CN113117635A - Preparation method of titanium-based lithium ion sieve - Google Patents
Preparation method of titanium-based lithium ion sieve Download PDFInfo
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- CN113117635A CN113117635A CN202110237447.0A CN202110237447A CN113117635A CN 113117635 A CN113117635 A CN 113117635A CN 202110237447 A CN202110237447 A CN 202110237447A CN 113117635 A CN113117635 A CN 113117635A
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Abstract
The invention discloses a preparation method of a titanium lithium ion sieve, which is prepared by mixing TiO2Compounding powder or tablets with a metal current collector to serve as a working electrode, using graphite as a counter electrode, performing cathodic polarization for 1-5 hours in an alkali metal halide at the temperature of 400-700 ℃ and the voltage of 2.0-3.2V in an argon atmosphere, performing anodic polarization for 1.0-2.6V on the working electrode for 0.5-2 hours, cooling to normal temperature, taking out, washing, and performing vacuum drying to obtain a polarization product; the obtained product is burned for 1-3 hours at the temperature of 600-900 ℃ in the air and then cooled, and the obtained product is subjected to acid leaching in 0.5-0.6 mol/L hydrochloric acidAnd (3) obtaining the titanium lithium ion sieve with richer lithium ion channels for 24-48 h, thereby effectively improving the adsorption capacity.
Description
The technical field is as follows:
the invention relates to a preparation method of a titanium lithium ion sieve.
Background art:
at present, manganese ion sieves are mainly researched for lithium ion sieves in a centralized mode, but the manganese ion sieves have the defects of large manganese dissolution loss, few cycle times and the like. The titanium-based lithium ion sieve has the advantages of less dissolution loss, stable structure and the like. However, the titanium-based lithium ion sieve prepared by the existing preparation method has the defects of slow elution and adsorption rate, uncontrollable particle size, poor adsorption quantity and the like, and is not beneficial to industrial application. Therefore, a new titanium-based lithium ion sieve is needed.
The invention content is as follows:
the invention aims to provide a preparation method of a titanium lithium ion sieve, which can realize controllable particle size, and ensure batch stability, consistency and high adsorption capacity.
The invention is realized by the following technical scheme:
a preparation method of a titanium lithium ion sieve comprises the following steps:
1) adding TiO into the mixture2Compounding powder or tablets and a metal current collector to form a working electrode, and performing cathode polarization on a graphite counter electrode in alkali metal halide under the protection of inert atmosphere at 400-700 ℃ and 2.0-3.2V for 0.5-5 hours;
2) and then carrying out anodic polarization on the working electrode at the voltage of 1.0-2.6V for 0.5-2 hours, cooling to room temperature after the anodic polarization is finished, cleaning, vacuum drying, firing for 1-3 hours in the air at the temperature of 600-900 ℃, cooling, and carrying out acid leaching on the obtained product in 0.5-0.6 mol/L hydrochloric acid for 24-48 hours to obtain the titanium lithium ion sieve.
The alkali metal halide is LiCl or a mixture of LiCl and one or two of Na or K chlorides.
The metal current collector is filiform, reticular or flaky titanium, stainless steel, molybdenum, tungsten or nickel with the melting point higher than the reaction temperature.
The TiO is2The powder is commercially available TiO2Sintering the powder at 600-900 ℃ in an inert atmosphere; the TiO is2Tabletting is to mix the commercially available TiO2And tabletting the powder under the pressure of 2-20 MPa, and sintering at the temperature of 600-900 ℃ in an inert atmosphere.
The principle of the invention is as follows: adding TiO into the mixture2Powder or tablet, cathodically polarized in LiCl-containing metal halide, and electrochemically quantitatively intercalates lithium ions into TiO2Then forming lithium ion channel in the material by anode polarization stripping or further burning stripping, and H is added to the part after subsequent acid leaching+Instead of forming a lithium ion sieve material.
The invention has the following beneficial effects: the lithium ion sieve material obtained by the invention has richer lithium ion channels, and the adsorption capacity of the lithium ion sieve material is effectively improved. Different from the previous method for preparing the titanium lithium ion sieve, the method for preparing the titanium lithium ion sieve by adopting electrochemical polarization can accurately control the stoichiometric ratio. In the whole process flow, lithium ions are firstly inserted into titanium oxide crystal lattices by means of electro-cathodic polarization, then are partially extracted by means of anodic polarization and are then burnt to form a compound oxide mixture, and finally, partial lithium ions are treated by means of acid leaching and are subjected to H+Replacing to obtain the titanium lithium ion sieve material. The process flow is through the process of lithium ion intercalation and deintercalation, so that the obtained lithium ion sieve material has richer lithium ion channels, and the adsorption capacity is effectively improved.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
adding commercially available 0.1-0.2 μm TiO2Taking 2g of the powder, pressing the powder under 8MPa to prepare a test piece with the diameter of 20mm and the thickness of 3mm, and sintering the test piece for 3 hours at 600 ℃ in an argon atmosphere to obtain TiO2A test piece. Tightly wrapping the test piece with molybdenum net, winding the test piece on a long molybdenum wire with a fine molybdenum wire as a working electrode, taking a graphite rod as a counter electrode, taking a mixture of LiCl and NaCl with a molar ratio of 2:1 as an electrolyte, polarizing the cathode for 5 hours at 500 ℃ and 3.2V in an argon atmosphere,and after the cathode polarization is finished, carrying out anode polarization on the working electrode, wherein the voltage is 2.6, the polarization time is 0.5 hour, lifting the polarization product out of the liquid level, cooling the polarization product to the normal temperature in an electrolytic tank, taking out the product, cleaning the product by distilled water, drying the product in vacuum at 60 ℃, burning the product in the air at 750 ℃ for 2 hours, and soaking the product in 0.6mol/L hydrochloric acid for 24 hours to obtain the titanium-based lithium ion sieve material. The material is put into 20mL lithium-containing lithium chloride solution with 0.2g/L, and the adsorption capacity is measured to be 45mg/g after 24 hours of adsorption at 30 ℃.
