CN114000030B - Titanium-chromium-manganese hydrogen storage alloy and preparation method and application thereof - Google Patents
Titanium-chromium-manganese hydrogen storage alloy and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
The invention discloses titanium chromiumManganese hydrogen storage alloy and its preparation method and application. The titanium-chromium-manganese hydrogen storage alloy has the composition shown in the formula (1): ti x Zr y Cr 1‑a‑b‑c Mn z V a Al b M c (1) (ii) a Wherein x is more than or equal to 0.7<1.0，0<y is less than or equal to 0.3, x + y is 1, and z is 1.0; 0<a≤0.2，0<b is less than or equal to 0.3, c is more than or equal to 0 and less than or equal to 0.2; wherein M is selected from one or more of Cu, Si, Fe, Co, Ni and Mo elements; wherein x, y, z, a, b, and c represent the atomic ratio of each element. The titanium-chromium-manganese hydrogen storage alloy has small hysteresis coefficient.
Description
Technical Field
The invention relates to a titanium-chromium-manganese hydrogen storage alloy and a preparation method and application thereof.
Background
The hydrogen energy and energy storage technology is a great strategic demand of global energy transformation and upgrading in the 21 st century, and is an effective way for realizing strategic goals of carbon peaking and carbon neutralization. The solid hydrogen storage alloy as a material capable of reversibly absorbing and desorbing hydrogen is an important energy conversion material for developing hydrogen energy and energy storage technology.
CN109957699A discloses a high-capacity titanium-manganese-based hydrogen storage alloy, the chemical composition of which is Ti a (M1) b Mn c (V 4 Fe) d Cr e (M2) f Wherein 0.9<a≤1.0，0<b≤0.1，0.9<(a+b)≤1.1，1.0<c≤1.5，0.3<d≤0.5，0<e≤0.1，0<f≤0.5，1.8<(c + d + e + f) is less than or equal to 2.1; m1 is any one or combination of several of Zr, Nb and Mo, and M2 is any one or combination of several of Cu, Ni and Co. The hydrogen storage alloy does not contain Al and has low Zr content, so that the plateau gradient of the hydrogen storage alloy is high.
CN113215467A discloses a solid hydrogen storage material for a hydrogen station, which is a TiCr-based high-entropy intermetallic compound with stable C14 Laves phase and the chemical general formula of the TiCr-based high-entropy intermetallic compound is Ti 1-x Zr x Cr 2-x Mn x Fe x Wherein x is more than or equal to 0.1 and less than 0.2. The Cr content of the hydrogen storage material is too high, so that the platform inclination rate of the hydrogen storage material is higher.
CN101538673A discloses an under-measured Laves phase hydrogen storage alloy, the chemical general formula of which is Ti u Zr x Mn v M y V z Wherein x is more than or equal to 0 and less than or equal to 0.2, y is more than or equal to 0.1 and less than or equal to 0.4, z is more than or equal to 0.1 and less than or equal to 0.5, u + x is 1, and v + y is 1.5; m element is one selected from Cr, Ni and Cu. The hydrogen storage alloy has high Mn content, large hysteresis coefficient and large absolute value of hydrogen absorption/desorption enthalpy change.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a titanium-chromium-manganese-based hydrogen storage alloy having a small hysteresis coefficient. Furthermore, the titanium chromium manganese hydrogen storage alloy has low gradient of the hydrogen release platform and small absolute value of hydrogen absorption/release enthalpy change. Furthermore, the titanium-chromium-manganese hydrogen storage alloy has higher hydrogen absorption amount and moderate hydrogen absorption/desorption platform pressure. The invention also aims to provide a preparation method of the titanium-chromium-manganese hydrogen storage alloy. Still another object of the present invention is to provide a use of the titanium chromium manganese-based hydrogen storage alloy.
The technical purpose is realized by the following technical scheme.
In one aspect, the present invention provides a titanium-chromium-manganese-based hydrogen storage alloy having a composition represented by formula (1):
Ti x Zr y Cr 1-a-b-c Mn z V a Al b M c (1)
wherein x is more than or equal to 0.7 and less than 1.0, y is more than 0 and less than or equal to 0.3, x + y is 1, and z is 1.0; a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.3, and c is more than or equal to 0 and less than or equal to 0.2;
wherein M is selected from one or more of Cu, Si, Fe, Co, Ni and Mo elements;
wherein x, y, z, a, b and c represent the atomic ratio of each element, respectively.
