CN107321297A - A kind of preparation of the mesoporous lithium ion sieve of three-dimensional macropore - Google Patents
A kind of preparation of the mesoporous lithium ion sieve of three-dimensional macropore Download PDFInfo
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Abstract
The present invention relates to a kind of preparation and its application of the lithium ion sieve with three-dimensional macropore meso-hole structure.The lithium ion sieve is using polystyrene microsphere array as template, using isopropyl titanate and anhydrous lithium acetate as titanium source and lithium source, and the lithium titanate 3DM Li with three-dimensional macropore meso-hole structure are obtained by the method for irrigating and calcining4Ti5O12.Finally, 3DM Li4Ti5O12Lithium process, which is taken off, by acidleach obtains the mesoporous lithium ion sieve 3DM H of three-dimensional macropore4Ti5O12.Macroporous structure in the lithium ion sieve is connected by mesoporous between Kong Yukong in regularly arranged, forms the three-dimensional macropore meso-hole structure being mutually communicated between a kind of duct.Compared with other materials, the unique pore passage structure of the lithium ion sieve is conducive to lithium ion out of all directions access aperture, reduces the internal diffusional resistance of lithium ion, reduces lithium ion adsorption/desorption equilibration time, increases lithium ion adsorption capacity.Many advantages above allow the lithium ion sieve as good lithium sorbing material.
Description
Technical field
The present invention relates to three-dimensional foramen magnum-mesoporous lithium ion sieve of one kind and preparation method thereof, belong to field of nanometer material technology.
Background technology
Lithium metal is widely used in multiple fields, demand and day of the mankind to lithium resource as a kind of novel energy metal
It is all to increase, but but there is the situation that supply falls short of demand in the yield of lithium metal.Lithium resource is primarily present in lithium ore, salt lake and seawater
In.But lithium ore resource is limited, and even most ripe ore puies forward lithium technique, will there is also high energy consumption, equipment
High, cost height is sought, the low shortcoming of the rate of recovery can not meet demand of the market for lithium metal.69 % of world's lithium storage level come
From in salt lake, at present for, the method that salt lake carries lithium mainly has evaporative crystallization hair, the precipitation method, solvent extraction and absorption method.Inhale
Attached method because its is simple to operate, Selective adsorption is good, recycle efficiency high, it is environmentally friendly the advantages of be considered as most before
Scape puies forward lithium method.
In recent years, the lithium ion sieve based on " ion sieve effect " obtains extensive concern due to its high lithium ion selectivity.
The technology is by first preparing the compound of lithium salts, then takes off lithium process by acidleach and obtain lithium room, contains " memory energy using this
The lithium void geometry of power " reaches the purpose of selective absorption enriching lithium.This technology directly can extract lithium from salt lake bittern,
It is great promising lithium adsorbent.
Lithium ion sieve oxide mainly includes lithium manganese oxide and Li-Ti oxide.At present with the research of manganese systems lithium ion sieve more
Extensively, but valence state changes during acidleach takes off lithium due to manganese ion, the loss of part manganese ion is caused, causes lithium ion
The change of sieve structure, causes the cyclical stability of manganese systems lithium ion sieve generally poor.Comparatively speaking, titanium based lithium-ion sieve is due to titanium
The stronger interaction of oxygen key so that it can still keep original structure during acid treatment, thus with more preferable
Cyclical stability.But conventional titanium source is easily hydrolyzed, and the research of relevant lithium titanate application structure-activity relationship is relatively fewer.At this stage
The titanium based lithium-ion of preparation is sieved based on body phase material, and the lithium ion room that surface is exposed is few, and granulation or cast film processes are entered
One step causes resistance to mass tranfer to increase, and rate of adsorption reduction, adsorption capacity is reduced.Therefore, a kind of efficient lithium sorbing material is invented
With considerable meaning.
It will be expected to build a kind of efficient titanium system by the method for increasing specific surface area, improving crystallinity and reducing resistance to mass tranfer
Lithium ion sieve.Therefore, we have invented a kind of three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM- with counter opal structure
H4Ti5O12.This three-dimensional foramen magnum-mesoporous lithium ion sieve reduces lithium ion in transmitting procedure by its special stephanoporate framework
Internal diffusional resistance, reduce adsorption-desorption equilibration time, and further increase lithium adsorbance.
