阅读说明：本技术 一种新型过渡金属铝氢化物及其制备方法 (Novel transition metal alanate and preparation method thereof ) 是由 曹志杰 李丽江 马晓波 于 2020-07-06 设计创作，主要内容包括：本发明公开了一种新型过渡金属铝氢化物及其制备方法,属于固态储氢材料技术领域。该过渡金属铝氢化物是氢化铝镱,其合成过程是将氯化镱和氢化铝锂按照一定摩尔比混合后在氢气气氛下进行充分球磨。本发明制备的过渡金属铝氢化物具有储氢量高、放氢温度低、放氢速率快、制备工艺简单、成本低廉,适合于大规模生产。(The invention discloses a novel transition metal alanate and a preparation method thereof, belonging to the technical field of solid hydrogen storage materials. The transition metal aluminum hydride is aluminum ytterbium hydride, and the synthesis process is to mix ytterbium chloride and lithium aluminum hydride according to a certain molar ratio and then perform full ball milling in a hydrogen atmosphere. The transition metal alanate prepared by the invention has the advantages of high hydrogen storage capacity, low hydrogen release temperature, high hydrogen release rate, simple preparation process and low cost, and is suitable for large-scale production.)

1. A transition metal alanate is characterized by that its chemical formula is Yb (AlH)₄)₃。

2. A method for producing a novel transition metal alanate using the novel transition metal alanate of claim 1, comprising the steps of:

(a) in a glove box protected by argon atmosphere, ytterbium chloride (YbCl)₃) And lithium aluminum hydride (LiAlH)₄) Mixing the materials according to a molar ratio of 1:3, and then putting the mixture and stainless steel balls into a ball milling tank;

(b) pumping the gas in the ball milling tank by using a vacuum pump, filling hydrogen, repeating the process for three times, and filling a certain amount of hydrogen;

(c) placing the charged ball milling tank into a planetary ball mill, setting the planetary ball mill to stop for 10min after 30min of ball milling, and obtaining Yb (AlH) after ball milling for a certain time₄)₃。

3. The method for preparing a novel transition metal alanate according to claim 2, wherein the ball-to-feed ratio in step (a) is preferably 30-60: 1.

4. The method as claimed in claim 2, wherein the hydrogen pressure in step (b) is preferably 5 to 10 MPa.

5. The method for preparing a novel transition metal alanate according to claim 2, wherein the ball milling speed in the step (c) is 200-500 rpm, and the ball milling time is preferably 2-8 h.

Technical Field

The invention relates to the technical field of solid hydrogen storage materials, in particular to a novel transition metal alanate and a preparation method thereof.

Background

The hydrogen storage technology is a key link for large-scale application of hydrogen energy. At present, the storage technology of hydrogen mainly comprises three major categories of high-pressure gaseous hydrogen storage, liquid hydrogen storage and solid hydrogen storage. The high-pressure gaseous hydrogen storage has higher mass hydrogen storage density, but has high cost and great potential safety hazard, and is not suitable for long-distance transportation; the mass and the volume density of low-temperature liquid hydrogen storage are very high, but the energy consumption in the liquid hydrogen refrigeration process is high, and the liquid hydrogen is extremely easy to volatilize and is not beneficial to long-term use; the solid hydrogen storage material has high volume hydrogen storage density and good safety, is one of the most promising hydrogen storage modes at present, but the problems of poor hydrogen storage kinetic performance, harsh reversible conditions and the like of the high-capacity hydrogen storage material are still not solved; none of these three hydrogen storage modes can meet the requirements of vehicle applications. In 2003, Takeichi et al propose a composite high-pressure metal hydride hydrogen storage system [ Takeichin, Senoh H, YokotaT, Tsurta H, Hamada K, Takeshita HT, Tanak H., Kiyobayashi T., Takano T., Kuriyama N., Int.J. hydrogen Energy,2003,28(10),1121-1129] formed by combining high-pressure gaseous hydrogen storage and metal hydride, wherein the composite hydrogen storage system not only utilizes the characteristics of solid hydrogen storage materials to improve the volume hydrogen storage density of the system, but also can exert the advantages of high mass density of gaseous hydrogen storage and high hydrogen charging and discharging speed, so that the composite hydrogen storage system is a method with high application value and provides an effective solution for a vehicle-mounted hydrogen storage technology.