Example 2
Adding commercially available 0.1-0.2 μm TiO25g of the powder was pressed under 5MPa to prepare two test pieces having a diameter of 20mm and a thickness of 5mm, and the two test pieces were sintered at 600 ℃ for 2 hours under an argon atmosphere. Tightly wrapping the test piece with a stainless steel net, winding the stainless steel wire on a long stainless steel wire to be used as a working electrode, using a graphite rod as a counter electrode, using a mixture of LiCl and KCl in a molar ratio of 1:1 as an electrolyte, in an argon atmosphere, at a temperature of 600 ℃, at a voltage of 2.8V, carrying out cathodic polarization for 4 hours, carrying out anodic polarization on the working electrode after the cathodic polarization is finished, at a voltage of 2.0V, and after the polarization time is 1 hour, extracting a polarization product out of the liquid level, cooling the polarization product to normal temperature in an electrolytic tank, taking out the product, cleaning the product with distilled water, drying the product in vacuum at a temperature of 60 ℃, firing the product in air at a temperature of 600 ℃ for 3 hours, and soaking the product in 0.5mol/L hydrochloric acid for 48 hours to obtain the titanium-based lithium ion. The material is put into 20mL lithium-containing lithium chloride solution with 0.2g/L, and the adsorption capacity is 60mg/g after 24 hours of adsorption at 30 ℃.
Example 3
Adding commercially available 0.1-0.2 μm TiO20.5g of the powder was pressed under 10MPa to prepare a test piece having a diameter of 5mm and a thickness of 1mm, and the test piece was sintered at 600 ℃ for 3 hours in an argon atmosphere. Winding a test piece with molybdenum wires to prepare a working electrode, taking a graphite rod as a counter electrode, taking a mixture of LiCl, KCl and NaCl in a molar ratio of 1:1:1 as an electrolyte, carrying out cathodic polarization for 5 hours at 400 ℃ in an argon atmosphere at a voltage of 3.2V, carrying out anodic polarization on the working electrode after the cathodic polarization is finished, carrying out anodic polarization on the working electrode at a voltage of 1.5V for 1.5 hours, taking out a polarization product after the polarization product is finished, cooling the polarization product to normal temperature in an electrolytic tank, taking out the product, and carrying out treatment by using distilled waterCleaning, vacuum drying at 60 ℃, burning for 1 hour at 850 ℃ in the air, and soaking for 24 hours by 0.5mol/L hydrochloric acid to obtain the titanium lithium ion sieve material. The material is put into 20mL lithium-containing lithium chloride solution with 0.2g/L, and the adsorption capacity is 70mg/g after 24 hours of adsorption at 30 ℃.
Example 4
Adding commercially available 0.1-0.2 μm TiO2Pressing 10g of the powder under 2MPa to obtain 5 test pieces with the diameter of 20mm and the thickness of 3mm, and sintering the test pieces at 700 ℃ for 3 hours under the argon atmosphere to obtain TiO2A test piece. Tightly wrapping a test piece with a titanium mesh, winding a thin titanium wire on a long titanium wire to serve as a working electrode, taking a graphite rod as a counter electrode, taking LiCl as electrolyte, in an argon atmosphere, at the temperature of 700 ℃, at the voltage of 3.1V, carrying out cathodic polarization for 5 hours, carrying out anodic polarization on the working electrode after the cathodic polarization is finished, at the voltage of 1.0V, for 2 hours, taking a polarization product out of the liquid level after the electrolysis is finished, cooling the polarization product in an electrolytic tank to the normal temperature, taking the product out, cleaning the product with distilled water, drying the product in vacuum at the temperature of 60 ℃, burning the product in the air at the temperature of 900 ℃ for 2 hours, and soaking the product in 0.5mol/L hydrochloric acid for 24 hours to obtain the titanium-based lithium ion sieve material. The material is put into 20mL lithium chloride solution containing 0.2g/L lithium, and the adsorption capacity is 63mg/g after 24 hours of adsorption at 30 ℃.
