CN110143577B - Preparation of NaBH by liquid phase precipitation 4 Method for the production of reversible hydrogen storage materials - Google Patents
Preparation of NaBH by liquid phase precipitation 4 Method for the production of reversible hydrogen storage materials Download PDFInfo
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Abstract
The invention discloses a method for preparing NaBH by liquid phase precipitation 4 A method for preparing reversible hydrogen storage material relates to the technical field of solid hydrogen storage, and comprises the following steps: reacting NaBH 4 Dissolving in isopropylamine, and stirring until the solution is transparent; adding GdF 3 Nano particles are continuously stirred; drying under vacuum. To obtain better raw materials, gdF used in the invention 3 The nano particles are obtained by the following method: gd (NO) 3 ) 3 ·6H 2 O and NH 4 Preparation of GdF by F reaction 3 A suspension; centrifuging, washing and drying the precipitate to obtain GdF 3 And (3) powder. The invention combines GdF 3 With NaBH 4 NaBH prepared in a composite manner 4 The reversible hydrogen storage material has the advantages of hydrogen storage amount of more than 3.0wt.%, total hydrogen absorption amount of 2.4wt.%, hydrogen release temperature of less than 460 ℃, lower hydrogen release temperature, obviously improved hydrogen absorption and release reversibility, simple preparation method, high product yield, short preparation period and low production cost.
Description
Technical Field
The invention relates to the technical field of solid hydrogen storage, in particular to a method for preparing NaBH by liquid phase precipitation 4 A method of producing a reversible hydrogen storage material.
Background
Since it is derived from water, the final product is also water, without any emission of carbonaceous material, hydrogen is considered as the cleanest new energy source in the future. The widespread use of hydrogen is currently limited by several bottleneck problems, of which one is the safe and compact storage technology. The current mainstream hydrogen storage technology is the storage of hydrogen in a gas steel cylinder, the method is dangerous, the hydrogen storage amount is very low, and the hydrogen storage amount in a 15MPa steel cylinder is less than 1wt.%. Because the boiling point of hydrogen is very low, liquid hydrogen storage needs to consume a large amount of energy to cool the hydrogen storage, and the high cost limits the use of hydrogen to special occasions such as aerospace and the like. Therefore, the solid-state hydrogen storage technology is widely considered as the final solution for hydrogen storage, and the hydrogen storage mode has the characteristics of good safety, very high density of hydrogen storage in weight and volume, and the like.
In a plurality of hydrogen storage mediaAmong mesomaterials, metal hydrides and complex hydrides are considered the most promising hydrogen storage materials. NaBH 4 As a common reducing agent in chemical production, the hydrogen storage agent is cheap and easy to obtain, has high safety in air, and has very high hydrogen storage capacity, and the mass hydrogen storage density is as high as 10.8wt.%. NaBH 4 The application in the field of hydrogen storage is mainly in two aspects, namely hydrolysis hydrogen release and pyrolysis hydrogen release. In terms of hydrolytic hydrogen release, naBH 4 Reaction with water in addition to the production of hydrogen gas, a by-product NaBO 2 ·xH 2 O (x =2 or 4) has very low solubility in water, shows a particularly fine suspended matter after reaction, easily covers the surface of the reactant, prevents the reaction from further proceeding, and needs to increase NaBO to improve the reaction efficiency 2 ·xH 2 The amount of O (x =2 or 4) dissolved in water, consuming a large amount of water, naBO 2 ·xH 2 The above-mentioned properties of O (x =2 or 4) make the hydrogen storage capacity of the process severely limited. In the aspect of hydrogen desorption by pyrolysis, due to NaBH 4 Limitation of self-thermodynamic properties, pyrolysis of NaBH 4 The hydrogen release requires a temperature higher than 500 ℃, and the hydrogen release product has almost no reversible hydrogen absorption capacity, so the practical application is extremely limited.
Earlier studies showed that the rare earth metal fluoride LnF 3 Addition of destabilizing NaBH 4 Can obviously improve the hydrogen absorption and desorption performance and realize the reversible hydrogen storage process. Due to Gd 3+ Has proper electronegativity and high stability of oxidation state, and NaBH 4 And GdF 3 Reaction product GdB 4 B in (A) has a more ideal geometrical configuration, so that among the numerous lanthanide rare earth fluorides, 3NaBH 4 -GdF 3 Has optimal hydrogen storage performance. Unfortunately, the ball milling method adopted in the preparation process of the material is long in time, the material is adhered to the inner side of the wall of the ball milling tank after more than 16 hours, and the product yield is low and is only about 85%.
