CN106622170A - Preparation method and application of lithium-titanium type ion sieve composite membrane - Google Patents
Preparation method and application of lithium-titanium type ion sieve composite membrane Download PDFInfo
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- CN106622170A CN106622170A CN201611191626.0A CN201611191626A CN106622170A CN 106622170 A CN106622170 A CN 106622170A CN 201611191626 A CN201611191626 A CN 201611191626A CN 106622170 A CN106622170 A CN 106622170A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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Abstract
The invention provides a preparation method and application of a lithium-titanium type ion sieve composite membrane. The preparation method comprises the following steps: step 1, preparing a lithium ion sieve Li2TiO3 precursor: adding TiO2 and Li2CO3 into absolute ethyl alcohol; after uniformly mixing, drying and baking; washing a baked lithium ion sieve Li2TiO3 with acid, so as to obtain the lithium ion sieve Li2TiO3 precursor; step 2, preparing the lithium-titanium type ion sieve composite membrane: dissolving the lithium ion sieve Li2TiO3 precursor, polyvinylidene fluoride powder and polyethylene glycol into an N-methyl pyrrolidone solution; mechanically stirring and uniformly mixing at constant temperature to prepare a lithium-titanium type ion sieve membrane casting solution; putting the lithium-titanium type ion sieve membrane casting solution into distilled water to obtain the lithium-titanium type ion sieve composite membrane capable of specifically identifying lithium ions. The prepared lithium-titanium type ion sieve composite membrane has good mechanical properties and stable structure and can be used for efficiently and selectively identifying and separating the lithium ions, such as selectively adsorbing and separating the lithium ions from salt lake brine.
Description
Technical field
The present invention relates to a kind of preparation method and its usage of lithium titanium-type ion sieve composite membrane, category environment functional material preparation
Technical field.
Background technology
Lithium is the alkali metal that atomic radius is minimum in nature, quality is most light, is silvery white in color, with many special things
Reason, chemical property.Lithium and its compound are widely used in the every field of national economy, not only in traditional consumer field such as glass
The fields such as glass, ceramics, lubricant play an important role, and have also promoted high-technology field such as lithium battery, nuclear energy, Aero-Space etc.
The development in field, is described as " new forms of energy of 21 century ", is significant strategic thing in national economy and national defense construction
Money.Constantly increase recently as the market demand of lithium, the lithium resource of land is provided far from demand is met from liquid lithium
Lithium is extracted in source becomes focus of concern, it has also become the main direction of lithium industrial development.
Lithium reserves in salt lake bittern are huge, and exist with ionic formses, provide preferable raw material shape for lithium salts production
State, the technological process complicated so as to avoid solid lithium ore deposit, can make production cost, gross investment reduce nearly 40% respectively.Therefore, from
In salt lake bittern, extraction lithium will replace pegmatite to carry lithium becomes the main flow of lithium industry, and longer-term accounts for leading in lithium industrial development
Status.Current solution carry the method for lithium mainly have the sedimentation method, evaporative crystallization method, solvent extraction, calcination leaching method, salting out method,
Carbonizatin method and adsorbent method.Wherein, it is one sedimentation method of evaporative crystallization that salt lake bittern puies forward the more ripe method of lithium, but the method is less
Suitable for the salt lake bittern of high Mg/Li ratio.Solvent extraction can avoid the lithium that the sedimentation method are brought from damaging with adsorbent method as far as possible
Lose, so as to become the method that salt lake brine with high magnesium-lithium ratio puies forward clang most prospect.Adsorbent method has process is simple, absorption property
The advantage such as good, economic and environment-friendly, compares solvent extraction and is more suitable for carrying lithium from low-grade sea water or salt lake saline, in recent years should be
The study hotspot in field.
And lithium ion sieve adsorbing material is considered as the most promising of lithium to be carried from sea water and most practicality
Method, at present, the research of the method obtains certain progress at home and abroad studying, but still belongs to advanced subject, skill
It is still immature in terms of art, need to make which become ripe technology in the near future by further research, it is wide so as to obtain
General application.Li-Ti oxide because with aboundresources, cheap, strong to the Selective adsorption of lithium, environmentally safe with
And the molten damage of titanium is extremely low, Stability Analysis of Structures and acid resistance is good, absorption property are stable and capable of circulation many advantages, such as use for several times, into
For the focus of scientists study.But for powdery, its mobility and permeability are all poor, are not easy to for lithium titanium-type oxide ion sieve
Industrial operation, hinders its commercial applications.Therefore many researcheres carry out pelletize research to powder body lithium ion sieve, synthesize granular
Lithium adsorbent.Also there is researcher that lithium ion sieve precursor powder is added in macromolecule member material casting solution in recent years, make
Lithium ion sieve precursor film, Jing after the de- lithium of pickling, obtains lithium ion sieve membrane.Extracted from liquid lithium resource using lithium ion sieve membrane
Lithium has relatively easy operating process, less energy consumption, non-secondary pollution, can operate continuously, low cost, can directly amplify, circulate and make
With the loss amount of rear lithium ion sieve it is less the advantages of.
