CN110860270A - Lithium-rich lithium metatitanate doped adsorption material and preparation method thereof - Google Patents
Lithium-rich lithium metatitanate doped adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lithium-rich lithium metatitanate doped adsorbing material, which is Li2TiO3Doping lattice with metal element M and Li2TiO3Coating oxide MO on microcrystal surface2Is represented by Li2MyTi1‑yO3/MO2The value range of y is 0.001-0.02, MO2The content is 0.1 wt% -1 wt%. A preparation method of a lithium-rich lithium metatitanate doped adsorption material comprises the following steps: obtaining mixed powder of a titanium source, an M salt and a lithium source; calcining the mixed powder to obtain the absorbing material Li2MyTi1‑yO3/MO2. After acid washing and lithium removal, the material has high adsorption efficiency, can efficiently extract lithium in brine with high magnesium-lithium ratio, is easy to recover and can be recycled.
Description
Technical Field
The invention relates to the technical field of lithium extraction from salt lake brine, and particularly relates to a lithium-rich lithium metatitanate doped adsorption material and a preparation method thereof.
Background
With the wide application of lithium ion batteries in various fields such as energy storage, automobiles, military, aerospace and the like, the demand of lithium products in the world is increasing, and the traditional lithium extraction from lithium ore cannot meet the market demand. Chinese salt lake brine resources are very rich and account for about 80 percent of lithium resources in China, so that the development of the salt lake brine lithium resources becomes more and more important.
The adsorption method is an important method for extracting lithium from salt lakes, has greater advantages than other methods from the aspects of economy and environmental protection, and particularly extracts lithium from brine with high magnesium and low lithium. The key of the method is to search for an adsorbent with good adsorption selectivity, high recycling rate and relatively low cost. The adsorbent may be classified into an organic adsorbent and an inorganic adsorbent. The organic adsorbent is typically an organic ion exchange resin, such as a cation exchange resin of the IR-120B type. The lithium ion battery has low selectivity to lithium ions and relatively high cost, so the application prospect is small. The inorganic adsorbing material mainly comprises manganese lithium oxide, titanium lithium oxide and the like. The manganese-lithium oxide has the advantages of large adsorption capacity, high adsorption efficiency and the like, but the adsorption material has poor acid and alkali resistance, and manganese dissolution loss exists in the acid pickling process, so that the crystal structure is unstable, and the cycle performance is poor. The titanium lithium oxide adsorbent has good acid and alkali resistance, but the migration speed of lithium ions in the adsorbent is slow, and the adsorption efficiency is low.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the titanium lithium oxide adsorbent is used as a lithium extraction adsorbing material, the migration speed of lithium ions in the adsorbent is low, and the adsorption efficiency is low. The invention provides a lithium-rich lithium metatitanate doped adsorption material and a preparation method thereof, which solve the problems.
The invention is realized by the following technical scheme:
a lithium-rich lithium metatitanate doped adsorption material is Li2TiO3Doping lattice with metal element M and Li2TiO3Coating oxide MO on microcrystal surface2Is represented by Li2MyTi1-yO3/MO2Y is in the range of 0.001-0.02, MO2The content is 0.1 wt% -1 wt%.
Further, the metal element M is one or more of V, Cr, Zr, Nb, Tc, Re, Ru, Rh, Ta, Ce and Ge.
The preparation method of the lithium-rich lithium metatitanate doped adsorbing material comprises the following steps: obtaining mixed powder of a titanium source, an M salt and a lithium source; calcining the mixed powder to obtain the absorbing material Li2MyTi1-yO3/MO2。
Further, adding acid liquor, M salt and a titanium source into water in sequence, and stirring and standing to obtain titanium slurry; adding a lithium source and an acid solution into water, and stirring to obtain lithium slurry; adding the lithium slurry into the titanium slurry, and stirring to obtain mixed slurry; and drying and grinding the mixed slurry to obtain mixed powder.
Further, the lithium source is one or more of lithium carbonate, lithium acetate, lithium hydroxide and lithium nitrate; the M salt is soluble salt or insoluble salt of one or more metals of V, Cr, Zr, Nb, Tc, Re, Ru, Rh, Ta, Ce and Ge; the titanium source is one or more of titanium dioxide, metatitanic acid and titanium tetrachloride; the acid liquor is one or more of glacial acetic acid, sulfuric acid and nitric acid.
Further, the M salt is two different salts, or a salt and an oxide of the M element.