Example 5
Adding commercially available 0.1-0.2 μm TiO22g of the powder was taken out and pressed under 20MPa to prepare a test piece having a diameter of 20mm and a thickness of 2 mm. Compounding a test piece and a tungsten mesh as a working electrode, taking a graphite rod as a counter electrode, taking LiCl as electrolyte, carrying out anodic polarization on the working electrode in an argon atmosphere at the temperature of 700 ℃, the voltage of 2.0V and the cathodic polarization time of 3 hours, carrying out anodic polarization on the working electrode after the cathodic polarization is finished, the voltage of 1.5V and the polarization time of 1 hour, taking out a polarization product out of the liquid level, cooling the polarization product to the normal temperature in an electrolytic tank, taking out the product, cleaning the product by distilled water, drying the product in vacuum at the temperature of 60 ℃, burning the product for 2 hours at the temperature of 800 ℃ in the air, and soaking the product for 48 hours by 0.5mol/L hydrochloric acid to obtain the titanium lithium ion sieve material. The material is put into 20mL lithium-containing lithium chloride solution with 0.2g/L, and the adsorption capacity is 58mg/g after 24 hours of adsorption at 30 ℃.
Example 6
Adding commercially available 0.1-0.2 μm TiO21g of the powder was pressed under 15MPa to prepare a test piece having a diameter of 20mm and a thickness of 2mm, and the test piece was sintered at 800 ℃ for 1 hour in an argon atmosphere. Wrapping a test piece with a nickel sheet, winding a molybdenum wire on a long molybdenum wire to serve as a working electrode, taking a graphite rod as a counter electrode, taking molten LiCl as electrolyte, carrying out anodic polarization on the working electrode at the temperature of 700 ℃ and the voltage of 2.4V in an argon atmosphere for 3 hours after cathodic polarization is finished, carrying out anodic polarization on the working electrode at the voltage of 2V for 1 hour after the cathodic polarization is finished, taking out a polarization product from the liquid level, cooling the polarization product to the normal temperature in an electrolytic cell, taking out the product, cleaning the product with absolute ethyl alcohol, drying the product at the temperature of 60 ℃ in vacuum, burning the product in the air at the temperature of 700 ℃ for 1.5 hours, and soaking the product in 0.6mol/L hydrochloric acid for 24 hours to obtain the titanium-based lithium ion sieve. The material is put into 20mL lithium-containing lithium chloride solution with 0.2g/L, and the adsorption capacity is 65mg/g after 24 hours of adsorption at 30 ℃.
Example 7
Adding commercially available 0.1-0.2 μm TiO2Taking 5g of powder, sintering the powder at 800 ℃ for 2 hours in an argon atmosphere, putting the powder into a nickel boat made of foamed nickel, winding a molybdenum wire on a long molybdenum wire to form a working electrode, taking a graphite rod as a counter electrode, taking molten LiCl as an electrolyte, performing cathodic polarization for 4 hours at the temperature of 700 ℃ and the voltage of 2.8V in the argon atmosphere, performing anodic polarization on the working electrode after the cathodic polarization is finished, performing 2-0V polarization for 2 hours, taking out a polarization product, cooling the polarization product in an electrolytic bath to normal temperature, taking out the product, cleaning the product with acetone, drying the polarization product in vacuum at the temperature of 60 ℃, firing the product in air at the temperature of 700 ℃ for 2 hours, and soaking the product in 0.6mol/L of hydrochloric acid for 48 hours to obtain the titanium-based lithium ion sieve material. The material was put into 20mL of lithium chloride solution containing 0.2g/L of lithium, and the adsorption capacity was 69mg/g after 24 hours at 30 ℃.
Claims (2)
1. A preparation method of a titanium lithium ion sieve is characterized by comprising the following steps:
1) adding TiO into the mixture2Compounding powder or tablet with metal current collector as working electrode, graphite as counter electrode, and protecting in inert atmosphereIn the alkali metal halide, performing cathode polarization at 400-700 ℃ and 2.0-3.2V for 0.5-5 hours; the alkali metal chloride is LiCl or a mixture of LiCl and one or two of Na or K chlorides; the metal current collector is filiform, reticular or flaky titanium, stainless steel, molybdenum, tungsten or nickel with the melting point higher than the reaction temperature;
2) then, carrying out anodic polarization on the working electrode at 1.0-2.6V for 0.5-2 hours, cooling to room temperature after the polarization is finished, and cleaning and vacuum drying; then burning the titanium-containing lithium ion sieve in the air at 600-900 ℃ for 1-3 hours, cooling, and performing acid leaching on the obtained product in 0.5-0.6 mol/L hydrochloric acid for 24-48 hours to obtain the titanium-containing lithium ion sieve.
2. The method of claim 1, wherein the TiO is selected from the group consisting of2The powder is commercially available TiO2Sintering the powder at 600-900 ℃ in an inert atmosphere; the TiO is2Tabletting is to mix the commercially available TiO2And tabletting the powder under the pressure of 2-20 MPa, and sintering at the temperature of 600-900 ℃ in an inert atmosphere.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116983948A (en) * | 2023-09-27 | 2023-11-03 | 赣州市力道新能源有限公司 | Preparation method of titanium lithium ion adsorption material |
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