JPH04198028A - Lithium manganese double oxide, its production and use - Google Patents
Lithium manganese double oxide, its production and useInfo
- Publication number
- JPH04198028A JPH04198028A JP2322351A JP32235190A JPH04198028A JP H04198028 A JPH04198028 A JP H04198028A JP 2322351 A JP2322351 A JP 2322351A JP 32235190 A JP32235190 A JP 32235190A JP H04198028 A JPH04198028 A JP H04198028A
- Authority
- JP
- Japan
- Prior art keywords
- lithium
- surface area
- crystal structure
- manganese dioxide
- type crystal
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000001989 lithium alloy Substances 0.000 claims abstract description 6
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001947 lithium oxide Inorganic materials 0.000 abstract description 3
- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 abstract 4
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000011572 manganese Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000002642 lithium compounds Chemical class 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- -1 alkyl lithium Chemical compound 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910008088 Li-Mn Inorganic materials 0.000 description 1
- 229910006327 Li—Mn Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PYRZPBDTPRQYKG-UHFFFAOYSA-N cyclopentene-1-carboxylic acid Chemical compound OC(=O)C1=CCCC1 PYRZPBDTPRQYKG-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical class O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
【発明の詳細な説明】
［産業上の利用分野］
本発明は新規なＬ ｉＭ ｎ ２０４に関するものであ
り、さらに詳しくは粒径１０μｍ以下の粒子から成るＬ
Ｉ Ｍ ｎ ２０４とその製造方法並びにその用途に
関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a novel LiM n 204, and more specifically, L iM n 204 consisting of particles with a particle size of 10 μm or less.
This article relates to I M n 204, its manufacturing method, and its uses.
近年Ｌ ｉＭ ｎ ２０４は、リチウム二次電池正極材
料として注目されている。In recent years, LiM n 204 has attracted attention as a positive electrode material for lithium secondary batteries.
［従来の技術］
スピネル骨格構造を持つ二酸化マンガンは、八面***置
及び四面***置にリチウムイオンが入ることができ、ま
たリチウムイオンが移動できる通路が三次元的に連なっ
ている。従って、スピネル骨格構造を持つＬ Ｉ Ｍ
ｎ ２０４は、リチウムイオンを結晶構造内にドープ、
脱ドープすることが可能である。[Prior Art] Manganese dioxide having a spinel skeleton structure allows lithium ions to enter octahedral and tetrahedral positions, and has a three-dimensional series of paths through which lithium ions can move. Therefore, L I M with a spinel skeleton structure
n 204 is doped with lithium ions into the crystal structure,
It is possible to dedope.
ｌこの特性から、ＬｉＭｎ２Ｏ４は近年リチウム二次電
池の正極材料として注目される゛ようになった。Due to this property, LiMn2O4 has recently attracted attention as a positive electrode material for lithium secondary batteries.
Ｌ ｓ Ｍ ｎ ２０４をリチウム二次電池の正極に用
いた場合、電気化学的な酸化還元を行うため、その際の
電荷補償としてリチウムイオンが、結晶格子内にドープ
又は脱ドープされる。この反応は、結晶格子の構造破壊
を伴わず、安定に繰り返し行えるため、二次電池用正極
材料として有望であり、実用化の検討が行なわれている
。When L s M n 204 is used as the positive electrode of a lithium secondary battery, electrochemical redox is performed, and lithium ions are doped or dedoped into the crystal lattice as charge compensation at that time. Since this reaction can be performed repeatedly and stably without destroying the structure of the crystal lattice, it is promising as a positive electrode material for secondary batteries, and its practical application is being studied.
例えば、特開昭６３−１８７５６９号公報ではＭｎ２Ｏ
３とＬｉ２ＣＯ３をＬｉ：Ｍｎ−に２（モル比）で混合
し、６５０℃で６時間、８５０℃で１４時間空気中で焼
成する方法で得られたしｓ Ｍ ｎ ２０４を正極に用
いているが、本発明者らの検討によれば、十分な正極性
能を得るに至っていない。これは、焼成を高温で長時間
行っているために粒子の焼結反応が進み、粒子径の成長
が起こして表面積が低下し、利用効率が低下するためで
ある。For example, in JP-A-63-187569, Mn2O
3 and Li2CO3 were mixed with Li:Mn- at a molar ratio of 2, and s M n 204 was used as the positive electrode. However, according to studies by the present inventors, sufficient positive electrode performance has not been achieved. This is because the sintering reaction of the particles progresses because the firing is carried out at high temperatures for a long time, causing growth in particle size, decreasing the surface area, and lowering the utilization efficiency.
