A novel perovskite structure hydride material and preparation method thereof

Abstract

The present invention discloses a novel perovskite structure hydride material and a preparation method thereof, belonging to the technical field of energetic materials. The present invention is used to solve the problem that the existing perovskite hydride material samples are few in variety and have low hydrogen content. The chemical formula of the novel perovskite structure hydride material of the present invention is AeNiH3, wherein Ae is Sr or Ba. The novel perovskite structure hydride material of the present invention has a high hydrogen content, improves the energy density of the perovskite hydride material, and further broadens the material system of energetic materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of energetic materials and specifically relates to a novel perovskite structure hydride material and a preparation method thereof. Background Art

[0002] Perovskite hydrides have hydrogen storage characteristics. Hydrogen-rich materials have potential application value in hydrogen storage. Hydrogen energy is stable, efficient, and pollution-free. The product after combustion is water. It is the cleanest energy in the world and is known as the "ultimate energy."

[0003] At present, the research on new perovskite hydride materials is in its infancy, and various aspects of performance have not yet been experimentally studied. In-depth exploration is very necessary to promote the advancement of emerging materials. Summary of the invention

[0004] The purpose of the present invention is to provide a novel perovskite structure hydride material and a preparation method thereof, which are used to solve one of the following technical problems: the perovskite hydride material samples prepared in the prior art are of few types and have low hydrogen content.

[0005] The above object of the present invention is achieved through the following technical solutions:

[0006] On the one hand, the present invention provides a novel perovskite structure hydride material, the chemical formula of the novel perovskite structure hydride material is AeNiH3, wherein Ae is Sr or Ba.

[0007] On the other hand, the present invention also provides a method for preparing the novel perovskite structure hydride material, the preparation method comprising the following steps:

[0008] S1. Encapsulating the hydrogen source material, the Ae-containing raw material, and the Ni-containing raw material in an inert metal cylinder, and then placing it in a high-pressure chamber;

[0009] S2, pressurizing the hydrogen source material, the Ae-containing raw material, and the Ni-containing raw material, and after reaching the target pressure, starting heating, and maintaining the pressure and temperature;

[0010] S3. Perform quenching treatment under high pressure conditions to quickly reduce the temperature of the sample to room temperature, and obtain a new perovskite structure hydride material AeNiH3 after pressure relief.

[0011] Furthermore, in S1, the dehydrogenation temperature of the hydrogen source material is lower than 800°C.

[0012] Furthermore, in S1, the hydrogen source material includes a boroamine complex, paraffin or an alkaline earth metal hydride.

[0013] Furthermore, in S1, the Ae-containing raw material includes Ae element or Ae dihydride.

[0014] Furthermore, in S2, the material of the inert metal cylinder is tantalum, stainless steel, gold or platinum.

[0015] Furthermore, in S2, the target pressure range is 1 GPa to 30 GPa.

[0016] Furthermore, in S2, the target temperature range is 800-1200°C.

[0017] Furthermore, in S3, the cooling rate of quenching is 80 to 200°C / s.

[0018] Furthermore, in S3, the pressure relief rate is 1 GPa / h to 40 GPa / h.

[0019] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0020] 1) The novel perovskite structure hydride material provided by the present invention has a high hydrogen content and a stable structure, which improves the energy density of the novel perovskite hydride material and further broadens the material system of hydrogen storage materials.

[0021] 2) In the preparation method of the novel perovskite structure hydride material provided by the present invention, the preparation pressure is 1GPa to 30GPa, which is relatively low and easy to achieve; on the other hand, the amount of hydride sample prepared by the diamond anvil cell technology under high pressure is at the micron level, and the novel perovskite hydride material prepared by the method of the present invention can achieve sample recovery under conventional conditions, and the process is simple and easy. The preparation method of the present invention ensures the repeatability of the experiment and reduces the difficulty of the experiment, which becomes an important technology for the application of novel perovskite structure hydride materials.

