WO2023087949A1

WO2023087949A1 - Hydrogen compression material, preparation method therefor, and use thereof

Info

Publication number: WO2023087949A1
Application number: PCT/CN2022/122730
Authority: WO
Inventors: 欧阳柳章; 彭琢雅; 王辉; 曾美琴; 朱敏
Original assignee: 华南理工大学
Priority date: 2021-11-18
Filing date: 2022-09-29
Publication date: 2023-05-25
Also published as: CN114214570B; CN114214570A

Abstract

Disclosed in the present invention is a hydrogen compression material, which has a structural general formula of Zr_1-xTi_xFe_1.7Cr_0.2V _0.1, wherein x = 0.1-0.4. Further disclosed in the present invention is a preparation method for the hydrogen compression material. The method comprises the following steps: weighing zirconium, titanium, iron, chromium and vanadium metals according to the structural general formula, mixing and then placing same in a crucible, cleaning same with an inert gas, vacuumizing same, introducing the inert gas, and smelting same under arc conditions to obtain the hydrogen compression material. Further disclosed in the present invention is the use of the hydrogen compression material as a self-pressurization hydrogen storage material for a mechanical hydrogen compressor of a hydrogen-fueling station. By using waste heat generated by the mechanical hydrogen compressor, the hydrogen compression material absorbs 4-6 MPa hydrogen at room temperature and discharges hydrogen with a pressure of 6 MPa or more at 60°C. The hydrogen compression material of the present invention has the advantages of a large platform width and a large effective hydrogen compression amount within the working temperature range.

Description

A kind of hydrogen compression material and its preparation method and application

technical field

The invention relates to a hydrogen storage material, in particular to a hydrogen compression material and its preparation method and application.

Background technique

Metal hydride hydrogen compressors use hydrogen storage alloys (hydrogen compression materials) to boost pressure at different temperatures. The alloy absorbs low-pressure hydrogen at low temperature and releases high-pressure hydrogen at high temperature. The whole process follows the Van't Hoff equation

In addition, the temperature rise in the pressurization process of the system can be provided by the heat generated by the friction drive of the mechanical hydrogen compressor, which can effectively utilize waste heat and achieve the purpose of energy saving and environmental protection.

ZrFe ₂ is one of the common high-pressure hydrogen storage alloys. It has a Laves phase structure, a dehydrogenation pressure of up to 33 MPa at room temperature, and a small α-hydrogen solid solution zone. It is a potential material used in the field of hydrogen compression. However, the slope and hysteresis of the ZrFe ₂ platform are relatively large, and it often needs to be modified by alloying, heat treatment and other methods to realize its application value.

Hydrogen fuel cell vehicles have gradually entered the public's field of vision due to their advantages of no pollution and zero emissions, and have aroused people's strong attention, which has also accelerated the process of building hydrogen refueling stations in my country. At this stage, most of the hydrogen refueling stations that have been built use mechanical hydrogen compressors, which can pressurize the hydrogen transported by long tube trailers through mechanical transmission and release a large amount of heat at the same time. However, limited by the compression ratio, the mechanical hydrogen compressor can only pressurize the hydrogen above 6MPa at the minimum, so the gas below 6MPa in the long tube trailer can only be transported back, which will cause huge waste in storage and transportation. If the remaining hydrogen in the above steps can be pressurized again to reach the minimum hydrogen filling pressure of the mechanical hydrogen compressor, the storage and transportation cost of hydrogen will be greatly reduced.

Contents of the invention

In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the object of the present invention is to provide a hydrogen compression material, which has the advantages of large platform width and large effective hydrogen compression capacity within the working temperature range.

Another object of the present invention is to provide a method for preparing the above-mentioned hydrogen compression material.

Another object of the present invention is to provide the application of the above-mentioned hydrogen compression material.