Further, the molar ratio of the lithium source to the M salt for doping to the titanium source is Li to M to Ti is 2.0: 0.001-0.02: 0.999-0.98; MO for coating2The mass percentage of the component (A) is 0.1-1%.
Further, the solid content of the mixed slurry is 30-65%.
Further, the calcination adopts sectional type firing: presintering at 400-600 deg.c for 1-10 hr; then sintering treatment is carried out, the sintering temperature is 650-950 ℃, and the sintering time is 2-20 h.
The application of the lithium-rich lithium metatitanate doped adsorption material is used as a lithium adsorbent for extracting lithium from salt lake brine or as a negative electrode material of a lithium ion battery.
The invention aims to provide a lithium-rich lithium metatitanate doped adsorbing material and a preparation method thereof, and the lithium-rich lithium metatitanate doped adsorbing material is realized by the following principle: the lithium-rich lithium metatitanate is formed by doping M element into Li2TiO3Part of Ti element is replaced by crystal lattice, and then M oxide MO is added2Coated with Li2TiO3Obtained on the surface of crystallites, which material can be expressed as Li2MyTi1-yO3/MO2Y is in the range of 0.001-0.02, MO2The mass percentage is 0.1-1%. M element into Li2TiO3Partial Ti is substituted by crystal lattices, which can effectively inhibit the agglomeration phenomenon generated in the growth process of microcrystals and is beneficial to improving Li2TiO3The microporous structure can increase the particle size and the specific surface area, improve the fluidity and reduce Li+The entrance and exit resistance of (2) and the promotion of Li+The migration rate of (2). The M element not substituted for Ti element is formed by MO oxide2The form of (A) is coated on the lithium metatitanate microcrystal interface. MO (metal oxide semiconductor)2The coating layer can prevent the acid liquor from directly contacting with the titanium lithium oxide, and the coated Li2TiO3The ion sieve formed by acid washing has better acid corrosion resistance and structural stability, and longer cycle service life.
The invention has the following advantages and beneficial effects:
1. the invention provides an adsorbing material Li2MyTi1-yO3/MO2In Li2TiO3In which M element is doped and MO is used2Coated Li2TiO3Improvement ofLi2TiO3The microporous structure of (1) improves the adsorption efficiency and the adsorption capacity, and MO2The coating layer enables the material to have excellent acid corrosion resistance, stable structure and long cycle service life.
2. The synthesis process of the lithium-rich metatitanic acid doped adsorbent provided by the invention is simple and easy to control, the operation is simple and convenient, the yield is high, the product is pure and environment-friendly, the product is easy to recover, and the industrialization is easy to realize.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:
FIG. 1 is a flow chart of a preparation process of a doped lithium-rich lithium metatitanate adsorbing material according to the invention;
fig. 2 is an XRD chart of the doped lithium-rich lithium metatitanate adsorbing material of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.
Example 1
The embodiment provides a lithium-rich lithium metatitanate doped adsorbing material, which is prepared by the following preparation method: mixing a lithium source, a vanadium salt (doping) and a titanium source according to a molar ratio of 2.0:0.001:0.999 to obtain VO2The mass percentage is 0.1%. The specific operation is as follows: taking 108.5g of pure water, heating to 65 ℃, sequentially adding 10g of glacial acetic acid, 1.57g of vanadyl sulfate and 1.72g of vanadyl oxalate into the heated pure water, stirring for 40min, adding 230.25g of metatitanic acid, continuously stirring for 150min, and standing for more than 12h in an environment with the temperature of more than 20 ℃ to obtain the titanium slurry. Taking 130g of pure water, heating to 65 ℃, adding 170g of lithium carbonate and 65g of glacial acetic acid into the heated pure water, and stirring for 60min to obtain the lithium slurry. And (3) heating the titanium slurry after standing to 65 ℃, adding the lithium slurry, and stirring for 60min to obtain the mixed slurry. Drying the mixed slurry at 150 deg.C for 6 hr, and grindingFinely obtaining mixed powder. Heating the obtained mixed powder to 430 ℃ at the speed of 4 ℃/min, presintering for 5h, then heating to 620 ℃ at the speed of 3 ℃/min, calcining for 5h, cooling, and grinding to obtain V and VO2Coating lithium-rich lithium metatitanate adsorbing material, Li2V0.001Ti0.999O3/VO2. The adsorption and desorption conditions of the material are shown in table 1.
