CN113292048B - Method for directly synthesizing magnesium borohydride through room-temperature oxidation reduction - Google Patents

Method for directly synthesizing magnesium borohydride through room-temperature oxidation reduction Download PDF

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CN113292048B
CN113292048B CN202110566571.1A CN202110566571A CN113292048B CN 113292048 B CN113292048 B CN 113292048B CN 202110566571 A CN202110566571 A CN 202110566571A CN 113292048 B CN113292048 B CN 113292048B
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ball milling
magnesium
ball
magnesium borohydride
borohydride
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CN113292048A (en
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欧阳柳章
朱用洋
王辉
刘江文
朱敏
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/10—Monoborane; Diborane; Addition complexes thereof
    • C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
    • C01B6/15—Metal borohydrides; Addition complexes thereof
    • C01B6/19—Preparation from other compounds of boron
    • C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data

Abstract

The invention discloses a method for directly synthesizing magnesium borohydride by oxidation reduction at room temperature. The method comprises the following steps: under the condition of room temperature, a mixture of a reducing agent and a reduced material is subjected to solid-phase ball milling by a ball mill, and high-purity magnesium borohydride is obtained after purification and desolvation; the reducing agent comprises more than one of cheaper magnesium hydride, magnesium and magnesium silicide; the reduced material is cheap boron oxide or boric acid, or a mixture of boron oxide and boric acid; the solid phase ball milling is carried out in the mixed atmosphere of argon and hydrogen, or in the argon atmosphere or hydrogen atmosphere. The method has the advantages of simple process, controllable and adjustable reaction process, mild reaction conditions, low energy consumption, low cost, high yield, no pollution, good safety and easy industrial production.

Description

Method for directly synthesizing magnesium borohydride through room-temperature oxidation reduction
Technical Field
The invention relates to the field of magnesium borohydride synthesis, in particular to a method for directly synthesizing magnesium borohydride by room-temperature oxidation reduction.
Background
The hydrogen is an excellent carrier for connecting various renewable energy sources, and has the advantages of rich content, high energy density, no pollution, storage and transportation and the like. Therefore, hydrogen energy is a high-quality secondary energy source matching renewable primary energy sources, and is one of the clean energy sources most likely to replace fossil fuels. The solid-state hydrogen storage technology with safety, high efficiency and low cost is the key for realizing the practicability and scale of hydrogen energy. And the metal borohydride is a relatively representative high-capacity solid hydrogen storage material. Wherein the magnesium borohydride has extremely high mass (14.9 wt%) and volume (145-147 kg-cm)-1) Hydrogen storage density and moderate hydrogen release enthalpy change (-39 kJ. mol)-1H2) And is widely considered as a promising hydrogen storage material. Magnesium borohydride is similar to alkali metal borides and has excellent hydrogen production performance through hydrolysis. However, magnesium borohydride is extremely expensive and the hydrolysis product is irreversible, which seriously hinders its practical applicationThe process. There is therefore a need to develop safe, economical and environmentally friendly methods for the synthesis of magnesium borohydride.
At present, the main preparation method of magnesium borohydride with high purity is based on ion exchange reaction between halides of magnesium such as magnesium chloride and magnesium bromide and alkali metal borohydride such as lithium borohydride and sodium borohydride, and the method is carried out by refluxing, ball milling, organic liquid phase ball milling and the like in appropriate organic solvents such as diethyl ether and tetrahydrofuran. According to international reports (AngewandteChemie,2007,46(30) 5765-. In addition, the LiCl and Li of the above method are caused by the fact that lithium ions and magnesium ions have similar ionic radii and lithium borohydride and lithium chloride can be dissolved in diethyl ether and tetrahydrofuran2MgCl4And LiBH4And the like, are difficult to separate, so that the high-purity magnesium borohydride is difficult to obtain. In order to obtain high-purity magnesium borohydride, sodium borohydride is used to replace lithium borohydride and reacts with magnesium chloride under the same conditions, but the yield of the magnesium borohydride is less than 5%. The yield of magnesium borohydride was increased to 50% by high energy ball milling of a mixture of sodium borohydride and magnesium chloride in a molar ratio of 2:1 (Journal of Materials Chemistry,2007,17(33): 3496-. Pure magnesium borohydride solid is obtained by ether purification and solvent removal. And a yield of approximately 77% was obtained by liquid phase ball milling of sodium borohydride and magnesium chloride in diethyl ether for 24h (International Journal of hydroenergy, 2009,34, 2144-. However, it has been reported internationally (Journal of Alloys and Compounds,2008,462,201-4A bi-ionic metal borohydride. Therefore, the method is difficult to obtain high-purity magnesium borohydride completely free of impurity ions, and the alkali metal borohydride raw material is expensive, so that the cost for preparing the magnesium borohydride is high, and the practical application and industrial production are difficult.