The titanium-chromium-manganese-based hydrogen storage alloy according to the present invention preferably has 0.1< y.ltoreq.0.3.
The titanium-chromium-manganese hydrogen storage alloy according to the invention is preferably 0.6. ltoreq. 1-a-b-c. ltoreq.0.9.
The titanium-chromium-manganese hydrogen storage alloy according to the present invention is preferably such that x/y is 2 or more.
According to the titanium-chromium-manganese-based hydrogen storage alloy of the present invention, preferably, M is Cu or Si, and 0< c.ltoreq.0.2.
According to the titanium-chromium-manganese hydrogen storage alloy, x is preferably more than or equal to 0.7 and less than or equal to 0.9, and y is more than or equal to 0.1 and less than or equal to 0.3.
The titanium-chromium-manganese-based hydrogen storage alloy according to the present invention preferably has 0.005. ltoreq. b.ltoreq.0.2.
The titanium-chromium-manganese-based hydrogen storage alloy according to the present invention preferably has a composition represented by one of the following formulae:
Ti 0.9 Zr 0.1 Cr 0.8 Mn 1.0 V 0.1 Al 0.1 ，
Ti 0.8 Zr 0.2 Cr 0.65 Mn 1.0 V 0.1 Al 0.15 Cu 0.1 ，
Ti 0.75 Zr 0.25 Cr 0.8 Mn 1.0 V 0.1 Al 0.1 ，
Ti 0.7 Zr 0.3 Cr 0.75 Mn 1.0 V 0.1 Al 0.05 Si 0.1 。
on the other hand, the invention also provides a preparation method of the titanium-chromium-manganese hydrogen storage alloy, which comprises the following steps:
smelting a metal raw material with the composition shown in the formula (1) under the protection of inert gas and under the condition that the relative vacuum degree is-0.01 to-0.1 MPa, and then cooling and forming; repeatedly smelting for 2-5 times to obtain the titanium-chromium-manganese hydrogen storage alloy.
In still another aspect, the invention also provides the use of the titanium-chromium-manganese hydrogen storage alloy in the preparation of a hydrogen compressor and/or a hydrogen storage tank.
The invention replaces the Cr element with proper amount of V element and Al element, and keeps proper atomic ratio of the Cr element and the Mn element, and can reduce the hysteresis coefficient, the gradient rate of the hydrogen discharging platform and the absolute value of the change of the hydrogen absorption/discharging enthalpy. By adopting proper Zr element to replace Ti element, the hysteresis coefficient, the platform gradient rate and the absolute value of the change of the hydrogen absorption/desorption enthalpy can be further reduced. Meanwhile, the hydrogen storage alloy has higher hydrogen absorption amount and moderate hydrogen absorption/desorption plateau pressure.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
In the present invention, the absolute vacuum degree indicates the actual pressure in the container. The relative vacuum represents the difference between the vessel pressure and 1 standard atmosphere. The inert gas includes nitrogen or argon, etc.
< titanium chromium manganese-based Hydrogen occluding alloy >
The titanium-chromium-manganese hydrogen storage alloy has the composition shown in the formula (1):
Ti x Zr y Cr 1-a-b-c Mn z V a Al b M c (1)。
the titanium-chromium-manganese hydrogen storage alloy of the invention does not contain Mg or rare earth elements, but may contain some inevitable impurities. The titanium-chromium-manganese hydrogen storage alloy has a Laves phase.
Ti represents a titanium element. x represents an atomic ratio of Ti. X is more than or equal to 0.7 and less than 1.0; preferably, 0.7. ltoreq. x.ltoreq.0.85; more preferably, 0.73. ltoreq. x.ltoreq.0.78.
Zr represents a zirconium element. y represents the atomic ratio of Zr. Y is more than 0 and less than or equal to 0.3; preferably, y is more than 0.1 and less than or equal to 0.3; more preferably, 0.15. ltoreq. y.ltoreq.0.27.
And x/y represents atoms of Ti element and Zr element. x/y is more than or equal to 2; preferably, 9 ≧ x/y ≧ 2; more preferably, 5. gtoreq.x/y. gtoreq.3.