Therefore by combining with membrane separation technique to lithium ion sieve, preparation carries the ion sieve of lithium to the present invention with selectivity
Composite membrane.
The content of the invention
The present invention relates to a kind of preparation method of lithium titanium-type ion sieve composite membrane.First, by TiO2And Li2CO3Material
Amount concentration ratio is dissolved in dehydrated alcohol for 1～1.05, after mix homogeneously, be placed in drying baker 85 DEG C dry after, by product with 5
DEG C/heating rate of min is warming up to 850 DEG C, maintains 24h, in atmosphere roasting to obtain lithium ion sieve Li2TiO3.To prepare
Good lithium ion sieve Li2TiO3In 0.1mol/L HCl solutions, 60 DEG C of magnetic agitation swap adsorption reaction, every certain
Time take supernatant 2.0mL, determine the concentration of Li+, be then centrifuged for and be placed in baking oven after repeatedly being washed with ethanol, obtain
Metatitanic acid type adsorbent H2TiO3.Finally, by 0.5g adsorbent H2TiO3, 3g Kynoar (PVDF) powder, 1g Polyethylene Glycol
It is dissolved in N-Methyl pyrrolidone (NMP) solution of 30mL, 50 DEG C of mechanical agitation 12h, after mixing, lithium titanium-type ion sieve is obtained
Casting solution is at the uniform velocity applied on a glass by casting solution with scraper, is subsequently placed in distilled water, that is, obtain having selection to lithium ion
Property absorption lithium titanium-type ion sieve composite membrane, can be used for being selectively adsorbing and separating for lithium ion.
The technical solution used in the present invention is：
A kind of preparation method of lithium titanium-type ion sieve composite membrane, step are as follows：
Step 1, prepare lithium ion sieve Li2TiO3Presoma：By TiO2And Li2CO3It is added in dehydrated alcohol, mix homogeneously
Afterwards, dry, roasting, by the lithium ion sieve Li after roasting2TiO3Pickling, that is, obtain lithium ion sieve Li2TiO3Presoma；
Step 2, prepare lithium titanium-type ion sieve composite membrane：By lithium ion sieve H2TiO3Presoma, Kynoar (PVDF) powder
End, Polyethylene Glycol are dissolved in N-Methyl pyrrolidone (NMP) solution, after constant temperature machinery stirring and evenly mixing, lithium titanium-type ion are obtained
Sieve casting solution, is subsequently placed in distilled water, that is, obtain the lithium titanium-type ion sieve composite membrane that there is to lithium ion particularity to recognize.
In step 1, the TiO for being used2And Li2CO3Substance withdrawl syndrome ratio in dehydrated alcohol is 1～1.05；It is described
Baking modes be warming up to 850 DEG C for the heating rate of 5 DEG C/min, roasting in atmosphere maintains 24h；During pickling, used
Acid is 0.1mol/L hydrochloric acid.
In step 2, the lithium ion sieve H2TiO3Presoma, Kynoar powder, Polyethylene Glycol are in N- crassitudes
The amount ratio of ketone is 0.25～1g：1.5～6g：0.5～2g：30mL；The churned mechanically temperature of the constant temperature is 50 DEG C, and machinery is stirred
The time is mixed for 12h.
Described lithium titanium-type ion sieve composite membrane is used for Selective recognition, separates lithium ion.
The beneficial effects of the present invention is：
(1) lithium titanium-type oxide of the present invention has the molten damage of titanium extremely low, Stability Analysis of Structures and acid resistance is good, and absorption property is stable
And it is capable of circulation for several times use many advantages, such as be great development prospect lithium adsorbent.
(2) lithium titanium-type ion sieve composite membrane good mechanical property, Stability Analysis of Structures obtained in, while can be known with efficient selective
Not, lithium ion is separated, selective absorption, separation lithium ion such as in salt lake bittern.