The addition reaction between organic compound based on magnesium hydride or magnesium alkyl, magnesium alkoxide and the like and borane or derivatives thereof can obtain high-purity magnesium borohydride, and the main reaction equation is as follows:
3MgR2+4B2H6→3Mg(BH4)2+2BR3
MgH2+B2H6→Mg(BH4)2
3MgBu2+8H3B·SMe2→3Mg(BH4)2·2SMe2+2BBu3·SMe2
although the reaction can obtain high-purity magnesium borohydride, the borane and the derivatives thereof used have high toxicity, are extremely flammable and have high price, so that the popularization of the borane and the derivatives thereof is limited to a certain extent.
In addition, magnesium borohydride is directly hydrogenated to release hydrogen product MgB through long-time high-temperature high-hydrogen-pressure heat treatment or long-time room-temperature high-hydrogen-pressure ball milling2Is also an important method for obtaining magnesium borohydride. For example, International reports (Journal of Physical Chemistry C, 2010, 114, 5224-2Hydrogenating for 72h at 390 ℃ under 90MPa of hydrogen to prepare magnesium borohydride; ball milling is carried out for 50h under the hydrogen pressure of 35MPa to prepare the magnesium borohydride. The method needs high temperature and high hydrogen pressure for a long time, and has high energy consumption, large danger coefficient and high requirement on equipment. In addition, high pressure hydrogen also increases the cost of synthesis and is not suitable for large scale production as well.
In conclusion, the current synthetic preparation method of magnesium borohydride has high requirements on preparation conditions and high preparation cost. In addition, it is difficult to obtain magnesium borohydride of high purity. As such, the large-scale application of magnesium borohydride as a hydrogen storage material is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for directly synthesizing magnesium borohydride by redox at room temperature.
The method for directly synthesizing high-purity magnesium borohydride by normal-pressure room-temperature oxidation reduction directly uses the oxygen-containing compound of boron to synthesize the magnesium borohydride in one step, and has the advantages of mild preparation conditions, simple process and cheap raw materials.
The purpose of the invention is realized by at least one of the following technical solutions.
The method for directly synthesizing magnesium borohydride by room-temperature oxidation reduction comprises the following steps: mixing a reducing agent and a reduced material at room temperature to obtain a mixture, performing solid-phase ball milling treatment (no solvent or fluxing agent is needed in the ball milling process) in a ball milling tank to obtain a ball-milled mixture, and purifying to obtain pure magnesium borohydride.
Further, the reducing agent is more than one of magnesium hydride, magnesium silicide and simple substance magnesium; the reduced material is more than one of boron oxide and boric acid. The reducing agent does not carry other cations than magnesium ions.
Further, the molar ratio of the reduced material to the reducing agent is 1-2.1: 3.5-8.5.
Preferably, the molar ratio of the reduced material to the reducing agent is 1-2: 5-8.5.
Further preferably, when the reduced material is boron oxide (B)2O3) When the molar ratio of the reduced material to the reducing agent is 1:5.
further preferably, when the reduced material is boric acid (B (OH)3) When the molar ratio of the reduced material to the reducing agent is 2: 8.5.
preferably, the reducing agent is magnesium hydride.
Preferably, if the molar quantity of the simple substance magnesium in the reducing agent is customized as n1Defining the molar quantity of the magnesium hydride as n2Defining the molar quantity of the magnesium silicide as n3Wherein n is1≥0，n2≥0，n3Not less than 0, but n1，n2And n3Not simultaneously 0; a represents the mol number of oxygen atoms, b represents the mol number of boron atoms and c represents the mol number of hydrogen atoms in the material to be reduced;
then (n)1+n2+0.5n3)：a＝(1+0.5b：1)-(1.375+0.69b：1)；2n2+c≥4b。
Further, the solid phase ball milling treatment is carried out under a non-oxidizing atmosphere or under vacuum conditions.