The object of the present invention is achieved through the following technical solutions:

A hydrogen compression material, the general structural formula is:

Zr _1-x Ti _x Fe _1.7 Cr _0.2 V _0.1 , where x=0.1-0.4.

Preferably, in the general structural formula of the hydrogen compression material, x=0.25-0.35, it can absorb hydrogen at 4-6 MPa at room temperature, and release hydrogen at a pressure above 6 MPa at 60°C.

Preferably, in the general structural formula of the hydrogen compression material, x=0.15-0.25, and has a large platform width.

The preparation method of the hydrogen compression material comprises the following steps:

(1) Weigh metal zirconium, titanium, iron, chromium and vanadium according to the general structural formula, and place them in the crucible of the vacuum arc melting furnace after mixing;

(2) Vacuumize after cleaning with inert gas, fill in inert gas, and melt under arc conditions to obtain hydrogen compressed material.

Preferably, the inert gas is argon.

Preferably, the evacuation specifically includes: evacuating by a vacuum pump and a molecular pump to a degree of vacuum lower than 3×10 ^-3 Pa.

Preferably, the inert gas filling is specifically:

Fill with inert gas of 0.05-0.07MPa.

Preferably, the smelting is carried out under arc conditions, specifically:

Melting is carried out under arc conditions above 1600°C.

The application of the hydrogen compression material is as a self-pressurized hydrogen storage material for a mechanical hydrogen compressor in a hydrogen refueling station.

Specifically, the hydrogen compression material utilizes waste heat generated by a mechanical hydrogen compressor to absorb hydrogen at 4-6 MPa at room temperature, and release hydrogen at a pressure above 6 MPa at 60°C.

The present invention reduces the ratio of the alpha hydrogen solid solution region and the beta hydride phase region in the PCI curve by adjusting the ratio of the elements on the A side and the elements on the B side, especially the substitution amount of Ti on the A side for Zr, and increases the absorption and release. The width of the hydrogen platform increases the effective hydrogen compression capacity of the alloy, realizes the regulation of the hydrogen storage thermodynamic properties of the alloy, and obtains a high-performance hydrogen compression material.

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) The hydrogen compression material of the present invention adopts the smaller ZrFe ₂ base alloy in the α hydrogen solid solution zone as the hydrogen compression material, and its A side is partially replaced by Ti atoms, which improves the plateau pressure value of the alloy matrix phase and increases The width of the pressure platform reduces the stability of its hydride; the B side is partially replaced by V and Cr atoms, which reduces the platform slope and hysteresis of the alloy matrix phase.

(2) The hydrogen compression material of Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 of the present invention can absorb hydrogen gas of 4-6 MPa at room temperature, and release hydrogen gas of a pressure above 6 MPa at 60 ° C, which can be used for existing hydrogenation The station mechanical hydrogen compressor effectively utilizes the waste heat generated by the friction transmission process of the mechanical hydrogen compressor to achieve the purpose of energy saving and environmental protection.

(3) The hydrogen compression material of the present invention replaces part of Zr with Ti atoms with smaller atomic radius. Since the price of metal zirconium is about 2.5 times that of metal titanium, the replacement of part of Ti to Zr is beneficial to reduce the overall hydrogen storage alloy. cost.

Description of drawings

Fig. 1 is an XRD spectrum of a hydrogen compression material Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 according to an embodiment of the present invention.

Fig. 2 is a backscattered image and an energy spectrum surface scan image of the hydrogen compression material Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 according to an embodiment of the present invention. Among them, (a) is the backscattering image; (b) to (f) are the energy spectrum surface scan images of Zr, Ti, Fe, Cr, V, respectively.

Fig. 3 is the pressure-composition isotherm (PCI) of the hydrogen compression material Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 according to the embodiment of the present invention.

Fig. 4(a) is the hydrogen absorption Van't Hoff fitting curve of the hydrogen compression material Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 according to the embodiment of the present invention.