(3) present invention ion sieve is combined with membrane separation technique has relatively easy operating process, less energy consumption, without secondary dirt
Contaminate, can operate continuously, low cost, can directly amplify, recycle after lithium ion sieve loss amount it is less the advantages of.
Description of the drawings
Fig. 1 is lithium titanium-type ion sieve composite membrane prepared by embodiment 2.
Specific embodiment
With reference to specific embodiment, the invention will be further described：
Embodiment 1：
(1) by TiO2And Li2CO3It is added in dehydrated alcohol for 1.00 by substance withdrawl syndrome ratio, after mix homogeneously, puts
After 85 DEG C of drying in drying baker, product is warming up to into 850 DEG C with the heating rate of 5 DEG C/min, 24h is maintained, is roasted in atmosphere
Burn, that is, obtain lithium ion sieve LiTiO3.By the lithium ion sieve Li for preparing2TiO3In 0.1mol/L HCl solutions, 60 DEG C of magnetic force
Stirring swaps adsorption reaction, per supernatant 2.0mL is taken at regular intervals, determines Li+Concentration, be then centrifuged for and use second
Alcohol is placed in baking oven after repeatedly washing, and obtains metatitanic acid type adsorbent H2TiO3。
(2) prepare lithium manganese type ion sieve composite membrane：By 0.25g lithium ion sieve H2TiO3Presoma, 1.5g Kynoar
(PVDF) powder, 0.5g Polyethylene Glycol are dissolved in 30mLN- methyl pyrrolidones (NMP) solution, and 50 DEG C of mechanical agitation 12h are mixed
After even, lithium titanium-type ion sieve casting solution be obtained, be subsequently placed in distilled water, that is, obtain the lithium that there is to lithium ion particularity to recognize
Titanium-type ion sieve composite membrane.
Embodiment 2：
(1) by TiO2And Li2CO3It is added in dehydrated alcohol for 1.02 by substance withdrawl syndrome ratio, after mix homogeneously, puts
After 85 DEG C of drying in drying baker, product is warming up to into 850 DEG C with the heating rate of 5 DEG C/min, 24h is maintained, is roasted in atmosphere
Burn, that is, obtain lithium ion sieve Li2TiO3.By the lithium ion sieve Li for preparing2TiO3In 0.1mol/L HCl solutions, 60 DEG C of magnetic
Power stirring swaps adsorption reaction, per supernatant 2.0mL is taken at regular intervals, determines Li+Concentration, be then centrifuged for being used in combination
Ethanol is placed in baking oven after repeatedly washing, and obtains metatitanic acid type adsorbent H2TiO3。
(2) prepare lithium manganese type ion sieve composite membrane：By 0.5g lithium ion sieve H2TiO3Presoma, 3g Kynoar
(PVDF) powder, 1g Polyethylene Glycol are dissolved in 30mL N-Methyl pyrrolidone (NMP) solution, and 50 DEG C of mechanical agitation 12h are mixed
Afterwards, lithium titanium-type ion sieve casting solution is obtained, is subsequently placed in distilled water, that is, obtain the lithium titanium that there is to lithium ion particularity to recognize
Type ion sieve composite membrane.
Fig. 1 is lithium titanium-type ion sieve composite membrane prepared by embodiment 2；PVDF lithium ion sieve precursor film rough surface, deposits
In polymer, show that presoma is successfully joined in film.
Embodiment 3：
(1) by TiO2And Li2CO3It is added in dehydrated alcohol for 1.05 by substance withdrawl syndrome ratio, after mix homogeneously, puts
After 85 DEG C of drying in drying baker, product is warming up to into 850 DEG C with the heating rate of 5 DEG C/min, 24h is maintained, is roasted in atmosphere
Burn, that is, obtain lithium ion sieve Li2TiO3.By the lithium ion sieve Li for preparing2TiO3In 0.1mol/L HCl solutions, 60 DEG C of magnetic
Power stirring swaps adsorption reaction, per supernatant 2.0mL is taken at regular intervals, determines Li+Concentration, be then centrifuged for being used in combination
Ethanol is placed in baking oven after repeatedly washing, and obtains metatitanic acid type adsorbent H2TiO3。
(2) prepare lithium manganese type ion sieve composite membrane：By 1g lithium ion sieve H2TiO3Presoma, 6g Kynoar (PVDF)
Powder, 2g Polyethylene Glycol are dissolved in 30mL N-Methyl pyrrolidone (NMP) solution, after 50 DEG C of mechanical agitation 12h are mixed, system
Lithium titanium-type ion sieve casting solution, be subsequently placed in distilled water, that is, obtain there is lithium ion the lithium titanium-type of particularity identification from
Son sieve composite membrane.