Example 2
The embodiment provides a lithium-rich lithium metatitanate doped adsorbing material, which is prepared by the following preparation method: mixing a lithium source, a cerium salt for doping and a titanium source according to a molar ratio of 2.0:0.01:0.99, and CeO2The mass percentage is 0.5 percent. The specific operation method comprises the following steps: taking 110g of pure water, heating to 70 ℃, sequentially adding 12g of glacial acetic acid, 13.50g of cerium nitrate and 6.45g of cerium sulfate into the heated pure water, stirring for 50min, adding 247.25g of metatitanic acid, continuously stirring for 120min, and standing for more than 9h in an environment with the temperature of more than 20 ℃ to obtain the titanium slurry. 115g of pure water was taken, the temperature was raised to 70 ℃, 171g of lithium carbonate and 67.5g of glacial acetic acid were added to the heated pure water, and stirring was carried out for 75min to obtain lithium slurry. And (3) heating the titanium slurry after standing to 70 ℃, adding the lithium slurry, and stirring for 60min to obtain the mixed slurry. And (3) drying the mixed slurry at 150 ℃ for 7h by blowing, and grinding to obtain mixed powder. Heating the obtained mixed powder to 400 ℃ at the speed of 4.5 ℃/min, presintering for 6h, then heating to 650 ℃ at the speed of 3.5 ℃/min, calcining for 3h, cooling, and grinding to obtain the Ce and CeO doped powder2Coating lithium-rich lithium metatitanate adsorbing material, Li2Ce0.01Ti0.99O3/CeO2. The adsorption and desorption conditions of the material are shown in table 1.
Example 3
The embodiment provides a lithium-rich lithium metatitanate doped adsorbing material, which is prepared by the following preparation method: mixing a lithium source, a ruthenium salt (doping) and a titanium source according to a molar ratio of 2.0:0.02:0.98, RuO2The mass percentage is 1%. Heating 132g of pure water to 75 ℃, sequentially adding 8g of glacial acetic acid, 17.12g of ruthenium acetate and 7.65g of ruthenium sulfate into the heated pure water, stirring for 45min, adding 212.75g of titanium dioxide (anatase type), stirring for 145min, and standing at 20 ℃ for more than 10h to obtain titaniumAnd (4) pulping. 105g of pure water is taken, the temperature is raised to 75 ℃, 172g of lithium carbonate and 85g of glacial acetic acid are added into the heated pure water, and the mixture is stirred for 90min to prepare lithium slurry. And (3) heating the titanium slurry after standing to 75 ℃, adding the lithium slurry, and stirring for 90min to obtain the mixed slurry. And (3) drying the mixed slurry at 150 ℃ for 8h by blowing, and grinding to obtain mixed powder. Heating the obtained mixed powder to 500 ℃ at the speed of 5 ℃/min, presintering for 12h, then heating to 730 ℃ at the speed of 2.5 ℃/min, calcining for 2h, cooling, and grinding to obtain the Ru and RuO doped powder2Coating lithium-rich lithium metatitanate adsorbing material, Li2Ru0.02Ti0.98O3/RuO2. The adsorption and desorption conditions of the material are shown in table 1.
Comparative example 1
This comparative example provides an adsorbent material with M doped with Li2TiO3Based on the preparation scheme of example 1, the difference is that: in the step of preparing the mixed powder, only 1.57g of vanadyl sulfate is added into the M salt, and vanadyl oxalate is not added; in the calcining step, the mixed powder is heated to 430 ℃ at the speed of 4 ℃/min, and presintered for 5h without sintering treatment.
Comparative example 2
This comparative example provides an adsorbent material, in the form of MO2Coated Li2TiO3Based on the preparation scheme of example 1, the difference is that: in the step of preparing the mixed powder, only 1.72g of vanadyl oxalate is added into M salt, and vanadyl sulfate is not added; in the calcining step, the obtained mixed powder is heated to 620 ℃ at the heating rate of 5 ℃/min, and is calcined for 5 hours without presintering treatment.
Comparative example 3
This comparative example provides an adsorbent material, based on the preparation scheme of example 1, with the following differences: in the step of preparing the mixed powder, acid liquor is not added in the process of preparing the titanium slurry and the lithium slurry.
Firstly, testing the adsorption performance:
in the brine to be adsorbed, the concentration of magnesium is 33.75g/L, the concentration of lithium is 1.14g/L, and the ratio of magnesium to lithium is as follows: 29.6,; the pH value of the brine is as follows: 6.5.
TABLE 1 adsorption and desorption conditions
Second, testing the adsorption performance of different magnesium-aluminum ratios and different pH values
1. In the brine to be adsorbed, the concentration of magnesium is 113.5g/L, the concentration of lithium is 1.12g/L, and the ratio of magnesium to lithium is 101.3; the pH value of the brine is as follows: 5.0.
