ion exchange rate.
【００２６】上記組成式中、ｘ、ｙ、ｚ、δは、それぞ
れ０＜ｘ≦０．４、０＜ｙ≦０．４、０≦ｚ＜０．４、
ｙ＋ｚ≦０．４、−０．２≦δ≦０．２を満たすもので
あるが、これらは合成条件により変化する。組成式Ｎａ
ｘＭｎＯ２＋δ（０＜ｘ≦０．４、−０．２≦δ≦０．
２）で表される化合物では、ｘ＝０．２付近において、
（２×２）トンネル構造を有する化合物が得られやすい
ので、ｘ＝０．２付近が好ましい。またイオン交換され
たＬｉｙＮａｚＭｎＯ２＋δ（０＜ｙ≦０．４、０≦ｚ
＜０．４、ｙ＋ｚ≦０．４、−０．２≦δ≦０．２）で
表される化合物では、出発物質中のナトリウムが、リチ
ウムが入った量ｙだけ脱離する（ｘ−ｙ＝ｚとなる）の
が通常であるが、反応条件によりマンガンの価数が変化
しうるため、出発物質のナトリウム量ｘと、生成物のナ
トリウム量ｙとリチウム量ｚとの和は、等しくない場合
もある。またイオン交換中に酸素の出入りが起こること
もあり、δ値が変化することもあり得る。In the above composition formula, x, y, z and δ are respectively 0 <x ≦ 0.4, 0 <y ≦ 0.4, 0 ≦ z <0.4 and
Although y + z ≦ 0.4 and −0.2 ≦ δ ≦ 0.2 are satisfied, these change depending on the synthesis conditions. Composition formula Na
x MnO 2 + δ (0 <x ≦ 0.4, −0.2 ≦ δ ≦ 0.
In the compound represented by 2), in the vicinity of x = 0.2,
Since it is easy to obtain a compound having a (2 × 2) tunnel structure, x is preferably around 0.2. Also, ion-exchanged Li y Na z MnO 2 + δ (0 <y ≦ 0.4, 0 ≦ z
In the compounds represented by <0.4, y + z ≦ 0.4, −0.2 ≦ δ ≦ 0.2), sodium in the starting material is desorbed by the amount y containing lithium (xy). However, since the valence of manganese may change depending on the reaction conditions, the sum of the sodium amount x of the starting material, the sodium amount y of the product, and the lithium amount z is not equal. In some cases. In addition, oxygen may flow in and out during ion exchange, and the δ value may change.
【００２７】本発明に係る電極材料を、リチウムイオン
が移動する電池に用いる際には、ｙ値を大きくして、ｚ
値を下げることが好ましい。（２×２）トンネル内に、
移動するイオン種であるリチウムイオンが多く存在する
ことにより、電極材料内のイオン拡散が容易になり、大
きな容量が得られるからである。When the electrode material according to the present invention is used in a battery in which lithium ions move, the y value is increased and z is increased.
It is preferable to lower the value. In the (2 x 2) tunnel,
This is because the presence of many lithium ions, which are ionic species that move, facilitates ion diffusion in the electrode material and provides a large capacity.
【００２８】本発明に係る電極材料を含む正極を形成す
るには、電極材料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、さらに、これ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
て正極を形成する。To form a positive electrode containing the electrode material according to the present invention, a mixture of the electrode material and a binder powder such as polytetrafluoroethylene is pressure-molded on a support such as stainless steel. Alternatively, in order to impart conductivity to the active material powder, a conductive powder such as acetylene black is mixed, and further, a binder powder such as polytetrafluoroethylene is added to the powder, if necessary. The mixture is placed in a metal container, pressure-molded on a support such as stainless steel, or dispersed in a solvent such as an organic solvent to form a slurry, which is applied on a metal substrate to form a positive electrode.
【００２９】本発明に係る電池は正極、負極及び電解質
物質を有し、その正極は本発明に係る電極材料を用いて
構成される。負極としては、例えば、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又は
その元素を可逆的に挿入・脱離あるいは吸蔵・放出でき
る物質を用いて構成され、電解質物質は、前記元素のイ
オンが前記正極及び前記負極と電気化学反応をするため
の移動を可能とする物質を含有し、この電池は、前記元
素のイオンが正極と負極の間を行き来することにより、
電池として機能する。The battery according to the present invention has a positive electrode, a negative electrode and an electrolyte substance, and the positive electrode is formed by using the electrode material according to the present invention. As the negative electrode, for example, a substance containing any one of lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, copper, and silver or a substance capable of reversibly inserting / desorbing or occluding / releasing the element thereof is used. The electrolyte material contains a material that allows the ions of the element to move to cause an electrochemical reaction with the positive electrode and the negative electrode, and in this battery, the ions of the element move between the positive electrode and the negative electrode. By doing
Functions as a battery.