The content of the invention
The purpose of the invention is the provision of a kind of preparation method with three-dimensional foramen magnum-mesoporous structure lithium ion sieve.Should
The macroporous structure of material is, using the polystyrene with opal structural as hard template, lithium titanate precursor liquid to be filled into template
In gap, polystyrene moulding is then removed by high-temperature calcination and obtains the lithium ion sieve presoma with counter opal structure
3DM-Li4Ti5O12, last 3DM-Li4Ti5O12Acidleach is completed with the reaction of certain density hydrochloric acid solution and takes off lithium process, is had
The three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H in lithium ion hole4Ti5O12。
The three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H that the invention is provided4Ti5O12Preparation process it is as follows：
（1）A certain amount of neopelex and potassium peroxydisulfate are added to containing certain volume water, alcohol mixed solution
Three neck round bottom flask in, at room temperature magnetic agitation dissolve.After solid dissolving, under nitrogen protection, solution is warming up to certain
The styrene of certain volume, is then quickly injected into three-necked flask by temperature with needle tubing, and uniform stirring produces vortex, and backflow is anti-
The regular hour is answered, milky white liquid is finally obtained.Obtained mixed emulsion filters out bulk condensation product with absorbent cotton, and bottling is protected
Deposit.The polystyrene emulsion prepared is added in beaker, and beaker is placed in 70 DEG C of baking ovens, until solvent evaporation is complete,
Obtain block white polystyrene template.
（2）By the anhydrous lithium acetate and P123 of certain mass, the glacial acetic acid and isopropanol of certain volume are added in round-bottomed flask,
Magnetic agitation is until solid dissolving, then pipettes a certain amount of isopropyl titanate in round-bottomed flask with pipette, and continuation is stirred
Regular hour, obtain faint yellow homogeneous phase solution.
（3）By step（2）The lithium titanate precursor liquid configured is injected into block polystyrene moulding, after complete wetting, room temperature
Under treat that solvent volatilization is put into 70 DEG C of baking ovens and solidifies the regular hour completely.Then step calcination method is utilized, polystyrene is removed
Template, obtains three-dimensional foramen magnum-mesoporous lithium titanate 3DM-Li4Ti5O12。
（4）Take appropriate step（3）The three-dimensional foramen magnum-mesoporous lithium titanate 3DM-Li prepared4Ti5O12It is added to certain volume certain
In the hydrochloric acid solution of concentration, the regular hour is reacted in constant temperature oscillator.After reaction terminates, mixture is centrifuged, fallen
Fall supernatant liquor, and remaining solid is washed with ultra-pure water, until the aobvious neutrality of supernatant liquor.By the solid after washing
70 DEG C of oven dryings are placed in, three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H is obtained4Ti5O12。
In above-mentioned preparation method, step（1）The quality of neopelex is 0.45 g, and the quality of potassium peroxydisulfate is 0.6
G, the volume of water is 150 mL, and the volume of ethanol is 270 mL, and the volume of styrene is 36 mL.Neopelex with
Potassium peroxydisulfate wants completely soluble and ethanol mixed solution, and is warming up under nitrogen protection after 71 DEG C, then will with syringe
Styrene is injected into three-necked flask.Add after styrene, 71 DEG C of 19 h of backflow.Styrene need to be first with 0.5 mol/L's
NaOH solution is washed, and removes polymerization inhibitor.
In above-mentioned preparation method, step（1）The height for the polystyrene emulsion being added to inside beaker is in 1 ~ 2 cm.
In above-mentioned preparation method, step（2）The quality of middle anhydrous lithium acetate is 1.32 g, and P123 quality is 0.55 g, ice vinegar
The volume of acid is 17 mL, and the volume of isopropanol is 37 mL, and the volume of isopropyl titanate is 7.4 mL, and mixing time is 10
min。
In above-mentioned preparation method, step（3）Middle hardening time is 24 h, and the heating schedule that removal polystyrene moulding is used is two
Segmentation, is first warming up to 200 DEG C of 2 h of calcining with 1 DEG C/min heating rate, then with 1 DEG C/min heating rate by temperature
600 ~ 800 DEG C are increased to, 0.5 ~ 12 h is calcined.Second segment calcination condition is with 600 DEG C, and 6 h are advisable.
