CN112226663B - ZrCo-based hydrogen isotope storage alloy with high cycle capacity and its preparation and application - Google Patents
ZrCo-based hydrogen isotope storage alloy with high cycle capacity and its preparation and application Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 120
- 239000001257 hydrogen Substances 0.000 title claims abstract description 120
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000000956 alloy Substances 0.000 title claims abstract description 104
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 102
- 238000003860 storage Methods 0.000 title claims abstract description 70
- 229910008008 ZrCo Inorganic materials 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 25
- 238000002844 melting Methods 0.000 claims abstract description 23
- 230000008018 melting Effects 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000006698 induction Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 6
- 238000005339 levitation Methods 0.000 claims abstract 2
- 229910000734 martensite Inorganic materials 0.000 claims description 20
- 229910008340 ZrNi Inorganic materials 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 5
- 229910001566 austenite Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000009466 transformation Effects 0.000 claims description 5
- 229910052722 tritium Inorganic materials 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 3
- 241000720974 Protium Species 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 11
- 239000012300 argon atmosphere Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 description 14
- 238000003795 desorption Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007323 disproportionation reaction Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910000568 zirconium hydride Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000012856 weighed raw material Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
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Abstract
本发明公开了一种高循环容量ZrCo基氢同位素贮存合金及其制备和在氢同位素的贮存、供给、回收中的应用。所述高循环容量ZrCo基氢同位素贮存合金的化学通式为Zr1‑xNbxCo1‑yNiy，其中，0<x≤0.5，0<y≤0.5，其制备方法包括步骤：(1)按所述化学通式中的比例混合Zr、Nb、Co、Ni单质原料，然后置入磁悬浮感应熔炼炉；(2)在氩气气氛保护下进行熔炼‑冷却凝固，制得所述高循环容量ZrCo基氢同位素贮存合金。本发明方法步骤简单，安全性高，所制得的氢同位素贮存合金在循环过程中无需经历真空操作，在复杂氢同位素场景下仍适用，对于促进ZrCo基合金在氢同位素储存领域的应用和推广具有长远的意义。
The invention discloses a ZrCo-based hydrogen isotope storage alloy with high circulation capacity and its preparation and application in the storage, supply and recovery of hydrogen isotopes. The general chemical formula of the high cycle capacity ZrCo-based hydrogen isotope storage alloy is Zr 1‑x Nb x Co 1‑y Ni y , wherein 0<x≤0.5, 0<y≤0.5, and its preparation method comprises the steps: ( 1) mixing Zr, Nb, Co, Ni elemental raw materials according to the ratio in the general chemical formula, then inserting into a magnetic levitation induction melting furnace; (2) smelting-cooling and solidifying under the protection of an argon atmosphere to obtain the high Cycling Capacity ZrCo-Based Hydrogen Isotope Storage Alloys. The method of the invention has simple steps and high safety, the prepared hydrogen isotope storage alloy does not need to undergo vacuum operation during the cycle process, and is still applicable in complex hydrogen isotope scenarios, which is useful for promoting the application and popularization of ZrCo-based alloys in the field of hydrogen isotope storage. have long-term meaning.
Description
Technical Field
The invention relates to the technical field of hydrogen isotope storage and supply, in particular to a ZrCo-based hydrogen isotope storage alloy with high cycle capacity and preparation and application thereof.
Background
The exploitation and use of traditional fossil energy cause two problems of energy crisis and environmental pollution which are difficult to solve, so the development of clean energy which is pollution-free, renewable and high in utilization rate has become a main melody in the field of energy research.
The fusion reaction of deuterium and tritium can release huge energy, and it has the characteristics of cleanness, safety and high efficiency. In view of this, International Thermonuclear Experimental reactors (ITER for short) are commonly built in countries around the world to further explore the controllable nuclear fusion technology. When a reactor is in operation, hydrogen isotope gas needs to be supplied or recovered to the reactor from the outside according to actual conditions, and considering that tritium in the gas is not only very scarce, but also has radioactivity, therefore, the realization of safe and efficient storage and supply of the hydrogen isotope gas becomes the key of large-scale development and application of the fusion energy.