[0022] 3) The preparation method of the present invention can prepare new perovskite structure hydride materials of micron size, and can also prepare large volume (e.g. 1-20 cm 3 ) is a new type of perovskite structure hydride material with strong versatility.

[0023] Other features and advantages of the present invention will be described in the following embodiments, and part of them can be obtained from the description, or understood by practicing the present invention. The purpose and other advantages of the present invention can be realized and obtained by the structures particularly pointed out in the written description and the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The accompanying drawings are only for the purpose of illustrating specific embodiments and are not to be considered as limiting the present invention. The same reference symbols denote the same contents throughout the accompanying drawings.

[0025] Figure 1 is the X-ray diffraction spectrum of SrNiH3 of Example 1 of the present invention;

[0026] Figure 2 The resistance of the SrNiH3 material of Example 1 of the present invention varies with temperature;

[0027] Figure 3 This is the in-situ high-pressure synchrotron radiation spectrum of SrNiH3 of Example 1 of the present invention;

[0028] Figure 4 This is a graph showing how the magnetic properties of the SrNiH3 material of Example 1 of the present invention vary with temperature.

[0029] Figure 5 is the X-ray diffraction spectrum of BaNiH3 of Example 2 of the present invention;

[0030] Figure 6 This is a graph showing the change in resistance of the BaNiH3 material of Example 2 of the present invention with respect to temperature.

[0031] Figure 7 This is a graph showing how the magnetic properties of the BaNiH3 material of Example 2 of the present invention vary with temperature. DETAILED DESCRIPTION

[0032] Preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, wherein the accompanying drawings constitute a part of the present invention and are used to explain the principles of the present invention together with the embodiments of the present invention.

[0033] The samples of perovskite structure hydride materials prepared in the prior art are of few types and have low hydrogen content. Therefore, how to provide perovskite hydride materials with high hydrogen content has become an urgent problem to be solved.

[0034] The invention provides a novel perovskite structure hydride material. The chemical formula of the novel perovskite structure hydride material is AeNiH3, wherein Ae is Sr or Ba.

[0035] Specifically, the density of the AeNiH3 material is 4.5 g / cm 3 Above, for example 4.995~5.5g / cm 3 .

[0036] The present invention also provides a method for preparing a novel perovskite structure hydride material, the preparation method comprising the following steps:

[0037] S1. Encapsulating the hydrogen source material, the Ae-containing raw material, and the Ni-containing raw material in an inert metal cylinder, and then placing it in a high-pressure chamber;

[0038] S2, pressurizing the hydrogen source material, the Ae-containing raw material, and the Ni-containing raw material, and after reaching the target pressure, starting heating, and maintaining the pressure and temperature;

[0039] S3. Perform quenching treatment under high pressure conditions to quickly reduce the temperature of the sample to room temperature, and obtain a large volume of new perovskite structure hydride material AeNiH3 after pressure relief.

[0040] Specifically, in S1, the dehydrogenation temperature of the hydrogen source material is lower than 800°C.

[0041] Specifically, in S1, the hydrogen source material includes solid hydrogen-containing materials such as boron ammonia complexes, paraffin, and alkaline earth metal hydrides.

[0042] Specifically, in S1, the Ae-containing raw material includes Ae simple substance, Ae dihydride, etc.

[0043] Specifically, in S1, the molar ratio of Ni to Ae in the raw material is 1:1, and the molar ratio of H to Ni in the hydrogen source material is controlled within a range of 4:1 to 6:1.

[0044] Specifically, in S1, the inert metal cylinder containing the raw materials is made of tantalum, stainless steel, gold, platinum, etc., which is not easy to react with hydrogen and can prevent hydrogen leakage during high-pressure and high-temperature reactions, thereby ensuring a higher hydrogen content in the product.

