JP2001157838A - Method for preparing lithium adsorbent - Google Patents
Method for preparing lithium adsorbentInfo
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- JP2001157838A JP2001157838A JP2000239027A JP2000239027A JP2001157838A JP 2001157838 A JP2001157838 A JP 2001157838A JP 2000239027 A JP2000239027 A JP 2000239027A JP 2000239027 A JP2000239027 A JP 2000239027A JP 2001157838 A JP2001157838 A JP 2001157838A
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- Prior art keywords
- lithium
- adsorbent
- adsorption
- limno
- manganese
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- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、新規なリチウム吸
着剤の製造方法、さらに詳しくいえば、本発明はリチウ
ムに対する選択的吸着性に優れ、しかも吸着容量及び吸
着速度が大きく、水溶液中で安定なリチウム吸着剤を簡
単に製造する方法に関するものである。The present invention relates to a method for producing a novel lithium adsorbent, and more specifically, the present invention is excellent in selective adsorptivity to lithium, has a large adsorption capacity and a large adsorption rate, and is stable in an aqueous solution. The present invention relates to a method for easily producing a novel lithium adsorbent.
【０００２】[0002]
【従来の技術】リチウムは、例えばセラミックス、グリ
ース、空調用冷媒、医薬品、電池などの原料として使用
されており、今後も大容量電池、アルミニウム合金材
料、核融合燃料などに用いられる重要な物質として注目
されている。しかるに、我が国においてはリチウム鉱石
資源がなく、リチウム金属やその化合物は全量輸入して
いるのが現状である。一方、海水中には微量のリチウム
が含まれており、海水からリチウムを効率よく回収する
技術が確立されたならば、これより、リチウムの供給が
可能になるため、その技術の出現が強く要望されてい
る。これまで、海水などリチウムを含む希薄溶液から該
リチウムを回収する方法としては、共沈法や蒸発法など
が提案されているが、これらの方法は経済的な面で問題
があり、現在では吸着法がもっとも経済的な方法である
と結論されている。したがって、リチウムに対し高い選
択吸着性を示し、かつ化学的に安定な吸着剤の開発が強
く要望されている。2. Description of the Related Art Lithium has been used as a raw material for ceramics, grease, refrigerants for air conditioning, pharmaceuticals, batteries, and the like. Attention has been paid. However, in Japan, there is no lithium ore resource, and at present, all lithium metal and its compounds are imported. On the other hand, seawater contains a very small amount of lithium, and if technology for efficiently recovering lithium from seawater has been established, it will be possible to supply lithium. Have been. To date, co-precipitation methods and evaporation methods have been proposed as methods for recovering lithium from a dilute solution containing lithium such as seawater, but these methods have problems in terms of economics. It is concluded that law is the most economical method. Therefore, there is a strong demand for the development of a chemically stable adsorbent which exhibits high selective adsorption to lithium.
【０００３】従来、リチウム吸着剤としては、ヒ酸トリ
ウム［「ジャーナル・オブ・インオーガニック・アンド
・ヌークリアー・ケミストリー（Ｊ．Ｉｎｏｒｇ．Ｎｕ
ｃｌ．Ｃｈｅｍ．）」，第３２巻，第１７１９ページ
（１９７０）］やアンチモン酸スズ［「ハイドロメタラ
ジー（Ｈｙｄｒｏｍｅｔａｌｌｕｒｇｙ）」，第１２
巻，第８３ページ（１９８４）］などが知られている
が、吸着量が低く実用に供することはできない。[0003] Conventionally, as a lithium adsorbent, thorium arsenate [Journal of Inorganic and Nuclear Chemistry (J. Inorg. Nu.
cl. Chem. 32), p. 1719 (1970)] and tin antimonate [“Hydrometallurgy”, twelfth.
Vol. 83, 1984], but the amount of adsorption is low and cannot be put to practical use.