There are several ways of storing hydrogen and its isotopes, and solid-state hydrogen storage technology is the most preferred way to meet the requirements of ITER applications from the standpoint of safety and efficiency. The solid hydrogen storage technology can utilize the hydrogen cycle characteristics of hydrogen absorption and hydrogen discharge of materials at low temperature and high pressure and high temperature and low pressure to realize the storage, supply and recovery of hydrogen isotope gas in the ITER operation process.
The ZrCo based alloy has low plateau pressure (10 to 10)-3Pa), high hydrogen absorption and desorption rate, no radioactivity and no spontaneous combustion, and the like, and is considered as an important candidate material for storing, supplying and recovering hydrogen isotopes by researchers.
However, the ZrCo based alloy is currently subjected to hydrogen absorption and desorption reaction (ZrCo + H)2→ZrCoH3) Disproportionation reaction (ZrCo + H) often occurs in the process2→ZrCo2+ZrH2、ZrCoH3→ZrCo2+ZrH2+H2) Gradually form ZrH which is difficult to decompose2Phase and non-hydrogen-absorbing ZrCo2Phase, with ZrH which is difficult to decompose2Phase and non-hydrogen-absorbing ZrCo2The hydrogen isotope is accumulated continuously in the circulation process, the circulation stable capacity of the ZrCo based alloy is obviously reduced, and the important functions of hydrogen isotope storage, supply and recovery are difficult to realize.
Research finds that ZrCo2And ZrH2The phase can be recovered to a ZrCo phase (a method for improving the hydrogen absorption and desorption cycle performance of a ZrCo-based hydrogen isotope storage material, the patent number is 201910995217.3) after the phase is vacuumized for 1 hour at 550 ℃. Therefore, researchers can remarkably improve the cycle stability of the ZrCo alloy by adjusting the process parameters of the ZrCo alloy in the cycle process, and obtain higher hydrogen absorption and desorption capacity (n)H/nM>2.5). However, the vacuum process regulation at the temperature of more than 400 ℃ in a tritium-involved system is difficult, high in cost and dangerous to some extent, and is not beneficial to practical engineering application.
Therefore, it is of great significance to develop the application of the ZrCo-based hydrogen isotope storage alloy with high cycle stability capacity in the hydrogen isotope field under mild operating environment.
Disclosure of Invention
Aiming at the defect that the ZrCo-based hydrogen isotope storage alloy in the prior art generally has poor circulation stability, the invention provides the ZrCo-based hydrogen isotope storage alloy with high circulation capacity.
A high-circulation-capacity ZrCo-based hydrogen isotope storage alloy with a chemical general formula of Zr1-xNbxCo1-yNiyWherein, 0<x≤0.5，0<y is less than or equal to 0.5. x and y both represent atomic ratios.
The hydrogen isotopes described in the present invention include one or more of protium, deuterium, and tritium.
Further research shows that x and y are gradually increased, when x is more than or equal to 0.2 and less than or equal to 0.5 and y is more than or equal to 0.2 and less than or equal to 0.5 in the chemical general formula, a martensite structure appears in the high-cycle-capacity ZrCo-based hydrogen isotope storage alloy, and the ZrCo-based hydrogen isotope storage alloy with the martensite structure has higher cycle capacity and better stability compared with an alloy without the martensite structure. The high-cycle-capacity ZrCo-based hydrogen isotope storage alloy with a martensite structure has a hydrogen release capacity n after 50 times of vacuum hydrogen release cycles at 20 ℃, 1bar hydrogen absorption and 380 DEG CH/nMStill less than 2.37 (n is further preferably achieved by x, y)H/nMStill not less than 2.45), the capacity retention rate is more than 98.7%. n isH/nMRepresents the ratio of the molar amount of hydrogen atoms to the molar amount of the alloy. The martensite structure is mainly a ZrNi phase.