Therefore, those skilled in the art have worked to develop a liquid phase precipitation process for preparing NaBH 4 The method based on the reversible hydrogen storage material can improve the product yield, shorten the preparation period, reduce the hydrogen release temperature and improve the hydrogen absorption reversibility.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the technical problem to be solved by the present invention is to obtain a hydrogen storage material with low hydrogen evolution temperature, high hydrogen absorption reversibility, high yield and short preparation period.
In order to realize the purpose, the invention provides a method for preparing NaBH by liquid phase precipitation 4 A method of reversibly storing hydrogen comprising the steps of:
preparation of NaBH 4 Solution: reacting NaBH 4 Dissolving in isopropylamine, and stirring to form a transparent solution;
mixed fluoride: adding GdF to the clear solution 3 Nano particles are stirred continuously;
drying and separating out: drying under vacuum to obtain NaBH 4 A reversible hydrogen storage material.
Further, the NaBH 4 The mass-to-volume ratio of the isopropyl amine to the isopropyl amine is 34.76g/L.
Further, the NaBH 4 And said GdF 3 The mass ratio of the nanoparticles is 1.5-2.
Further, in the fluoride mixing step, the stirring time is 30min.
Further, in the drying and precipitation step, the drying time is 3 hours.
Further, the GdF 3 The method for producing nanoparticles comprises the steps of:
preparing a precursor solution: gd (NO) 3 ) 3 ·6H 2 Dissolving O in diethylene glycol or water, stirring to obtain clear solution, heating under protective atmosphere while stirring, and adding NH 4 Keeping the temperature of diethylene glycol or aqueous solution of F to obtain suspension;
precursor treatment: cooling the suspension to room temperature, centrifuging, washing and collecting precipitate, and drying the precipitate to obtain GdF 3 And (3) powder.
Further, the Gd (NO) 3 ) 3 ·6H 2 O and said NH 4 The molar ratio of F is 1; dissolving 1mmol of Gd (NO) 3 ) 3 ·6H 2 O is 10-15 ml of the diethylene glycol or the diethylene glycolAnd (3) water.
Further, the protective atmosphere is any one or more of argon, helium and nitrogen.
Further, the heating mode is oil bath heating, and the heating is carried out to 50-160 ℃; the heat preservation time is 1-1.5 h, the drying temperature is 50-100 ℃, and the drying time is 2-3 h.
NaBH prepared by the method of the invention 4 Based on the reversible hydrogen storage material, the hydrogen storage amount is more than 3.0wt.%, the total hydrogen absorption amount reaches 2.4wt.%, and the hydrogen release temperature is lower than 460 ℃.
Compared with the prior art, the invention has at least the following beneficial technical effects:
(1) GdF 3 With NaBH 4 Compounding, preparing the obtained NaBH 4 The reversible hydrogen storage material has lower hydrogen releasing temperature and obviously improved hydrogen absorbing and releasing reversibility.
(2) Provides a brand new NaBH 4 The liquid phase compounding process with RE fluoride has simple process, high product yield and short preparation period.
(3) Gd (NO) as starting material 3 ) 3 ·6H 2 O and NH 4 F is cheap and easy to obtain, the solvent propylamine can be recycled, and the production cost is low.
The conception, specific structure and technical effects of the present invention will be further described in conjunction with the accompanying drawings to fully understand the purpose, characteristics and effects of the present invention.
Drawings
FIG. 1 is NaBH prepared in accordance with a preferred embodiment of the present invention 4 DSC and TG curves of the reversible hydrogen storage material powder;
FIG. 2 is a GdF prepared according to a preferred embodiment of the present invention 3 Powder and commercial GdF 3 An XRD pattern of (a);
FIG. 3 is a GdF prepared according to a preferred embodiment of the present invention 3 TEM pictures of the powder;
FIG. 4 is NaBH prepared in accordance with a preferred embodiment of the present invention 4 TPD curve of the reversible hydrogen storage material powder;
FIG. 5 is NaBH prepared in accordance with a preferred embodiment of the present invention 4 The hydrogen absorption kinetic curve of the reversible hydrogen storage material at the initial hydrogen pressure of 400 ℃ and 3.2 MPa.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be made clear and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
In the drawings, elements that are structurally identical are represented by like reference numerals, and elements that are structurally or functionally similar in each instance are represented by like reference numerals. The size and thickness of each component shown in the drawings are arbitrarily illustrated, and the present invention is not limited to the size and thickness of each component. The thickness of the components has been exaggerated in some places in the drawings where appropriate for clarity of illustration.