Claims (4)
1. a kind of preparation method of lithium titanium-type ion sieve composite membrane, it is characterised in that step is as follows：
Step 1, prepare lithium ion sieve Li2TiO3Presoma：By TiO2And Li2CO3It is added in dehydrated alcohol, after mix homogeneously,
Drying, roasting, by the lithium ion sieve Li after roasting2TiO3Pickling, that is, obtain lithium ion sieve Li2TiO3Presoma；
Step 2, prepare lithium titanium-type ion sieve composite membrane：By lithium ion sieve H2TiO3Presoma, Kynoar powder, poly- second two
Alcohol is dissolved in N-Methyl pyrrolidone solution, after constant temperature machinery stirring and evenly mixing, lithium titanium-type ion sieve casting solution is obtained, then puts
In distilled water, that is, obtain the lithium titanium-type ion sieve composite membrane that there is to lithium ion particularity to recognize.
2. the preparation method of a kind of lithium titanium-type ion sieve composite membrane according to claim 1, it is characterised in that in step 1,
The TiO for being used2And Li2CO3Substance withdrawl syndrome ratio in dehydrated alcohol is 1～1.05；Described baking modes be 5 DEG C/
The heating rate of min is warming up to 850 DEG C, in atmosphere roasting, maintains 24h；During pickling, the acid for being used is 0.1mol/L salt
Acid.
3. the preparation method of a kind of lithium titanium-type ion sieve composite membrane according to claim 1, it is characterised in that in step 2,
The lithium ion sieve H2TiO3Presoma, Kynoar powder, Polyethylene Glycol are 0.25 in the amount ratio of N-Methyl pyrrolidone
～1g：1.5～6g：0.5～2g：30mL；The churned mechanically temperature of the constant temperature is 50 DEG C, and the mechanical agitation time is 12h.
4. the purposes of lithium titanium-type ion sieve composite membrane prepared by method described in claims 1 to 3 any one, its feature exist
In described lithium titanium-type ion sieve composite membrane is used for Selective recognition, separates lithium ion.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199010A (en) * | 2017-05-23 | 2017-09-26 | 江苏大学 | A kind of multistage core shell structure carries lithium material and preparation method thereof |
| CN108114693A (en) * | 2018-01-07 | 2018-06-05 | 天津市职业大学 | A kind of glass fibre is lithium ion sieve adsorbed film of matrix and preparation method thereof |
| CN108636341A (en) * | 2018-04-18 | 2018-10-12 | 南京工业大学 | Forming method of lithium extraction adsorbent |
| CN111233084A (en) * | 2020-02-14 | 2020-06-05 | 青岛科技大学 | Ion sieve for adsorbing cesium ions and preparation method thereof |
| CN111558350A (en) * | 2020-06-16 | 2020-08-21 | 东北林业大学 | Preparation method of HTO/cellulose aerogel microspheres for extracting lithium from seawater |
| CN111704160A (en) * | 2020-06-02 | 2020-09-25 | 常州大学 | Titanium-based ion sieve for selectively extracting lithium, preparation method and application |
| CN112619621A (en) * | 2020-12-22 | 2021-04-09 | 天津科技大学 | Preparation method of porous spinning composite material and application of porous spinning composite material in lithium extraction |
| CN113262648A (en) * | 2021-05-17 | 2021-08-17 | 郑州大学 | Lithium ion selective permeation membrane and application thereof |
| CN113307334A (en) * | 2019-12-30 | 2021-08-27 | 江苏大学 | Ionic sieve cathode for electrolytic cells for extracting lithium in aqueous solutions containing lithium |
| CN113522061A (en) * | 2021-07-21 | 2021-10-22 | 昆明理工大学 | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane |
| CN114377551A (en) * | 2022-01-11 | 2022-04-22 | 江苏巨之澜科技有限公司 | Positively charged polyimide nanofiltration membrane for magnesium-lithium separation and preparation method and application thereof |
| CN115624958A (en) * | 2022-09-23 | 2023-01-20 | 佛山(华南)新材料研究院 | Film for extracting lithium from salt lake brine, preparation method of film and lithium extraction method |
| CN115672256A (en) * | 2022-11-01 | 2023-02-03 | 北京碧水源膜科技有限公司 | Micron-sized lithium ion sieve micro-H 2 TiO 3 Preparation method of the ion sieve and salt lake lithium extraction system applying the ion sieve |
