CN110918043A - Doped and coated lithium-rich layered lithium manganese oxide adsorption material and preparation method thereof - Google Patents
Doped and coated lithium-rich layered lithium manganese oxide adsorption material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a doped and coated lithium-rich layered lithium manganese oxide adsorbing material, which is prepared by mixing xLi with a carrier2MnO3·(1‑x)LiMnO2In-doped with metal element M and coating oxide M' O on the surface of microcrystal thereof2Is expressed as { My—[xLi2MnO3·(1‑x)LiMnO2]}/M’O2，0<x≤0.8，0.01≤y≤0.5，M’O2The content is 0.1 wt% -1 wt%; wherein M' represents a metal element. The preparation method of the doped and coated lithium-rich layered lithium manganese oxide adsorbing material comprises the following steps: obtaining mixed powder of a manganese source, an M salt, an M' salt and a lithium source; calcining the mixed powder to obtain the adsorbing material { My—[xLi2MnO3·(1‑x)LiMnO2]}/M’O2. The adsorbing material provided by the invention can efficiently adsorb and extract lithium in brine with a high magnesium-lithium ratio, and has the advantages of low manganese dissolution loss, stable structure and good cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium extraction from salt lake brine, in particular to a doped and coated lithium-rich spinel type lithium manganese oxide adsorption material and a preparation method thereof.
Background
The world economy has rapidly developed, and lithium compounds are widely used in the fields of glass, ceramics, medicine, aviation, batteries, and the like. The traditional lithium extraction from lithium ore is far from meeting the market demand due to high cost, long flow and large energy consumption. The salt lake brine has rich lithium resource and relatively low extraction cost, and can gradually replace lithium ore to become a main raw material for lithium industrial production. The method for extracting and separating lithium from salt lake brine mainly comprises a precipitation method, a calcination leaching method, a solvent extraction method, a membrane separation method, an adsorption method and the like. The adsorption method has greater advantages than other methods from the aspects of environment and economy, particularly has more obvious advantages in the aspect of extracting lithium from low-grade brine, and the key point is to develop an adsorbent with excellent performance. Inorganic ion sieve adsorption material to Li+The manganese element which shows good shape memory function and practical application prospect, has the characteristics of no toxicity, rich resources, environmental friendliness and the like, leads the Li-Mn-O series compounds to be always paid attention by researchers, and more layered Li is researched2MnO3、LiMnO2And LiMn of spinel2O4、Li4Mn5O12. The lithium ion sieve developed from the lithium manganese oxide has the characteristics of good lithium ion selectivity, large adsorption capacity, relatively low cost and environmental friendliness, and is particularly suitable for treating salt lake brine with low lithium concentration and high magnesium-lithium ratio. ItThe principle is that lithium is eluted by acid from lithium manganese oxide and H is used+Exchanging Li+Obtaining a lithium ion sieve, and exchanging Li in the brine by using the lithium ion sieve+Thereby realizing the extraction of the lithium resource in the brine. The problem of manganese dissolution loss exists in the acid washing process, which can cause the structure of the adsorbent to be unstable and the cycle performance to be reduced. There are two ways of loss of manganese, one is the small amount of Mn present in the ion sieve3+The disproportionation reaction occurs to cause manganese dissolution loss; the other is MnO formed by acid elution of lithium2·xH2O reacts with the acid resulting in manganese dissolution loss. Therefore, the research on the lithium ion sieve precursor and the ion sieve thereof with excellent performance has great economic value and significance for developing rich salt lake brine resources.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a doped and coated lithium-rich layered lithium manganese oxide adsorbing material and a preparation method thereof, which solve the problems.
The invention is realized by the following technical scheme:
a doped and coated lithium-rich laminated Li-Mn oxide as adsorbing material is prepared from the lithium-rich laminated material xLi2MnO3·(1-x)LiMnO2In which the metal element M is doped to replace part of Mn, and in xLi2MnO3·(1-x)LiMnO2The microcrystalline surface is coated with an oxide M' O2Obtained, denoted as { My-[xLi2MnO3·(1-x)LiMnO2]}/M′O2，0<x is less than or equal to 0.8, and y is less than or equal to 0.01 and less than or equal to 0.5; wherein M' represents a metal element.