Preferably, the non-oxidizing atmosphere is one of an argon atmosphere, a hydrogen atmosphere, and a mixed atmosphere of argon and hydrogen.
Preferably, the pressure of the argon atmosphere is 0-2 MPa; the pressure of the hydrogen atmosphere is 0-2 MPa; the pressure of the mixed atmosphere of argon and hydrogen in the ball milling tank is 0-2 MPa.
Further, the ball-material ratio of the solid-phase ball milling treatment is 5-50:1, and the ball milling time is 0.5-45 h; and the solid-phase ball milling treatment adopts a pendulum vibration ball mill or a planetary ball mill.
Preferably, when the solid-phase ball milling treatment adopts a pendulum vibration ball mill, the rotating speed of the pendulum vibration ball mill is 1000 revolutions per minute to 1200 revolutions per minute; when the solid-phase ball milling treatment adopts a planetary ball mill, the rotating speed of the planetary ball mill is 300-500 r/min.
Further, the purifying comprises:
and dissolving the ball-milled mixture with a solvent, filtering to obtain filtrate (clear liquid), and drying in vacuum to remove solvent to obtain the magnesium borohydride.
Preferably, the solvent (purification solvent) is diethyl ether but is not limited to diethyl ether;
preferably, the vacuum drying to remove solvation comprises:
firstly, pumping the filtrate by using a Schlenk technology, wherein the pumping temperature is 25-60 ℃ to obtain a magnesium borohydride solvent compound, then transferring the magnesium borohydride solvent compound into a metal tube, heating under a vacuum condition to perform desolvation treatment, wherein the desolvation treatment temperature is 200-220 ℃, the desolvation treatment time is 12-24h, and repeating the desolvation treatment for 2-4 times.
Preferably, the filtrate is firstly pumped by a Schlenk technology, the temperature of the pump-out is 50 ℃, a magnesium borohydride solvent compound is obtained, then the magnesium borohydride solvent compound is transferred into a metal tube and heated under the vacuum condition for desolvation treatment, the temperature of the desolvation treatment is 200 ℃, the time of the desolvation treatment is 24 hours, the magnesium borohydride solvent compound is ground into powder after the desolvation treatment, and the desolvation treatment is repeated for 4 times.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the prior art, the invention adopts the oxygen-containing compound of boron (boron oxide or boric acid or the mixture of boron oxide and boric acid) as the boron source, has the advantages that firstly, the boron source can be simply prepared from natural boron source, has rich sources and low price, and is suitable for mass production; secondly, it has low toxicity and high safety.
(2) The reducing agent used in the invention is one or more of magnesium, magnesium silicide or magnesium hydride, and the reducing agent has low price and is suitable for mass production.
(3) The raw materials used by the invention consist of Mg, O, Si, B and H elements, wherein only the Mg element can be used as metal complex ions of borohydride, thus solving the problem that in the prior art, the synthesized magnesium borohydride is impure due to the substitution of Li, Na, Cl and other elements in ion exchange reaction and ions in the magnesium borohydride or the dissolution of the elements in a purification solvent; secondly, the by-products formed by Si or O elements can be completely removed by the purification process of the invention, so the method of the invention can obtain high-purity magnesium borohydride.
(4) The method not only avoids the use of the commonly used expensive alkali metal borohydrides such as lithium borohydride, sodium borohydride and the like in the prior art, such as the commonly used high-toxicity, high-cost and extremely flammable borane and derivatives thereof in the addition reaction method, but also uses boric acid as a boron source, can use the normal hydrogen in the boron source as a hydrogen source for synthesizing the magnesium borohydride, reduces the use of additional hydrogen sources from fossil fuels, and has positive significance for the magnesium borohydride as a hydrogen storage/production material.
(5) The invention realizes solid-phase oxidation-reduction reaction by high-energy ball milling, can synthesize magnesium borohydride by short-time ball milling, and has the highest yield of 82.3 percent; compared with the prior art, the invention avoids the problems of serious corrosion, environmental pollution, difficult operation and the like caused by an organic liquid phase ball milling method; and high-risk reaction conditions caused by high-temperature high-hydrogen pressure required by a high-temperature high-hydrogen pressure method are avoided.
Drawings
FIG. 1 is an FTIR spectrum of a product of ball milling of boron oxide and magnesium hydride according to an embodiment of the present invention, wherein the corresponding embodiments of the lines are as follows: 1) example 1; 2) example 2; 3) example 3; 4) example 4; 5) example 5; 6) example 6.