In above-mentioned preparation method, step（4）Middle three-dimensional foramen magnum-mesoporous lithium titanate 3DM-Li4Ti5O12Quality take 0.2 g, hydrochloric acid
The volume of solution is 20 mL, and the concentration of hydrochloric acid solution is 0.05 ~ 5.0 mol/L, and the reaction time is 96 h.Wherein, optimum salt
Acid concentration is 0.1 mol/L.
In above-mentioned preparation method, step（4）Middle centrifugation rate is 4000 r/min, and centrifugation time is 10 min.
The advantage of the present invention is embodied in：
1st, the invention material has the foramen magnum-mesoporous structure that is mutually communicated, can significantly reduce lithium ion between channels interior
Portion's diffusional resistance, improves the rate of adsorption, reduces the adsorption-desorption time.
2nd, the invention material has larger specific surface area, can increase the adsorbance to lithium ion.
3rd, raw material economics involved in material preparation process of the present invention is easy to get, and experimental procedure is simply easily operated.
It is as follows that the three-dimensional foramen magnum-mesoporous lithium ion sieve that the present invention is provided investigates method to lithium ion adsorbance：
Take 0.15 g 3DM-H4Ti5O12It is added in 30 mL, 0.05 mol/L LiOH solution, it is anti-in constant temperature oscillator
Answer 24 h.Supernatant liquor is measured, the concentration that lithium ion is remained in solution is measured using plasma emission spectrometer, three-dimensional is obtained
Foramen magnum-mesoporous lithium ion sieve 3DM-H4Ti5O12For the saturated extent of adsorption of lithium ion.
The three-dimensional foramen magnum-mesoporous lithium ion sieve circulation absorption Performance method that the present invention is provided is as follows：
Take 0.15 g 3DM-H4Ti5O12It is anti-in constant temperature oscillator in the LiOH solution for being added to the mol/L of 30 mL 0.05
Answer 24 h.Supernatant liquor is measured, the concentration that lithium ion is remained in solution is measured using plasma emission spectrometer, by calculating
Obtain three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H4Ti5O12For lithium ion first time circulation absorption amount（Q）.After reaction terminates,
Mixture is centrifuged, supernatant liquor is outwelled, and remaining solid is washed with ultra-pure water, until during supernatant liquor is aobvious
Property.Solid after washing is placed in 70 DEG C of oven dryings, three-dimensional foramen magnum-mesoporous lithium ion sieve presoma 3DM- is obtained
Li4Ti5O12.Then by above-mentioned dried 3DM-Li4Ti5O12It is added in the mol/L HCl solutions of 20 mL 0.1, in constant temperature
Reacted 72 hours in oscillator.After reaction terminates, it is still that mixture is centrifuged, outwells supernatant liquor, and use ultra-pure water
Remaining solid is washed, until the aobvious neutrality of supernatant liquor.Solid after washing is placed in 70 DEG C of oven dryings, obtained
To three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H4Ti5O12.Repeat the above steps five times, complete to three-dimensional foramen magnum-mesoporous lithium ion
Sieve the investigation of circulation absorption performance.
The three-dimensional foramen magnum-mesoporous lithium ion sieve that the present invention is provided selects Performance method as follows lithium ion：
Take the three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H of 0.15 g4Ti5O12It is added to 20 mL 0.01mol/L hybrid ionics（Bag
Include LiCl, NaCl, KCl, MgCl2、CaCl2）NH3·H2O-NH4In Cl cushioning liquid, 24 h are reacted in constant temperature oscillator.
Supernatant liquor is measured, the concentration that various ions are remained in solution is measured using plasma emission spectrometer, is obtained by calculating
Saturated extent of adsorption of the three-dimensional foramen magnum-mesoporous lithium ion sieve for various ions（Q）, distribution coefficient（Kd）And separation factor（αLi Me）.
Brief description of the drawings
Fig. 1 is the three-dimensional foramen magnum-mesoporous lithium ion sieve presoma 3DM-Li that embodiment 3 is obtained4Ti5O12SEM figure and TEM
Figure, can clearly be seen that the presence of three-dimensional ordered macroporous structure from figure.Wherein, the size of macropore is about 165 nm, hole wall
Thickness is about 12.5 nm.