Further, the metal element M is one or more of V, Cr, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce; the metal element M' is one or a combination of more of V, Cr, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce.
The above-mentionedThe preparation method of the hybrid and coated lithium-rich layered lithium manganese oxide adsorbing material comprises the following steps: obtaining mixed powder of a manganese source, an M salt, an M' salt and a lithium source; calcining the mixed powder to obtain the adsorbing material { My—[xLi2MnO3·(1-x)LiMnO2]}/M′O2。
Further, adding the acid liquor, the M salt and the M' salt into pure water, and stirring to obtain an additive; taking pure water, adding a lithium source and an acid solution, and stirring to obtain lithium slurry; adding an additive into the lithium slurry, then adding a manganese source, and stirring to obtain a mixed slurry; and drying and grinding the mixed slurry to obtain mixed powder. The drying process can adopt at least one of spray drying and blast drying, the temperature of the blast drying is 60-150 ℃, and the drying time is 3-10 h. The calcining atmosphere adopts air atmosphere, and the heating rate can be controlled between 2 ℃/min and 5 ℃/min.
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, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce; the M' salt is soluble salt or insoluble salt of one or more metals of V, Cr, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce; the manganese source is one or more of manganese monoxide, manganese dioxide, manganese sesquioxide, manganous manganic oxide, manganese carbonate and manganese nitrate; the acid solution is one or more of glacial acetic acid, hydrochloric acid and nitric acid.
Further, the molar ratio of the lithium source, the M salt and the manganese source is Li, Mn and M is 1.0-1.8: 0.5-1.0: 0.01-0.5, and the coating oxide M' O2The mass percentage is 0.1-1%.
Further, the solid content of the mixed slurry is 30-70%.
Further, the calcination adopts sectional type firing: presintering at 400-550 deg.c for 20-30 hr; then sintering treatment is carried out, the sintering temperature is 700-900 ℃, and the sintering time is 10-20 h.
The metal element is calcined in the pre-sintering treatmentThe element M enters the crystal structure to partially replace the Mn position, and the element M ' does not enter the structure because the temperature of the reaction participated by the salt M is higher than that of the salt M, and the element M ' is in the form of M ' O during the sintering treatment2The form of (2) is coated on the surface of the microcrystal.
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 lithium ion battery anode material.
The doping and the cladding are realized by calcining treatment and are divided into a pre-sintering process and a firing process, wherein the pre-sintering process realizes the doping of an M element, and the firing process realizes an oxide M' O2Coating of (2). The specific realization principle of the material is as follows: the doped and coated lithium-rich layered lithium manganese oxide adsorbing material is prepared by coating the doped and coated lithium-rich layered lithium manganese oxide adsorbing material on xLi2MnO3·(1-x)LiMnO2In which the metal element M is doped to replace part of Mn, and coating the microcrystalline surface of the metal element M and the part of Mn with oxide M' O2Obtained in the manner of (1), and is denoted as { My-[xLi2MnO3·(1-x)LiMnO2]}/M′O2，0<x≤0.8，0.01≤y≤0.5，M′O2The content is 0.1 wt% -1 wt%; wherein M' represents a metal element.