FIG. 2 is a graph showing the yields of magnesium borohydride from ball milling products of boron oxide and magnesium hydride according to examples 1-6 of the present invention.
FIG. 3 is FTIR, XRD and EDX spectra of the purified product and commercially available magnesium borohydride after 4 days of annealing.
FIG. 4 is an FTIR spectrum of a product of ball milling of boron oxide and magnesium hydride of example 7 of the present invention.
FIG. 5 is an FTIR spectrum of a product of ball milling of boron oxide and magnesium hydride according to an embodiment of the present invention, wherein the corresponding embodiments of the lines are: 1) example 8; 2) example 9; 3) example 10.
FIG. 6 is a graph showing the yields of magnesium borohydride from ball milling products of boron oxide and magnesium hydride according to examples 8-10 of the present invention.
FIG. 7 is an FTIR spectrum of a product of ball milling of boron oxide and magnesium hydride according to an embodiment of the present invention, wherein the corresponding embodiments of the lines are: 1) example 11; 2) example 12; 3) example 13.
FIG. 8 is a FTIR spectrum of boron oxide, magnesium hydride and magnesium spheronization products of example 14 of the present invention.
FIG. 9 is an FTIR spectrum of boric acid and magnesium hydride ball milling products of examples of the present invention, wherein the corresponding examples of the lines are: 1) example 15; 2) example 16; 3) example 17; 4) example 18.
FIG. 10 is an FTIR spectrum of a product of ball milling of boric acid and magnesium hydride of example 19 of the present invention.
FIG. 11 is an FTIR spectrum of a product of ball milling of boric acid and magnesium hydride of example 20 of the present invention.
FIG. 12 is a FTIR spectrum of boric acid, magnesium hydride and magnesium ball milling products of examples of the present invention, wherein the lines are: 1) example 21; 2) example 22; 3) example 23; 4) example 24; 5) example 25.
FIG. 13 is a graph showing the magnesium borohydride yields of boric acid, magnesium hydride and magnesium ball-milled products of examples 21, 23, 24 and 25 of the present invention.
FIG. 14 is an FTIR spectrum of a product of ball milling of boric acid, boron oxide and magnesium hydride of example 26 of this invention.
FIG. 15 is an FTIR spectrum of the product of ball milling of boric acid, boron oxide, magnesium hydride and magnesium silicide for the examples, wherein the lines correspond to the examples respectively: 1) example 27; 2) example 28.
FIG. 16 is a FTIR spectrum of the product of ball milling of boron oxide and magnesium hydride of examples, wherein the corresponding lines of the examples are: 1) example 29; 2) example 30; 3) example 31; 4) example 32.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
The specific processes of purification and desolvation are not specifically described in the examples, but the following methods are used: in an argon atmosphere glove box, dissolving the ball-milled mixture by using diethyl ether which is subjected to sodium distillation to remove water, filtering to obtain clear filtrate, performing vacuum drying to obtain a magnesium borohydride solvent compound, digesting the magnesium borohydride solvent compound by using a 4mol/L sulfuric acid solution, preparing into a 250mL solution, diluting to 0-5mg/L according to actual conditions, measuring the concentration of magnesium ions by using an inductively coupled plasma spectrometer, calculating the mass of the generated magnesium borohydride, and further calculating the yield of the magnesium borohydride. And (3) performing Schlenk technology on the obtained clear filtrate, performing extraction and drying of diethyl ether at 25-60 ℃ to obtain a magnesium borohydride solvent compound, transferring the solvent compound into a metal tube, performing vacuum extraction at 200-220 ℃ for 12-24h, taking out and grinding, and repeating for 2-4 times until the diethyl ether is removed completely to obtain pure magnesium borohydride powder. The target products in the examples were analyzed by Fourier Infrared Spectroscopy (FT-IR) or X-ray diffractometry (XRD).
In the examples, ball milling was carried out at room temperature.
Example 1
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:5, mixed and then put into a ball milling tank, the ball milling tank is placed in a pendulum vibration type ball mill (QM-3C), ball milling rotation speed is 1000 r/min according to the ball-material ratio of 50:1, and ball milling is directly carried out for 1.25h under the argon atmosphere, so that a ball milling product is obtained. Curve 1) in FIG. 1 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond absorption peaks (v in the figure, the same below) and the rocking vibration (delta in the figure, the same below) in the B-H bond prove that the magnesium borohydride is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 26.7% by conversion, as shown in fig. 2.