[0045] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0046] S01. Select the corresponding high-pressure equipment according to the synthetic pressure of the target material, the high-pressure equipment includes a six-sided top press and a two-stage push press;

[0047] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0048] Specifically, in S1, the assembling method of the raw materials includes packaging the raw materials after uniformly mixing them.

[0049] Taking into account the sufficiency of the reaction between the hydrogen source material and the Ae-containing raw material and the Ni-containing raw material and the difficulty of stripping the sample by-products, in S1, the raw materials are assembled in a "sandwich" manner with the hydrogen source material placed at the bottom and top and the Ae-containing raw material and the Ni-containing raw material placed in the middle.

[0050] Specifically, in S2, the target pressure ranges from 1 GPa to 30 GPa. For example, the target pressure is 1 GPa, 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, 7 GPa, 8 GPa, 9 GPa, 10 GPa, 11 GPa, 12 GPa, 13 GPa, 14 GPa, 15 GPa, 16 GPa, 17 GPa, 18 GPa, 19 GPa, 20 GPa, 21 GPa, 22 GPa, 23 GPa, 24 GPa, 25 GPa, 26 GPa, 27 GPa, 28 GPa, 29 GPa, and 30 GPa.

[0051] Specifically, in S2, the target temperature range is 800-1200°C, for example, 800°C, 900°C, 1000°C, 1100°C, 1200°C.

[0052] Specifically, in S2, the insulation time is 10 min to 4 h, for example, 20 min, 30 min, 40 min, 50 min, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, and 3.5 h.

[0053] Specifically, in S3, the cooling rate of the quenching treatment is 80 to 200°C / s, for example, 90°C / s, 100°C / s, 110°C / s, 120°C / s, 130°C / s, 140°C / s, 150°C / s, 160°C / s, 170°C / s, 180°C / s, and 190°C / s.

[0054] Specifically, in S3, the pressure relief rate is 1 GPa / h to 40 GPa / h, for example, 2 GPa / h, 3 GPa / h, 4 GPa / h, 5 GPa / h, 6 GPa / h, 7 GPa / h, 8 GPa / h, 9 GPa / h, 10 GPa / h, 15 GPa / h, 20 GPa / h, 25 GPa / h, 30 GPa / h, and 35 GPa / h.

[0055] Specifically, when the new perovskite structure hydride material is SrNiH3, the target pressure is 3 to 15 GPa, the target temperature is 1000 to 1200°C, the insulation time is 50 to 120 minutes, and the pressure relief rate is 20 to 40 GPa / h.

[0056] Specifically, when the new perovskite structure hydride material is BaNiH3, the target pressure is 1 to 4 GPa, the target temperature is 900 to 1150°C, the insulation time is 50 to 120 minutes, and the pressure relief rate is 20 to 40 GPa / h.

[0057] Specifically, the above preparation method can prepare a new type of perovskite structure hydride material of micron size, and can also prepare a large volume (e.g., 1 to 20 cm 3 )'s new perovskite structure hydride material.

[0058] Example 1

[0059] This embodiment provides a novel perovskite structure hydride material and a preparation method thereof.

[0060] The novel perovskite structure hydride material of this embodiment is SrNiH3.

[0061] The preparation method of the novel perovskite structure hydride material of this embodiment comprises the following steps:

[0062] S1. Encapsulating the hydrogen source material, the Sr-containing raw material, and the Ni-containing raw material in an inert metal cylinder, and then placing it in a high-pressure chamber;

[0063] S2. Pressurize the hydrogen source material, the Sr-containing raw material, and the Ni-containing raw material. After reaching the target pressure, start heating and maintain the pressure and temperature.

[0064] S3, quenching treatment is carried out under high pressure conditions to quickly reduce the temperature of the sample to room temperature, and a large volume (10cm 3 )New perovskite structure hydride material SrNiH3.

[0065] Specifically, in step S1, the hydrogen source material is a borammane complex, the Sr-containing raw material is SrH2, and the Ni-containing raw material is metallic Ni.