The invention provides a method for preparing NaBH by liquid phase precipitation 4 The method for preparing the reversible hydrogen storage material specifically comprises the following steps:
preparation of NaBH 4 Solution: reacting NaBH 4 Dissolving in isopropylamine, and stirring to form a transparent solution;
mixed fluoride: adding GdF to the clear solution 3 Nano particles are stirred continuously;
drying and separating out: drying under vacuum to obtain the nano composite hydrogen storage material.
In order to obtain pure GdF with good performance 3 Nanoparticles, the present invention can self-prepare GdF by the following method 3 Nano-particles:
preparing a precursor solution: gd (NO) 3 ) 3 ·6H 2 Dissolving O in diethylene glycol or water, stirring to obtain clear solution, heating under protective atmosphere while stirring, and adding NH 4 Keeping the temperature of the diglycol or the water solution of F to obtain a suspension;
precursor treatment: cooling the suspension to room temperature, centrifuging, cleaning and collecting precipitate, and drying the precipitate to obtain GdF 3 And (3) powder.
In a preferred embodiment of the invention, naBH 4 The preparation steps of the reversible hydrogen storage material are as follows:
(1) Preparing a fluoride precursor solution: 4mmol of Gd (NO) 3 ) 3 ·6H 2 O (1.804 g) was mixed with 50ml of water in a 100ml round bottom flask and stirred to a clear solution, heated using a silicon oil bath, vigorously stirred under Ar atmosphere and heated to 120 ℃. When the temperature reached 120 ℃, the round-bottom flask was charged with a solution containing 12mmol of NH 4 F (0.444 g) in water, and the temperature is kept for 1h to obtain GdF 3 A suspension;
(2) Treating the precursor solution: gdF 3 Cooling the suspension to room temperature, centrifuging, cleaning, collecting precipitate, and oven-drying the precipitate at 60 deg.C for 3 hr to obtain GdF 3 A powder;
(3) Preparation of NaBH 4 Solution: 0.3476g of NaBH 4 Dissolving in 10ml of isopropylamine, and stirring for 30min to form a transparent solution;
(4) Mixed fluoride: adding GdF obtained in step 2 3 0.6524g of powder, and stirring for 30min to allow NaBH 4 And GdF 3 Powder reaction to obtain 3NaBH 4 -GdF 3 Compounding the solution;
(5) Drying and separating out: drying the 3NaBH at low temperature under the vacuum-pumping condition 4 -GdF 3 Compounding the solution for 3h to obtain dried 3NaBH 4 -GdF 3 I.e. NaBH 4 Based on reversible hydrogen storage materials.
The products of the invention were further tested as follows.
Firstly, gdF prepared by the invention 3 The purity of the nanoparticles is superior to that of the commercially available GdF 3 And (3) nanoparticles. As shown in FIG. 2, the GdF obtained in the preferred embodiment 3 Powder, taking part of the sample and GdF purchased commercially 3 XRD detection is carried out together. With GdF purchased commercially 3 In contrast, the GdF obtained in the preferred embodiment 3 The purity of the powder is higher and the particle size is smaller. As shown in FIG. 3, the GdF obtained in the preferred embodiment 3 TEM analysis of the powder revealed that the GdF produced 3 The powder particles are spindle-shaped, have a length of 200-500 nm and a width of 50-100 nm.
Secondly, for the NaBH prepared by the invention 4 And (3) carrying out performance test on the reversible hydrogen storage material. A temperature programmed dehydrogenation Test (TPD) was performed using a Differential Scanning Calorimeter (DSC) and a Sievert-type PCT setup to comprehensively characterize the NaBH obtained in the preferred embodiment 4 Based on the hydrogen evolution behavior of the reversible hydrogen storage material. As shown in FIG. 1, the DSC curve has a peak hydrogen release temperature of 454 deg.C, which indicates that the hydrogen release temperature is higher than that of pure NaBH 4 The hydrogen release temperature is greatly reduced (the hydrogen release temperature is higher than 500 ℃); the TG curve shows a weight loss of 3.65wt.% after the end of the temperature rise, approaching 3NaBH 4 -GdF 3 The theoretical hydrogen storage capacity of the hydrogen storage material, 3.66wt.%, indicates that NaBH was obtained in the preferred embodiment 4 The base reversible hydrogen storage material has been completely dehydrogenated.