Fig. 2 is obtained three-dimensional foramen magnum-mesoporous lithium ion sieve presoma 3DM-Li in embodiment 34Ti5O12N2Adsorption desorption curve
And its pore size distribution curve.BET results show 3DM-Li4Ti5O12Mesoporous pore size be about 20 nm, specific surface area is 39.25
m2/g。
Fig. 3 is obtained three-dimensional foramen magnum-mesoporous lithium ion sieve presoma 3DM-Li in embodiment 3-94Ti5O12Wide-angle XRD.
It can be seen that calcining heat is higher, calcination time is longer, TiO2Dephasign it is fewer, the crystal of lithium titanate can also become
It is relatively pure.But with the rise of calcining heat, the aggravation of crystal grain shrinkage phenomenon can influence the integrality and stability of skeleton.
In order to ensure product purity and structure it is complete, calcining heat be 600 DEG C, calcination time be 6 h it is most appropriate.
Fig. 4 is lithium ion and dissolution situation map of the titanium ion under different acidic conditions in embodiment 10-14.As seen from the figure, when
When the concentration of hydrochloric acid is 0.1 mol/L, lithium ion has a higher dissolution rate, and titanium ion dissolution rate is close to 0.Therefore, hydrochloric acid
Concentration takes 0.1 mol/L most appropriate.
Fig. 5 is three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H4Ti5O12Circulation absorption performance map.As seen from the figure, three-dimensional macropore-Jie
Hole lithium ion sieve 3DM-H4Ti5O12Saturated extent of adsorption can reach 5.51 mmol/L, after circulation 6 times, the lithium ion sieve is still
Similar adsorbance can be kept.Result above shows that the cyclical stability of the material is preferable.
Following table is that three-dimensional foramen magnum-mesoporous lithium ion sieve is containing Li+、Na+、K+、Mg2+、Ca2+Mixed solution in lithium ion
Adsorption selectivity figure.Wherein C0For the initial concentration of various ions in mixed solution, CeTo reach mixed solution after adsorption equilibrium
In various ions concentration, Q be three-dimensional foramen magnum-mesoporous lithium ion sieve for the saturated extent of adsorption of various ions, KdFor distribution system
Number, αLi MeFor separation factor.By following table, the lithium ion sieve is for the selectivity order of various ions：Li+ > Na+ ~
Ca2+ > K+ > Mg2+。
Specific embodiment
The present invention is described in further detail below in conjunction with example.
Embodiment 1
The preparation of opal polystyrene hard template
0.45 g neopelexes and 0.6 g potassium peroxydisulfates are added to three mouthfuls equipped with 150 ml water and 270 ml ethanol
In round-bottomed flask, magnetic agitation dissolves at room temperature.After solid dissolving, under nitrogen protection, solution is warming up to 71 DEG C, Ran Houyong
36 ml styrene is quickly injected into three-necked flask by needle tubing（Styrene need to be washed first with 0.5 mol/L NaOH solutions, be removed
Remove polymerization inhibitor）, uniform stirring produces vortex, and the h of back flow reaction 19 at 71 DEG C finally obtains milky white solution.Obtained solution
Bulk condensation product is filtered out with absorbent cotton, bottling is preserved.The polystyrene emulsion prepared is added in beaker, the height of solution
Spend and be advisable for 1 ~ 2 cm, and beaker is placed in 70 DEG C of baking ovens, until solvent evaporation is complete, obtain block white polystyrene
Template.
Embodiment 2
Three-dimensional foramen magnum-mesoporous lithium titanate 3DM-Li4Ti5O12The preparation of precursor liquid
By 1.32 g anhydrous lithium acetates, 0.55 g P123,17 mL glacial acetic acid and 37 mL isopropanols are added in round-bottomed flask,
Magnetic agitation is until solid dissolving, then pipettes 7.4 mL isopropyl titanates in round-bottomed flask with pipette, and continuation stirs 10
Min, obtains faint yellow homogeneous phase solution.