この問題点を解決するために、幾つかの方法が提案され
ている。Several methods have been proposed to solve this problem.
特開昭６３−２１８１５６号公報では、前記特開昭６３
−１８７５６９号公報の方法でＬ ｉ Ｍ ｎ２０４を
焼成終了後直ちに水中にて急速冷却を行い、結晶粒子を
微粉化することで表面積を増大させて利用効率を向上さ
せることを提案している。In JP-A No. 63-218156, the above-mentioned JP-A-63-218156
It is proposed that LiM n204 be rapidly cooled in water immediately after firing by the method of Publication No. 187569, and the crystal particles will be pulverized to increase the surface area and improve the utilization efficiency.
しかし、この方法では、Ｌｌ イオンの拡散が容易なス
ピネル構造が歪められ、さらに水分が混入するために、
性能及び保存性の点で問題点かある。However, in this method, the spinel structure, which allows easy diffusion of Ll ions, is distorted and water is mixed in, resulting in
There are some problems in terms of performance and storage stability.
一方、特開平２−１３９８６０号公報では、出発マンガ
ン種としてＬｌ イオンが拡散しやすいγ型構造の二酸
化マンガンを用いて、４３０℃から５１０℃の低温で短
時間で焼成する方法が提案されている。この提案は、低
温で短い時間焼成することで粒子成長を抑え、表面積の
低下の抑制を狙ったものである。しかし、本発明者らの
検討によれば、この焼成温度で得られるＬｉＭｎ２Ｏ４
は、表面積の低下は抑制されるものの、結晶格子は小さ
くなり、そのためＬｌ イオンが拡散する３次元チャン
ネルが狭くなる。従って電池正極に用いたときの過電圧
が上昇し、利用率が低下する問題がある。On the other hand, JP-A-2-139860 proposes a method of firing at a low temperature of 430°C to 510°C in a short time using manganese dioxide having a γ-type structure in which Ll ions easily diffuse as the starting manganese species. . This proposal aims to suppress particle growth and reduce surface area by firing at low temperatures for a short period of time. However, according to the studies of the present inventors, LiMn2O4 obtained at this firing temperature
Although the decrease in surface area is suppressed, the crystal lattice becomes smaller and the three-dimensional channel through which Ll ions diffuse becomes narrower. Therefore, when used as a battery positive electrode, there is a problem in that the overvoltage increases and the utilization rate decreases.
［本発明が解決しようとする課題］
これまでに提案されているＬ ｉＭ ｎ ２０４では、
電気化学活性が不十分であり、正極に用いた場合、サイ
クル特性に優れた非水リチウム二次電池を構成すること
は、困難である。[Problems to be solved by the present invention] In the L iM n 204 proposed so far,
Electrochemical activity is insufficient, and when used as a positive electrode, it is difficult to construct a non-aqueous lithium secondary battery with excellent cycle characteristics.
［課題を解決するための手段］
本発明者らは、上記課題を解決するために鋭意検討を行
った結果、マンガン酸化物とリチウム材料との混合物を
焼成するＬ ｒ Ｍ ｎ ２０４の製造方法において、
前記マンガン酸化物にＢＥＴ比表面積が１５０ｍ／ｇか
ら５００ ｍ ２／ ｇのγ型結晶構造を有する二酸化
マンガンを用いてＬ ｉ Ｍ ｎ２０４の焼成を行うこ
とで、粒子成長が抑制され、粒径１０μｍ以下の粒子か
ら成り、高い表面積を持つ、電気化学的に高活性なＬ
ｉＭ ｎ ２０４が合成できることを見出だした。さら
に、これを正極に用い、負極にリチウム又はリチウム合
金、電解質に非水電解質を用いると、高いサイクル放電
容量を持つ非水リチウム二次電池が構成できることを見
出し、本発明を完成するに至った。[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have developed a manufacturing method for L r M n 204 in which a mixture of manganese oxide and lithium material is fired. ,
By firing LiM n204 using manganese dioxide having a γ-type crystal structure with a BET specific surface area of 150 m/g to 500 m 2 / g as the manganese oxide, particle growth is suppressed and the particle size is reduced to 10 μm. Electrochemically highly active L, consisting of the following particles and having a high surface area
It has been found that iM n 204 can be synthesized. Furthermore, they discovered that by using this for the positive electrode, lithium or a lithium alloy for the negative electrode, and a nonaqueous electrolyte for the electrolyte, a nonaqueous lithium secondary battery with high cycle discharge capacity could be constructed, and the present invention was completed. .
