JPS6364919A - Novel manganese compound and production thereof - Google Patents
Novel manganese compound and production thereofInfo
- Publication number
- JPS6364919A JPS6364919A JP61207152A JP20715286A JPS6364919A JP S6364919 A JPS6364919 A JP S6364919A JP 61207152 A JP61207152 A JP 61207152A JP 20715286 A JP20715286 A JP 20715286A JP S6364919 A JPS6364919 A JP S6364919A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- manganese
- adsorption
- solution
- lithium
- 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
- 150000002697 manganese compounds Chemical class 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 15
- 239000003929 acidic solution Substances 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims description 18
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000000243 solution Substances 0.000 abstract description 8
- 239000013535 sea water Substances 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 5
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 24
- 229910052744 lithium Inorganic materials 0.000 description 24
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910015645 LiMn Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規なマンガン化合物及びその製造方法に関す
るものである。さらに詳しくいえば、本発明は、リチウ
ムに対する選択吸着性に優れ、かつ吸着速度及び吸着容
量が極めて大きく、リチウム吸着材料として好適であり
、また電池活性電極材料などとしても有用な新規なマン
ガン化合物及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel manganese compound and a method for producing the same. More specifically, the present invention provides a novel manganese compound that has excellent selective adsorption properties for lithium, has an extremely high adsorption rate and adsorption capacity, is suitable as a lithium adsorption material, and is also useful as a battery active electrode material. The present invention relates to a manufacturing method thereof.
従来の技術
マンガン酸化物は種々の結晶形態が知られており、天然
においては、例えば軟マンガン鉱やナスタイトなどとし
て存在している。このマンガン酸化物は、一般に乾電池
、バッテリーなどの電気化学電池における活性カソード
物質として用いられており、その代表的な電池としては
、例えばマンガン酸化物カソードと亜鉛アノードと電解
質水溶液（塩化アンモニウム及び塩化亜鉛を含む水溶液
）とから成るものが知られている。BACKGROUND OF THE INVENTION Various crystal forms of manganese oxide are known, and exist in nature as, for example, soft manganese ore and nastite. Manganese oxide is generally used as an active cathode material in electrochemical cells such as dry cells and batteries. Typical batteries include, for example, a manganese oxide cathode, a zinc anode, and an electrolyte aqueous solution (ammonium chloride and zinc chloride). An aqueous solution containing
従来、このような電池用マンガン酸化物は一般に電解法
で調製されているが、最近ＬｉＭｎ、０４から調製する
方法が提案されている（特公昭５８−３４４１４号公報
）。このＬｉＭｎ、 Ｏ，から調製したマンガン酸化物
は電気化学活性を有し、水性電解質のみならず、非水性
電解質においても有効であるといわれている。Conventionally, such manganese oxides for batteries have generally been prepared by an electrolytic method, but recently a method of preparing them from LiMn, 04 has been proposed (Japanese Patent Publication No. 34414/1983). Manganese oxide prepared from LiMn, O, has electrochemical activity and is said to be effective not only in aqueous electrolytes but also in non-aqueous electrolytes.
該ＬｉＭｎ２Ｏ４はスピネル構造を有し、炭酸リチウム
とマンガン酸化物とを、マンガンとリチウムとの原子比
が２：１になるような割合で混合し、８００〜９００’
Ｃの範囲の温度において加熱処理することにより、ある
いは水酸化リチウムと炭酸マンガンなどのリチウム塩°
酸化物とマンガン塩°酸化物との適当な組合せの混合物
を５００〜９００°Ｃの範囲の温度において加熱処理す
ることにより得られる。The LiMn2O4 has a spinel structure, and is made by mixing lithium carbonate and manganese oxide in a ratio such that the atomic ratio of manganese and lithium is 2:1,
or lithium salts such as lithium hydroxide and manganese carbonate by heat treatment at temperatures in the range of °C.
It is obtained by heat treating a mixture of an appropriate combination of oxide and manganese salt oxide at a temperature in the range of 500 to 900°C.