【０００４】また、加熱処理したリチウム含有マンガン
酸化物を酸処理して得られるリチウム吸着剤（特開昭６
１−１７１５３５号公報）や、マグネシウムを含むマン
ガン−アルミニウム複合酸化物の加熱処理物からマグネ
シウムを酸で溶出して得られる複合型リチウム吸着剤も
知られている（特開昭６３−６２５４６号公報）。これ
らの吸着剤は海水からリチウムを選択的に吸着すること
ができ、吸着量も大きいが、実用性を考えるとまだ十分
な性能には達していない。Further, a lithium adsorbent obtained by subjecting a heat-treated lithium-containing manganese oxide to an acid treatment (Japanese Patent Application Laid-Open No.
And a composite lithium adsorbent obtained by eluting magnesium with an acid from a heat-treated manganese-aluminum composite oxide containing magnesium (JP-A-63-62546). ). These adsorbents are capable of selectively adsorbing lithium from seawater and have a large amount of adsorption, but have not yet achieved sufficient performance in view of practicality.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、リチウムに
対する選択的吸着性に優れ、しかも吸着速度及び吸着容
量が大きく、かつ化学的に安定で、吸着、脱着の繰り返
しにより性能が低下しないリチウム吸着剤を提供するこ
とを目的としてなされたものである。DISCLOSURE OF THE INVENTION The present invention relates to a lithium adsorbent which is excellent in selective adsorption to lithium, has a large adsorption speed and adsorption capacity, is chemically stable, and does not deteriorate in performance due to repeated adsorption and desorption. The purpose is to provide an agent.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、リチウム
吸着剤について種々研究を重ねた結果、γ‐オキシ水酸
化マンガンと水酸化リチウムとの反応によって得られる
ＬｉＭｎＯ2を酸素の存在下で焼成して得たＬｉ2Ｍｎ2
Ｏ5を酸処理することにより、リチウムに対する選択的
吸着性が優れたリチウム吸着剤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。The present inventors have conducted various studies on lithium adsorbents and found that LiMnO 2 obtained by the reaction of γ-manganese oxyhydroxide with lithium hydroxide was converted in the presence of oxygen. Li 2 Mn 2 obtained by firing
It has been found that by treating O 5 with an acid, a lithium adsorbent excellent in selective adsorptivity to lithium can be obtained, and the present invention has been accomplished based on this finding.
【０００７】すなわち、本発明は、γ‐オキシ水酸化マ
ンガンと水酸化リチウムとを反応させてＬｉＭｎＯ2を
生成させたのち、これを酸素の存在下４００℃以上で焼
成してＬｉ2Ｍｎ2Ｏ5に変換し、次いでこれを酸処理す
ることを特徴とするリチウム吸着剤の製造方法を提供す
るものである。That is, according to the present invention, LiMnO 2 is produced by reacting γ-manganese oxyhydroxide with lithium hydroxide and then calcined at 400 ° C. or higher in the presence of oxygen to produce Li 2 Mn 2 O 2. It is intended to provide a method for producing a lithium adsorbent, which comprises converting the lithium adsorbent to 5 , followed by acid treatment.
【０００８】[0008]
【発明の実施の形態】本発明に従ってリチウム吸着剤を
製造するには、先ずγ‐オキシ水酸化マンガンと水酸化
リチウムとを反応させてＬｉＭｎＯ2を生成させること
が必要である。このＬｉＭｎＯ2は、γ‐オキシ水酸化
マンガンと水酸化リチウムとを含む水溶液を加圧下１０
０〜１４０℃において水熱反応させるか、あるいはγ‐
オキシ水酸化マンガンと水酸化リチウムとを含む水溶液
を加熱還流させることによって生成することができる。To produce the lithium adsorbent in accordance with the present invention DETAILED DESCRIPTION OF THE INVENTION, it is necessary to first γ- manganese oxyhydroxide and by reacting lithium hydroxide produce LiMnO 2. This LiMnO 2 is obtained by subjecting an aqueous solution containing γ-manganese oxyhydroxide and lithium hydroxide to 10
Hydrothermal reaction at 0-140 ° C or γ-
It can be produced by heating and refluxing an aqueous solution containing manganese oxyhydroxide and lithium hydroxide.