［作用］ 以下本発明を具体的に説明する。[Effect] The present invention will be specifically explained below.
本発明のＬ Ｉ Ｍ ｎ ２０４は、出発マンガン種と
してＢＥＴ比表面積が１５０ ｍ ２／ ｇから５００
ｍ２／ｇのγ型結晶構造を有する二酸化マンガンを用い
て製造することで得られる。本発明者らの検討によれば
、マンガン酸化物とリチウム材料との混合物を焼成する
ＬｉＭｎ２Ｏ４の製造方法において、マンガン酸化物に
ＢＥＴ比表面積が１５０ｍ／ｇから５００ｍ２／ｇのγ
型結晶構造を有する二酸化マンガンを用いることで、粒
子成長が顕著に抑制されることが分かっている。詳細に
ついては明らかではないが、この効果は以下のように考
えられる。本発明で用いるγ型結晶構造を有する二酸化
マンガンは、ＢＥＴ比表面積が１５０ｍ／ｇから５００
ｍ２／ｇであり、リチウム化合物との反応性が極めて高
く、均一組成のＬｉＭｎ２Ｏ４が生成しやすい。また、
結晶構造はγ型であり、γ型の結晶構造を有する二酸化
マンガンは、（ＩＸ２）のチャンネル構造を持ち、リチ
ウムの結晶内部への拡散が容易であることから、リチウ
ム化合物と反応させた場合、反応は容易に進行し、二酸
化マンガン粒子表面には過剰のリチウムが残ること無く
反応が進む。即ち、表面にはリチウムが過剰で電気化学
的に不活性なＬ ｉ −Ｍｎ系複合酸化物、例えばＬｉ
ＭｎＯ３等が生成しない。さらに、リチウムには粒子成
長を促す為、表面のリチウム濃度が過剰になる状態では
粒子成長が容易に起こると考えられる。従って、本発明
のように二酸化マンガン表面と内部のリチウム濃度が均
一になる条件では、粒子成長が抑制され、粒子径が１０
μｍ以下の高表面積のＬ Ｉ Ｍ ｎ ２０４が得られ
ると考えられる。The L I M n 204 of the present invention has a BET specific surface area of 150 m 2 / g to 500 m 2 / g as the starting manganese species.
It can be obtained by manufacturing using manganese dioxide having a γ-type crystal structure of m2/g. According to the studies of the present inventors, in a method for producing LiMn2O4 in which a mixture of manganese oxide and lithium material is fired, manganese oxide has a BET specific surface area of γ of 150 m/g to 500 m2/g.
It has been found that particle growth is significantly suppressed by using manganese dioxide having a type crystal structure. Although the details are not clear, this effect is thought to be as follows. Manganese dioxide having a γ-type crystal structure used in the present invention has a BET specific surface area of 150 m/g to 500 m/g.
m2/g, the reactivity with lithium compounds is extremely high, and LiMn2O4 with a uniform composition is easily generated. Also,
The crystal structure is γ type, and manganese dioxide having the γ type crystal structure has a (IX2) channel structure, and lithium can easily diffuse into the crystal, so when reacted with a lithium compound, The reaction progresses easily, without leaving excess lithium on the surface of the manganese dioxide particles. That is, an electrochemically inactive Li-Mn complex oxide with excess lithium on the surface, such as Li
MnO3 etc. are not generated. Furthermore, since lithium promotes particle growth, particle growth is thought to occur easily when the lithium concentration on the surface is excessive. Therefore, under conditions where the lithium concentration on the surface and inside the manganese dioxide is uniform as in the present invention, particle growth is suppressed and the particle size is reduced to 10
It is believed that a L I M n 204 with a high surface area of less than μm can be obtained.
