Enriching lithium and separating lithium to magnesium from sulfate type salt lake brine

Journal Pre-proof Enriching lithium and separating lithium to magnesium from sulfate type salt lake brine

Xuheng Liu, Maoli Zhong, Xingyu Chen, Jiangtao Li, Lihua He, Zhongwei Zhao PII:

S0304-386X(19)30552-3

DOI:

https://doi.org/10.1016/j.hydromet.2020.105247

Reference:

HYDROM 105247

To appear in:

Hydrometallurgy

Received date:

18 June 2019

Revised date:

12 November 2019

Accepted date:

4 January 2020

Please cite this article as: X. Liu, M. Zhong, X. Chen, et al., Enriching lithium and separating lithium to magnesium from sulfate type salt lake brine, Hydrometallurgy(2020), https://doi.org/10.1016/j.hydromet.2020.105247

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Journal Pre-proof

Enriching lithium and separating lithium to magnesium from sulfate type salt lake brine Xuheng Liu, Maoli Zhong, Xingyu Chen*, Jiangtao Li, Lihua He, Zhongwei Zhao (School of Metallurgy and environment, Central South University, ChangSha, 410083, China) Abstract: Extraction of lithium from salt lake brine has become a research highlights due to the rapid development of lithium ion battery. There are abundant lithium

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resources in sulfate type salt lake in China. In this work, the process of enriching lithium and separating lithium to magnesium from simulated sulfate type brine was

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carried out based on the reaction of Al/Na2SO4 composite with brine. The results show that Al/Na2SO4 composite can be used to enrich lithium from Li2SO4 solution in

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the form of Li2Al4(OH)12SO4·xH2O and the lithium precipitation efficiency reaches

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89.2% under the optimal conditions. The existence of magnesium in solution is adverse to the precipitation process of lithium. The coating of compact Mg-Al

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hydrotalcite on the surface of aluminum based material hinders the reaction of Al/Na2SO4 composite with brine and the lithium precipitation efficiency decreases to 54.7% when the Mg/Li mass ratio in solution is 20:1. However, the Mg/Li mass ratio

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in precipitate is less than 0.3 under the optimal conditions. The results are beneficial

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for the enriching lithium and separating lithium to magnesium from sulfate type brine.

Keywords: Sulfate type brine; Al/Na2SO4 composite; Lithium extraction; Separation of magnesium and lithium; High Mg/Li mass ratio

1. Introduction Lithium is known as the "new energy metal of the 21st century" [1,2]. Especially with the rapid development of lithium-ion battery, the market demand for lithium has increased dramatically. The increase speed maintains 8~11% in annual [3,4]. Driven by the demand of lithium, the utilization of lithium resources has entered a rapid development stage. Lithium resources on earth are mainly composed of mineral lithium resources and brine resources, and most of that is stored in salt lake brine[5-8]. *Corresponding author, Tel.: +86 0731 88830476; fax: +86 0731 88830477; E-mail address: [email protected]

Journal Pre-proof The lithium reserves in salt lake brine accounting for more than 80% of the total lithium reserves [9,10]. China's lithium resources in salt lake are also very rich. These salt lakes are mainly distributed in Qinghai-Tibet Plateau, with lithium reserves of more than 5 million tons [11-14]. The Mg/Li mass ratio in most salt lake brine in China is very high, generally above 40:1, and the highest in Cha’erhan salt lake reaches 1814:1[15-17]. Because the properties of magnesium and lithium are very similar, it is difficult to separate them to each other, which seriously restricts the utilization of lithium resources in salt lakes.