Fig. 4(b) is the hydrogen desorption Van't Hoff fitting curve of the hydrogen compression material Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 according to the embodiment of the present invention.

Fig. 5 is the measured hydrogen compression performance of the hydrogen compression material Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 at its working temperature according to the embodiment of the present invention.

Figure 6(a) shows the pressure-composition isotherm (PCI) of ZrFe _1.7 Cr _0.2 V _0.1 .

Figure 6(b) shows the pressure-composition isotherm (PCI) of Zr _0.9 Ti _0.1 Fe _1.7 Cr _0.2 V _0.1 .

Figure 6(c) shows the pressure-composition isotherm (PCI) of Zr _0.8 Ti _0.2 Fe _1.7 Cr _0.2 V _0.1 .

Figure 6(d) shows the pressure-composition isotherm (PCI) of Zr _0.6 Ti _0.4 Fe _1.7 Cr _0.2 V _0.1 .

Detailed ways

The present invention will be described in further detail below in conjunction with the examples, but the embodiments of the present invention are not limited thereto.

Example 1

(1): Put 3.3865gZr, 0.7681gTi, 0.5538g Cr, 5.0342g Fe and 0.2714g V with a purity of more than 99.9% in the crucible of the electric arc melting furnace, cover the furnace cover, and vacuum the furnace chamber until the vacuum degree is 3× 10 ^-3 Pa, filled with argon to a pressure of 0.06MPa, and melted in an arc above 1600°C. After that, the residual oxygen in the furnace chamber is absorbed by melting the pre-placed pure zirconium blocks in the furnace chamber by electric arc. In order to improve the uniformity, each sample was turned over and remelted 5 times, each melting time was about 30s, and 9.9950g ingot was obtained after cooling by a water-cooled copper mold for 15min. The theoretical composition of the alloy ingot is Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 .

(2) Grinding the alloy ingot in step (1) with a grinder to remove surface scale. Then the alloy was crushed into a powder state in a glove box, and screened with a 100-mesh sieve to obtain a Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 hydrogen compression material.

The ingot in step (1) is broken in a glove box, then passed through a 400-mesh sieve, and the obtained powder is subjected to XRD testing; the results are shown in Figure 1: the alloy has a dual-phase structure, and both phases are C14Laves phases. The crystal structures are the same but the lattice constants are different.

The bulk ingot was mounted with epoxy resin and analyzed by scanning electron microscope. The results are shown in Figure 2: there are two-phase contrast in the alloy. Combined with energy spectrum, it can be observed that the matrix phase is Zr-rich phase, and the second The phase is Ti-rich phase, which is consistent with the XRD characterization results.

Carry out pressure-composition isotherm (PCI) test to the hydrogen storage material powder in step (2), the test instrument is the Sieverts type hydrogen storage performance tester that American Advance Material Corporation produces, test temperature is 243K-333K, test pressure 0.01-10MPa. The results are shown in Figure 3: the α hydrogen solid solution region of the alloy accounts for a small proportion in the PCI curve, the β hydride phase region accounts for a moderate proportion, the slope and hysteresis of the pressure plateau are small, and the hydrogen release plateau pressure at 50°C is 5.08 MPa, the maximum hydrogen storage capacity (10MPa) at 0°C is 1.47wt%.

The PCI performance of the Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 hydrogen compression material prepared in this example was fitted by Van't Hoff, and the results are shown in Figure 4(a) to Figure 4(b): The hydrogen absorption plateau pressure is 3.72MPa, and the hydrogen release plateau pressure at 60°C is 6.61MPa.

The hydrogen compression performance of the Zr _0.7 Ti _0.3 Fe _1.7 Cr _0.2 V _0.1 hydrogen compression material prepared in this example was actually measured at the working temperature, and the results are shown in Figure 5: the alloy can compress hydrogen in the temperature range of 25-60 °C The pressurization is above 6MPa, and it has an effective hydrogen compression capacity of 0.85wt.%.