Lithium-rich layered composite material xLi2MnO3·(1-x)LiMnO2Has a complex structure consisting of the component Li2MnO3And LiMnO2The two-component structure is substantially equal to α -NaFeO2The structure of the device is similar. Wherein the component Li2MnO3Having a rock-salt structure, also denoted Li [ Li ]1/3Mn2/3]O2，Li+With Mn4+Together forming an M layer, each Li+Is covered with 6 Mn4+Surrounded to form a superstructure LiMn6Such that Li2MnO3Is composed of
Conversion to monoclinic system C2/m; li2MnO3Can play a role of stabilizing the structureSo that the lithium ions are deeply deintercalated without causing structural collapse, and the mixed discharge of metal ions can be suppressed. Ideal layered LiMnO2The structure belongs to trigonal system, in O2-In the slightly distorted cubic close packing of ions, Mn atoms and Li atoms are respectively in adjacent octahedral layers. Layered LiMnO2Is a homogeneous heterogeneous compound, and has two orthorhombic LiMnO structures belonging to Pmnm space group and orthorhombic C2/m space group2Although the amount of delithiation is high, its preparation is rather difficult, layered LiMnO2In fact, the lithium-doped lithium iron phosphate is in a thermodynamically metastable state, and the structure is unstable after lithium removal, slowly changes to a spinel structure and is irreversible. The stability of the alloy can be improved by doping metal ions (Co, Ni, Mo, Cr and the like) and the cycle performance is improved. The coating treatment can prevent the acid liquor from directly contacting with the adsorption material, and greatly slow down the dissolution loss of manganese in the process of acid-eluting lithium, thereby improving the stability of the adsorbent structure and greatly prolonging the service life.
The invention has the following advantages and beneficial effects:
1. the doped and coated lithium-rich layered lithium manganese oxide adsorbing material provided by the invention is applied to xLi2MnO3·(1-x)LiMnO2The structure of the material is doped with M element, thereby greatly slowing down the occurrence of phase change, improving the stability of the structure and improving the cycle performance of the material. Oxide M' O2The coating ensures that the material has excellent acid and alkali resistance and low manganese dissolution loss. The adsorbing material provided by the invention also has the characteristics of high adsorption capacity, high adsorption rate, high lithium selectivity, good structural stability and the like.
2. The doped and coated lithium-rich layered lithium manganese oxide adsorbing material provided by the invention has the advantages of wide raw material source, simple process, high product purity, environmental friendliness and easiness in realizing industrialization.
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 and coated lithium-rich layered lithium manganese oxide adsorbent material according to the present invention.
Fig. 2 is an XRD chart of the doped and coated lithium-rich layered lithium manganese oxide adsorbent 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 doped and coated lithium-rich layered lithium manganese oxide adsorbing material, and the preparation method is as follows: mixing a lithium source, a nickel salt and a manganese source according to a molar ratio of 1.1:0.01:0.99, and adding CeO2Coating, the mass percent is 0.1%. The specific operation is as follows: taking 70g of pure water, heating to 70 ℃, adding 12g of glacial acetic acid into the heated pure water, then sequentially adding 1.52g of nickel nitrate and 1.7g of cerium sulfate, and stirring for 30min to obtain the additive solution. 179.5g of pure water is taken, the temperature is raised to 70 ℃, 185g of lithium carbonate is added into the pure water after the temperature is raised, 62g of glacial acetic acid is added, and the mixture is stirred for 45min to prepare the lithium slurry. And adding the prepared additive into the lithium slurry, then adding 170g of manganese oxide, and stirring for 75min to obtain a mixed slurry. And (3) drying the mixed slurry at 140 ℃ by air blast for more than 5h, and grinding to obtain mixed powder. Heating the obtained mixed powder to 400 ℃ at the heating rate of 4 ℃/min, presintering for 20h, heating to 750 ℃ at the heating rate of 3 ℃/min, calcining for 14h, cooling, and grinding to obtain the nickel-doped and CeO-doped powder2Coated lithium-rich layered lithium manganese oxide adsorbing material { Ni0.01-[xLi2MnO3·(1-x)LiMnO2]}/CeO2The value of x is determined by a combination of complexometric titration and redox titration. The adsorption and desorption conditions of the material are shown in table 1.