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There are many methods to extract lithium from salt lake brine, such as

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precipitation method [18,19], calcination leaching method [20], ion exchange adsorption method [21], solvent extraction method [22], electrodialysis method[23],

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solar ponds method and so on [24]. Recently, it is reported that Al-Ca alloy is used to

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extract lithium from LiCl solution[25]. Lithium in solution is enriched in the form of

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LiCl·2Al(OH)3·xH2O and the lithium extraction rate is high up to 94.6%. As is known to all, salt lakes in China can be divided into three types: chloride type, sulfate type

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and carbonate type. The area of sulfate type salt lakes in China accounts for 55% of the total salt lake area[26]. For example, Lop Nur Salt Lake, East Taijinar Salt Lake,

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West Taijinar Salt Lake and Zhabei Salt Lake all belong to sulfate type. Since Al-Ca alloy can be used to extract lithium from LiCl solution, aluminum based materials should be able to precipitate lithium from sulfate brine. However, not only Li+ but also a mass of Mg2+ coexists in sulfate brine. So, it is necessary to survey the migration behavior of lithium during precipitation process and the effect of Mg2+ on the migration of lithium in this work. 2. Experimental 2.1 Experimental procedure The Al/Na2SO4 composite was prepared according to the following procedure: aluminum powder was well mixed with Na2SO4 (mass ratio of Al/ Na2SO4 is 7:3) and then ground by vibratory mill for 20 minutes. It is generally known that there exists compact oxide film on the surface of aluminum powder, which will seriously hinder the reaction between aluminum powder and brine. So, it is necessary to remove the

Journal Pre-proof compact oxide film by vibratory mill. In order to eliminate the adverse influence of other anions such as Cl- on the lithium precipitation behavior from sulfate type brine, Na2SO4 was chosen as grinding aid to mix with aluminum powder in this work. The experiments of precipitating lithium and separating lithium to magnesium were carried out in flask (250ml) with three necks. Li2SO4 solution or Li2SO4 and MgSO4 mixed solution was added into the flask and agitated with magnetic stirrer. Constant temperature water bath was used to keep the solution at the predetermined temperature. When the predesigned temperature is reached, Al/Na2SO4 composite was

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added into the flask. After the predesigned reaction time, the solution and the

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precipitate were separated by vacuum filtration. The precipitate was washed several times using deionized water and then dissolved in acid solution completely, and the

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content of Li and Mg was analyzed by atomic absorption spectroscopy (AAS). The

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precipitation efficiency of lithium and magnesium and mass ratio of Mg/Li in

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precipitate can be calculated respectively according to the analysis results of AAS. 2.2 Analysis

The phase structure of the samples was characterized by X-ray diffraction

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analysis (XRD, Rint-2000, Rigaku) using Cu-Kα radiation. The morphologies of the

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precipitates were investigated by scanning electron microscope (JSM-5600, JEOL, Tokyo, Japan). The concentrations of Li+ and Mg2+ in solution were measured by atomic absorption spectroscopy (AAS, Persee of Beijing, China). 3. Results and discussion

3.1 Precipitation behavior of lithium in Li2SO4 solution Fig. 1 shows the XRD pattern of reaction products of Al/Na2SO4 composite with Li2SO4 solutions. The experimental conditions are as follows: initial Li+ concentration 1g/L, Al/Li mole ratio 3:1, reaction temperature 70℃ and reaction time 3h. It can be seen that the precipitate is mainly composed of Li2Al4(OH)12SO4·xH2O and Al(OH)3, and no diffraction peak of aluminum can be observed, indicating that the Al/Na2SO4 composite react completely with Li2SO4 solution. Li+ in solution react with Al/Na2SO4 composite and finally transfer to the precipitate in the form of Li2Al4(OH)12SO4·xH2O. The enrichment of lithium in brine is achieved by this

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means.