ところで、最近リチウムを含有するマンガン酸化物から
調製したマンガン化合物が、リチウム吸着剤として優れ
ていることが認められ〔化学工業第６８６ページ（１９
８５年）〕、希薄溶液からのリチウム採取用吸着剤とし
ての応用が期待されている。By the way, it has recently been recognized that manganese compounds prepared from manganese oxide containing lithium are excellent as lithium adsorbents [Kagaku Kogyo, page 686 (19)]
(1985)], and is expected to be used as an adsorbent for extracting lithium from dilute solutions.
例えば、前記ＬｉＭｎ、０４を酸処理したマンガン化合
物はＬｉＭｎ、 ０４とほぼ同様のＸ線回折特性を有し
、海水中のリチウムの選択吸着性に優れ、そのリチウム
平衡吸着量は８．５グ／、９で、Ｌ１２０の含有量に換
算すると１．８％になり、リチウム鉱石の約半分にも達
する。For example, the manganese compound obtained by acid-treating LiMn,04 has almost the same X-ray diffraction characteristics as LiMn,04, and has excellent selective adsorption of lithium in seawater, with an equilibrium adsorption amount of lithium of 8.5 g/ , 9, the L120 content is 1.8%, which is about half of that of lithium ore.
このように、リチウムを含有するマンガン酸化物から調
製されたマンガン化合物は、リチウム吸着材料や電池活
性電極材料などとして有用であるが、高価なリチウムを
原料として用いているため、コスト高になるのを免れな
いという問題がある。As described above, manganese compounds prepared from manganese oxide containing lithium are useful as lithium adsorption materials and battery active electrode materials, but they are expensive because they use expensive lithium as a raw material. There is a problem that cannot be avoided.
発明が解決しようとする問題点
本発明の目的は、リチウム吸着材料や電池活性電極材料
などとして有用で、かつ製造コストの低い新規なマンガ
ン化合物を提供することにある。Problems to be Solved by the Invention An object of the present invention is to provide a novel manganese compound that is useful as a lithium adsorption material, a battery active electrode material, etc., and is inexpensive to produce.
問題点を解決するための手段
本発明者らは、先にリチウムよりイオン半径がわずかに
小さいマグネシウムを用いて調製したＭｇＭｎ２０．を
酸処理することにより、ＬｉＭｎ２Ｏ４から得られるも
のとは明らかに異なったＸ線回折特性を示し、しかも同
じような物性を有する新規なマグネシウム化合物を得る
こと（＝成功したが、さらに研究を重ねた結果、原料と
してＭｇ２Ｍｎ０．を用い、これを酸処理すれば、さら
に別の新規なマンガン化合物が得られることを見出し、
この知見に基づいて、本発明をなすに至った。Means for Solving the Problems The present inventors previously prepared MgMn20. By acid treatment, we obtained a new magnesium compound that showed clearly different X-ray diffraction characteristics from those obtained from LiMn2O4, but also had similar physical properties (=successful, but required further research). As a result, they discovered that by using Mg2Mn0. as a raw material and treating it with acid, another new manganese compound could be obtained.
Based on this knowledge, the present invention was accomplished.
すなわち、本発明は、Ｍｇ２ＭｎＯ４の酸処理物からな
り、かつ主要Ｘ線回折ピークの相対強度が４．７５±０
．０５強
２．９２±０．０３弱
２．４９±０．０３強
２．６８±０．０６弱
２．０６±０．０３強
１．５９±０．０６中
１．４６±０．０３中
であるマンガン化合物を提供するものである。That is, the present invention consists of an acid-treated product of Mg2MnO4, and the relative intensity of the main X-ray diffraction peak is 4.75±0.
．． 05 strong 2.92 ± 0.03 weak 2.49 ± 0.03 strong 2.68 ± 0.06 weak 2.06 ± 0.03 strong 1.59 ± 0.06 out of 1.46 ± 0.03 The present invention provides a manganese compound that is
このものは、ＬｉＭｎ２０．の酸処理物及びＭｇＭｎ２
０４の酸処理物とは明らか（二異なったＸ線回折特性を
示す新規な化合物であって、Ｍｇ、 ＭｎＯ，をｐ８５
以下の酸性溶液で処理し、その中のマグネシウムを溶出
させることによって製造することができる。This one is LiMn20. acid-treated product and MgMn2
It is clear that the acid-treated product of No. 04 is a new compound showing two different X-ray diffraction characteristics,
It can be produced by treating with the following acidic solution and eluting the magnesium therein.