Embodiment 2-5

The alloy compositions and hydrogen storage thermodynamic properties of Examples 2-5 are shown in Table 1, and the preparation process is the same as that of Example 1.

Table 1 Hydrogen storage thermodynamic properties of Zr _1-x Ti _x Fe _1.7 Cr _0.2 V _0.1 (x=0,0.1,0.2,0.4) alloys in Examples 2-5

*The plateau pressure values of the alloys at 298K and 333K are extrapolated from the van't Hoff equation.

Figure 6(a), Figure 6(b), Figure 6(c), Figure 6(d) are the Zr _1-x Ti _x Fe _1.7 Cr _0.2 V _0.1 (x=0,0.1,0.2,0.4) alloys respectively From the PCI curve, it can be observed that with the increase of the substitution amount of Ti to Zr, the hydrogen desorption plateau pressure of the alloy at the same temperature (273K) is significantly increased, and the hydrogen storage capacity is significantly reduced. In addition, the proportion of the α hydrogen solid solution region in the PCI curve decreases, and the proportion of the β hydride phase region increases. It can be seen that the appropriate Ti doping amount in Zr _1-x Ti _x Fe _1.7 Cr _0.2 V _0.1 can increase the width of the pressure plateau, reduce the stability of its hydride, and increase the effective hydrogen compression in the actual working temperature range. As a preferred solution, Zr _0.8 Ti _0.2 Fe _1.7 Cr _0.2 V _0.1 alloy (Fig. 6(c)) has the largest platform width.

It can be seen that the embodiment of the present invention improves the ratio of reducing the α hydrogen solid solution region and the β hydride phase region in the PCI curve by adjusting the ratio of the A-side element and the B-side element, especially the replacement amount of Ti on the A-side for Zr. The ratio increases the width of the hydrogen absorption and desorption platform, increases the effective hydrogen compression capacity of the alloy, realizes the regulation of the hydrogen storage thermodynamic properties of the alloy, and obtains a high-performance hydrogen compression material.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the embodiment, and any other changes, modifications, substitutions and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Claims

A hydrogen compression material is characterized in that the general structural formula is:

Zr 1-x Ti x Fe 1.7 Cr 0.2 V 0.1 , where x=0.1-0.4.
The hydrogen compression material according to claim 1, wherein x=0.25-0.35.
The hydrogen compression material according to claim 1, characterized in that x=0.15-0.25.
The preparation method of the hydrogen compression material according to any one of claims 1 to 3, characterized in that it comprises the following steps:

(1) Weigh metal zirconium, titanium, iron, chromium and vanadium according to the general structural formula, and place them in the crucible of the vacuum arc melting furnace after mixing;

(2) Vacuumize after cleaning with inert gas, fill in inert gas, and melt under arc conditions to obtain hydrogen compressed material.
The method for preparing a hydrogen compression material according to claim 4, characterized in that the inert gas is argon.
The method for preparing a hydrogen-compressed material according to claim 4, wherein the vacuuming is specifically: vacuuming by a vacuum pump and a molecular pump until the vacuum degree is lower than 3×10 -3 Pa.
The method for preparing a hydrogen compression material according to claim 4, characterized in that the charging of an inert gas is specifically: charging an inert gas of 0.05-0.07 MPa.
The preparation method of hydrogen compressed material according to claim 4, characterized in that, the smelting is carried out under arc conditions, specifically:

Melting is carried out under arc conditions above 1600°C.
The application of the hydrogen compression material according to claim 2 is characterized in that it is used as a self-pressurized hydrogen storage material for a mechanical hydrogen compressor in a hydrogen refueling station.
The application of the hydrogen compression material according to claim 9, characterized in that the hydrogen compression material absorbs 4-6 MPa of hydrogen at room temperature and releases a pressure above 6 MPa at 60°C by using waste heat generated by a mechanical hydrogen compressor of hydrogen.