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Fig.1 XRD pattern of precipitate in Li2SO4 solution patter

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3.1.1 Effect of Al/Li mole ratio on lithium precipitation

Fig.2 Effect of Al/Li mole ratio on lithium precipitation

In order to investigate the effect of Al/Li mole ratio on lithium precipitation process, the experiments were carried out under the conditions of initial Li+ concentration 1g/L, reaction temperature 70℃ and reaction time 3h. The results in Fig. 2 show that the lithium precipitation efficiency is the highest when the Al/Li mole ratio is 3:1, which reaches 88.8%. According to the molecular formula of Li2Al4(OH)12SO4·xH2O, theoretically lithium in solution can be transferred into the precipitate completely when the Al/Li mole ratio is 2:1. But this is not the case in practice. Because of the low concentration of lithium in solution, it’s difficult for Al/Na2SO4 composite to react with Li+ in solution adequately, which leads to the low efficiency of lithium precipitation and the existence of Al(OH)3 in precipitate as

Journal Pre-proof shown in Fig. 1. When the Al/Li mole ratio increases to 3.5:1 or 4:1, the lithium precipitation efficiency decreases to nearly 83%. Excessive Al/Li molar ratio leads to the increase of Al(OH)3 yield, which is harmful to the reaction of Al/Na2SO4 composite with Li+ in solution. 3.1.2 Effect of initial Li+ concentration on lithium precipitation The effect of initial Li+ concentration on lithium precipitation was investigated under the conditions of Al/Li mole ratio 3:1, reaction temperature 70℃ and reaction time 3h. It can be seen from Fig. 3(a) that the residual Li+ concentration in solution

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increases slowly with the increase of initial Li+ concentration, which is in the range of

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0.1g/L to 0.2g/L. However, the lithium precipitation efficiency increases sharply along with the increase of initial Li+ concentration as shown in Fig. 3(b). The lithium

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precipitation efficiency increases from 55% to 88.2% when the initial Li+

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concentration increases from 0.2g/L to 1g/L. Although the higher initial Li+ concentration leads to the higher residual Li+ concentration in solution, for the

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more than 1g/L is reasonable.

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purpose of precipitating lithium as much as possible, the initial Li+ concentration of

Fig.3 Effect of initial Li+ concentration on lithium precipitation (a)-Residual Li+ concentration; (b)-lithium precipitation efficiency

3.1.3 Effect of reaction temperature on lithium precipitation Fig. 4 displays the effect of reaction temperature on the precipitation efficiency of lithium with an initial Li+ concentration 1g/L, Al/Li mole ratio 3:1 and reaction time 3h. It can be seen that the reaction temperature exhibits a significant influence on the precipitation efficiency of lithium. The increase of temperature is beneficial to

Journal Pre-proof enhance the reaction speed and make the reaction more completely. The precipitation efficiency of lithium increases rapidly from 77.3% to 88.8% when the temperature increases from 20℃ to 70℃. When the temperature is over 70℃, the precipitation

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efficiency of lithium keeps stable.

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Fig.4 Effect of reaction temperature on lithium precipitation

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3.1.4 Effect of reaction time on lithium precipitation

Fig.5 Effect of reaction time on lithium precipitation

The effect of reaction time on the precipitation efficiency of lithium was studied with the time varying from 30min to 240min under the conditions of the Al/Li mole ratio 3:1, initial Li+ concentration 1 g/L and reaction temperature 70℃. The results are shown in Fig. 5. It can be seen that the reaction of Al/Na2SO4 composite with Li2SO4 solution is very quick and the precipitation efficiency of lithium reaches 82% after

Journal Pre-proof 0.5h. The precipitation efficiency of lithium does not change when the reaction time is more than 3h, indicating that the reaction time of 3 h is enough for the precipitation of lithium.

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3.2 Separation process of lithium and magnesium

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Fig.6 Effect of operating parameters on separation of lithium and magnesium (a)- Effect of Al/Li mole ratio; other conditions: Initial Li+ concentration 1g/L; Initial Mg2+ concentration 20g/L; temperature 70℃; reaction time 3h. (b)- Effect of Initial Li+ concentration; other conditions: Al/Li mole ratio 3:1; Initial Mg2+ concentration 20g/L; temperature 70℃; reaction time 3h. (c)- Effect of temperature; other conditions: Al/Li mole ratio 3:1; Initial Li+ concentration 1g/L; Initial Mg2+ concentration 20g/L; reaction time 3h. (d)- Effect of time; other conditions: Al/Li mole ratio 3:1; Initial Li+ concentration 1g/L; Initial Mg2+ concentration 20g/L; temperature 70℃.