Example 2
The embodiment provides a doped and coated lithium-rich layered lithium manganese oxide adsorbing material, and the preparation method is as follows: mixing a lithium source, a molybdenum salt and a manganese source according to a molar ratio of 1.4:0.1:0.9, ZrO2Coating ofAnd the mass percent is 0.4%. The specific operation is as follows: taking 75g of pure water, heating to 70 ℃, adding 20g of glacial acetic acid into the heated pure water, then sequentially adding 4.65g of molybdenum nitrate and 7.5g of zirconium sulfate, and stirring for 45min to obtain the additive solution. 181g of pure water is taken, the temperature is raised to 70 ℃, 185.5g of lithium carbonate is added into the heated pure water, 67g of glacial acetic acid is added, and the mixture is stirred for 40min to prepare the lithium slurry. And adding the prepared additive solution into the lithium slurry, adding 165g of manganese monoxide, and stirring for 90min to obtain a mixed slurry. And (3) drying the mixed slurry at 150 ℃ for more than 4h by air blasting, and grinding to obtain mixed powder. Heating the mixed powder to 450 ℃ at the speed of 5 ℃/min, presintering for 24h, heating to 800 ℃ at the temperature of 4 ℃/min, calcining for 18h, cooling, and grinding to obtain the Mo and ZrO doped powder2Coated lithium-rich layered lithium manganese oxide adsorbing material { Mo0.1-[xLi2MnO3·(1-x)LiMnO2]}/ZrO2The value of x is determined by a combination of complexometric titration and redox titration. The adsorption and desorption conditions of the material are shown in table 1.
Example 3
The embodiment provides a doped and coated lithium-rich layered lithium manganese oxide adsorbing material, and the preparation method is as follows: mixing a lithium source, a ruthenium salt and a manganese source in a molar ratio of 1.7:0.4:0.6, and NbO2And (4) coating, wherein the mass percent is 0.7%. Taking 80g of pure water, heating to 75 ℃, adding 8g of glacial acetic acid into the heated pure water, then sequentially adding 10.85g of ruthenium acetate and 9.3g of niobium oxalate, and stirring for 35min to obtain the additive solution. 173g of pure water is taken, the temperature is raised to 75 ℃, 190g of lithium carbonate is added into the heated pure water, 110g of glacial acetic acid is added, and the mixture is stirred for 35min to prepare the lithium slurry. The prepared additive solution was added to lithium slurry, 159g of manganese dioxide was added, and stirred for 50min to obtain a mixed slurry. And (3) drying the mixed slurry at 130 ℃ by air blast for more than 7h, and grinding to obtain mixed powder. Heating the mixed powder to 500 ℃ at the heating rate of 4 ℃/min, presintering for 27h, then heating to 850 ℃ at the heating rate of 3 ℃/min, calcining for 10h, cooling, and grinding to obtain the Ru and NbO doped powder2Coated lithium-rich layered lithium manganese oxide adsorbing material { Ru0.4-[xLi2MnO3·(1-x)LiMnO2]}/NbO2The value of x is determined by a combination of complexometric titration and redox titration. The adsorption and desorption conditions of the material are shown in table 1.
Comparative example 1
This comparative example provides an adsorbent material doped with Mo and xLi2MnO3·(1-x)LiMnO2Based on the preparation scheme of example 2, the difference is that: in the step of preparing the mixed powder, only molybdenum nitrate is added, and zirconium sulfate is not added; in the calcining step, the temperature of the mixed powder is raised to 450 ℃ at the speed of 5 ℃/min, the mixed powder is presintered for 24h, and the calcining treatment is not carried out.
Comparative example 2
This comparative example provides an adsorbent material based on ZrO2Coated xLi2MnO3·(1-x)LiMnO2Based on the preparation scheme of example 2, the difference is that: in the step of preparing the mixed powder, only zirconium sulfate is added, and molybdenum nitrate is not added; in the calcining step, the temperature of the mixed powder is raised to 800 ℃ at the temperature raising rate of 4 ℃/min, and the mixed powder is calcined for 18 hours without pre-sintering treatment.
Comparative example 3
This comparative example provides an adsorbent material, based on the preparation scheme of example 2, with the following differences: in the step of preparing the mixed powder, acid liquor is not added in the process of preparing the additive solution and the 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
As shown in fig. 2, which is an XRD chart of the doped and coated lithium-rich layered lithium manganese oxide adsorbent of the present invention, it can be seen that: 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 to the right, which is caused by the fact that the doping atoms cause the lattice constant to be reduced, and indicates that the doping elements enter the lattice to replace titanium atoms, 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, and the characteristic diffraction peaks are shifted to the right. 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.