この効果は、ＢＥＴ比表面積が１５０ ｍ ２／ ｇか
ら５００ｍ２／ｇの間で顕著である。これは、次の理由
に基ずくと考えられる。ＢＥＴ比表面積が１５０ ｍ
２／ ｇ未満では、二酸化マンガンとリチウム化合物と
の均一混合を十分に行うことができず、従ってリチウム
が過剰な組成物が二酸化マンガン表面に生成し易くなり
、焼成の際に凝集が起こり易くなる。また、５００ ｍ
２／ ｇを越えた場合では、二酸化マンガンの熱相転
移のほうがリチウム化合物との焼成反応よりも起こり易
くなり、リチウムが内部に拡散しやすいγ型結晶構造が
歪められるために、組成が不均一となり、凝集が起こり
易くなる。このため、１５０ｍ２／ｇがら５００ｍ２／
ｇが最適な条件となり、凝集が抑制され、均一組成で粒
径が１０μｍ以下の高表面積なＬ Ｉ Ｍ ｎ ２０４
が得られると考えられる。これを正極に用い、負極にリ
チウム又はリチウム合金、電解質に非水電解質を用いる
と、高いサイクル放電容量を持つ非水リチウム二次電池
が構成できる。This effect is remarkable when the BET specific surface area is between 150 m 2 /g and 500 m 2 /g. This is considered to be based on the following reasons. BET specific surface area is 150 m
If it is less than 2/g, the manganese dioxide and the lithium compound cannot be mixed sufficiently uniformly, and therefore a composition containing excessive lithium is likely to be formed on the surface of the manganese dioxide, and agglomeration is likely to occur during firing. . Also, 500 m
When the amount exceeds 2/g, the thermal phase transition of manganese dioxide is more likely to occur than the calcination reaction with the lithium compound, and the γ-type crystal structure in which lithium easily diffuses into the interior is distorted, resulting in non-uniform composition. Therefore, aggregation is likely to occur. Therefore, from 150m2/g to 500m2/g
L I M n 204 with a uniform composition and a high surface area with a particle size of 10 μm or less, with optimum g conditions and suppressed aggregation.
is considered to be obtained. If this is used for the positive electrode, lithium or a lithium alloy for the negative electrode, and a nonaqueous electrolyte for the electrolyte, a nonaqueous lithium secondary battery with high cycle discharge capacity can be constructed.
本発明で用いるγ型結晶構造を有する二酸化マンガンは
、例えば、特公昭４１−１６９６号公報に示されている
ように、通常の電解二酸化マンガンの製造条件よりも高
い硫酸濃度及び高い電流密度で電解反応を行うことで製
造される。通常の製造条件では、電解二酸化マンガンは
（１）式に示した酸化反応により陽極上に析出する。Manganese dioxide having a γ-type crystal structure used in the present invention can be electrolyzed at a higher sulfuric acid concentration and a higher current density than the normal production conditions for electrolytic manganese dioxide, as shown in Japanese Patent Publication No. 1696/1983, for example. Manufactured by performing a reaction. Under normal manufacturing conditions, electrolytic manganese dioxide is deposited on the anode by the oxidation reaction shown in equation (1).
このため、電解終了後陽極から剥離し粉砕して粒子状の
二酸化マンガンとするが、この方法で得られる二酸化マ
ンガンのＢＥＴ比表面積は１００ｍ２／ｇ以下である。For this reason, after the electrolysis is completed, it is peeled from the anode and pulverized to produce particulate manganese dioxide, but the BET specific surface area of the manganese dioxide obtained by this method is 100 m2/g or less.
一方、本発明で用いるγ型結晶構造を有する二酸化マン
ガンは、通常の電解二酸化マンガンの製造条件よりも電
解液中の硫酸濃３ ＋
度を高くすることでＭｎ イオンの安定性を増３
＋
加させ、（２）式に示すようにＭｎ イオンのみを
陽極生成物とし、電解液中で（３）式で示される加水分
解反応を行わせることで製造される。On the other hand, the manganese dioxide having a γ-type crystal structure used in the present invention increases the stability of Mn ions by increasing the concentration of sulfuric acid in the electrolytic solution compared to the normal production conditions of electrolytic manganese dioxide.
+ is added, and as shown in equation (2), only Mn ions are used as an anode product, and the hydrolysis reaction shown in equation (3) is performed in an electrolytic solution.
２＋ ３＋
Ｍｎ −＋Ｍｎ ＋ｅ （２）３＋
’ｌ＋ 十
２Ｍｎ ＋２ＨＯ→ＭｎＯ２＋Ｍｎ ＋４Ｈ上記方
法で、ＢＥＴ比表面積が１５０ｍ２／ｇから５００ｍ２
／ｇのγ型結晶構造をもつ二酸化マンガンが製造される
。2+ 3+ Mn −+Mn +e (2) 3+
'l+ 12Mn +2HO→MnO2+Mn +4H By the above method, the BET specific surface area ranges from 150m2/g to 500m2
/g of manganese dioxide having a γ-type crystal structure is produced.