本発明：二おいて原料として用いられるＭｇ２ＭｎＯ４
は、例えばＭｇＯとＭｎＯ２とをモル比で２：１の割合
で混合して、８００°Ｃの温度で数日間加熱処理するこ
とにより〔「レビュー・ケミカル・ミネラル（Ｒｅｖ、
Ｃｈｅｍ、 Ｍｉｎｅｒａｌ） Ｊ第１巻、第１７５ベ
ージ（１９５４） ）、あるいはマグネシウムの水酸化
物、酸化物、炭酸塩、重炭酸塩、硝酸塩、ハロゲン化物
などと、マンガンの含水酸化物、酸化物、炭酸塩、重炭
酸塩、硝酸塩、ハロゲン化物などとを適当な組合せで混
合したのち、４００°Ｃ以上の温度で加熱処理すること
により製造することができる。The present invention: Mg2MnO4 used as a raw material
For example, by mixing MgO and MnO2 at a molar ratio of 2:1 and heat-treating the mixture at a temperature of 800°C for several days [Rev.
Chem, Mineral) J Vol. 1, No. 175 (1954)), or magnesium hydroxides, oxides, carbonates, bicarbonates, nitrates, halides, etc., and manganese hydrated oxides, oxides, It can be produced by mixing a suitable combination of carbonates, bicarbonates, nitrates, halides, etc., and then heat-treating the mixture at a temperature of 400°C or higher.
このＭｇ、 ＭｎＯ，を、塩酸、硫酸、硝酸、リン酸な
どの鉱酸や、ギ酸、酢酸などの有機酸を１種以上含有し
、かつｐＨ５以下、好ましくは１〜３の範囲に調整され
た酸性溶液中に浸せきし、通常室温で１時間以上、好ま
しくは数日間かきまぜて、マグネシウムを溶出除去した
のち、固形物を水洗し、好ましくは７０°Ｃ以下の温度
において乾燥することにより、目的のマンガン化合物が
得られる。This Mg, MnO, is contained in a solution containing one or more mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or organic acids such as formic acid and acetic acid, and whose pH is adjusted to 5 or less, preferably in the range of 1 to 3. The solid substance is immersed in an acidic solution and stirred at room temperature for at least 1 hour, preferably for several days to elute and remove the magnesium. A manganese compound is obtained.
このマンガン化合物のＸ線回折特性を下記に示す。比較
としてＡＳＴＭカードのＭｇ、 ＭｎＯ４及びＬｉＭｎ
４０４から調製したマンガン化合物（特公昭５８−３４
４１４号公報）のＸ線回折特性を併記する。The X-ray diffraction characteristics of this manganese compound are shown below. For comparison, ASTM cards Mg, MnO4 and LiMn
Manganese compound prepared from 404 (Japanese Patent Publication No. 58-34
The X-ray diffraction characteristics of JP 414) are also shown.
４．７５ 強 ４．８５ 強 ４
．６４ 強２．９２ 弱 ２．９５
中 −−２，４９強 ２．５２
強 ２．４２ 中２．３８ 弱
２．４１ 弱 ２．３１ 弱２
．０６ 強 ２．０９ 強 ２
．０１ 中−−１，７０弱 １．８４
弱１．５９ 中 １．６１ 中
１．５５ 弱１．４６ 中 １．
４８ 強 −−このように、本発明の
マンガン化合物はＬｉＭｎ２Ｏ４からのマンガン化合物
とは明らかに異なり、出発原料のＭｇ、 ＭｎＯ４とほ
とんど同様なＸ線回折特性を示すものである。4.75 strong 4.85 strong 4
．． 64 Strong 2.92 Weak 2.95
Medium --2.49+ 2.52
Strong 2.42 Medium 2.38 Weak
2.41 Weak 2.31 Weak 2
．． 06 strong 2.09 strong 2
．． 01 Medium--1,70 little 1.84
Weak 1.59 Medium 1.61 Medium
1.55 Weak 1.46 Medium 1.
48 Strong As described above, the manganese compound of the present invention is clearly different from the manganese compound derived from LiMn2O4, and exhibits almost the same X-ray diffraction characteristics as the starting materials Mg and MnO4.