The specific surface area of the adsorbing material prepared by the invention reaches 0.6-0.8 m2/g。
II, testing the manganese dissolution loss rate:
1. the materials obtained in examples 1 to 3 were delithiated with 0.1mol/L HCl solution, the concentration of manganese in the desorption solution was measured, and the manganese dissolution rate was calculated, with the results shown in Table 2.
TABLE 2 sorbent dissolution rate TABLE
| Name (R) | Example 1 | Example 2 | Example 3 |
| Dissolution loss rate of manganese | 0.021％ | 0.014％ | 0.017％ |
For the material of example 2, the manganese dissolution rate of the material under different key influencing factors (pH of the eluting hydrochloric acid/number of cycles) is shown in table 3.
Table 3 manganese dissolution rate table for example 2 under different conditions (pH of eluted hydrochloric acid/number of cycles)
The manganese dissolution rate of the adsorption material provided by the invention is within the range of 0.01-0.05%, and the adsorbent has good acid corrosion resistance.
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 (9)
1. The doped and coated lithium-rich layered lithium manganese oxide adsorbing material is characterized in that the adsorbing material is prepared by coating a lithium-rich layered material xLi2MnO3·(1-x)LiMnO2In which the metal element M is doped to replace part of Mn, and in xLi2MnO3·(1-x)LiMnO2The microcrystalline surface is coated with an oxide M' O2Obtained, denoted as { My-[xLi2MnO3·(1-x)LiMnO2]}/M’O2，0<x is less than or equal to 0.8, and y is less than or equal to 0.01 and less than or equal to 0.5; wherein M' represents a metal element.
2. The doped and coated lithium-rich layered lithium manganese oxide adsorbent material according to claim 1, wherein said metal element M is one or more of V, Cr, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re, Ce; the metal element M' is one or a combination of more of V, Cr, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce.
3. The preparation method of the doped and coated lithium-rich layered lithium manganese oxide adsorbent material according to claim 1 or 2, comprising the following steps: obtaining manganese source MMixed powder of salt, M' salt and lithium source; calcining the mixed powder to obtain the adsorbing material { My-[xLi2MnO3·(1-x)LiMnO2]}/M’O2。
4. The preparation method of the doped and coated lithium-rich layered lithium manganese oxide adsorbing material as claimed in claim 3, wherein the acid solution, M salt and M' salt are added into pure water, and the additive is prepared after stirring; taking pure water, adding a lithium source and an acid solution, and stirring to obtain lithium slurry; adding an additive into the lithium slurry, then adding a manganese source, and stirring to obtain a mixed slurry; and drying and grinding the mixed slurry to obtain mixed powder.
5. The method for preparing the doped and coated lithium-rich layered lithium manganese oxide adsorbent 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, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce; the M' salt is soluble salt or insoluble salt of one or more metals of V, Cr, Co, Ni, Mo, Zr, Ti, Tc, Ru, Rh, Ta, W, Re and Ce; the manganese source is one or more of manganese monoxide, manganese dioxide, manganese sesquioxide, manganous manganic oxide, manganese carbonate and manganese nitrate; the acid solution is one or more of glacial acetic acid, hydrochloric acid and nitric acid.
6. The preparation method of the doped and coated lithium-rich layered lithium manganese oxide adsorbing material as claimed in claim 5, wherein the molar ratio of the lithium source, the M salt and the manganese source is Li, Mn and M is 1.0-1.8, 0.5-1.0, 0.01-0.5, and the coating oxide is M' O2The mass percentage is 0.1-1%.
7. The method for preparing the doped and coated lithium-rich layered lithium manganese oxide adsorbent material according to claim 4, wherein the solid content of the mixed slurry is 30-70%.
8. The method for preparing the doped and coated lithium-rich layered lithium manganese oxide adsorbent material according to any one of claims 3 to 7, wherein the calcination is performed by sectional calcination: presintering at 400-550 deg.c for 20-30 hr; then sintering treatment is carried out, the sintering temperature is 700-900 ℃, and the sintering time is 10-20 h.
9. The application of the doped lithium-rich lithium metatitanate adsorbing material according to any one of claims 1 to 8, 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 positive electrode material of a lithium ion battery.
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