本発明のＬ ｉＭ ｎ ２０４の製造において用いられ
るリチウム材料は、特に限定されるものではなく、リチ
ウム金属及び／またはリチウム化合物であれば如何なる
ものを用いても良い。例えば、リチウム金属、酸化リチ
ウム、水酸化リチウム、硝酸リチウム、シュウ酸リチウ
ム、炭酸リチウム、ヨウ化リチウム、アルキルリチウム
等が例示される。The lithium material used in the production of LiM n 204 of the present invention is not particularly limited, and any lithium metal and/or lithium compound may be used. Examples include lithium metal, lithium oxide, lithium hydroxide, lithium nitrate, lithium oxalate, lithium carbonate, lithium iodide, and alkyl lithium.
リチウム材料と二酸化マンガンの混合方法は、特に制限
されるものではなく、固相及び／または液相で混合を行
えば良い。例えば、二酸化マンガン及びリチウム材料の
粉末を、乾式及び／または湿式で混合する方法や、リチ
ウム材料を溶解及び／または懸濁させた溶液中で二酸化
マンガン粉末を撹拌することで混合する方法等が例示さ
れる。The method for mixing the lithium material and manganese dioxide is not particularly limited, and the mixing may be performed in a solid phase and/or liquid phase. Examples include a method of dry and/or wet mixing of manganese dioxide and lithium material powders, and a method of mixing manganese dioxide powder by stirring it in a solution in which a lithium material is dissolved and/or suspended. be done.
本発明において、焼成は６５０”Ｃ以上の温度で行うこ
とが必要である。この温度以下では、反応が十分に進行
せず、均一組成のＬ Ｉ Ｍ ｎ ２０４を得ることが
できない。また、焼成時の雰囲気は特に制限されないが
、好ましくは酸素含有雰囲気が良い。In the present invention, it is necessary to perform the firing at a temperature of 650"C or higher. Below this temperature, the reaction will not proceed sufficiently and it will not be possible to obtain L I M n 204 with a uniform composition. The atmosphere at the time is not particularly limited, but preferably an oxygen-containing atmosphere.
本発明の非水リチウム二次電池の負極としてはリチウム
金属、リチウム合金を用いることができる。リチウム合
金としては、例えばリチウム／スズ合金、リチウム／鉛
合金等が挙げられる。As the negative electrode of the non-aqueous lithium secondary battery of the present invention, lithium metal or lithium alloy can be used. Examples of lithium alloys include lithium/tin alloys and lithium/lead alloys.
また、本発明の非水リチウム二次電池の電解質は特に制
限されないが、例えば、カーボネート類、スルホラン類
、ラクトン類、エーテル類等の有機溶媒中にリチウム塩
を溶解したものや、リチウムイオン導電性の固体電解質
を用いることができる。Further, the electrolyte of the non-aqueous lithium secondary battery of the present invention is not particularly limited, but examples include those in which a lithium salt is dissolved in an organic solvent such as carbonates, sulfolanes, lactones, and ethers, and electrolytes with lithium ion conductivity. solid electrolyte can be used.
本発明で得られたＬ ｉＭ ｎ ２０４を正極に用い、
上記の負極及び電解質を使用して第１図に示す二次電池
を構成した。図中に於いて、１：正極用リード線、２：
正極集電用メツシュ、３：正極、４：セバレーター、５
二負極、６：負極集電用メツシュ、７：負極用リード線
、８：容器を示す。Using LiM n 204 obtained in the present invention as a positive electrode,
A secondary battery shown in FIG. 1 was constructed using the above negative electrode and electrolyte. In the figure, 1: positive electrode lead wire, 2:
Positive electrode current collection mesh, 3: Positive electrode, 4: Separator, 5
Two negative electrodes, 6: mesh for negative electrode current collection, 7: lead wire for negative electrode, 8: container.
［実施例］
以下実施例を述べるが、本発明はこれに限定されるもの
ではない。[Example] Examples will be described below, but the present invention is not limited thereto.
実施例１
（Ｌ Ｉ Ｍ ｎ ２０４の作成）
実施例１として、Ｌ ｉＭ ｎ ２０４を次のようにし
て製造した。Example 1 (Preparation of L I M n 204) As Example 1, L i M n 204 was manufactured as follows.