Therefore, the high-cycle-capacity ZrCo-based hydrogen isotope storage alloy preferably has a martensite structure, wherein x is 0.2 to 0.5, and y is 0.2 to 0.5 in the chemical formula. More preferably, x is more than or equal to 0.2 and less than or equal to 0.3, and y is more than or equal to 0.2 and less than or equal to 0.3 in the chemical general formula. When the substitution amount is insufficient, a ZrNi phase with a martensite structure cannot be formed in the alloy, so that the cycle stability of the alloy cannot be effectively improved; when the substitution amount is too high, Nb is likely to precipitate6Co7Phase, thereby affecting the capacity of the alloy.
Preferably, x ═ y in the chemical formula. Partial substitution of Nb atoms for Zr decreases the cell parameters of the alloy, while partial substitution of Ni atoms for Co increases the cell parameters of the alloy. Equivalent substitution of both sides of Zr and Co is beneficial to reducing the influence of the change of unit cell parameters on the properties of the alloy plateau.
According to the invention, with the increase of the substitution amount of Nb and Ni, the main phase of the alloy is gradually transformed from a ZrCo phase with an austenite structure into a ZrNi phase with a martensite structure, wherein the ZrCo phase and the ZrNi phase are both composed of Zr, Nb, Co and Ni;
the high cycle stability capacity of the ZrCo based hydrogen isotope storage alloy comes from a ZrNi phase and a ZrCoH phase with similar martensite structure3The same structure and phase transformation between the phases.
The invention also provides a preparation method of the high-circulation-capacity ZrCo-based hydrogen isotope storage alloy, which comprises the following steps:
(1) mixing Zr, Nb, Co and Ni elementary substance raw materials according to the proportion in the chemical general formula, and then putting the mixture into a magnetic suspension induction smelting furnace;
(2) and smelting, cooling and solidifying under the protection of argon atmosphere to obtain the high-circulation-capacity ZrCo-based hydrogen isotope storage alloy.
Preferably, in the step (2), the pressure of the argon gas is 1.2-1.4 bar, so that air infiltration is prevented.
Preferably, in the step (2), the smelting temperature is 1800-2600 ℃ and the smelting time is 45-60 s. The boiling point of Ni is 2870 ℃, the melting point of Nb is 2468 ℃, the smelting temperature and time need to be properly controlled, and the smelting time is too short or the temperature is too low, so that Nb is not completely melted and the components are not uniformly mixed; too long a melting time or too high a temperature may result in element burn-out and composition deviation from design.
Preferably, the step (2) is repeated for 3-5 times of smelting-cooling solidification to prepare the high-circulation-capacity ZrCo-based hydrogen isotope storage alloy, so that the uniformity of alloy components is ensured. The alloy can be turned over in the repeated process.
Although some researches report methods for improving the cycling stability of the ZrCo-based hydrogen isotope storage alloy, no method can effectively solve the problem of the cycling capacity attenuation, and no strategy for maintaining the high cycling capacity of the ZrCo-based hydrogen isotope storage alloy in a complex and variable practical application scene is reported. The method has simple steps and high safety, the prepared hydrogen isotope storage alloy does not need to undergo vacuum operation in the circulating process, the method is still suitable for the complex hydrogen isotope scene, and the method has long-term significance for promoting the application and popularization of the ZrCo-based alloy in the field of hydrogen isotope storage.
The invention also provides application of the high-cycle-capacity ZrCo-based hydrogen isotope storage alloy in storage, supply and recovery of hydrogen isotopes. The hydrogen isotopes include one or more of protium, deuterium, tritium.
Compared with the prior art, the invention has the main advantages that:
(1) the hydrogen isotope storage alloy of the invention not only has higher initial hydrogen release capacity, but also keeps stable capacity in the circulation process, and the hydrogen release capacity after 50 times of circulation can reach nH/nMThe capacity retention ratio of 2.45 to 98.8% is particularly suitable for storage, supply, and recovery of hydrogen isotopes for ITER.
(2) The hydrogen isotope storage alloy can partially or completely generate martensite phase transformation to form a ZrNi phase with a martensite structure, and the original austenite structure (ZrCo phase) of the alloy is changed, so that the ZrNi phase is converted into the ZrCoH phase3The same structure of the phase (with similar martensite structure) absorbs and releases hydrogen, thus effectively avoiding the occurrence of disproportionation reaction.