【００３０】上記の負極としてリチウムを含む物質を用
いる場合には、そのような物質として、例えば、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。When a substance containing lithium is used as the negative electrode, a conventionally known material such as lithium metal, lithium-aluminum alloy, lithium-carbon compound or lithium-containing nitride is used as the substance. be able to.
【００３１】上記の電解質物質としては、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。Examples of the above-mentioned electrolyte substance include methoxyethane, diethoxyethane, 2-methyltetrahydrofuran, ethylene carbonate, propylene carbonate, methyl formate, dimethyl sulfoxide, acetonitrile, butyrolactone, dimethylformamide,
Dimethyl carbonate, diethyl carbonate, sulfolane, an organic solvent such as ethylmethyl carbonate, a non-aqueous electrolyte solvent in which a salt of an alkali metal, an alkaline earth metal or the like is dissolved, or a solid electrolyte, a polymer electrolyte, the organic solvent was carried. A polymer electrolyte or the like can be used.
【００３２】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, it can be used as a secondary battery.
【００３３】さらにセパレータ、電池ケース等の構造材
料等、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。Further, conventionally known various materials can be used for other elements such as a structural material such as a separator and a battery case, and there is no particular limitation.
【００３４】[0034]
【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。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
【００３５】［実施例１］図２は、本発明に係る製造方
法によって製造された（２×２）トンネル構造を有する
二酸化マンガンを正極活物質として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。Example 1 FIG. 2 shows a coin-type battery which is a specific example of a battery using manganese dioxide having a (2 × 2) tunnel structure manufactured by the manufacturing method according to the present invention as a positive electrode active material. It is a sectional view, in which 1 is a sealing plate, 2 is a gasket, 3 is a positive electrode case, 4 is a negative electrode, 5 is a separator, and 6 is a positive electrode material mixture pellet.
【００３６】本実施例では、正極活物質として、次のよ
うにして製造した試料ａを用いた。炭酸ナトリウムとβ
二酸化マンガン（鉱物名：パイロルサイト）を、モル比
で、Ｎａ：Ｍｎ＝１：５の割合で混合して、酸素分圧が
４気圧の雰囲気中で、６００℃、１０時間熱処理するこ
とにより、組成Ｎａ０．２０ＭｎＯ２を有する試料ａを
得た。In this example, the sample a manufactured as follows was used as the positive electrode active material. Sodium carbonate and β
By mixing manganese dioxide (mineral name: pyrolusite) in a molar ratio of Na: Mn = 1: 5, and heat treating at 600 ° C. for 10 hours in an atmosphere with an oxygen partial pressure of 4 atm. , A sample having the composition Na 0.20 MnO 2 was obtained.
【００３７】このようにして製造した試料ａを、粉末Ｘ
線回折測定法を用いて解析したところ、図３に示すよう
に、ＪＣＰＤＳ（Joint Committee on Powder Diffract
ionStandards）のデータとよく一致し、（２×２）トン
ネル構造を有していることが分かった。すなわち、試料
ａは、組成式ＮａｘＭｎＯ２＋δ（ここに、０＜ｘ≦
０．４、−０．２≦δ≦０．２とする）で表され、（２
×２）トンネル構造を有する化合物であることを特徴と
する電極材料の１つである。この場合に、試料ａの構造
は図１で示され、図中のＡ＋はＮａ＋に該当する。The sample a produced in this way was powder X
As a result of analysis using the line diffraction measurement method, as shown in FIG. 3, JCPDS (Joint Committee on Powder Diffract
It was found to have a (2 × 2) tunnel structure in good agreement with the data of (ionStandards). That is, the sample a has a composition formula Na x MnO 2 + δ (where 0 <x ≦
0.4, −0.2 ≦ δ ≦ 0.2), and (2
X2) One of the electrode materials, which is a compound having a tunnel structure. In this case, the structure of the sample a is shown in FIG. 1, and A + in the figure corresponds to Na + .
【００３８】この試料ａを得る上記の工程は、水を用い
ない乾式工程である。The above step of obtaining the sample a is a dry process using no water.