In the present invention, x + y is 1. The hydrogen absorbing element on the A side is the combination of Ti and Zr, and the atomic ratio of the Ti to the Zr is within the range of the invention, so that the hydrogen absorbing alloy can be matched with the non-hydrogen absorbing element on the B side, and the hydrogen absorbing alloy which has low hysteresis coefficient, platform gradient rate and absolute value of hydrogen absorption/desorption enthalpy change, higher hydrogen absorption capacity and moderate hydrogen absorption/desorption platform pressure can be obtained.
Mn represents a manganese element. z represents an atomic ratio of Mn. In the present invention, z is 1.0.
Cr represents a chromium element. 1-a-b-c represents the atomic ratio of Cr. The atomic ratio of Cr can be determined by the values of a, b and c. 0.6-1-a-b-c-0.9; preferably 0.63. ltoreq.1-a-b-c. ltoreq.0.85. In some embodiments, 0.78. ltoreq.1-a-b-c. ltoreq.0.82. In other embodiments, 0.6. ltoreq.1-a-b-c. ltoreq.0.67.
The ratio of Mn and Cr elements can reduce the hysteresis coefficient, the platform gradient rate and the absolute value of the change of the hydrogen absorption/desorption enthalpy of the hydrogen storage alloy.
V represents a vanadium element. a represents the atomic ratio of V. A is more than 0 and less than or equal to 0.2; preferably, 0.05. ltoreq. a.ltoreq.0.15; more preferably, 0.08. ltoreq. a.ltoreq.0.12. The amount of the Al element is matched with the added Al element, so that the hysteresis coefficient, the platform gradient rate and the absolute value of the change of the hydrogen absorption/desorption enthalpy of the hydrogen storage alloy can be reduced.
Al represents an aluminum element. b represents an atomic ratio of Al. B is more than 0 and less than or equal to 0.3; preferably, 0.03. ltoreq. b.ltoreq.0.17; more preferably, 0.08. ltoreq. b.ltoreq.0.12. The hysteresis coefficient, the platform gradient rate and the absolute value of the change of the hydrogen absorption/desorption enthalpy can be reduced by replacing Cr with proper Al element.
M is selected from one or more of Cu, Si, Fe, Co, Ni and Mo elements; preferably, M is selected from one or more of Cu and Si elements. In certain embodiments M is Cu. This enables further reduction in the absolute value of change in hydrogen absorption/desorption enthalpy of the hydrogen storage alloy. In other embodiments, M is Si. This can further reduce the plateau tilt rate of the hydrogen occluding alloy. c represents the atomic ratio of M. In certain embodiments, c is 0. In other embodiments, 0< c ≦ 0.2; preferably, 0.5. ltoreq. c.ltoreq.0.15. This enables the hysteresis coefficient, the plateau tilt rate, and the absolute value of the enthalpy change of absorption/desorption of hydrogen in the hydrogen occluding alloy to be kept at low values.
Specific examples of the titanium-chromium-manganese-based hydrogen storage alloy of the present invention include, but are not limited to, alloys represented by one of the following formulas:
Ti 0.9 Zr 0.1 Cr 0.8 Mn 1.0 V 0.1 Al 0.1 ，
Ti 0.8 Zr 0.2 Cr 0.65 Mn 1.0 V 0.1 Al 0.15 Cu 0.1 ，
Ti 0.75 Zr 0.25 Cr 0.8 Mn 1.0 V 0.1 Al 0.1 ，
Ti 0.7 Zr 0.3 Cr 0.75 Mn 1.0 V 0.1 Al 0.05 Si 0.1 。
the hydrogen absorption capacity of the titanium-chromium-manganese hydrogen storage alloy can be more than or equal to 1.7 wt% under 313K; preferably, the hydrogen absorption amount is 1.7 to 2.0 wt%; more preferably, the amount of hydrogen absorption is 1.8 to 1.9 wt%. The pressure of the hydrogen absorption platform can be 1-10 MPa; preferably 1-5 MPa; more preferably 2 to 3 MPa. The pressure of the hydrogen discharge platform can be 1-10 MPa; preferably 1-5 MPa; more preferably 1.5 to 3.5 MPa. The hysteresis coefficient can be less than or equal to 0.1; preferably, the hysteresis coefficient is 0.01-0.07; more preferably, the hysteresis coefficient is 0.02 to 0.05. The inclination rate of the hydrogen discharging platform can be less than or equal to 1.2; preferably, the inclination rate of the hydrogen discharging platform is 0.4-0.9; more preferably, the inclination rate of the hydrogen discharging platform is 0.5-0.7. Absolute value of change in hydrogen absorption/desorption enthalpy (. DELTA.H (H) 2 ) Less than 20kJ. mol) -1 (ii) a Preferably 15 to 19.5kJ -1 (ii) a More preferably 16 to 18.5kJ.mol -1 。
< preparation of titanium chromium manganese-based Hydrogen storage alloy >
The titanium-chromium-manganese-based hydrogen storage alloy of the present invention can be obtained by various methods such as a high-temperature melting casting method, a high-temperature melting-rapid quenching method, a mechanical alloying method, a powder sintering method, a high-temperature melting-gas atomization method, a reduction diffusion method, a displacement diffusion method, a combustion synthesis method, a self-propagating high-temperature synthesis method, and a chemical synthesis methodA method. In order to better improve the performance of the hydrogen storage alloy, metal raw materials are smelted and then cooled and formed to obtain the titanium-chromium-manganese hydrogen storage alloy. The Ti-Cr-Mn hydrogen storage alloy consists of Ti x Zr y Cr 1-a-b-c Mn z V a Al b M c (1) For example, the elements and their occupied atoms are as described above, and are not described herein again.