【０００９】γ‐オキシ水酸化マンガンと水酸化リチウ
ムとの水熱反応は、例えば両者を含む水溶液をオートク
レーブのような耐圧容器に入れ、自生圧力下、１２０〜
１７０℃で３〜１０時間反応させることにより行うこと
ができる。他方、γ‐オキシ水酸化マンガンと水酸化リ
チウムとを含む水溶液を加熱還流させる方法は、両者を
含む水溶液を８〜４８時間という長時間にわたって還流
させることによって行われる。For the hydrothermal reaction between γ-manganese oxyhydroxide and lithium hydroxide, for example, an aqueous solution containing both of them is placed in a pressure vessel such as an autoclave and subjected to autogenous pressure for 120 to 120 hours.
The reaction can be carried out at 170 ° C. for 3 to 10 hours. On the other hand, a method of heating and refluxing an aqueous solution containing γ-manganese oxyhydroxide and lithium hydroxide is performed by refluxing an aqueous solution containing both for a long time of 8 to 48 hours.
【００１０】この際の水酸化リチウムは、γ‐オキシ水
酸化マンガンよりも過剰に用いるのが好ましい。これら
の方法により得られるＬｉＭｎＯ2を熱質量分析すると
３３０〜３８０℃の範囲で質量上昇が認められる。本発
明方法においては、このように比較的低温において酸素
が取り込まれ、質量が上昇するＬｉＭｎＯ2を用いるこ
とが重要である。In this case, it is preferable to use lithium hydroxide in excess of γ-manganese oxyhydroxide. When thermal mass spectrometry is performed on LiMnO 2 obtained by these methods, an increase in mass is observed in the range of 330 to 380 ° C. In the method of the present invention, it is important to use LiMnO 2 whose oxygen is taken in at such a relatively low temperature and whose mass increases.
【００１１】このようにして得られたＬｉＭｎＯ2は、
５０〜８０℃で乾燥させたのち、４００℃以上の温度、
好ましくは４００〜７００℃の範囲の温度で焼成する
と、骨格構造の大きな変化なしに三価のＭｎが安定な四
価のＭｎに変化し、安定なＬｉ 2Ｍｎ2Ｏ5を生成する。
この温度が４００℃未満であると、三価から四価への変
換が不十分になるし、７００℃を越えると焼結反応が進
行し、骨格構造が変化するので好ましくない。The LiMnO thus obtained isTwoIs
After drying at 50-80 ° C, a temperature of 400 ° C or more,
Firing at a temperature preferably in the range of 400 to 700 ° C.
And trivalent Mn is stable without significant changes in the skeletal structure.
Li into stable Mn TwoMnTwoOFiveGenerate
If this temperature is lower than 400 ° C., the conversion from trivalent to tetravalent will occur.
Exchange becomes insufficient, and the sintering reaction proceeds
This is not preferable because the skeleton structure changes.
【００１２】この加熱処理によって結晶化反応が進行
し、均一な構造の結晶を生成する。この加熱時間は、少
なくとも１０分、好ましくは６０分以上である。この加
熱処理は、酸素の存在下、例えば大気中で行う必要があ
る。酸素雰囲気中で行えば、反応時間を短縮することが
できる。By this heat treatment, a crystallization reaction proceeds, and crystals having a uniform structure are produced. This heating time is at least 10 minutes, preferably 60 minutes or more. This heat treatment needs to be performed in the presence of oxygen, for example, in the atmosphere. When the reaction is performed in an oxygen atmosphere, the reaction time can be reduced.
【００１３】このようにして得られるＬｉ2Ｍｎ2Ｏ
5は、文献未載の新規物質であり、非常に安定である。
従来の方法、例えばマンガン化合物とリチウム化合物と
を機械的に混合して加熱処理する方法では、リチウムと
マンガンの混合状態や加熱処理時の反応状態によって結
晶の構造が不均一になり、均質な結晶の生成が困難であ
るため、Ｌｉ2Ｍｎ2Ｏ5は生成しなかった。The thus obtained Li 2 Mn 2 O
5 is a novel substance which is not listed in the literature and is very stable.
In a conventional method, for example, in a method in which a manganese compound and a lithium compound are mechanically mixed and heat-treated, the crystal structure becomes non-uniform due to a mixed state of lithium and manganese or a reaction state during the heat treatment, and a homogeneous crystal is formed. Li 2 Mn 2 O 5 was not produced because of the difficulty in producing Li 2 Mn 2 O 5 .