【００３９】次に、この試料ａを、硝酸リチウムと塩化
リチウムのモル比３：１混合溶融塩中でイオン交換処理
した。試料ａの溶融塩中における量は、モル比で、溶融
塩中のＬｉ：試料ａ中のＮａ＝２０：１とし、溶融塩の
温度は３５０℃とした。このイオン交換処理を３回行
い、得られた固体をメタノールで洗浄、乾燥して試料ｂ
を得た。この試料ｂの化学組成を分析し、組成式とし
て、Ｌｉ０．１０Ｎａ０． １０ＭｎＯ２を得た。Next, this sample a was subjected to ion exchange treatment in a molten salt of a mixture of lithium nitrate and lithium chloride in a molar ratio of 3: 1. The amount of the sample a in the molten salt was a molar ratio of Li in the molten salt: Na in the sample a = 20: 1, and the temperature of the molten salt was 350 ° C. This ion exchange treatment was performed 3 times, and the obtained solid was washed with methanol and dried to obtain sample b.
Got The chemical composition of this sample b was analyzed, and as a composition formula, Li 0.10 Na 0. 10 MnO 2 was obtained.
【００４０】このようにして製造した試料ｂを、粉末Ｘ
線回折測定法を用いて解析したところ、図４に示すよう
に、イオン交換前の試料と同様なパターンを保っている
ことから、（２×２）トンネル構造を有していることが
分かった。すなわち、試料ｂは、組成式ＬｉｙＮａｚＭ
ｎＯ２＋δ（ここに、０＜ｙ≦０．４、０≦ｚ＜０．
４、ｙ＋ｚ≦０．４、−０．２≦δ≦０．２とする）で
表され、（２×２）トンネル構造を有する化合物である
ことを特徴とする電極材料の１つである。この場合に、
試料ｂの構造は図１で示され、図中のＡ＋はＬｉ＋又は
Ｎａ＋に該当する。The sample b manufactured in this manner was used as powder X
As a result of analysis using a line diffraction measurement method, as shown in FIG. 4, it was found that the sample had a (2 × 2) tunnel structure because it had the same pattern as the sample before ion exchange. . That is, the sample b is a composition formula Li y Na z M.
nO 2 + δ (where 0 <y ≦ 0.4, 0 ≦ z <0.
4, y + z ≦ 0.4, −0.2 ≦ δ ≦ 0.2), and is a compound having a (2 × 2) tunnel structure. In this case,
The structure of the sample b is shown in FIG. 1, and A + in the figure corresponds to Li + or Na + .
【００４１】この試料ａ又は試料ｂの粉末を導電剤（ア
セチレンブラック）及び結着剤（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 a or the sample b was mixed with a conductive agent (acetylene black) and a binder (polytetrafluoroethylene) and roll-formed, and the positive electrode mixture pellets 6 (thickness 0.5 mm, diameter 15 mm).
【００４２】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、リチウムイオンが前記正極及び前記
負極と電気化学反応をするための移動を可能とする電解
質物質である電解液として、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（図２
に、上下を逆にして示す）を作製した。Next, a metallic lithium negative electrode 4 placed under pressure on a stainless steel sealing plate 1 is inserted into a recess of a polypropylene gasket 2, and a polypropylene microporous separator 5 is placed on the negative electrode 4. The positive electrode material mixture pellets 6 are arranged in this order, and as the electrolytic solution, which is an electrolyte substance that enables lithium ions to move for electrochemical reaction with the positive electrode and the negative electrode, an equal volume of ethylene carbonate and dimethyl carbonate is used. After injecting an appropriate amount of 1N solution in which LiPF 6 is dissolved in a mixed solvent to impregnate it, a positive electrode case 3 made of stainless steel is covered and caulked, so that a coin type battery having a thickness of 2 mm and a diameter of 23 mm (see
Is shown upside down).
【００４３】このようにして製造した試料ａ又は試料ｂ
を正極活物質とする電池を、０．１ｍＡ／ｃｍ２の電流
密度で、４．５Ｖまで充電を行った後に２．０Ｖまで放
電を行った。すると、試料ａでは１６０ｍＡｈ／ｇ、試
料ｂでは１８０ｍＡｈ／ｇの容量を得ることができた。
従って、上記本発明に係る製造方法で製造された（２×
２）トンネル構造を有する電極材料を用いることによ
り、大きな放電容量を持つ電池を実現できることが判
る。Sample a or sample b manufactured in this way
The battery using as a positive electrode active material was charged to 4.5 V and then discharged to 2.0 V at a current density of 0.1 mA / cm 2 . Then, it was possible to obtain a capacity of 160 mAh / g for sample a and a capacity of 180 mAh / g for sample b.
Therefore, it is manufactured by the manufacturing method according to the present invention (2 ×
2) It can be seen that a battery having a large discharge capacity can be realized by using an electrode material having a tunnel structure.