| CN115676877A (en) * | 2022-10-31 | 2023-02-03 | 江苏海普功能材料有限公司 | Silica gel modified metatitanic acid type lithium ion sieve precursor and preparation method thereof |
| CN115701807A (en) * | 2022-11-08 | 2023-02-14 | 北京碧水源膜科技有限公司 | Preparation method of lithium ion sieve H2TiO3 adsorption curtain type membrane and salt lake lithium extraction system applying curtain type membrane |
| CN115970661A (en) * | 2023-01-30 | 2023-04-18 | 江苏海普功能材料有限公司 | Preparation method of high-adsorption-capacity lithium ion imprinted nano composite particles |
| WO2024011760A1 (en) * | 2022-07-15 | 2024-01-18 | 广东邦普循环科技有限公司 | Plglu-ss-lithium ion sieve composite material, preparation method therefor, and use thereof |
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Cited By (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107199010B (en) * | 2017-05-23 | 2019-10-01 | 江苏大学 | A kind of multistage core-shell structure mentions lithium material and preparation method thereof |
| CN107199010A (en) * | 2017-05-23 | 2017-09-26 | 江苏大学 | A kind of multistage core shell structure carries lithium material and preparation method thereof |
| CN108114693A (en) * | 2018-01-07 | 2018-06-05 | 天津市职业大学 | A kind of glass fibre is lithium ion sieve adsorbed film of matrix and preparation method thereof |
| CN108114693B (en) * | 2018-01-07 | 2020-07-17 | 天津市职业大学 | Lithium ion sieve adsorption membrane with glass fiber as matrix and preparation method thereof |
| CN108636341A (en) * | 2018-04-18 | 2018-10-12 | 南京工业大学 | Forming method of lithium extraction adsorbent |
| CN113307334A (en) * | 2019-12-30 | 2021-08-27 | 江苏大学 | Ionic sieve cathode for electrolytic cells for extracting lithium in aqueous solutions containing lithium |
| CN113307334B (en) * | 2019-12-30 | 2022-08-26 | 江苏大学 | Ionic sieve cathode for electrolytic cells for extracting lithium in aqueous solutions containing lithium |
| CN111233084A (en) * | 2020-02-14 | 2020-06-05 | 青岛科技大学 | Ion sieve for adsorbing cesium ions and preparation 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 |
| CN111558350A (en) * | 2020-06-16 | 2020-08-21 | 东北林业大学 | Preparation method of HTO/cellulose aerogel microspheres for extracting lithium from seawater |
| CN112619621A (en) * | 2020-12-22 | 2021-04-09 | 天津科技大学 | Preparation method of porous spinning composite material and application of porous spinning composite material in lithium extraction |
| CN112619621B (en) * | 2020-12-22 | 2023-02-24 | 天津科技大学 | Preparation method of porous spinning composite material and application of porous spinning composite material in lithium extraction |
| CN113262648A (en) * | 2021-05-17 | 2021-08-17 | 郑州大学 | Lithium ion selective permeation membrane and application thereof |
| CN113262648B (en) * | 2021-05-17 | 2022-07-22 | 郑州大学 | Lithium ion selective permeation membrane and application thereof |
| CN113522061A (en) * | 2021-07-21 | 2021-10-22 | 昆明理工大学 | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane |
| CN113522061B (en) * | 2021-07-21 | 2022-06-21 | 昆明理工大学 | Preparation method of high-adsorption-capacity lithium ion imprinting nano composite membrane |
| CN114377551A (en) * | 2022-01-11 | 2022-04-22 | 江苏巨之澜科技有限公司 | Positively charged polyimide nanofiltration membrane for magnesium-lithium separation and preparation method and application thereof |
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| WO2024011760A1 (en) * | 2022-07-15 | 2024-01-18 | 广东邦普循环科技有限公司 | Plglu-ss-lithium ion sieve composite material, preparation method therefor, and use thereof |
| CN115624958A (en) * | 2022-09-23 | 2023-01-20 | 佛山(华南)新材料研究院 | Film for extracting lithium from salt lake brine, preparation method of film and lithium extraction method |
| CN115624958B (en) * | 2022-09-23 | 2024-05-28 | 佛山(华南)新材料研究院 | Film for extracting lithium from salt lake brine, preparation method thereof and lithium extraction method |
| CN115676877A (en) * | 2022-10-31 | 2023-02-03 | 江苏海普功能材料有限公司 | Silica gel modified metatitanic acid type lithium ion sieve precursor and preparation method thereof |
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