(3) The method has simple steps and high safety, the prepared hydrogen isotope storage alloy does not need to undergo vacuum operation in the circulating process, the method is still suitable for the complex hydrogen isotope scene, and the method has milestone significance for promoting the application and popularization of the ZrCo-based alloy in the field of hydrogen isotope storage.
Drawings
FIG. 1 is an XRD pattern of a hydrogen isotope storage alloy prepared in comparative example 1 and examples 1 to 3;
FIG. 2 is a pressure-composition-temperature (P-C-T) graph of the hydrogen isotope storage alloy prepared in example 2 at 250 deg.C, 275 deg.C, and 300 deg.C, respectively;
FIG. 3 is a pressure-composition-temperature (P-C-T) graph at 250 ℃ for the hydrogen isotope storage alloys prepared in comparative example 1 and examples 1 to 3;
FIG. 4 is a hydrogen absorption/desorption Van't Hoff diagram of the hydrogen isotope storage alloy prepared in examples 1 to 2;
FIG. 5 is a graph showing changes in the cyclic capacity of hydrogen isotope storage alloys prepared in comparative example 1 and examples 1 to 3;
fig. 6 is an XRD pattern after the hydrogen isotope storage alloy in example 6 is cycled.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Comparative example 1
The chemical composition of the alloy is ZrCo, and the addition amount of Zr and Co simple substance raw materials is calculated according to the chemical formula of the hydrogen isotope storage alloy. Wherein, the purity of the used simple substance raw materials of Zr and Co reaches more than 99 percent. The raw materials are cleaned and dried and then weighed according to the calculated addition amount. Placing the weighed raw materials into a water-cooled copper crucible of a magnetic suspension induction melting furnace, evacuating and exhausting to a vacuum degree of less than 0.1Pa, and then melting under the protection of an argon atmosphere of 1.2bar, wherein the melting temperature is 1800 ℃, the melting time is 60 seconds, and in order to ensure that the components are uniform, the ZrCo hydrogen isotope storage alloy ingot is prepared by repeatedly melting for four times by turning over.
Example 1
The chemical component of the alloy is Zr0.9Nb0.1Co0.9Ni0.1The addition amounts of the Zr, Nb, Co and Ni elemental raw materials are calculated according to the chemical formula of the hydrogen isotope storage alloy. Wherein the purity of the used simple substance raw materials of Zr, Nb, Co and Ni reaches more than 99 percent. The raw materials are cleaned and dried and then weighed according to the calculated addition amount. Placing the weighed raw materials into a water-cooled copper crucible of a magnetic suspension induction melting furnace, evacuating and exhausting to a vacuum degree of less than 0.1Pa, and then melting under the protection of argon atmosphere of 1.2bar, wherein the melting temperature is 2400 ℃, the melting time is 60 seconds, and in order to ensure that the components are uniform, turning over is needed to repeatedly melt for four times to obtain Zr0.9Nb0.1Co0.9Ni0.1And (3) hydrogen isotope storage alloy ingot casting, namely the hydrogen isotope storage alloy.
Example 2
The chemical component of the alloy is Zr0.8Nb0.2Co0.8Ni0.2The addition amounts of the Zr, Nb, Co and Ni elemental raw materials are calculated according to the chemical formula of the hydrogen isotope storage alloy. Wherein the purity of the used simple substance raw materials of Zr, Nb, Co and Ni reaches more than 99 percent. The raw materials are cleaned and dried and then weighed according to the calculated addition amount. Placing the weighed sample into a water-cooled copper crucible of a magnetic suspension induction melting furnace, evacuating and exhausting to a vacuum degree of less than 0.1Pa, and then melting under the protection of argon atmosphere of 1.2bar, wherein the melting temperature is 2400 ℃, the melting time is 60 seconds, and in order to ensure that the components are uniform, the melting is repeated for four times by turning over to obtain Zr0.8Nb0.2Co0.8Ni0.2And (3) hydrogen isotope storage alloy ingot casting, namely the hydrogen isotope storage alloy.