Specifically, the method comprises the following steps of:
smelting a metal raw material with the composition shown in the formula (1) under the protection of inert gas and under the condition that the relative vacuum degree is-0.01 to-0.1 MPa, and then cooling and forming; repeatedly smelting for 2-5 times to obtain the titanium-chromium-manganese hydrogen storage alloy. Preferably, the melting is repeated 3 to 4 times. This enables the alloy composition to be uniform.
The metal raw materials are weighed so that the obtained titanium-chromium-manganese hydrogen storage alloy has the composition shown in the formula (1). The metal raw material has heat loss and volatilization in the smelting process, so that the Mn element in the metal raw material can be 103 wt% of the feeding amount of the composition shown by the titanium chromium manganese hydrogen storage alloy, the V element can be 102 wt% of the feeding amount of the composition shown by the titanium chromium manganese hydrogen storage alloy, the Al element can be 105 wt% of the feeding amount of the composition shown by the titanium chromium manganese hydrogen storage alloy, and the Cu element can be 102 wt% of the feeding amount of the composition shown by the titanium chromium manganese hydrogen storage alloy. The purities of the metal raw materials are more than or equal to 99 wt%.
According to one embodiment of the invention, the inert gas is used for scrubbing for 2-5 times; vacuumizing the high-frequency magnetic suspension induction smelting furnace until the absolute vacuum degree is less than or equal to 1Pa, and filling inert gas until the relative vacuum degree is-0.01 to-0.1 MPa; setting the power of the high-frequency magnetic suspension induction smelting furnace to 2-7 kW, keeping for 1-4 min, increasing to 8-13 kW, keeping for 1-4 min, and then increasing to 14-18 kW, and keeping until the metal raw material is melted. After the metal raw materials are melted, maintaining the state for 0.5-2 min at 14-18 kW, and then gradually reducing the power to 0 to obtain an alloy; and cooling the alloy to a temperature of less than 333K, and taking out. And repeatedly smelting for 2-5 times to obtain the titanium-chromium-manganese hydrogen storage alloy.
In the present invention, the inert gas may be high-purity nitrogen or high-purity argon, preferably argon.
< use >
The titanium-chromium-manganese hydrogen storage alloy has the advantages of small hysteresis coefficient, small platform inclination rate, small absolute value of hydrogen absorption/desorption enthalpy change, higher hydrogen absorption amount and moderate hydrogen absorption/desorption platform pressure. Therefore, the compound can be used as a raw material for producing a hydrogen compressor or a hydrogen storage tank. Therefore, the invention provides the application of the titanium-chromium-manganese hydrogen storage alloy in preparing a hydrogen compressor and/or a hydrogen storage tank.
The method of testing PCT curves of hydrogen occluding alloys obtained in the following examples and comparative examples is described below:
the hydrogen absorbing alloys obtained in examples and comparative examples were crushed and then sieved through a 200 mesh standard sieve to obtain hydrogen absorbing alloy powders having a particle size of < 75 μm. 1g of hydrogen storage alloy powder is weighed and loaded into a PCT testing device, vacuum pumping is carried out for 1h under 423K (high-temperature vacuum pumping step), and then water bath is carried out to maintain the hydrogen storage alloy powder at 313K. Filling hydrogen gas at 5MPa to activate the hydrogen storage alloy powder, and recording the hydrogen absorption amount of the alloy powder; and if the maximum hydrogen absorption amount is reached within 30min, starting to test the PCT curve, and if the maximum hydrogen absorption amount cannot be reached within 30min, repeating the high-temperature vacuumizing step until the hydrogen storage alloy powder can reach the maximum hydrogen absorption amount, and starting to test the PCT curve.