Embodiment 3
Three-dimensional foramen magnum-mesoporous lithium titanate 3DM-Li4Ti5O12Preparation
The lithium titanate precursor liquid configured is injected into block polystyrene moulding, after complete wetting, treats that solvent is waved at room temperature
The h of fixed line 24 in 70 DEG C of baking ovens is put into after distributing.Utilize step calcination method, first 200 DEG C of calcinings in Muffle furnace by block product
2 h, heating rate is 1 DEG C/min, and temperature then is increased into 600 DEG C, calcines 6 h, and heating rate is 1 DEG C/min.
Embodiment 4-9
Embodiment 4-9 experimental procedures are same as Example 3, three-dimensional foramen magnum-mesoporous lithium titanate 3DM-Li4Ti5O12 calcining
Temperature and time is different, is embodied as shown in the table：
| Embodiment | Calcining heat（℃） | Calcination time（h） |
| Embodiment 4 | 600 | 3 |
| Embodiment 5 | 600 | 12 |
| Embodiment 6 | 700 | 3 |
| Embodiment 7 | 700 | 6 |
| Embodiment 8 | 700 | 12 |
| Embodiment 9 | 800 | 0.5 |
Embodiment 10
Three-dimensional foramen magnum-mesoporous lithium ion sieve 3DM-H4Ti5O12Preparation
By 0.2 g 3DM-Li4Ti5O12With the mol/L of 20 mL 0.1 hydrochloric acid reaction, sampled in 24,48,72 and 96 h, profit
The concentration of lithium ion and titanium ion in solution is measured with plasma emission spectrometer.According to lithium ion in solution and titanium ion
Concentration obtains lithium ion and the respective dissolution rate of titanium ion.
Embodiment 11-14
Embodiment 11-14 experimental procedures are same as in Example 10, and concentration of hydrochloric acid used in during the de- lithium of acidleach is not
Together, specific concentration is as follows：
| Embodiment | HCl concentration（mol/L） |
| Embodiment 11 | 0.05 |
| Embodiment 12 | 0.5 |
| Embodiment 13 | 1.0 |
| Embodiment 14 | 5.0 |
Claims (7)
1. for three-dimensional foramen magnum-mesoporous lithium ion sieve, it is characterised in that described material has three-dimensional ordered macroporous-mesoporous knot
It is mutually communicated between structure, each hole, these structures can reduce the diffusional resistance of lithium ion between the materials, and further improve
Absorption property of the material for lithium ion.
2. the preparation method of three-dimensional foramen magnum-mesoporous lithium ion sieve according to claim 1, it is characterised in that this method is taken
Following experimental procedure：
（1）, that a certain amount of neopelex and potassium peroxydisulfate are added to the water containing certain volume, ethanol mixing is molten
In the three neck round bottom flask of liquid, magnetic agitation is dissolved at room temperature, and after solid dissolving, under nitrogen protection, solution is warming up to necessarily
Temperature, then quickly the styrene of certain volume is injected into three-necked flask with needle tubing, uniform stirring produce vortex, backflow
The regular hour is reacted, milky white solution is finally obtained, obtained mixed emulsion filters out bulk condensation product with absorbent cotton, bottled
Preserve；The polystyrene emulsion prepared is added in beaker, and beaker is placed in 70 DEG C of baking ovens, until solvent is evaporated
Entirely, block white polystyrene template is obtained；（2）, by the anhydrous lithium acetate and P123 of certain mass（PEO-PPO-PEO）, one
The glacial acetic acid and isopropanol for determining volume are added in round-bottomed flask, and magnetic agitation is until solid dissolving, is then pipetted with pipette
A certain amount of isopropyl titanate continues to stir the regular hour, obtains faint yellow homogeneous phase solution in round-bottomed flask；（3）, will step
Suddenly（2）The lithium titanate precursor liquid configured is injected into block polystyrene moulding, after complete wetting, treats that solvent volatilizees at room temperature
It is put into completely in 70 DEG C of baking ovens and solidifies the regular hour, then using step calcination method, removes polystyrene moulding, obtain three
Tie up foramen magnum-mesoporous lithium titanate 3DM-Li4Ti5O12；（4）, take appropriate step（3）The three-dimensional foramen magnum-mesoporous lithium titanate prepared
3DM-Li4Ti5O12It is added in the certain density hydrochloric acid solution of certain volume, the regular hour is reacted in constant temperature oscillator,
After reaction terminates, mixture is centrifuged, supernatant liquor is outwelled, and remaining solid is washed with ultra-pure water, until
The aobvious neutrality of supernatant liquor, is placed in 70 DEG C of oven dryings by the solid after washing, obtains three-dimensional foramen magnum-mesoporous lithium ion sieve
3DM-H4Ti5O12。
3. preparation method according to claim 2, it is characterised in that：Step（1）The quality of middle neopelex
For 0.45 g, the quality of potassium peroxydisulfate is 0.6 g, and the volume of water is 150 mL, and the volume of ethanol is 270 mL, the body of styrene
Product is 36 mL, and neopelex wants completely soluble and ethanol mixed solution with potassium peroxydisulfate, and in nitrogen protection
Under be warming up to after 71 DEG C, then styrene is injected into three-necked flask with syringe, adds 71 DEG C of backflows 19 after styrene
H, styrene need to be washed first with 0.5 mol/L NaOH solution, remove polymerization inhibitor.