【００１４】このようにして得たＬｉ2Ｍｎ2Ｏ5を、次
いで酸処理することにより、その中のリチウムを溶出す
る。この酸処理は、ｐＨ３以下の弱酸水溶液に数時間な
いし数日間浸せきすることによって行われる。この際用
いる酸としては、塩酸、硫酸、硝酸、リン酸などの鉱酸
が好ましい。The Li 2 Mn 2 O 5 thus obtained is then treated with an acid to elute lithium therein. This acid treatment is carried out by immersing in a weak acid aqueous solution having a pH of 3 or less for several hours to several days. The acid used at this time is preferably a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.
【００１５】[0015]
【発明の効果】本発明の方法で調製した吸着剤は、吸着
サイトの生成量が多く、かつ均質であり、また酸強度が
高く、リチウムに対する選択吸着性に優れ、海水のよう
な希薄溶液からでもリチウムを効率よく回収することが
できる。また、吸着速度及び吸着容量が極めて大きく、
しかも水溶液中で安定であり、実用的な吸着剤である。The adsorbent prepared by the method of the present invention has a large amount of adsorbed sites, is homogeneous, has a high acid strength, has excellent selective adsorption to lithium, and can be prepared from a dilute solution such as seawater. However, lithium can be efficiently recovered. In addition, the adsorption speed and adsorption capacity are extremely large,
Moreover, it is stable in an aqueous solution and is a practical adsorbent.
【００１６】[0016]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
【００１７】実施例１ １Ｍ塩化マンガン水溶液中に、過酸化水素１０質量％を
含む１Ｍアンモニア水を添加し、生成する沈殿を捕集
し、ろ過、水洗、乾燥することにより、γ‐オキシ水酸
化マンガンをかっ色固体として得た。次に、この固体１
ｇを１Ｍ水酸化リチウム水溶液４０ｍｌ中に加え、１２
０℃で６時間水熱処理した。このようにして得られたＬ
ｉＭｎＯ2のＤＴＡ−ＴＧ曲線を図１に示す。図中の実
線はＤＴＡを、破線はＴＧを示す（以下同じ）。このＬ
ｉＭｎＯ2を空気雰囲気中、５００℃で４時間加熱処理
することにより、Ｌｉ2Ｍｎ2Ｏ5を暗かっ色結晶として
得た。EXAMPLE 1 1M aqueous ammonia containing 10% by mass of hydrogen peroxide was added to a 1M aqueous solution of manganese chloride, and the resulting precipitate was collected, filtered, washed with water and dried to obtain γ-oxyhydroxide. Manganese was obtained as a brown solid. Next, this solid 1
g in 40 ml of a 1 M aqueous lithium hydroxide solution,
Hydrothermal treatment was performed at 0 ° C. for 6 hours. L thus obtained
The DTA-TG curve of iMnO 2 is shown in FIG. The solid line in the figure indicates DTA, and the broken line indicates TG (the same applies hereinafter). This L
Heat treatment of iMnO 2 at 500 ° C. for 4 hours in an air atmosphere gave Li 2 Mn 2 O 5 as dark brown crystals.
【００１８】次に、この結晶を０．５Ｍ塩酸水溶液中に
３日間浸せきしてリチウムを完全に抽出したのち、ろ別
し、乾燥することにより、式ＭｎＯ2・０．５Ｈ2Ｏに相
当する組成をもつリチウム吸着剤を得た。このもののＤ
ＴＡ−ＴＧ曲線を図２に示す。このリチウム吸着剤０．
１ｇを、リチウム５ｐｐｍを含む海水１リットル中に添
加し、３日間かきまぜた。吸着前後のリチウム濃度の差
からリチウム吸着量を求めたところ、３７ｍｇ／ｇであ
った。Next, the crystals are immersed in a 0.5 M hydrochloric acid aqueous solution for 3 days to completely extract lithium, filtered, and dried to obtain a compound of the formula MnO 2 · 0.5H 2 O. A lithium adsorbent having a composition was obtained. D of this thing
The TA-TG curve is shown in FIG. This lithium adsorbent 0.1.
1 g was added to 1 liter of seawater containing 5 ppm of lithium and stirred for 3 days. The amount of lithium adsorbed was determined from the difference in lithium concentration before and after adsorption to be 37 mg / g.