TPD can provide the change of hydrogen discharge behavior of the material in a large temperature range with the temperature, as shown in FIG. 4, it can be seen that NaBH is obtained in the preferred embodiment 4 The hydrogen evolution process of the reversible hydrogen storage material is one-step hydrogen evolution, which corresponds to the DSC curve in fig. 1 showing only one endothermic peak, with a total hydrogen evolution of 3.17wt.%, reaching 87% of theoretical.
The NaBH obtained in the preferred embodiment was tested using a Sievert-type PCT apparatus at 400 deg.C and an initial hydrogen pressure of 3.2MPa 4 The hydrogen absorption kinetic curve of the reversible hydrogen storage material is based on, so as to evaluate the hydrogen absorption behavior and reversibility of the material. Before testing, the samples were first placed under dynamic vacuum conditions at 450 ℃ for 2h to ensure complete dehydrogenation. As shown in fig. 5, the sample after dehydrogenation showed better hydrogen uptake kinetics, with 1.5wt.% hydrogen uptake in 1h, 2.0wt.% hydrogen uptake in 2h, and 2.4wt.% total hydrogen uptake after the end of the test. With pure NaBH 4 Compared with the method that the hydrogen absorption reversibility is completely absent, the NaBH obtained in the preferred embodiment 4 The hydrogen absorption reversibility of the reversible hydrogen storage material is obviously improved.
In the preferred embodiment, 3NaBH 4 -GdF 3 In a composite solution of (3) NaBH 4 -GdF 3 The content is 1g, and NaBH is finally produced 4 The reversible hydrogen storage material is more than 0.96g, the yield is more than 96 percent, the preparation time is 9.5h (including 2.5h for preparing fluoride precursor solution, the precursor solutionAnd (4) treating for 3h, compounding liquid phase for 1h, and drying and precipitating for 3 h).
The ball milling method only has 85 percent of yield due to the adhesion of the inner wall of the tank body, and takes 16 hours. Compared with the prior art, the invention has the advantages of obviously higher product yield and shorter preparation period.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (7)
1. Preparation of NaBH by liquid phase precipitation 4 A method of producing a reversible hydrogen storage material, comprising the steps of:
preparation of NaBH 4 Solution: reacting NaBH 4 Dissolving in isopropylamine, and stirring to obtain transparent solution of NaBH 4 The mass-to-volume ratio of the isopropyl amine to the isopropyl amine is 34.76g/L;
mixed fluoride: adding GdF to the clear solution 3 Nano particles and continuing stirring, the NaBH 4 And said GdF 3 The mass ratio of the nano particles is 1.5-2, and the stirring time is 30min;
drying and separating out: drying under vacuum to obtain NaBH 4 Based on reversible hydrogen storage materials.
2. The liquid phase precipitation process of NaBH according to claim 1 4 The method for preparing the reversible hydrogen storage material is characterized in that in the drying and precipitation step, the drying time is 3 hours.
3. The liquid phase precipitation process of NaBH according to claim 1 4 A method of based on a reversible hydrogen storage material, characterized in that said GdF 3 The method for producing nanoparticles comprises the steps of:
preparing a precursor solution: gd (NO) 3 ) 3 ·6H 2 Dissolving O in diethylene glycol or water, stirring to obtain clear solution, heating under protective atmosphere while stirring, and adding NH 4 Keeping the temperature of diethylene glycol or aqueous solution of F to obtain suspension;
precursor treatment: cooling the suspension to room temperature, centrifuging, cleaning and collecting precipitate, and drying the precipitate to obtain GdF 3 And (3) powder.
4. Liquid phase precipitation preparation of NaBH according to claim 3 4 Method for the reversible hydrogen storage material, characterized in that said Gd (NO) 3 ) 3 ·6H 2 O and said NH 4 The molar ratio of F is 1; dissolving 1mmol of Gd (NO) 3 ) 3 ·6H 2 10 to 15ml of the diethylene glycol or the water is used for O.
5. The liquid phase precipitation method of claim 3 for the production of NaBH 4 The method of reversible hydrogen storage material is characterized in that the protective atmosphere is one or more of argon, helium and nitrogen.
6. The liquid phase precipitation method of claim 3 for the production of NaBH 4 The method of reversible hydrogen storage material is characterized in that the heating mode is oil bath heating, and the heating is carried out to 50-160 ℃; the heat preservation time is 1 to 1.5 hours, the drying temperature is 50 to 100 ℃, and the drying time is 2 to 3 hours.
7. NaBH prepared by the method of any of claims 1-6 4 Based on reversible hydrogen storage materials.
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| CN101269317B (en) * | 2007-03-23 | 2011-06-08 | 中国科学院大连化学物理研究所 | Load type stephanoporate metal organic compound hydrogen storing material |
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