【００４４】［比較例１］本比較例においては、従来の
湿式法に従い、次のようにして製造した試料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。[Comparative Example 1] In this comparative example, a lithium battery was manufactured in the same manner as in Example 1 except that the sample c manufactured as follows was used according to the conventional wet method.
【００４５】まず、希硫酸中に、硝酸マンガンと過マン
ガン酸ナトリウムをモル比１：１で混合し、１００℃で
５時間反応させ、液中に生成する粉末を濾過によって液
から分離し、１００℃で乾燥させて試料ｃを得た。First, manganese nitrate and sodium permanganate were mixed in diluted sulfuric acid at a molar ratio of 1: 1 and reacted at 100 ° C. for 5 hours, and the powder produced in the solution was separated from the solution by filtration. A sample c was obtained by drying at 0 ° C.
【００４６】このようにして製造した試料ｃを、粉末Ｘ
線回折測定法を用いて解析したところ、試料ａと類似の
パターンが得られ、（２×２）トンネル構造を有してい
ることが分かった。The sample c produced in this manner was used as powder X
An analysis using a line diffraction measurement method revealed that a pattern similar to that of the sample a was obtained and that it had a (2 × 2) tunnel structure.
【００４７】このようにして製造した試料ｃを正極活物
質とする電池を実施例１と同様にして作成し、その電池
を０．１ｍＡ／ｃｍ２の電流密度で４．５Ｖまで充電を
行った後に２．０Ｖまで放電しても１２０ｍＡｈ／ｇの
容量しか得られなかった。この電池と比較すると、本発
明の実施例１で製造された試料を正極活物質として含む
電池は、より大きな放電容量を持つことが分かる。A battery using the sample c thus produced as a positive electrode active material was prepared in the same manner as in Example 1, and the battery was charged to 4.5 V at a current density of 0.1 mA / cm 2 . Even after discharging to 2.0 V, only a capacity of 120 mAh / g was obtained. As compared with this battery, it can be seen that the battery including the sample manufactured in Example 1 of the present invention as the positive electrode active material has a larger discharge capacity.
【００４８】本比較例における電池の容量が、上記実施
例１の電池の容量よりも小さい理由は、試料ｃの（２×
２）トンネル構造中に存在する水分子が電極特性に及ぼ
す悪影響にあると考えられる。The reason why the capacity of the battery in this comparative example is smaller than that of the battery of Example 1 is that the value of (2 ×
2) It is considered that the water molecules present in the tunnel structure have an adverse effect on the electrode characteristics.
【００４９】以上説明したように、本発明に係る（２×
２）トンネル構造を有する二酸化マンガン類電極材料の
製造方法、及びその方法により製造された（２×２）ト
ンネル構造を有する二酸化マンガン類電極材料を正極と
して含む電池によれば、大きな放電容量を持つ電池を実
現することができ、本発明は種々の電子機器の電源をは
じめ、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 present invention, (2 ×
2) A method for producing a manganese dioxide electrode material having a tunnel structure and a battery including the (2 × 2) tunnel structure manganese dioxide electrode material produced as a positive electrode have a large discharge capacity. A battery can be realized, and the present invention can be used in various fields including a power source for various electronic devices.
【００５０】[0050]
【発明の効果】本発明の実施によって、（２×２）トン
ネル構造を有する二酸化マンガン類であって、大きな放
電容量を有する電極材料、その製造方法及びその電極材
料を用いた電池を提供することができる。The present invention provides an electrode material which is a manganese dioxide having a (2 × 2) tunnel structure and has a large discharge capacity, a method for producing the same, and a battery using the electrode material. You can
【図１】本発明に係る電極材料の構造模式図である。FIG. 1 is a structural schematic view of an electrode material according to the present invention.
【図２】本発明の実施例１におけるコイン型電池の構成
例を示す断面図である。FIG. 2 is a cross-sectional view showing a configuration example of a coin-type battery in Example 1 of the present invention.
【図３】粉末Ｘ線回折測定により同定した、本発明の実
施例１における試料ａのＸ線回折パターン及びＪＣＰＤ
Ｓによる（２×２）トンネル構造を有する二酸化マンガ
ンのピークデータを比較して示す図である。FIG. 3 is an X-ray diffraction pattern and JCPD of the sample a in Example 1 of the present invention identified by powder X-ray diffraction measurement.
It is a figure which compares and shows the peak data of manganese dioxide which has a (2x2) tunnel structure by S.