硫酸マンガンを２５ｇ／ｌ、硫酸を１５０ｇ／ｌの濃度
で含む水溶液中で、陽極にｐｔ板を用いて、５０ Ａ
／ ｄ ｍ ２の電流密度で電解することによって、粒
子状の電解二酸化マンガンを得た。この電解二酸化マン
ガンは分析の結果、ＢＥＴ比表面積１９０ｍ２／ｇ、粒
径１μｍ以下、γ型の結晶構造を持つ二酸化マンガンで
あった。第２図に、この二酸化マンガンのＸ線回折図を
示すが、得られた二酸化マンガンの結晶構造は明らかに
γ型結晶構造を有する。In an aqueous solution containing manganese sulfate at a concentration of 25 g/l and sulfuric acid at a concentration of 150 g/l, a PT plate was used as the anode, and the temperature was 50 A.
Particulate electrolytic manganese dioxide was obtained by electrolysis at a current density of /d m2. As a result of analysis, this electrolytic manganese dioxide was found to be manganese dioxide having a BET specific surface area of 190 m2/g, a particle size of 1 μm or less, and a γ-type crystal structure. FIG. 2 shows an X-ray diffraction diagram of this manganese dioxide, and the crystal structure of the obtained manganese dioxide clearly has a γ-type crystal structure.
次に、この二酸化マンガン４３．５ｇと酸化リチウム３
．７５ｇを乳鉢で混合した後、８５０℃で２０時間焼成
した。得られた化合物のＸ線回折及び化学組成分析を行
った。結果をそれぞれ第３図及び以下の表１に示す。分
析の結果から、この化合物はＬｉＭｎ２Ｏ４であると同
定できた。Next, 43.5g of this manganese dioxide and 3g of lithium oxide
．． After mixing 75 g in a mortar, it was baked at 850° C. for 20 hours. The obtained compound was subjected to X-ray diffraction and chemical composition analysis. The results are shown in FIG. 3 and Table 1 below. From the results of the analysis, this compound was identified as LiMn2O4.
また、ＳＥＭ観察から粒径は５μｍ以下であることが分
かった。Furthermore, SEM observation revealed that the particle size was 5 μm or less.
表１ 化学組成分析値
（電池の構成）
得られたＬｉＭｎ０ 導電材のカーボン粉２４ゝ
末及び結着材のポリテトラフルオロエチレン粉末を重量
比で、８８ ： ９ ： ３の割合で混合した。この混
合物７５ｍｇを５ ｔ ｏ ｎ ／ ｃ ｍ ２の圧力
で８ｍｍφのベレットに成型した。これを第１図３の正
極として用い、第１図５の負極にはリチウム箔（厚さ０
．２ｍｍ）から切り抜いたリチウム片を用い、電解液に
は、プロピレンカーボネートと１゜２ジメトキシエタン
を体積比で１：１の割合で混合した混合液に過塩素酸リ
チウムを１ ｍ ｏ １ ／ ｄｍ３濃度で溶解した電
解液を第１図４のセパレータに含浸させて、第１図に示
す断面積０．５ｃｍ２の電池を構成した。Table 1 Chemical Composition Analysis Values (Battery Structure) Obtained LiMn0 Carbon powder 24mm powder as a conductive material and polytetrafluoroethylene powder as a binder were mixed in a weight ratio of 88:9:3. 75 mg of this mixture was molded into a pellet of 8 mmφ at a pressure of 5 tons/cm 2 . This was used as the positive electrode in Figure 1 3, and the negative electrode in Figure 1 5 was a lithium foil (thickness 0
．． Using a lithium piece cut out from a 2mm thick piece, the electrolyte was a mixture of propylene carbonate and 1゜2 dimethoxyethane in a volume ratio of 1:1, and lithium perchlorate was added at a concentration of 1 m o 1 / dm3. The separator shown in FIG. 1 and 4 was impregnated with the electrolytic solution dissolved in 1 to form a battery having a cross-sectional area of 0.5 cm 2 as shown in FIG.
（電池性能評価）
上記方法で作成した電池を用いて、５ｍＡの一定電流で
、電池電圧が２ｖ〜４■の範囲で充放電を繰り返した。(Battery Performance Evaluation) Using the battery prepared by the above method, charging and discharging were repeated at a constant current of 5 mA at a battery voltage in the range of 2 V to 4 ■.