このマンガン化合物と原料Ｍｇ２ＭｎＯ４のＸ線回折特
性の相違点は、マンガンの新規な形態の形成に際して格
子の収縮を示し、わずかにピーク位置の変化がみられる
ことである。The difference between the X-ray diffraction characteristics of this manganese compound and the raw material Mg2MnO4 is that the lattice shrinks when a new form of manganese is formed, and a slight change in the peak position is observed.
また、本発明のマンガン化合物は面間隔１．４６Ａ及び
２，９２ Ａに回折ピークを示し、ＬｉＭｎ２Ｏ４から
調製したマンガン酸化物とは微細構造の異なった化合物
である。Furthermore, the manganese compound of the present invention exhibits diffraction peaks at interplanar spacings of 1.46 A and 2,92 A, and has a different microstructure from the manganese oxide prepared from LiMn2O4.
さらに、本発明のマンガン化合物は、化学分析の結果、
マグネシウム含有率が１０重量％以下であり、原料のＭ
ｇ、 ＭｎＯ４の理論マグネシウム含有率２９．０重量
％と異なることから、Ｍｇ、 ＭｎＯ４とは組成の異な
る全く新規な物質と認められる。Furthermore, as a result of chemical analysis, the manganese compound of the present invention has
The magnesium content is 10% by weight or less, and the M of the raw material is
Since it is different from the theoretical magnesium content of Mg and MnO4, which is 29.0% by weight, it is recognized as a completely new substance with a different composition from Mg and MnO4.
発明の効果
本発明のマンガン化合物はリチウム吸着に適した層間隔
を有しており、リチウムに対する選択吸着性が優れ、か
つ吸着速度及び吸着容量が極めて大きり、シかも毒性が
なく、水溶液中で安定であり、吸着剤中のリチウム濃度
はリチウム含有鉱石なみになり、希薄溶液、例えば海水
や地熱水から効率よく経済的に該リチウムを回収するこ
とができる。Effects of the Invention The manganese compound of the present invention has a layer spacing suitable for lithium adsorption, has excellent selective adsorption for lithium, has an extremely high adsorption rate and adsorption capacity, is non-toxic, and is resistant to lithium in aqueous solution. It is stable, the lithium concentration in the adsorbent is comparable to that of lithium-containing ores, and the lithium can be efficiently and economically recovered from dilute solutions, such as seawater or geothermal water.
また、該マンガン化合物は電池活性電極材料としても有
用である。The manganese compounds are also useful as battery active electrode materials.
実施例 次に実施例により本発明の詳細な説明する。Example Next, the present invention will be explained in detail with reference to Examples.
実施例１
１Ｍ塩化マグネシウム水溶液２００．７と１Ｍ塩化マン
ガン水溶液１００ｇ／との混合溶液をかきまぜながら、
ｐＨ１０，５以上になるまでアンモニア水（１：１）を
加え、さらに３０％過酸化水素溶液１００ｇ／を添加し
た。生成物を母液中で３日間熟成したのち、ろ別し、ｐ
）１１０．５のアンモニア水で数回洗浄した。生成物中
のマグネシウムとマンガン含量の原子比は２：１であっ
た。これを８００°Ｃで１時間加熱処理してＭｇ２Ｍｎ
Ｏ４を調製した。この加熱生成物１１を０．５ Ｎ塩酸
溶液１１中に加えて、３０日間かきまぜたのち、生成物
をろ別、洗浄し、７゜°Ｃで乾燥してマンガン化合物を
調製した。第１表に得られた加熱生成物及びマンガン化
合物のＸ線回折特性を示す。なお、比較のためにＡＳＴ
Ｍカード１９−７７３記載のＭｇ２ＭｎＯ４のＸ線回折
特性を示す。Example 1 While stirring a mixed solution of 200.7 g of 1M magnesium chloride aqueous solution and 100 g/1M manganese chloride aqueous solution,
Aqueous ammonia (1:1) was added until the pH reached 10.5 or higher, and then 100 g of 30% hydrogen peroxide solution was added. After aging the product in the mother liquor for 3 days, it was filtered and p
) Washed several times with 110.5 ammonia water. The atomic ratio of magnesium and manganese content in the product was 2:1. This was heat treated at 800°C for 1 hour to produce Mg2Mn.