[0066] Specifically, in step S1, the molar ratio of the borammane complex, SrH2 and Ni is 1 / 3:1:1.

[0067] Specifically, in step S1, the inert metal cylinder containing the raw material is a platinum cylinder.

[0068] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0069] S01. Select a six-sided press machine based on the synthetic pressure of the target material;

[0070] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0071] Specifically, in step S1, the raw material assembly method is to place a uniform mixture of SrH2 and Ni raw materials in the middle of the inert metal cylinder, and place a "sandwich" assembly structure of boron ammonia complex at both ends.

[0072] Specifically, in step S2, the target pressure is 6 GPa.

[0073] Specifically, in step S2, the target temperature is 1150°C and the holding time is 60 minutes.

[0074] Specifically, in step S3, the cooling rate of the quenching treatment is 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0075] Specifically, in step S3, the pressure relief rate is 0.6 GPa / min.

[0076] The X-ray diffraction spectrum of SrNiH3 prepared in this example is as follows Figure 1 As shown, its unit cell volume is The density of SrNiH3 is about 4.995g / cm 3 .

[0077] The resistance of SrNiH3 in this embodiment varies with temperature. Figure 2 As shown, the resistivity increases with increasing temperature, proving that SrNiH3 is a metal.

[0078] The in-situ high-pressure synchrotron radiation experimental results of SrNiH3 in this example are as follows Figure 3 As shown, the crystal structure of SrNiH3 is relatively stable within the pressure range of 7.4 to 50.13 GPa.

[0079] The magnetic properties of SrNiH3 in this embodiment are as follows Figure 4 As shown in the figure, the magnetization intensity changes with temperature under an external field strength of 100Oe. The MT test results show paramagnetic signals at low temperatures.

[0080] The novel perovskite structure hydride material SrNiH3 of this embodiment is different from conventional perovskite type composite oxides. The hydrogen content of SrNiH3 is relatively high, which improves the energy density of the perovskite structure hydride material; and the method of the present invention effectively reduces the pressure required for the synthesis of SrNiH3; and realizes the recovery and physical property characterization of the perovskite type hydride material under normal pressure conditions. Through the method of the present invention, the experimental difficulty is reduced, and a stable and easy way is provided for exploring the performance of the novel perovskite hydride.

[0081] Example 2

[0082] This embodiment provides a novel perovskite structure hydride material and a preparation method thereof.

[0083] The novel perovskite structure hydride material of this embodiment is BaNiH3.

[0084] The preparation method of the novel perovskite structure hydride material of this embodiment comprises the following steps:

[0085] S1, encapsulating the hydrogen source material, the Ba-containing raw material, and the Ni-containing raw material in an inert metal cylinder, and then placing it in a high-pressure chamber;

[0086] S2, pressurizing the hydrogen source material, the Ba-containing raw material, and the Ni-containing raw material, and after reaching the target pressure, starting heating, and maintaining the pressure and temperature;

[0087] S3, quenching treatment is carried out under high pressure conditions to quickly reduce the temperature of the sample to room temperature, and a large volume (12cm 3 )New perovskite structure hydride material BaNiH3.

[0088] Specifically, in step S1, the hydrogen source material is a boron ammonia complex, the Ba-containing raw material is metal Ba, and the Ni-containing raw material is metal Ni.

[0089] Specifically, in step S1, the molar ratio of the boron ammonia complex, Ba and Ni is 1:1:1.

[0090] Specifically, in step S1, the inert metal cylinder containing the raw material is a platinum cylinder.

[0091] Specifically, before S1, the preparation work for high-voltage assembly is completed, including the following steps:

[0092] S01. Select a six-sided press machine based on the synthetic pressure of the target material;

[0093] S02. According to the type of high-voltage equipment, select the corresponding high-voltage assembly, including pressure transmission medium, sample chamber, heating component, inert metal cylinder, thermocouple, etc.