その結果を第４図に示す。結果から、５０サイクル目の
放電容量は、１サイクル目の放電容量に対して約８０％
の容量を保持していた。The results are shown in FIG. From the results, the discharge capacity at the 50th cycle is approximately 80% of the discharge capacity at the 1st cycle.
It held a capacity of
比較例１
比較例１として、二酸化マンガンに市販の電解二酸化マ
ンガン（ＢＥＴ比表面積５０ ｍ ２／ ｇ 。Comparative Example 1 As Comparative Example 1, commercially available electrolytic manganese dioxide (BET specific surface area 50 m 2 / g) was used as manganese dioxide.
γ型結晶構造）を用いたこと以外は、実施例１と同様に
Ｌ ｉＭ ｎ ２０４を作成した。Ｘ線回折からは、得
られた化合物は、Ｌ ｉＭ ｎ ２０４であると同定さ
れたが、ＳＥＭ観察から粒径は約５０μｍであることが
分かった。次に、これを第１図３の正極に用いた以外は
実施例１と同様な電池を構成した。第４図に示した電池
評価の結果から、５０サイクル目の放電容量は、１サイ
クル目の放電容量に対して約３０％の容量しか保持して
いなかった。LiM n 204 was produced in the same manner as in Example 1, except that a γ-type crystal structure) was used. The obtained compound was identified as LiM n 204 by X-ray diffraction, and the particle size was found to be about 50 μm by SEM observation. Next, a battery similar to that of Example 1 was constructed except that this was used as the positive electrode in FIG. 1 and 3. From the battery evaluation results shown in FIG. 4, the discharge capacity at the 50th cycle was only about 30% of the discharge capacity at the 1st cycle.
［発明の効果］
以上述べてきたとおり、本発明の方法により、粒子成長
が抑制され、粒子径が１０μｍ以下の粒径を持ち、高表
面積なＬ ｉＭ ｎ ２０４が製造でき、これを正極に
用いることで、サイクル放電容量の大きい非水リチウム
二次電池が構成可能となる。[Effects of the Invention] As described above, according to the method of the present invention, LiM n 204 with suppressed particle growth, a particle size of 10 μm or less, and a high surface area can be produced, and this can be used for a positive electrode. This makes it possible to construct a non-aqueous lithium secondary battery with a large cycle discharge capacity.
第１図は、実施例１及び比較例１で作成した電池の実施
態様を示す断面概略図である。
図中、
１：正極用リード線、２：正極集電用メツシュ３：正極
４：セバレータ−５：負極 ６
：負極集電用メツシュ７：負極用リード線 ８：容器
を示す。
第２図は実施例１で用いた二酸化マンガンのＸ線回折図
を示す。
第３図は実施例１において作成したＬｉＭｎ２Ｏ４のＸ
線回折図を示す。
第４図は、実施例１及び比較例１で作成した電池の各サ
イクル毎の放電容量の初期放電容量に対する維持率を示
す図である。
特許出願人 東ソー株式会社
第２図
２ｅ／ｄｅｇ （Ｃｕ）
第３図
２０んｅｇ（Ｃｕ）FIG. 1 is a schematic cross-sectional view showing embodiments of batteries prepared in Example 1 and Comparative Example 1. In the figure, 1: Lead wire for positive electrode, 2: Mesh for positive electrode current collection 3: Positive electrode 4: Separator 5: Negative electrode 6
: Negative electrode current collection mesh 7: Negative electrode lead wire 8: Indicates a container. FIG. 2 shows an X-ray diffraction pattern of manganese dioxide used in Example 1. Figure 3 shows the X of LiMn2O4 prepared in Example 1.
A line diffraction diagram is shown. FIG. 4 is a diagram showing the retention rate of the discharge capacity for each cycle of the batteries prepared in Example 1 and Comparative Example 1 with respect to the initial discharge capacity. Patent applicant Tosoh Corporation Fig. 2 2e/deg (Cu) Fig. 3 20n eg (Cu)
Claims (3)
＿４。(1) LiMn_2O consisting of particles with a particle size of 10 μm or less
＿４.
することによりＬｉＭｎ＿２Ｏ＿４を製造する方法にお
いて、前記マンガン酸化物に、ＢＥＴ比表面積が１５０
ｍ＾２／ｇから５００ｍ＾２／ｇのγ型結晶構造を有す
る二酸化マンガンを用いることを特徴とする、特許請求
の範囲第一項記載のＬｉＭｎ＿２Ｏ＿４の製造方法。(2) In a method for producing LiMn_2O_4 by firing a mixture of manganese oxide and lithium material, the manganese oxide has a BET specific surface area of 150
A method for producing LiMn_2O_4 according to claim 1, characterized in that manganese dioxide having a γ-type crystal structure of m^2/g to 500 m^2/g is used.