O4 was prepared. This heated product 11 was added to 0.5 N hydrochloric acid solution 11 and stirred for 30 days, and then the product was filtered, washed, and dried at 7°C to prepare a manganese compound. Table 1 shows the X-ray diffraction characteristics of the heated product and manganese compound obtained. For comparison, AST
The X-ray diffraction characteristics of Mg2MnO4 described in M Card 19-773 are shown.
第 １ 表
実施例において調製したＭｇ、 ＭｎＯ４のＸ線回折特
性はＡＳＴＭカード記載ものと極めてよく一致した。The X-ray diffraction characteristics of Mg and MnO4 prepared in the Examples in Table 1 were in excellent agreement with those described in the ASTM card.
また、本発明のＭｇ２ＭｎＯ４を酸処理して調製したマ
ンガン化合物はＭｇ、 ＭｎＯ４と比較して、わずかな
がら面間隔が小さくなっているが、元の構造を維持して
いることは明らかである。Furthermore, it is clear that the manganese compound prepared by acid-treating Mg2MnO4 of the present invention maintains its original structure, although the interplanar spacing is slightly smaller than that of Mg and MnO4.
第２表にこれらのマンガン化合物の化学分析値を示す。Table 2 shows the chemical analysis values of these manganese compounds.
第 ２ 表
本実験で調製したＭｇ２Ｍｎ０．の化学分析値はほぼ理
論値に一致した。本発明のマンガン化合物はＭｇ、、
ＭｎＯ，よりマグネシウム含量が著しく少なく、組成の
異なる新規な化合物である。Table 2 Mg2Mn0. prepared in this experiment. The chemical analysis values almost agreed with the theoretical values. The manganese compound of the present invention is Mg,
It is a new compound with a significantly lower magnesium content and a different composition than MnO.
実施例２
１Ｍ塩化マグネシウム水溶液２００９１と１Ｍ塩化マン
ガン水溶液１００ｇ／との混合溶液をかきまぜながら、
ｐ）（１０，５になるまでアンモニア水（１： １）を
加え、さらに５０％過酸化水素溶液１００ｇ、！’を添
加した。生成物を母液中で３日間熟成したのち、ろ別し
、ＰＩ（１０，５のアンモニア水で数回洗浄し島生成物
中のマグネシウムとマンガン含量の原子比は２：１であ
った。これを５００°Ｃで１時間加熱処理してＭｇ、
ＭｎＯ４を調製した。この加熱処理物１ｇを０．１Ｍ硝
酸溶液１１中に加えて、５日間かきまぜたのち、生成物
をろ別°洗浄し、乾燥した。生成物のＸ線回折特性を第
３表に示す。得られたマンガン化合物は実施例１と同様
にわずかに収縮が認められたが、Ｍｇ２ Ｍ ｎ Ｏａ
と同様の構造を有していることは明らかである。これら
の化合物の化学分析結果を第４表に示す。Example 2 While stirring a mixed solution of 1M magnesium chloride aqueous solution 20091 and 1M manganese chloride aqueous solution 100g/
p) Added aqueous ammonia (1:1) to (10.5) and further added 100 g of 50% hydrogen peroxide solution, !'. The product was aged in the mother liquor for 3 days and then filtered off. After washing several times with PI (10,5) ammonia water, the atomic ratio of magnesium and manganese content in the island product was 2:1.This was heat-treated at 500°C for 1 hour to obtain Mg,
MnO4 was prepared. 1 g of this heat-treated product was added to 0.1M nitric acid solution 11, and after stirring for 5 days, the product was filtered, washed, and dried. The X-ray diffraction properties of the product are shown in Table 3. The obtained manganese compound showed slight shrinkage as in Example 1, but Mg2 M n Oa
It is clear that it has a similar structure. The chemical analysis results of these compounds are shown in Table 4.