Example 3
The chemical component of the alloy is Zr0.7Nb0.3Co0.7Ni0.3The addition amounts of the Zr, Nb, Co and Ni elemental raw materials are calculated according to the chemical formula of the hydrogen isotope storage alloy. Wherein the purity of the used simple substance raw materials of Zr, Nb, Co and Ni reaches more than 99 percent. The raw materials are cleaned and dried and then weighed according to the calculated addition amount. Placing the weighed sample into a water-cooled copper crucible of a magnetic suspension induction melting furnace, evacuating and exhausting to a vacuum degree of less than 0.1Pa, and then melting under the protection of argon atmosphere of 1.2bar, wherein the melting temperature is 2400 ℃, the melting time is 60 seconds, and in order to ensure that the components are uniform, the melting is repeated for four times by turning over to obtain Zr0.7Nb0.3Co0.7Ni0.3And (3) hydrogen isotope storage alloy ingot casting, namely the hydrogen isotope storage alloy.
Example 4
In order to compare the changes of the phase structure of the alloy of the present invention, XRD patterns of the as-cast alloys of comparative example 1 and examples 1-3 are shown in FIG. 1. It was found that the main phase of the as-cast alloy gradually changed from the ZrCo phase having the austenite structure with the increase in the substitution amount of Nb and NiThe ZrNi phase with martensite structure is gradually transformed, and the ZrCo phase and the ZrNi phase are both composed of Zr, Nb, Co and Ni. Therefore, the change of Nb and Ni content in the alloy plays a key role in the phase composition. Meanwhile, ZrCo in the alloy2The content of phase increased and in the sample with higher substitution amount (Zr)0.7Nb0.3Co0.7Ni0.3) Generation of Nb6Co7And (4) phase(s). It can be found that partial replacement of Zr and Co by Nb and Ni, respectively, can cause the alloy to have martensite phase transformation, so as to realize transformation of ZrCo phase with austenite structure in the alloy and ZrCoH3The purpose of the ZrNi phase is that the phase has the same martensite structure.
Example 5
In order to test the P-C-T curve of the alloy, the samples were first subjected to an activation and dehydrogenation operation. First, Zr in example 20.8Nb0.2Co0.8Ni0.2Cleaning and polishing the surface of the alloy cast ingot, putting the alloy cast ingot into a stainless steel container, and vacuumizing for 30min at room temperature. Then, high-purity hydrogen gas of 80bar is introduced, and a completely activated sample is obtained after a certain time of keeping. The fully activated Zr was introduced into a glove box filled with argon0.8Nb0.2Co0.8Ni0.2Putting a sample into a stainless steel reactor, heating the reactor to 600 ℃ at the heating rate of 10 ℃/min, preserving heat for 1h, cooling the reactor to room temperature along with a furnace, and vacuumizing the reactor all the time during the heating process to obtain dehydrogenated Zr0.8Nb0.2Co0.8Ni0.2And (3) sampling. After obtaining the dehydrogenated state sample, starting to test the P-C-T curve of the hydrogen absorption and desorption of the alloy at different temperatures. Adding Zr0.8Nb0.2Co0.8Ni0.2The dehydrogenated sample is heated to 250 deg.C, 275 deg.C and 300 deg.C respectively, and the P-C-T test of hydrogen evolution is carried out at corresponding temperature.
Zr0.8Nb0.2Co0.8Ni0.2The P-C-T curve of (A) is shown in FIG. 2, wherein the abscissa represents the amount of hydrogen absorbed or desorbed (n is used)H/nMExpressed) and the ordinate is the hydrogen pressure (in bar). Hydrogen isotope storage alloy Zr0.8Nb0.2Co0.8Ni0.2Has a maximum theoretical hydrogen storage amount of nH/nMThe hydrogen absorption plateau pressures at 250 deg.C, 275 deg.C and 300 deg.C are 0.294bar, 0.722bar and 1.451bar, respectively, and the hydrogen desorption plateau pressures are 0.221bar, 0.461bar and 1.072bar, respectively.