【図４】粉末Ｘ線回折測定により同定した、本発明の実
施例１における試料ｂのＸ線回折パターンをイオン交換
前の試料ａと比較して示す図である。FIG. 4 is a diagram showing an X-ray diffraction pattern of a sample b in Example 1 of the present invention identified by powder X-ray diffraction measurement, in comparison with a sample a before ion exchange.
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。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 林 政彦 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 (72)発明者 斉藤 景一 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 (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 AB01 AC06 AD03 AE05 5H029 AJ03 AK03 AL01 AL06 AL11 AL12 AM03 AM04 AM05 AM07 AM12 AM16 BJ03 BJ12 CJ15 CJ28 DJ17 HJ02 5H050 AA08 BA15 BA16 BA17 CA09 CB01 CB07 CB11 CB12 FA19 GA16 HA02 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Masahiko Hayashi 2-3-1, Otemachi, Chiyoda-ku, Tokyo Inside Telegraph and Telephone Corporation (72) Inventor Keiichi Saito 2-3-1, Otemachi, Chiyoda-ku, Tokyo Inside Telegraph and Telephone Corporation (72) Inventor Youji Sakurai 2-3-1, Otemachi, Chiyoda-ku, Tokyo Inside Telegraph and Telephone Corporation F-term (reference) 4G048 AA04 AB01 AC06 AD03 AE05 5H029 AJ03 AK03 AL01 AL06 AL11 AL12 AM03 AM04 AM05 AM07 AM12 AM16 BJ03 BJ12 CJ15 CJ28 DJ17 HJ02 5H050 AA08 BA15 BA16 BA17 CA09 CB01 CB07 CB11 CB12 FA19 GA16 HA02
Claims (7)
×２）トンネル構造を有する電極材料であって、前記ｘ
及びδが不等式０＜ｘ≦０．４及び−０．２≦δ≦０．
２を満足することを特徴とする電極材料。1. A composition formula represented by Na x MnO 2 + δ ,
X2) An electrode material having a tunnel structure, wherein x
And δ are inequalities 0 <x ≦ 0.4 and −0.2 ≦ δ ≦ 0.
An electrode material characterized by satisfying 2.
合物及びマンガン化合物を出発原料とし、水を用いない
乾式工程により製造することを特徴とする電極材料の製
造方法。2. A method for producing an electrode material, which comprises producing the electrode material according to claim 1 by a dry process using a sodium compound and a manganese compound as starting materials and not using water.
れ、（２×２）トンネル構造を有する電極材料であっ
て、前記ｙ、ｚ及びδが不等式０＜ｙ≦０．４、０≦ｚ
＜０．４、ｙ＋ｚ≦０．４及び−０．２≦δ≦０．２を
満足することを特徴とする電極材料。3. An electrode material having a composition formula of Li y Na z MnO 2 + δ and having a (2 × 2) tunnel structure, wherein the y, z and δ are inequalities 0 <y ≦ 0.4, 0 ≦. z
<0.4, y + z <0.4 and -0.2 <(delta) <0.2 are satisfy | filled, The electrode material characterized by the above-mentioned.
リウムの一部又は全部を、イオン交換処理によって、リ
チウムに置換することにより、請求項３記載の電極材料
を得ることを特徴とする電極材料の製造方法。4. The electrode material according to claim 3, wherein part or all of sodium contained in the electrode material according to claim 1 is replaced with lithium by an ion exchange treatment. Manufacturing method of electrode material.
て、前記イオン交換処理を、リチウム化合物を含有する
溶融塩中、又はリチウム化合物を溶解した有機溶剤中に
おいて行うことを特徴とする電極材料の製造方法。5. The method for producing an electrode material according to claim 4, wherein the ion exchange treatment is carried out in a molten salt containing a lithium compound or in an organic solvent in which the lithium compound is dissolved. Manufacturing method.
おいて、前記正極は請求項１又は請求項３記載の電極材
料を用いて構成されることを特徴とする電池。6. A battery having a positive electrode, a negative electrode and an electrolyte substance, wherein the positive electrode is formed by using the electrode material according to claim 1 or 3.
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、銅及び銀のう
ちの何れかの元素を含む物質、又は、前記元素を可逆的
に挿入・脱離あるいは吸蔵・放出できる物質を含有し、
前記電解質物質は、前記元素のイオンの前記電解質物質
中での移動を可能とする物質を含有することを特徴とす
る電池。7. The battery according to claim 6, wherein the negative electrode is a substance containing any element of lithium, sodium, potassium, magnesium, calcium, strontium, aluminum, copper and silver, or the element is reversible. Contains a substance that can be inserted and removed or occluded and released,
The battery according to claim 1, wherein the electrolyte substance contains a substance that enables migration of ions of the element in the electrolyte substance.
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