CN112110452B - Method for synthesizing lithium borate halide by gas-solid reaction - Google Patents
Method for synthesizing lithium borate halide by gas-solid reaction Download PDFInfo
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- CN112110452B CN112110452B CN202010749398.4A CN202010749398A CN112110452B CN 112110452 B CN112110452 B CN 112110452B CN 202010749398 A CN202010749398 A CN 202010749398A CN 112110452 B CN112110452 B CN 112110452B
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Abstract
The invention belongs to the field of new material synthesis, and mainly relates to a synthesis method of halogenated lithium borate. The invention discloses a method for synthesizing lithium halide borate by utilizing a gas-solid reaction, aiming at the problems of less traditional synthesis method, large process energy consumption, complex synthesis route and the like. The method is characterized in that lithium borohydride, boron oxide, lithium halide, lithium hydroxide and carbon dioxide are reacted, and pure-phase lithium borate halide is synthesized through gas-solid reaction at certain temperature and pressure. The invention effectively fixes and utilizes the greenhouse gas carbon dioxide, and provides a novel, efficient, low-cost, environment-friendly and industrial production-easy method for synthesizing lithium halide borate.
Description
Technical Field
The invention belongs to the field of new material synthesis, and mainly relates to a method for synthesizing lithium borate halide by using a gas-solid reaction.
Background
The lithium halide borate is an inorganic compound, is stable in air, is insoluble in water and has high ionic conductivity. However, there are few reports on the synthesis of lithium haloborate. Naoto TEZUKA reports the synthesis of lithium borate halides, Li, by melt quench crystallization technique2CO3-B2O3Melting LiCl at a high temperature of 1000 ℃ to form lithium borate halide [ Naoto TEZUKA, Yuta OKAWA, Koichi KAJIHARA, Kiyoshi KANAMURA. Synthesis and catalysis of lithium-ion-conductive glass ceramics of lithium chloride Li4+xB7O12+x/2Cl(x＝0–1).Journal of the Ceramic Society of Japan.2017,125,348-352.]. However, the method has the defects of high synthesis temperature, high energy consumption, complex synthesis route and the like.
Therefore, the research of a novel, efficient and environment-friendly lithium halide borate synthesis method is of great significance.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing lithium halide borate, which is efficient, low in cost, environment-friendly and easy for industrial production. The method for synthesizing the lithium halogenated borate by using the gas-solid reaction comprises the step of synthesizing a pure-phase lithium halogenated borate material by reacting carbon dioxide with lithium borohydride, boron oxide, lithium halide and lithium hydroxide at a certain temperature, wherein the chemical component is Li4+xB7O12+x/2Y (Y ═ Cl, Br, I, or any mixture thereof) (x ═ 0 to 2).
The technical solution of the present invention is explained in detail below.
The synthesis method of the lithium halide borate is mainly realized by a gas-solid reaction method, and particularly relates to a method for synthesizing the lithium halide borate by the gas-solid reaction, which comprises the following steps:
(1) in an inert atmosphere, putting lithium borohydride, boron oxide, lithium halide and lithium hydroxide in a certain proportion into a sealed ball milling tank, and uniformly mixing by mechanical ball milling;
(2) transferring the uniformly mixed material in the step (1) to a sealed reactor under inert atmosphere, and introducing excessive carbon dioxide into the reactor;
(3) heating the gas-solid mixture in the reactor to a certain temperature and preserving heat for a period of time;
(4) after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor and realizing gas-solid separation;
(5) and (4) calcining the solid powder obtained in the step (4) in the air or oxygen atmosphere to obtain the lithium borate halide powder.
In the step (1), boron oxide, lithium halide and lithium hydroxide are anhydrous reagents.
The conditions of mechanical ball milling and mixing in the step (1) are as follows: the ball-material mass ratio is (10-80):1, the ball-milling rotation speed is 100-.
In the step (1), the molar ratio of lithium borohydride, boron oxide, lithium halide and lithium hydroxide is 1:3:1 (2-4).
The molar ratio of the excessive carbon dioxide to the lithium hydroxide in the step (2) is 1 (2-4), and the pressure of the carbon dioxide is 10-20 bar.
The heating temperature in the step (3) is 350-800 ℃, and the heat preservation time is 1-100 h.
The calcination condition in the step (5) is that the heating temperature is 400-500 ℃ and the heat preservation time is 0.1-10h under the atmosphere of air or oxygen at normal pressure.
The inert atmosphere in the steps (1) and (2) is any one or more of argon and helium.
The lithium halogenated borate in the step (5) is Li4+xB7O12+x/2Y is any one or more of Cl, Br and I, and x is 0-2.