Example 2
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:5, mixed and then put into a ball milling tank, the ball milling tank is placed in a pendulum vibration type ball mill (QM-3C), ball milling rotation speed is 1000 r/min according to the ball-material ratio of 50:1, and ball milling is directly carried out for 2.5h under the argon atmosphere, so that a ball milling product is obtained. Curve 2) in FIG. 1 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting the viscous magnesium borohydride solvent compound by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductive coupling plasma spectrometer, and finally calculating the yield to be 62.8% by conversion, wherein the yield is shown in figure 2.
Example 3
Weighing boron oxide and magnesium hydride in a molar ratio of 1:5 in a glove box with an argon atmosphere of 0.1MPa, and mixingThen the mixture is put into a ball milling tank, the ball milling tank is placed in a pendulum vibration type ball mill (QM-3C), ball milling is carried out for 5 hours under the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotating speed of 1000 r/min, and a ball milling product is obtained. Curve 3) in FIG. 1 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 68.6% by conversion, as shown in fig. 2.
Example 4
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 10 hours in the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and thus obtaining a ball milling product. Curve 4) in FIG. 1 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting the viscous magnesium borohydride solvent compound by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductively coupled plasma spectrometer, and finally calculating the yield to be 73.8% by conversion, wherein the yield is shown in figure 2.
Example 5
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 15 hours in the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and thus obtaining a ball milling product.Curve 5 in FIG. 1) is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting the viscous magnesium borohydride solvent compound by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductive coupling plasma spectrometer, and finally calculating the yield to be 76.9% by conversion, wherein the yield is shown in figure 2. The clear filtrate obtained was again obtained by Schlenk technique, most of the ether was extracted at 50 ℃ to obtain magnesium borohydride solvent compound, the solvent compound was transferred into a metal tube, after evacuation at 200 ℃ for 24 hours, removal and grinding, and repeated 4 times to obtain white powder, and the FTIR pattern and XRD pattern of the white powder are shown in part a and part (b) of fig. 3, respectively. As can be seen in part a of FIG. 3, 2800cm after the 4 th desolvation by heating-1The C-H absorption band disappeared, similar to the FTIR spectrum of commercially available 95% pure magnesium borohydride, indicating that the ether had been removed. In addition, the XRD pattern of the desolvated magnesium borohydride observed in section b of FIG. 3 is also similar to that of commercially available 95% pure magnesium borohydride. Therefore, the method can obtain high-purity magnesium borohydride. To further prove the absence of impurity elements such as Li, Na, Cl, etc., the desolvated magnesium borohydride was subjected to a spectroscopic test, and the result is shown in part c of FIG. 3, in which impurity elements such as Li, Na, Cl, etc. were absent. Wherein C is used for testing the conductive adhesive, and O is generated by hydrolyzing magnesium borohydride to generate magnesium metaborate in the testing process.
Example 6
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 20 hours in the argon atmosphere at the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and thus obtaining a ball milling product. Curve 6 in FIG. 1) is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting the viscous magnesium borohydride solvent compound by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductive coupling plasma spectrometer, and finally calculating the yield to be 81.4% by conversion, wherein the yield is shown in figure 2.
Example 7
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 15 hours in the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1200 r/min to obtain a ball milling product. The FTIR spectrum of the ball-milled product is plotted in FIG. 4, wherein the plot is 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 8
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:4, mixing, filling the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 15 hours in the argon atmosphere at the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and thus obtaining a ball milling product. Curve 1) in FIG. 5 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 62.6% by conversion, as shown in fig. 6.
Example 9
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:4.5, mixed and then put into a ball milling tank, the ball milling tank is placed in a pendulum vibration type ball mill (QM-3C), ball milling is carried out for 15h under the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and a ball milling product is obtained. Curve 2) in FIG. 5 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 72.6% by conversion, as shown in fig. 6.
Example 10
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:5.5, mixed and then put into a ball milling tank, the ball milling tank is placed in a pendulum vibration type ball mill (QM-3C), ball milling is carried out for 15h under the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and a ball milling product is obtained. Curve 3 in FIG. 5) is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 82.3% by conversion, as shown in fig. 6.