2. in the brine to be adsorbed, the concentration of magnesium is 390g/L, the concentration of lithium is 0.95g/L, and the ratio of magnesium to lithium is 410.5; the pH value of the brine is as follows: 10.
3. in the brine to be adsorbed, the concentration of magnesium is 1150.5g/L, the concentration of lithium is 1.21g/L, and the ratio of magnesium to lithium is 950.8; the pH value of the brine is as follows: 11.5.
as shown in fig. 2, the XRD pattern of the doped lithium-rich lithium metatitanate adsorbing material of the present invention is shown as follows: the XRD pattern of the sample has obvious characteristic diffraction peaks which are basically consistent with the standard pattern of the sample, and the diffraction peaks are sharp and have higher intensity, which shows that the crystallization performance of the material is good; the characteristic diffraction peaks of the sample are shifted rightward, which is caused by the fact that the doping atoms cause the lattice constant to be smaller, and indicates that the doping elements enter the lattice to replace titanium atoms, and because the atomic radius of the doping elements is smaller than that of the titanium atoms, the doping atoms occupy the original atomic positions to increase the unit cell volume, so that the unit cell parameters are changed. The presence of the coated oxide is indicated by the presence of a diffraction peak in the sample corresponding to the standard spectrum of the coated oxide.
In addition, the specific surface area of the adsorbing material prepared by the invention can reach 0.9g/m2～1.1g/m2Is suitable forThe lithium extraction treatment method is used for lithium extraction treatment of brine with the pH value within the range of 5-12, and has excellent acid corrosion resistance. The adsorption material provided by the invention is suitable for the range of the concentration ratio of magnesium to lithium: 10 to 1000.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A lithium-rich lithium metatitanate doped adsorption material is characterized in that the adsorption material is Li2TiO3Doping lattice with metal element M and Li2TiO3Coating oxide MO on microcrystal surface2Is represented by Li2MyTi1-yO3/MO2Y is in the range of 0.001-0.02, MO2The content is 0.1 wt% -1 wt%.
2. The doped lithium-rich lithium metatitanate adsorbing material of claim 1, wherein the metal element M is one or more of V, Cr, Zr, Nb, Tc, Re, Ru, Rh, Ta, Ce and Ge.
3. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to claim 1 or 2, characterized by comprising the following steps: obtaining mixed powder of a titanium source, an M salt and a lithium source; calcining the mixed powder to obtain the absorbing material Li2MyTi1-yO3/MO2。
4. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to claim 1, wherein acid solution, M salt and a titanium source are sequentially added into water, and titanium slurry is obtained after stirring and standing; adding a lithium source and an acid solution into water, and stirring to obtain lithium slurry; adding the lithium slurry into the titanium slurry, and stirring to obtain mixed slurry; and drying and grinding the mixed slurry to obtain mixed powder.
5. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to claim 4, wherein the lithium source is one or more of lithium carbonate, lithium acetate, lithium hydroxide and lithium nitrate; the M salt is soluble salt or insoluble salt of one or more metals of V, Cr, Zr, Nb, Tc, Re, Ru, Rh, Ta, Ce and Ge; the titanium source is one or more of titanium dioxide, metatitanic acid and titanium tetrachloride; the acid liquor is one or more of glacial acetic acid, sulfuric acid and nitric acid.
6. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to claim 5, wherein the M salt is two different salts or a salt and an oxide of M element.
7. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to claim 6, wherein the molar ratio of the lithium source to the M salt used for doping to the titanium source is Li to M to Ti of 2.0: 0.001-0.02 to 0.999-0.98; MO for coating2The mass percentage of the component (A) is 0.1-1%.
8. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to claim 4, wherein the solid content of the mixed slurry is 30-65%.
9. The preparation method of the doped lithium-rich lithium metatitanate adsorbing material according to any one of claims 3 to 8, characterized in that the calcination adopts segmented calcination: presintering at 400-600 deg.c for 1-10 hr; then sintering treatment is carried out, the sintering temperature is 650-950 ℃, and the sintering time is 2-20 h.
10. The application of the doped lithium-rich lithium metatitanate adsorbing material according to any one of claims 1 to 9, wherein the doped lithium-rich lithium metatitanate adsorbing material is used as a lithium adsorbent for extracting lithium from salt lake brine or used as a negative electrode material of a lithium ion battery.
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