4. preparation method according to claim 2, it is characterised in that：Step（1）It is added to the polystyrene inside beaker
The height of emulsion is in 1 ~ 2 cm.
5. preparation method according to claim 2, it is characterised in that：Step（2）The quality of middle anhydrous lithium acetate is 1.32
G, P123 quality are 0.55 g, and the volume of glacial acetic acid is 17 mL, and the volume of isopropanol is 37 mL, the volume of isopropyl titanate
For 7.4 mL, mixing time is 10 min.
6. preparation method according to claim 2, it is characterised in that：Step（3）Middle hardening time is 24 h, removes polyphenyl
The heating mode that ethene template is used first is warming up to 200 DEG C of 2 h of calcining, then for two-part with 1 DEG C/min heating rate
Temperature is increased to 600 DEG C ~ 800 DEG C with 1 DEG C/min heating rate, 0.5 ~ 12 h is calcined, second segment calcination condition with
600 DEG C, 6 h are advisable.
7. preparation method according to claim 2, it is characterised in that：Step（4）Middle three-dimensional foramen magnum-mesoporous lithium titanate 3DM-
Li4Ti5O12Quality take 0.2 g, the volume of hydrochloric acid solution is 20 mL, and the concentration of hydrochloric acid solution is 0.05 ~ 5.0 mol/L, instead
96 h between seasonable, wherein, optimum concentration of hydrochloric acid is 0.1 mol/L, and centrifugation rate is 4000 r/min, and centrifugation time is 10
min。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973339A (en) * | 2017-11-24 | 2018-05-01 | 武汉理工大学 | The three-dimensional ordered macroporous calcium titanate photonic crystal and its synthetic method that a kind of porous nano-sheet is constructed |
| CN111704160A (en) * | 2020-06-02 | 2020-09-25 | 常州大学 | Titanium-based ion sieve for selectively extracting lithium, preparation method and application |
| CN114917862A (en) * | 2022-06-10 | 2022-08-19 | 中国科学院青海盐湖研究所 | Porous lithium adsorbent and preparation method and application thereof |
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2017
- 2017-07-03 CN CN201710531604.2A patent/CN107321297A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973339A (en) * | 2017-11-24 | 2018-05-01 | 武汉理工大学 | The three-dimensional ordered macroporous calcium titanate photonic crystal and its synthetic method that a kind of porous nano-sheet is constructed |
| CN107973339B (en) * | 2017-11-24 | 2020-04-21 | 武汉理工大学 | Three-dimensional ordered macroporous calcium titanate photonic crystal constructed by porous nanosheets and synthetic method thereof |
| CN111704160A (en) * | 2020-06-02 | 2020-09-25 | 常州大学 | Titanium-based ion sieve for selectively extracting lithium, preparation method and application |
| CN114917862A (en) * | 2022-06-10 | 2022-08-19 | 中国科学院青海盐湖研究所 | Porous lithium adsorbent and preparation method and application thereof |
| CN114917862B (en) * | 2022-06-10 | 2024-04-12 | 中国科学院青海盐湖研究所 | Porous lithium adsorbent and preparation method and application thereof |
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