Example 11
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:4, mixing, filling into a ball milling tank, and placing the ball milling tank in a pendulum vibration modeIn a ball mill (QM-3C), ball milling is directly carried out for 1h in the argon atmosphere at a ball-material ratio of 50:1 and a ball milling rotation speed of 1000 r/min, so as to obtain a ball milling product. Curve 1) in FIG. 7 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 12
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:4, mixing, filling the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 2 hours in the argon atmosphere at the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and thus obtaining a ball milling product. Curve 2) in FIG. 7 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 13
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide and magnesium hydride according to the molar ratio of 1:4, mixing, filling the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 5 hours in the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 3 in FIG. 7) is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 14
In a glove box with 0.1MPa argon atmosphere, weighing boron oxide, magnesium hydride and magnesium in a molar ratio of 1:4:1, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 15 hours in the argon atmosphere at a ball-material ratio of 30:1 and a ball milling rotation speed of 1000 r/min to obtain a ball milling product. The FTIR spectrum of the ball-milled product is plotted in FIG. 8, wherein the plot is 2150-2400cm-1And 1100-1300cm-1Has shown a correspondenceMg(BH4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 15
In a glove box with 0.1MPa argon atmosphere, weighing boric acid and magnesium hydride according to the molar ratio of 2:7, mixing, filling the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 0.5h in the argon atmosphere at the ball-material ratio of 50:1 and the ball milling rotation speed of 1200 r/min, and thus obtaining a ball milling product. Curve 1) in FIG. 9 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 16
In a glove box with 0.1MPa argon atmosphere, weighing boric acid and magnesium hydride according to the molar ratio of 2:7, mixing, filling the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 2 hours in the argon atmosphere at the ball-material ratio of 50:1 and the ball milling rotation speed of 1200 r/min, and thus obtaining a ball milling product. Curve 2) in FIG. 9 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 17
In a glove box with 0.1MPa argon atmosphere, weighing boric acid and magnesium hydride according to the molar ratio of 2:7, mixing, filling the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 5 hours in the argon atmosphere at the ball-material ratio of 50:1 and the ball milling rotation speed of 1200 r/min, and thus obtaining a ball milling product. Curve 3 in FIG. 9) is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 18
In a glove box with 0.1MPa argon atmosphere, weighing boric acid and magnesium hydride according to the molar ratio of 2:7, and mixingAnd (3) putting the mixture into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 10 hours in the argon atmosphere at a ball-material ratio of 50:1 and a ball milling rotating speed of 1200 r/min to obtain a ball milling product. Curve 4) in FIG. 9 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 19
In a glove box with 0.1MPa argon atmosphere, boric acid and magnesium hydride are weighed according to the molar ratio of 2:8.75, mixed and then put into a ball milling tank, the ball milling tank is placed in a pendulum vibration type ball mill (QM-3C), ball milling rotation speed is 1200 r/min according to the ball-material ratio of 50:1, and ball milling is directly carried out for 15h under the argon atmosphere, so that a ball milling product is obtained. The FTIR spectrum of the ball-milled product is plotted in FIG. 10, wherein the plot is 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 20
In a glove box with 0.1MPa argon atmosphere, weighing boric acid and magnesium hydride according to the molar ratio of 2:7.875, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), performing ball milling for 15 hours in the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and thus obtaining a ball milling product. FIG. 11 is a graph of FTIR spectra of the ball-milled product, wherein the graph shows 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductively coupled plasma spectrometer, and finally calculating the yield to be 67.4% by conversion.
Example 21
Gloves under 0.1MPa argon atmosphereIn the box, boric acid and magnesium are weighed according to the molar ratio of 2:8.44, mixed and then put into a ball milling tank, the ball milling tank is placed into a pendulum vibration type ball mill (QM-3C), ball milling is carried out for 20 hours under the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min, and a ball milling product is obtained. Curve 1) in FIG. 12 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 0.14% by conversion, as shown in fig. 13.
Example 22
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, magnesium hydride and magnesium in a molar ratio of 2:1:7.5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 20 hours in the argon atmosphere at a ball-material ratio of 50:1 and a ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 2) in FIG. 12 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the magnesium borohydride compound proves that the magnesium borohydride compound is successfully synthesized.