In order to develop hydrogen storage materials meeting the use requirements of vehicle-mounted composite hydrogen storage systems, researchers have conducted modification research on various hydrogen storage materials in recent years, and the research mainly comprises TiCr₂Group and ZrFe₂Radical AB₂Type hydrogen storage alloys and V-based BCC type hydrogen storage alloys, however, these alloys tend to have low reversible hydrogen storage at a specific hydrogen pressure (<2 wt%), it is difficult to achieve the target of 3-4 wt% of hydrogen storage material for the vehicle-mounted composite hydrogen storage system. The complex alanate is a kind of light high-capacity hydrogen storage material (>5 wt%), and most transition metal alanates have low hydrogen evolution temperatures, and decomposition has occurred at normal or even low temperatures [ kostm.e., Golovanova a.l., russ.chem.bull.,1975,24(5),905-907]And the requirement of low-temperature hydrogen supply of the vehicle-mounted composite hydrogen storage system can be met. Therefore, the development of transition metal alanates helps to drive the on-board application of the hybrid hydrogen storage system.

Disclosure of Invention

The invention aims to provide a novel transition metal alanate and a preparation method of the metal alanate.

The invention is realized by the following technical scheme:

a transition metal alanate is characterized by that its chemical formula is Yb (AlH)₄)₃。

Further, a method for preparing a novel transition metal alanate, which uses a novel transition metal alanate, comprises the following steps:

(a) in a glove box protected by argon atmosphere, YbCl is added₃And LiAlH₄Mixing the materials according to a molar ratio of 1:3, and then putting the mixture and stainless steel balls into a ball milling tank;

(b) pumping the gas in the ball milling tank by using a vacuum pump, filling hydrogen, repeating the process for three times, and filling a certain amount of hydrogen;

(c) placing the charged ball milling tank into a planetary ball mill, setting the planetary ball mill to stop for 10min after 30min of ball milling, and obtaining Yb (AlH) after ball milling for a certain time₄)₃。

Further, the ball-to-feed ratio in the step (a) is preferably 30-60: 1.

Further, in the preparation method of the novel transition metal alanate, the hydrogen pressure in the step (b) is preferably 5-10 MPa.

Further, the preparation method of the novel transition metal alanate comprises the step (c) of ball milling at the rotating speed of 200-500 rpm for 2-8 h.

Novel transition metal alanate Yb (AlH)₄)₃The preparation steps are as follows:

(a) in a glove box protected by argon atmosphere, YbCl is added₃And LiAlH₄Mixing the materials according to a molar ratio of 1:3, and then putting the mixture and stainless steel balls into a ball milling tank, wherein the ball-material ratio is 30-60: 1;

(b) pumping the gas in the ball milling tank by using a vacuum pump, filling hydrogen, repeating the process for three times, and filling the hydrogen with the pressure of 5-10 MPa;

(c) putting the ball milling tank after charging hydrogen into a planetary ball mill, wherein the process is that the ball milling is stopped for 10min after each ball milling for 30min, and Yb is obtained after ball milling for 2-8 h(AlH₄)₃。

The prepared Yb (AlH) was placed in a glove box protected with argon atmosphere₄)₃The amorphous transition metal alanate Yb (AlH) prepared by the method is packaged in a glass capillary tube with the diameter of 0.5mm for XRD detection, and the amorphous transition metal alanate Yb (AlH) is proved to be obtained by the preparation method₄)₃。

In summary, the following beneficial effects of the invention are:

1. the invention relates to a novel transition metal alanate and a preparation method thereof, Yb (AlH)₄)₃Has the characteristics of high hydrogen storage capacity, low hydrogen release temperature, high hydrogen release rate and the like.

2. The invention relates to a novel transition metal alanate and a preparation method thereof, which can prevent metastable transition metal alanate Yb (AlH) by ball milling in hydrogen atmosphere₄)₃Decomposition occurs during the ball milling process.

3. The novel transition metal alanate and the preparation method thereof have the advantages of simple and convenient operation, low cost, energy conservation and controllability, and are suitable for large-scale production.

Drawings

The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention. In the drawings:

FIG. 1 shows Yb (AlH) produced in example 3₄)₃XRD pattern of (a).

FIG. 2 shows Yb (AlH) produced in example 7₄)₃Infrared spectrum of (1).

FIG. 3 shows Yb (AlH) produced in example 3₄)₃DSC-MS spectrum of (1).

FIG. 4 shows Yb (AlH) produced in example 7₄)₃TPD hydrogen discharge curve of (a).

FIG. 5 shows Yb (AlH) produced in example 10₄)₃Hydrogen evolution curves at different temperatures.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples and accompanying drawings, and the exemplary embodiments and descriptions thereof are only used for explaining the present invention and are not meant to limit the present invention.