In the invention, the room temperature is about 0-40 ℃.
In the present invention, lithium haloborate material Li is synthesized4+xB7O12+x/2The chemical formula of the reaction of Y (Y ═ Cl, Br, I, or any mixture thereof) (x ═ 0 to 2) is as follows:
4LiBH4+12B2O3+4LiY+(8+4x)LiOH+(2-x)CO2→4Li4+xB7O12+x/2Y+(12+2x)H2+(2-x)C
compared with the prior art, the invention has the following beneficial effects:
according to the invention, carbon dioxide, lithium borohydride, boron oxide, lithium halide and lithium hydroxide are used to generate lithium borate halide under the heating condition, carbon generated by the reaction is removed through calcination, the carbon dioxide is used as greenhouse gas, the fixation and utilization method of the carbon dioxide is beneficial to alleviating greenhouse effect, and the method is an environment-friendly behavior with reasonable utilization of resources. The technology is simple and convenient to operate, fast, efficient, environment-friendly and easy to industrially implement.
Drawings
FIG. 1 is an X-ray diffraction pattern of the reaction product of example 1.
Detailed description of the invention
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
In argon atmosphere, lithium borohydride, boron oxide, lithium chloride and lithium hydroxide are placed into a sealed ball-milling tank according to the molar ratio of 1:3:1:2, and are mechanically ball-milled for 12 hours and uniformly mixed according to the ball-material ratio of 40:1 and the rotating speed of 500 rpm/min. Transferring the uniformly mixed materials to a sealed reactor, introducing carbon dioxide into the reactor, wherein the molar ratio of the carbon dioxide to the lithium hydroxide is 1:4, and the pressure is 10 bar. Heating the gas-solid mixture in the reactor to 600 ℃ and preserving the heat for 10 h. And after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor to realize gas-solid separation. Calcining the obtained solid powder for 2h at 500 ℃ in the air atmosphere of normal pressure to obtain Li4B7O12The powder of Cl and the X-ray diffraction pattern are shown in figure 1.
Example 2
In argon atmosphere, lithium borohydride, boron oxide, lithium chloride and lithium hydroxide are placed into a sealed ball-milling tank according to the molar ratio of 1:3:1:3, and are mechanically ball-milled for 12 hours and uniformly mixed according to the ball-material ratio of 10:1 and the rotating speed of 500 rpm/min. The homogeneously mixed material was transferred to a sealed reactor, into which carbon dioxide was introduced in a molar ratio of carbon dioxide to lithium hydroxide of 1:2 at a pressure of 20 bar. Heating the gas-solid mixture in the reactor to 600 ℃ and preserving the heat for 10 h. And after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor to realize gas-solid separation. Calcining the obtained solid powder for 10 hours at 400 ℃ in the atmosphere of air at normal pressure to obtain Li5B7O12.5And (3) Cl powder.
Example 3
In argon atmosphere, lithium borohydride, boron oxide, lithium chloride and lithium hydroxide are placed into a sealed ball-milling tank according to the molar ratio of 1:3:1:3.4, and are mechanically ball-milled for 100 hours and uniformly mixed according to the ball-material ratio of 80:1 and the rotating speed of 100 rpm/min. The homogeneously mixed material was transferred to a sealed reactor, into which carbon dioxide was introduced in a molar ratio of carbon dioxide to lithium hydroxide of 1:3 at a pressure of 15 bar. Heating the gas-solid mixture in the reactor to 800 ℃ and preserving the heat for 1 h. And after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor to realize gas-solid separation. The obtained solid powder is used as the raw materialCalcining the mixture for 0.1h at 500 ℃ in the atmosphere of pressurized oxygen to obtain Li5.4B7O12.5And (3) Cl powder.
Example 4
In a helium atmosphere, lithium borohydride, boron oxide, lithium chloride, lithium bromide and lithium hydroxide are placed into a sealed ball milling tank in a molar ratio of 1:3:0.7:0.3:2, and are mechanically ball milled for 2 hours and uniformly mixed in a ball-material ratio of 60:1 at a rotating speed of 500 rpm/min. The homogeneously mixed material was transferred to a sealed reactor, into which carbon dioxide was introduced in a molar ratio of carbon dioxide to lithium hydroxide of 1:2 at a pressure of 20 bar. Heating the gas-solid mixture in the reactor to 350 ℃ and preserving the temperature for 100 h. And after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor to realize gas-solid separation. Calcining the obtained solid powder for 5 hours at 450 ℃ in the air atmosphere of normal pressure to obtain Li4B7O12Cl0.7Br0.3And (3) powder.