Example 23
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, magnesium hydride and magnesium in a molar ratio of 2:3:5.5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 20 hours in the argon atmosphere at a ball-material ratio of 50:1 and a ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 3 in FIG. 12) is an FTIR spectrum of the ball-milled product, curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; by distillation of sodiumThe mixture was dissolved in an ether solvent of water and filtered to obtain a clear filtrate, the filtrate was dried by Schlenk technique to obtain a viscous magnesium borohydride solvent compound, which was digested with acid to prepare a solution, and then the concentration of magnesium ions was measured by an inductively coupled plasma spectrometer, and finally the yield was calculated to be 0.014% by conversion, as shown in fig. 13.
Example 24
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, magnesium hydride and magnesium in a molar ratio of 2:5:3.5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 20 hours in the argon atmosphere at a ball-material ratio of 50:1 and a ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 4) in FIG. 12 is an FTIR spectrum of the ball-milled product, curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; the mixture was dissolved using an ether solvent with sodium distilled to remove water and filtered to obtain a clear filtrate, the filtrate was dried using Schlenk technology to obtain a viscous magnesium borohydride solvent compound, which was digested with acid and formulated into a solution, and then the magnesium ion concentration was measured using an inductively coupled plasma spectrometer, and finally the yield was calculated as 14.1% by conversion, as shown in fig. 13.
Example 25
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, magnesium hydride and magnesium in a molar ratio of 2:7:1.5, mixing, filling into a ball milling tank, putting the ball milling tank into a pendulum vibration type ball mill (QM-3C), and directly performing ball milling for 20 hours in the argon atmosphere at a ball-material ratio of 50:1 and a ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 5 in FIG. 12) is an FTIR spectrum of the ball-milled product, curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture with diethyl ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by Schlenk technology to obtain viscous magnesium borohydride solvent compound, and adding acidThe solution is digested and prepared, then the magnesium ion concentration is measured by using an inductively coupled plasma spectrometer, and finally the yield is calculated to be 62.1% through conversion, as shown in figure 13.
Example 26
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, boron oxide and magnesium hydride according to the molar ratio of 1:1:7.5, mixing, then filling into a ball milling tank, then filling 0.7MPa argon, placing the ball milling tank into a pendulum vibration type ball mill (QM-3C), and carrying out ball milling for 15 hours according to the ball material ratio of 30:1 and the ball milling rotation speed of 1000 r/min to obtain a ball milling product. FIG. 14 is a graph of FTIR spectra of the ball-milled product, wherein the graph shows 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 27
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, boron oxide, magnesium hydride and magnesium silicide according to the molar ratio of 1:1:6:0.75, mixing, then filling into a ball milling tank, vacuumizing, filling 0.5MPa hydrogen and 0.5MPa argon, placing the ball milling tank into a pendulum vibration type ball mill (QM-3C), and performing ball milling for 10 hours according to the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 1) in FIG. 15 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 28
In a glove box with 0.1MPa argon atmosphere, weighing boric acid, boron oxide, magnesium hydride and magnesium silicide according to the molar ratio of 1:1:6:0.75, mixing, then filling into a ball milling tank, vacuumizing, filling 2MPa hydrogen, placing the ball milling tank into a pendulum vibration type ball mill (QM-3C), and performing ball milling for 10 hours at the ball-material ratio of 50:1 and the ball milling rotation speed of 1000 r/min to obtain a ball milling product. Curve 2) in FIG. 15 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2The B-H bond stretching and swinging vibration absorption peak in the synthesis proves that the magnesium borohydride is successfully synthesized.
Example 29
Boron oxide and magnesium hydride are weighed in a molar ratio of 1:4.5 in a glove box with 0.1MPa argon atmosphere, mixed and then put into a ball milling tank, the ball milling tank is placed in a planetary ball mill (QM-3SP4), ball milling is carried out for 15 hours in the argon atmosphere at a ball-to-material ratio of 50:1 and a ball milling rotating speed of 500 r/min. Curve 1) in FIG. 16 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductive coupling plasma spectrometer, and finally calculating the yield to be 4.8% by conversion.
Example 30
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:4.5, mixed and then put into a ball milling tank, the ball milling tank is placed in a planetary ball mill (QM-3SP4), ball milling is carried out for 45 hours under the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotating speed of 500 r/min, and a ball milling product is obtained. Curve 2) in FIG. 16 is an FTIR spectrum of the ball-milled product, in which curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductively coupled plasma spectrometer, and finally calculating the yield to be 49.3% by conversion.