The Al/Na2SO4 composite exhibit excellent performance of precipitating lithium from pure Li2SO4 solution in the form of Li2Al4(OH)12SO4·xH2O. However, the majority of salt lakes in China are characterized with a high Mg/Li mass ratio. A small quantity of Li+ and a large quantity of Mg2+ coexist within the salt lake brine. If magnesium also transfers into the precipitate during the process of precipitating lithium, it will be impossible to separate lithium and magnesium from brine.

Journal Pre-proof Therefore, it is necessary to study the reaction process of Al based materials with Mg-Li mixed solution. Fig. 6 shows the effect of operating parameters on separation of lithium and magnesium. It can be seen that the precipitation efficiencies of magnesium are very low under vary conditions. Although the initial Mg2+ concentration in solution is high up to 20g/L, the highest magnesium precipitation efficiency is no more than 2%. At the same time, the Mg/Li mass ratios in precipitate are very small. The Mg/Li mass ratios in all precipitates are no more than 0.5, which is far lower than the value of 20 in mixed solution. These results show that the

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Al/Na2SO4 composite can achieve excellent separation of magnesium and lithium in

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sulfate solution. However, the precipitation efficiency of lithium from Li2SO4 and

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MgSO4 mixed solution decreases a lot compared to that from pure Li2SO4 solution.

Fig.7 Comparison of lithium precipitation efficiency in different solutions

Fig.8 Effect of Mg/Li mass ratio on separation of Li and Mg

Fig. 7 exhibits the difference of lithium precipitation efficiency when Al/Na2SO4 composite react with different solutions. The experiments are carried out under the conditions of Al/Li mole ratio 3:1 and reaction time 3h. It can be seen that the existence of Mg2+ in sulfate solution is harmful to lithium precipitation process. The lithium precipitation efficiency can reach 89.2% under 70℃ when the Al/Na2SO4 composite react with pure Li2SO4 solution. However, the lithium precipitation efficiency decreases to 54.7% when Al/Na2SO4 composite reacts with mixed solution of Li2SO4 and MgSO4. Furthermore, the effect of Mg/Li mass ratio in mixed solution on the precipitation process is studied and the results are shown in Fig. 8. It can be seen that the increase of Mg/Li mass ratio seriously hamper the precipitation process

Journal Pre-proof of lithium in mixed solution. The lithium precipitation efficiency decreases from 89.2% to 59.2% when the Mg/Li mass ratio in solution changes from 0 to 5:1, and furtherly decreases to 40.6% when the Mg/Li mass ratio in solution increases to 40:1. Meantime, the Mg/Li mass ratio in precipitate increases to 0.4:1. There are obvious differences in the color of different precipitates. It can be observed that the precipitate obtained from pure Li2SO4 solution is grayish white during the experimental process, while the precipitate obtained from Li2SO4 and MgSO4 mixed solution is black, which is closer to the color of Al/Na2SO4 composite.

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In order to reveal the reason for this phenomenon, the analysis for the phase and

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micromorphology of precipitate were achieved, and the results are shown in Fig. 9

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and Fig. 10.

Fig.9 X-ray patterns of the Al/Na2SO4 composite and precipitates (a)- Al/Na2SO4 composite; (b)-Precipitate in pure Li2SO4 solution; (c)-Precipitate in Li2SO4 and MgSO4 mixed solution;

It can be seen from Fig.9 that the precipitate obtained from pure Li2SO4 solution was mainly composed of Li2Al4(OH)12SO4·xH2O and Al(OH)3, while the diffraction peaks of aluminum metal were observed obviously in Fig. 9(c), indicating that the Al/Na2SO4 composite does not react completely with the mixed solution. The residual aluminum metal in precipitate did not react with lithium ion to form