【００１９】実施例２ 実施例１と同様にして製造したオキシ水酸化マンガン１
ｇを１Ｍ水酸化リチウム水溶液４０ｍｌ中に加え、１日
間還流させることによりＬｉＭｎＯ2を得た。このもの
のＤＴＡ−ＴＧ曲線を図３に示す。次に、このようにし
て得たＬｉＭｎＯ2を電気炉に入れ、大気中４５０℃で
４時間加熱処理することにより、Ｌｉ2Ｍｎ2Ｏ5を暗か
っ色結晶として得た。このＬｉ2Ｍｎ2Ｏ5を実施例１と
同様にして酸処理することにより、式ＭｎＯ2・０．５
Ｈ2Ｏに相当する組成をもつリチウム吸着剤を得た。こ
のもののＤＴＡ−ＴＧ曲線を図４に示す。この吸着剤を
実施例１と同様な条件でリチウム吸着実験を行った。リ
チウム吸着量は３６ｍｇ／ｇであった。Example 2 Manganese oxyhydroxide 1 produced in the same manner as in Example 1
g was added to 40 ml of a 1 M aqueous lithium hydroxide solution, and the mixture was refluxed for 1 day to obtain LiMnO 2 . The DTA-TG curve of this is shown in FIG. Next, the thus obtained LiMnO 2 was placed in an electric furnace and subjected to a heat treatment at 450 ° C. for 4 hours in the air, thereby obtaining Li 2 Mn 2 O 5 as dark brown crystals. By subjecting this Li 2 Mn 2 O 5 to acid treatment in the same manner as in Example 1, the formula MnO 2 .0.5 was obtained.
A lithium adsorbent having a composition corresponding to H 2 O was obtained. The DTA-TG curve of this is shown in FIG. This adsorbent was subjected to a lithium adsorption experiment under the same conditions as in Example 1. The lithium adsorption amount was 36 mg / g.
【００２０】比較例 炭酸マンガンと炭酸リチウムをＬｉ／Ｍｎモル比１で混
合し、４００℃に加熱処理し、結晶を生成させた。この
生成物を０．５Ｍ塩酸水溶液で処理してリチウムを抽出
し吸着剤を製造した。この吸着剤のリチウム吸着性能を
実施例１と同じ条件で測定したところ、リチウム吸着量
は１９ｍｇ／ｇであった。このことから、本発明方法に
従いＬｉ2Ｍｎ2Ｏ5を中間体として用いることによりリ
チウム吸着性能が飛躍的に上昇することが分る。Comparative Example Manganese carbonate and lithium carbonate were mixed at a Li / Mn molar ratio of 1 and heated at 400 ° C. to form crystals. This product was treated with a 0.5 M hydrochloric acid aqueous solution to extract lithium to produce an adsorbent. When the lithium adsorption performance of this adsorbent was measured under the same conditions as in Example 1, the lithium adsorption amount was 19 mg / g. This shows that the use of Li 2 Mn 2 O 5 as an intermediate according to the method of the present invention dramatically improves the lithium adsorption performance.
【図１】 水熱法により得られるＬｉＭｎＯ2のＤＴＡ
−ＴＧ曲線。FIG. 1 DTA of LiMnO 2 obtained by hydrothermal method
-TG curve.
【図２】 図１のＬｉＭｎＯ2を用いて得たリチウム吸
着剤のＤＴＡ−ＴＧ曲線。FIG. 2 is a DTA-TG curve of a lithium adsorbent obtained using the LiMnO 2 of FIG.
【図３】 還流法により得られるＬｉＭｎＯ2のＤＴＡ
−ＴＧ曲線。FIG. 3 DTA of LiMnO 2 obtained by a reflux method
-TG curve.