第 ３ 表
第 ４ 表
本発明のマグネシウム化合物はＭｇ、 ＭｎＯ，とは組
成の異なる新規な化合物であることは明らかである。Table 3 Table 4 It is clear that the magnesium compound of the present invention is a novel compound having a composition different from Mg and MnO.
実施例３
実施例１及び２において調製したマンガン化合物につい
て海水中におけるリチウム吸着性を調べた。すなわち、
マンガン化合物５０ｍ９を海水２Ｅに加え、７日間かき
まぜた。吸着前後の海水中のリチウム濃度を原子吸光法
で定量し、リチウム吸着量を求めた。結果を第５表に示
す。Example 3 The lithium adsorption properties of the manganese compounds prepared in Examples 1 and 2 in seawater were investigated. That is,
50m9 of manganese compound was added to seawater 2E and stirred for 7 days. The lithium concentration in seawater before and after adsorption was determined by atomic absorption spectrometry to determine the amount of lithium adsorbed. The results are shown in Table 5.
この結果から本発明のマンガン化合物は海水中のリチウ
ムを約４万倍に濃縮しており、リチウム吸着性が優れて
いることは明らかである。From these results, it is clear that the manganese compound of the present invention concentrates lithium in seawater approximately 40,000 times, and has excellent lithium adsorption properties.
第 ５ 表Table 5
Claims (1)
示すＸ線回折ピークの相対強度を有するマンガン化合物
。 ▲数式、化学式、表等があります▼ ２ Ｍｇ＿２ＭｎＯ＿４をｐＨ５以下の酸性溶液で処理
し、その中のマグネシウムを溶出させることを特徴とす
る、次に示すＸ線回折ピークの相対強度を有するマンガ
ン化合物の製造方法。 ▲数式、化学式、表等があります▼ ３ ｐＨ５以下の酸性溶液が鉱酸及び有機酸の中から選
ばれた少なくとも１種を含有するものである特許請求の
範囲第２項記載の方法。[Scope of Claims] 1. A manganese compound which is an acid-treated product of Mg_2MnO_4 and has the following relative intensity of the X-ray diffraction peak. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 2. A manganese compound having the relative intensity of the X-ray diffraction peak shown below, which is characterized by treating Mg_2MnO_4 with an acidic solution of pH 5 or less and eluting the magnesium therein. Production method. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 3. The method according to claim 2, wherein the acidic solution with a pH of 5 or less contains at least one selected from mineral acids and organic acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61207152A JPS6364919A (en) | 1986-09-02 | 1986-09-02 | Novel manganese compound and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61207152A JPS6364919A (en) | 1986-09-02 | 1986-09-02 | Novel manganese compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6364919A true JPS6364919A (en) | 1988-03-23 |
| JPH0232218B2 JPH0232218B2 (en) | 1990-07-19 |
Family
ID=16535079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61207152A Granted JPS6364919A (en) | 1986-09-02 | 1986-09-02 | Novel manganese compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6364919A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03154396A (en) * | 1989-11-10 | 1991-07-02 | Matsushita Electric Ind Co Ltd | Manufacture of enameled board used for circuit |
| CN108251918A (en) * | 2018-01-09 | 2018-07-06 | 哈尔滨理工大学 | A kind of MgMn2O4Nano-fiber electrode material and preparation method thereof |
-
1986
- 1986-09-02 JP JP61207152A patent/JPS6364919A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03154396A (en) * | 1989-11-10 | 1991-07-02 | Matsushita Electric Ind Co Ltd | Manufacture of enameled board used for circuit |
| CN108251918A (en) * | 2018-01-09 | 2018-07-06 | 哈尔滨理工大学 | A kind of MgMn2O4Nano-fiber electrode material and preparation method thereof |
| CN108251918B (en) * | 2018-01-09 | 2020-05-12 | 哈尔滨理工大学 | MgMn2O4Nanofiber electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0232218B2 (en) | 1990-07-19 |
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