Journal Pre-proof Li2Al4(OH)12SO4·xH2O, which leads to the serious decreases of lithium precipitation efficiency in mixed solution. The Al/Na2SO4 composite can react completely in Li2SO4 solution, but why can't they react completely in Li2SO4 and MgSO4 mixed solution? Li2Al4(OH)12SO4·xH2O belongs to Li-Al hydrotalcite in essence, and many researchers have done a lot of study work on hydrotalcite[27,28]. Al-Li hydrotalcite is a kind of layered double hydroxides (LDHs), which can be expressed as follow:

[M12x M3x (OH) 2 ]x [X n ]x / n  mH 2O

X n  — CO32- , SO 24 , F , Cl  , NO3

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M3 — Cr 3 , Fe3 , Mn3 , Co3 , Al3

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M 2 — Mg2 , Mn2 , Fe2 , Co 2 , Ni2

Usually, layered double hydroxides are made up of divalent cations and trivalent

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cations, but there are also layered double hydroxides consisting of monovalent cations

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n and trivalent cations such as LiAl 2 (OH) 6 X1/ n  mH 2 O [29]. Due to this characteristic,

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it is possible to enrich lithium in solution with Al/Na2SO4 composite. However, magnesium ion and aluminum ion can also be formed the layered double hydroxides

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when magnesium ion exists in solution. Different from Li-Al hydrotalcite, Mg-Al hydrotalcite shows lamellar crystallization. The crystalline grain is regular and

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uniform, which leads to the dense surface morphology of Mg-Al hydrotalcite [30]. The morphologies of precipitates obtained from different solutions are compared and the results are shown in Fig. 10. It can be seen that the surface of precipitate obtained from Li2SO4 solution is porous and loose, while the surface of precipitate obtained from MgSO4 and Li2SO4 mixed solution seems smooth and compact. Therefore, the reaction of Al/Na2SO4 composite with solution will be slowed down or cut out when Mg-Al hydrotalcite is coated on the surface of Al/Na2SO4 composite. Finally, the precipitation efficiency of lithium will decrease sharply.

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Fig.10 SEM images of precipitates in different solutions (a)-Precipitate in pure Li2SO4 solution; (b)-Precipitate in Li2SO4 and MgSO4 mixed solution;

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4. Conclusions

In this study, the process of enriching lithium and separating lithium to

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magnesium from simulated sulfate type brine was achieved by the reaction of

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Al/Na2SO4 composite with brine. Lithium in simulated brine is transferred into the

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precipitate in the form of Li2Al4(OH)12SO4·xH2O. The lithium precipitation efficiency can reach 89.2% under the optimal conditions in pure Li2SO4 solution. The existence

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of magnesium in solution is adverse to the precipitation process of lithium and the lithium precipitation efficiency decreases to 54.7% when the Mg/Li mass ratio in

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solution is 20:1. The generation of compact Mg-Al hydrotalcite on the surface of Al/Na2SO4 composite hinders the reaction of Al/Na2SO4 composite with brine. However, the Mg/Li mass ratio in precipitate is less than 0.3 under the optimal conditions, which indicates that Al/Na2SO4 composite exhibits the feasibility of enriching lithium and separating lithium to magnesium from sulfate type brine.

Acknowledgement This work was financially supported by National Natural Science Foundation of China (U1407137).

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Conflict of interest

The authors declared that they have no conflicts of interest to this work. We declare that we do not have any commercial or associative interest that represents a conflict

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of interest in connection with the work submitted.

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Lithium resources in sulfate type brine can be extracted by aluminum based material.

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The migration behavior of lithium during precipitation process was investigated.

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The Mg/Li mass ratio in precipitate can be less than 0.3 when that in solution is

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high up to 20:1.

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[M1-x2+Mx3+(OH)2]x+[Xn-]x/n·mH2O M2+ — Mg2+, Mn2+, Fe2+, Co2+, Ni2+ M3+ — Cr3+, Fe3+, Mn3+, Co3+, Al3+ Xn- — CO32-, SO42-, F-, Cl-, NO3-

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LiAl2(OH)6X1/nn-·mH2O