に非水電解質を用いる非水リチウム二次電池において、
正極に特許請求の範囲第一項記載のＬｉＭｎ＿２Ｏ＿４
を用いることを特徴とする非水リチウム二次電池(3) In a nonaqueous lithium secondary battery that uses lithium or a lithium alloy for the negative electrode and a nonaqueous electrolyte for the electrolyte,
LiMn_2O_4 described in claim 1 for the positive electrode
A non-aqueous lithium secondary battery characterized by using
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322351A JP3057755B2 (en) | 1990-11-28 | 1990-11-28 | Method for producing lithium manganese composite oxide and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2322351A JP3057755B2 (en) | 1990-11-28 | 1990-11-28 | Method for producing lithium manganese composite oxide and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04198028A true JPH04198028A (en) | 1992-07-17 |
| JP3057755B2 JP3057755B2 (en) | 2000-07-04 |
Family
ID=18142675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2322351A Expired - Fee Related JP3057755B2 (en) | 1990-11-28 | 1990-11-28 | Method for producing lithium manganese composite oxide and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3057755B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5683835A (en) * | 1993-03-17 | 1997-11-04 | Ultralife Batteries (Uk) Limited | Lithiated manganese oxide |
| US5728367A (en) * | 1996-06-17 | 1998-03-17 | Motorola, Inc. | Process for fabricating a lithiated transition metal oxide |
| US5807646A (en) * | 1995-02-23 | 1998-09-15 | Tosoh Corporation | Spinel type lithium-mangenese oxide material, process for preparing the same and use thereof |
| US5985237A (en) * | 1996-10-29 | 1999-11-16 | Honjo Chemical Corporation | Process for producing lithium manganese oxide suitable for use as cathode material of lithium ion secondary batteries |
| US6348182B1 (en) | 1996-06-27 | 2002-02-19 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
| US6506493B1 (en) | 1998-11-09 | 2003-01-14 | Nanogram Corporation | Metal oxide particles |
| JP2008041577A (en) * | 2006-08-09 | 2008-02-21 | Kanto Denka Kogyo Co Ltd | Spinel type manganate lithium and its manufacturing method, and cathode active material using spinel type manganate lithium and nonaqueous electrolyte battery |
| CN111655625A (en) * | 2017-11-17 | 2020-09-11 | 昂泰克***公司 | Solid state synthesis method for metal mixed oxides and surface modification of these materials and use of these materials in batteries, especially as positive electrode materials |
-
1990
- 1990-11-28 JP JP2322351A patent/JP3057755B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5683835A (en) * | 1993-03-17 | 1997-11-04 | Ultralife Batteries (Uk) Limited | Lithiated manganese oxide |
| US5807646A (en) * | 1995-02-23 | 1998-09-15 | Tosoh Corporation | Spinel type lithium-mangenese oxide material, process for preparing the same and use thereof |
| US5728367A (en) * | 1996-06-17 | 1998-03-17 | Motorola, Inc. | Process for fabricating a lithiated transition metal oxide |
| US6348182B1 (en) | 1996-06-27 | 2002-02-19 | The Honjo Chemical Corporation | Process for producing lithium manganese oxide with spinel structure |
| US5985237A (en) * | 1996-10-29 | 1999-11-16 | Honjo Chemical Corporation | Process for producing lithium manganese oxide suitable for use as cathode material of lithium ion secondary batteries |
| US6506493B1 (en) | 1998-11-09 | 2003-01-14 | Nanogram Corporation | Metal oxide particles |
| US6680041B1 (en) | 1998-11-09 | 2004-01-20 | Nanogram Corporation | Reaction methods for producing metal oxide particles |
| JP2008041577A (en) * | 2006-08-09 | 2008-02-21 | Kanto Denka Kogyo Co Ltd | Spinel type manganate lithium and its manufacturing method, and cathode active material using spinel type manganate lithium and nonaqueous electrolyte battery |
| CN111655625A (en) * | 2017-11-17 | 2020-09-11 | 昂泰克***公司 | Solid state synthesis method for metal mixed oxides and surface modification of these materials and use of these materials in batteries, especially as positive electrode materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3057755B2 (en) | 2000-07-04 |
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