Example 31
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:5.5, mixed and then put into a ball milling tank, and the ball milling tank is placed in a planetary ball mill (QM-3S)P4), ball milling for 15h under the argon atmosphere directly at a ball-to-material ratio of 50:1 and a ball milling rotation speed of 500 r/min, so as to obtain a ball milling product. Curve 3 in FIG. 16) is an FTIR spectrum of the ball-milled product, curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductive coupling plasma spectrometer, and finally calculating the yield to be 4.1% by conversion.
Example 32
In a glove box with 0.1MPa argon atmosphere, boron oxide and magnesium hydride are weighed according to the molar ratio of 1:4.5, mixed and then put into a ball milling tank, the ball milling tank is placed in a planetary ball mill (QM-3SP4), ball milling is carried out for 45 hours under the argon atmosphere according to the ball-material ratio of 50:1 and the ball milling rotating speed of 500 r/min, and a ball milling product is obtained. Curve 4) in FIG. 16 is an FTIR spectrum of the ball-milled product, curve 2150-2400cm-1And 1100-1300cm-1In the presence of corresponding Mg (BH)4)2B-H bond stretching and swinging vibration absorption peaks in the magnesium borohydride compound prove that the magnesium borohydride compound is successfully synthesized; dissolving the mixture by using an ether solvent with sodium distilled water removed, filtering to obtain clear filtrate, drying the filtrate by using a Schlenk technology to obtain a viscous magnesium borohydride solvent compound, digesting by using acid to prepare a solution, measuring the concentration of magnesium ions by using an inductive coupling plasma spectrometer, and finally calculating the yield to be 48.2% by conversion.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (9)

1. A method for directly synthesizing magnesium borohydride by room-temperature oxidation reduction is characterized by comprising the following steps:
mixing a reducing agent and a reduced material to obtain a mixture, then carrying out solid-phase ball milling treatment in a ball milling tank to directly synthesize magnesium borohydride in one step to obtain a ball-milled mixture, and purifying to obtain the magnesium borohydride; the reducing agent is more than one of magnesium hydride, magnesium silicide and simple substance magnesium; the reduced material is more than one of boron oxide and boric acid.
2. The method for direct synthesis of magnesium borohydride by room temperature oxidation-reduction according to claim 1, wherein the molar ratio of the reduced material to the reducing agent is 1-2.1: 3.5-8.5.
3. The method for direct room temperature redox synthesis of magnesium borohydride according to claim 1, characterized in that the solid phase ball milling treatment is performed under non-oxidizing atmosphere or vacuum condition.
4. The method for direct room temperature magnesium borohydride according to claim 3, wherein the non-oxidizing atmosphere is one of argon, hydrogen, and a mixture of argon and hydrogen.
5. The method for direct synthesis of magnesium borohydride according to room temperature redox as claimed in claim 4, wherein the pressure of argon atmosphere in the ball mill is 0-2 MPa; the pressure of the hydrogen atmosphere in the ball milling tank is 0-2 MPa; the pressure of the mixed atmosphere of argon and hydrogen in the ball milling tank is 0-2 MPa.
6. The method for directly synthesizing magnesium borohydride by room temperature oxidation-reduction according to claim 1, wherein the ball-to-material ratio of the solid phase ball milling treatment is 5-50:1, and the time of the solid phase ball milling treatment is 0.5-45 h; and the solid-phase ball milling treatment adopts a pendulum vibration ball mill or a planetary ball mill.
7. The method for directly synthesizing magnesium borohydride by room temperature oxidation-reduction according to claim 1, wherein when the solid phase ball milling treatment adopts a pendulum ball mill, the rotating speed of the pendulum ball mill is 1000 rpm to 1200 rpm; when the solid-phase ball milling treatment adopts a planetary ball mill, the rotating speed of the planetary ball mill is 300-500 r/min.
8. A room temperature redox direct synthesis method of magnesium borohydride according to any of claims 1-7, characterized in that the purification comprises:
and dissolving the ball-milled mixture with a solvent, filtering to obtain filtrate, and drying in vacuum to remove the solvent to obtain the magnesium borohydride.
9. The method for direct synthesis of magnesium borohydride according to claim 8, characterized in that the solvent is diethyl ether; the vacuum drying to remove the solvent comprises:
firstly, pumping the filtrate by using a Schlenk technology, wherein the pumping temperature is 25-60 ℃, then heating under the vacuum condition for desolvation treatment, the temperature of the desolvation treatment is 200-220 ℃, the time of the desolvation treatment is 12-24h, and repeating the desolvation treatment for 2-4 times.
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