Example 5
In argon atmosphere, lithium borohydride, boron oxide, lithium bromide and lithium hydroxide are placed into a sealed ball-milling tank according to the molar ratio of 1:3:1:2, and are mechanically ball-milled for 12 hours and uniformly mixed according to the ball material ratio of 50:1 by the rotating speed of 500 rpm/min. Transferring the uniformly mixed materials to a sealed reactor, introducing carbon dioxide into the reactor, wherein the molar ratio of the carbon dioxide to the lithium hydroxide is 1:4, and the pressure is 10 bar. Heating the gas-solid mixture in the reactor to 600 ℃ and preserving the heat for 10 h. And after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor to realize gas-solid separation. Calcining the obtained solid powder for 2h at 500 ℃ in the air atmosphere of normal pressure to obtain Li4B7O12Br powder.
Example 6
In argon atmosphere, lithium borohydride, boron oxide, lithium iodide and lithium hydroxide are placed into a sealed ball-milling tank according to the molar ratio of 1:3:1:2, and are mechanically ball-milled for 12 hours and uniformly mixed according to the ball-material ratio of 70:1 and the rotating speed of 500 rpm/min. Transferring the uniformly mixed materials to a sealed reactor, introducing carbon dioxide into the reactor, wherein the molar ratio of the carbon dioxide to the lithium hydroxide is 1:4, and the pressure is 10 bar.Heating the gas-solid mixture in the reactor to 600 ℃ and preserving the heat for 10 h. And after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor to realize gas-solid separation. Calcining the obtained solid powder for 3h at 400 ℃ in the atmosphere of air at normal pressure to obtain Li4B7O12I, powder.
Claims (10)
1. A method for synthesizing lithium borate halide by gas-solid reaction is characterized by comprising the following steps:
(1) in an inert atmosphere, putting lithium borohydride, boron oxide, lithium halide and lithium hydroxide in a certain proportion into a sealed ball milling tank, and uniformly mixing by mechanical ball milling;
(2) transferring the uniformly mixed material in the step (1) to a sealed reactor under inert atmosphere, and introducing excessive carbon dioxide into the reactor;
(3) heating the gas-solid mixture in the reactor to a certain temperature and preserving heat for a period of time;
(4) after the reaction is finished and the temperature is reduced to room temperature, collecting gas in the reactor and realizing gas-solid separation;
(5) and (4) calcining the solid powder obtained in the step (4) in the air or oxygen atmosphere to obtain lithium halide borate powder.
2. The method for synthesizing lithium haloborate by a gas-solid reaction according to claim 1, wherein in the step (1), the boron oxide, the lithium halide and the lithium hydroxide are anhydrous reagents.
3. The method for synthesizing lithium haloborate by gas-solid reaction according to claim 1, wherein the mechanical ball milling mixing conditions in step (1) are as follows: the ball-material mass ratio is (10-80):1, the ball-milling rotation speed is 100-.
4. The method for synthesizing lithium borate halide by using a gas-solid reaction as claimed in claim 1, wherein the molar ratio of lithium borohydride, boron oxide, lithium halide and lithium hydroxide in step (1) is 1:3:1 (2-4).
5. The method for synthesizing lithium haloborate by a gas-solid reaction according to claim 1, wherein the molar ratio of the excess carbon dioxide to the lithium hydroxide in the step (2) is 1 (2-4), and the pressure of the carbon dioxide is 10-20 bar.
6. The method for synthesizing lithium borate halide by gas-solid reaction as claimed in claim 1, wherein the heating temperature in step (3) is 350-.
7. The method for synthesizing lithium borate halide by gas-solid reaction as claimed in claim 1, wherein the calcination condition in step (5) is heating temperature of 400-500 ℃ under atmospheric air or oxygen atmosphere, and holding time of 0.1-10 h.
8. The method for synthesizing lithium haloborate by a gas-solid reaction according to claim 1, wherein the inert atmosphere is any one or more of argon or helium.
9. The method for synthesizing lithium haloborate by a gas-solid reaction according to claim 1, wherein the lithium haloborate in the step (5) contains Li as a component4+xB7O12+x/2Y is any one or more of Cl, Br and I, and x is 0-2.
10. The method of claim 9, wherein the lithium haloborate is synthesized by a gas-solid reaction according to the chemical formula: 4LiBH4+12B2O3+4LiY+(8+4x)LiOH+(2-x)CO2→4Li4+ xB7O12+x/2Y+(12+2x)H22-x C, wherein x is more than or equal to 0<2。
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