[0094] Specifically, in step S1, the raw material assembly method is to place a uniform mixture of metal Ba and Ni raw materials in the middle of an inert metal cylinder, and place a "sandwich" assembly structure of a boron ammonia complex at both ends.

[0095] Specifically, in step S2, the target pressure is 3 GPa.

[0096] Specifically, in step S2, the target temperature is 1000°C and the holding time is 60 minutes.

[0097] Specifically, in step S3, the cooling rate of the quenching treatment is 150°C / s, and rapid cooling is achieved by controlling the cooling water temperature.

[0098] Specifically, in step S3, the pressure relief rate is 0.6 GPa / min.

[0099] The X-ray diffraction pattern of BaNiH3 in this example is as follows Figure 5 As shown, its unit cell volume is The density of BaNiH3 is about 5.387g / cm 3 .

[0100] The electrical test diagram of BaNiH3 in this embodiment is as follows Figure 6As shown, the resistivity decreases with increasing temperature, proving that BaNiH3 is a semiconductor.

[0101] The magnetic properties of BaNiH3 in this embodiment are as follows Figure 7 As shown in the figure, the magnetization intensity changes with temperature under an external field strength of 500Oe. The MT test results show paramagnetic signals at low temperatures.

[0102] The inventor has conducted a large number of experimental studies during the research process, and now uses some solutions with poor effects as comparative examples.

[0103] Comparative Example 1

[0104] This comparative example provides a method for preparing a hydride material, and the overall steps are the same as those in Example 1, except that:

[0105] In step S2, the target temperature is 850° C. SrO, Ni and an unknown impurity phase are obtained in this comparative example.

[0106] Comparative Example 2

[0107] This comparative example provides a method for preparing a hydride material. The overall steps are the same as those in Example 2, except that:

[0108] In step S2, the target pressure is 6 GPa, and BaH2 and Ni are obtained in this comparative example.

[0109] Comparative Example 3

[0110] This comparative example provides a method for preparing a hydride material, and the overall steps are the same as those in Example 1, except that:

[0111] In S1, the raw materials are directly placed in a high pressure chamber. The prepared sample is a mixture of SrO, NiO and Ni.

[0112] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.

Claims

1. A method for preparing a perovskite structure hydride material, characterized in that: The preparation method comprises the following steps: S1. Encapsulating the hydrogen source material, the Ae-containing raw material, and the Ni-containing raw material in an inert metal cylinder, and then placing it in a high-pressure chamber; S2, pressurizing the hydrogen source material, the Ae-containing raw material, and the Ni-containing raw material, and after reaching the target pressure, starting heating, and maintaining the pressure and temperature; S3, performing quenching treatment under high pressure conditions, lowering the temperature of the sample to room temperature, and obtaining the perovskite structure hydride material AeNiH3 after pressure relief; wherein Ae is Sr or Ba; In S1, the hydrogen source material includes boron ammonia complex, paraffin or alkaline earth metal hydride; the Ae-containing raw material includes Ae element or Ae dihydride; In S2, the target pressure range is 1 GPa~30 GPa, and the temperature range of pressure and heat preservation is 800~1200°C; In S3, the cooling rate of quenching is 80-200°C / s; The perovskite structure hydride material prepared by the preparation method can realize sample recovery under conventional conditions.

2. The preparation method according to claim 1, characterized in that: In S2, the material of the inert metal cylinder is tantalum, stainless steel, gold or platinum.

3. The preparation method according to claim 1, characterized in that: In S2, the target pressure range is 2 GPa~30 GPa.

4. The preparation method according to claim 1, characterized in that: In S2, the temperature range of pressure and heat preservation is 900-1200°C.

5. The preparation method according to claim 1, characterized in that: In S3, the cooling rate of quenching is 80-150°C / s.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In S3, the pressure relief rate is 1 GPa / h~40 GPa / h.

7. A perovskite structure hydride material, characterized in that: The perovskite structure hydride material is prepared by the preparation method according to any one of claims 1 to 6.

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