【図４】 図３のＬｉＭｎＯ2を用いて得たリチウム吸
着剤のＤＴＡ−ＴＧ曲線。FIG. 4 is a DTA-TG curve of the lithium adsorbent obtained using the LiMnO 2 of FIG.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宮井 良孝 香川県高松市林町2217番14 工業技術院四 国工業技術研究所内 (72)発明者 大井 健太 香川県高松市林町2217番14 工業技術院四 国工業技術研究所内 Ｆターム(参考） 4G048 AA04 AB02 AB05 AC08 AE05 4G066 AA13A AA26B AA34D AE01D BA36 BA38 CA45 DA07 FA11 FA20 FA34 ──────────────────────────────────────────────────の Continuing from the front page (72) Inventor Yoshitaka Miyai 2217-14 Hayashi-cho, Takamatsu-shi, Kagawa Pref. F-Term (in reference) 4G048 AA04 AB02 AB05 AC08 AE05 4G066 AA13A AA26B AA34D AE01D BA36 BA38 CA45 DA07 FA11 FA20 FA34
Claims (3)
ウムとを反応させてＬｉＭｎＯ2を生成させたのち、こ
れを酸素の存在下４００℃以上で焼成してＬｉ2Ｍｎ2Ｏ
5に変換し、次いでこれを酸処理することを特徴とする
リチウム吸着剤の製造方法。1. LiMnO 2 is produced by reacting γ-manganese oxyhydroxide with lithium hydroxide and then calcined at 400 ° C. or higher in the presence of oxygen to produce Li 2 Mn 2 O
5. A method for producing a lithium adsorbent, which comprises converting the compound to 5 , followed by acid treatment.
ウムとを含む水溶液を加圧下１００〜１４０℃において
水熱反応させてＬｉＭｎＯ2を生成させる請求項１記載
のリチウム吸着剤の製造方法。2. The method for producing a lithium adsorbent according to claim 1, wherein an aqueous solution containing γ-manganese oxyhydroxide and lithium hydroxide undergoes a hydrothermal reaction under pressure at 100 to 140 ° C. to produce LiMnO 2 .
ウムとを含む水溶液を加熱還流させてＬｉＭｎＯ2を生
成させる請求項１記載のリチウム吸着剤の製造方法。3. The method for producing a lithium adsorbent according to claim 1, wherein an aqueous solution containing γ-manganese oxyhydroxide and lithium hydroxide is heated to reflux to generate LiMnO 2 .
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| KR100972140B1 (en) | 2006-11-20 | 2010-07-23 | 한국지질자원연구원 | Method for synthesis of lithium manganese oxide by hydroysis and solvent-exchange process and preparation of ion-exchange type lithium adsorbent using the lithium manganese oxide |
| CN109289757A (en) * | 2018-12-07 | 2019-02-01 | 中国科学院青海盐湖研究所 | Six square bar shape manganese systems lithium ion sieve adsorbants of one kind and preparation method thereof |
| CN111601656A (en) * | 2018-04-20 | 2020-08-28 | 住友金属矿山株式会社 | Method for producing precursor of lithium adsorbent |
| CN115253999A (en) * | 2022-07-13 | 2022-11-01 | 中国科学院青海盐湖研究所 | Lithium adsorption material and preparation method and application thereof |
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| WO2020115948A1 (en) | 2018-12-07 | 2020-06-11 | 住友金属鉱山株式会社 | Method for producing lithium-containing solution |
| DE102021108442B4 (en) | 2021-04-01 | 2023-01-26 | EnBW Energie Baden-Württemberg AG | Process for preparing a lithium adsorbent |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100972140B1 (en) | 2006-11-20 | 2010-07-23 | 한국지질자원연구원 | Method for synthesis of lithium manganese oxide by hydroysis and solvent-exchange process and preparation of ion-exchange type lithium adsorbent using the lithium manganese oxide |
| CN111601656A (en) * | 2018-04-20 | 2020-08-28 | 住友金属矿山株式会社 | Method for producing precursor of lithium adsorbent |
| CN109289757A (en) * | 2018-12-07 | 2019-02-01 | 中国科学院青海盐湖研究所 | Six square bar shape manganese systems lithium ion sieve adsorbants of one kind and preparation method thereof |
| CN109289757B (en) * | 2018-12-07 | 2021-03-16 | 中国科学院青海盐湖研究所 | Hexagonal dendritic manganese lithium ion sieve adsorbent and preparation method thereof |
| CN115253999A (en) * | 2022-07-13 | 2022-11-01 | 中国科学院青海盐湖研究所 | Lithium adsorption material and preparation method and application thereof |
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| JP3388406B2 (en) | 2003-03-24 |
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