ZrCo of comparative example 1 and Zr of example 1 were measured in the same manner0.9Nb0.1Co0.9Ni0.1And Zr of example 30.7Nb0.3Co0.7Ni0.3The P-C-T curve of the alloy absorbing and desorbing hydrogen at 250 ℃ is shown in figure 3. ZrCo and Zr are obtained by calculation0.9Nb0.1Co0.9Ni0.1、Zr0.8Nb0.2Co0.8Ni0.2The hydrogen absorption plateau pressures of the alloy at 250 ℃ are 0.066bar, 0.151bar and 0.294bar, respectively. Zr0.7Nb0.3Co0.7Ni0.3The sample had difficulty calculating its plateau pressure due to the plateau being too inclined. Compared with ZrCo alloy, the hydrogen absorbing and releasing terrace of the hydrogen isotope storage alloy prepared by the invention is obviously improved, so that the hydrogen isotope storage alloy is more suitable for hydrogen isotope storage and supply of ITER.
FIG. 4 shows Zr as the hydrogen isotope storage alloy0.9Nb0.1Co0.9Ni0.1And Zr0.8Nb0.2Co0.8Ni0.2The absorption and desorption hydrogen Van Tehouf line graph is used for displaying the relation between the hydrogen plateau pressure and the temperature, and can calculate Zr0.9Nb0.1Co0.9Ni0.1And Zr0.8Nb0.2Co0.8Ni0.2The enthalpy change values of the absorbed hydrogen of the alloy are respectively 88.43kJ/mol H2And 79.70kJ/mol H2The enthalpy change values of hydrogen release are 86.16kJ/mol H respectively2And 78.54kJ/mol H2。
Example 6
In order to compare the effects of the present invention, the ZrCo alloy of comparative example 1 was subjected to the same test in particular.
Cycling stability is an important indicator of ite for hydrogen isotope storage and supply alloys. The hydrogen absorption condition of the sample in circulation is room temperature (20 ℃), 1bar hydrogen absorption, and the hydrogen discharge condition is 380 ℃ for discharging hydrogen to the vacuum chamber. MeasuringIn this test, Zr in example 5 was first introduced into a glove box filled with argon gas0.8Nb0.2Co0.8Ni0.2The dehydrogenated sample is loaded into the reactor and the cycle operation is carried out according to the above conditions. The resulting cycle curve is shown in fig. 5. Zr0.8Nb0.2Co0.8Ni0.2The first hydrogen evolution capacity of the sample is nH/nM2.48, the hydrogen release capacity after 50 cycles is nH/nM2.45. The hydrogen release capacity retention rate after 50 cycles was 98.8%. ZrCo of comparative example 1 and Zr of example 1 were measured in the same manner0.9Nb0.1Co0.9Ni0.1And Zr of example 30.7Nb0.3Co0.7Ni0.3The cycle characteristics of the alloy under the same conditions are shown in FIG. 5. Wherein ZrCo, Zr0.9Nb0.1Co0.9Ni0.1、Zr0.7Nb0.3Co0.7Ni0.3The initial hydrogen release capacity of the alloy is nH/nM2.69, 2.40, the capacity after 50 cycles is nH/nMThe capacity retention rates were 22.3%, 59.1%, and 98.8%, respectively, for 0.60, 1.59, and 2.37. It can be found that the alloy provided by the invention has far better performance than that of ZrCo alloy, in particular to Zr with a main phase containing a large amount of ZrNi phase with a martensite structure0.8Nb0.2Co0.8Ni0.2And Zr0.7Nb0.3Co0.7Ni0.3And (3) alloying. The XRD pattern after the cyclic hydrogen desorption is shown in FIG. 6, and it can be found that the phase of the ZrCo alloy after the hydrogen desorption contains a large amount of disproportionation phase (ZrH)2And ZrCo2) It is indicated that a severe disproportionation reaction occurs during the hydrogen absorption and desorption. The alloy provided by the invention has less content of disproportionation phase, especially Zr0.8Nb0.2Co0.8Ni0.2And Zr0.7Nb0.3Co0.7Ni0.3The alloy only generates trace amount of disproportionation phase in the circulating process, and further proves that the alloy with martensite structure (ZrNi phase) has better circulating stability.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
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