Coefficient of hysteresis (H) f ) Calculating by using a formula shown in formula (I):
H f ＝ln(p a /p b ) (I)
wherein p is a Is hydrogen absorption plateau pressure with unit of MPa;
p b the hydrogen release plateau pressure is expressed in MPa.
The gradient (F) of the hydrogen discharging platform is calculated by adopting a formula shown in a formula (II):
wherein p is 25％ The hydrogen pressure corresponding to the hydrogen content on the hydrogen discharge curve equal to 25% of the hydrogen absorption amount is expressed in MPa;
p 75％ indicating hydrogen content on the hydrogen discharge curve, etcThe hydrogen pressure corresponding to 75% of the hydrogen absorption is in MPa;
25％w max represents 25% hydrogen absorption;
75％w max represents 75% hydrogen absorption.
Examples 1 to 4 and comparative examples 1 to 5
The metal raw materials were prepared according to the composition of the alloy elements shown in table 1, and the purity of each raw material was 99 wt% or more.
The prepared metal raw materials are placed in a water-cooled copper crucible, and the water-cooled copper crucible is placed in a high-frequency magnetic suspension induction smelting furnace. Vacuumizing the pressure in the high-frequency magnetic suspension induction melting furnace to 10 DEG -3 Pa (absolute pressure), then filling argon into the high-frequency magnetic suspension induction melting furnace to ensure that the pressure in the furnace is-0.06 MPa (relative pressure), repeating the vacuumizing and the argon filling for three times, and exhausting the air in the high-frequency magnetic suspension induction melting furnace.
Starting the high-frequency magnetic suspension induction smelting furnace, adjusting the power of the high-frequency magnetic suspension induction smelting furnace to 5kW, keeping for 2min, increasing to 10kW, keeping for 2min, and increasing to 15kW until the metal raw material is melted; after the metal raw materials are melted, keeping the temperature for 1min at 15kW, and then gradually reducing the power to 0 to obtain an alloy; and cooling the alloy to a temperature of less than 333K, and taking out. Repeating the steps for three times, and repeatedly smelting the raw materials for three times to obtain the titanium-chromium-manganese hydrogen storage alloy.
TABLE 1
| Numbering | Hydrogen storage alloy composition |
| Example 1 | Ti 0.9 Zr 0.1 Cr 0.8 Mn 1.0 V 0.1 Al 0.1 |
| Example 2 | Ti 0.8 Zr 0.2 Cr 0.65 Mn 1.0 V 0.1 Al 0.15 Cu 0.1 |
| Example 3 | Ti 0.75 Zr 0.25 Cr 0.8 Mn 1.0 V 0.1 Al 0.1 |
| Example 4 | Ti 0.70 Zr 0.3 Cr 0.75 Mn 1.0 V 0.1 Al 0.05 Si 0.1 |
| Comparative example 1 | TiCr 0.7 Mn 1.0 V 0.1 Al 0.2 |
| Comparative example 2 | TiCrMn |
| Comparative example 3 | Ti 0.9 Zr 0.1 Cr 0.8 Mn 1.0 Cu 0.1 V 0.1 |
| Comparative example 4 | Ti 0.9 Zr 0.1 Cr 0.2 Mn 1.3 V 0.1 Al 0.1 |
| Comparative example 5 | Ti 0.9 Zr 0.1 Cr 1.7 Mn 0.1 V 0.1 Al 0.1 |
TABLE 2
Remarking: Δ H (H) 2 ) The absolute value of the change in the hydrogen absorption/desorption enthalpy is shown.
The A-side hydrogen absorbing element of comparative example 1 does not contain Zr, and both the gradient of the hydrogen desorption plateau and the absolute values of the hydrogen absorption/desorption heat contents are higher than those of examples 1 to 4. In comparative example 2, the hydrogen absorbing element on the A side does not contain Zr, and the non-hydrogen absorbing element on the B side does not contain V and Al, so that the hysteresis coefficient, the gradient rate of the hydrogen releasing platform and the absolute values of the hydrogen absorbing/releasing heat change are all higher than those of examples 1-4, and the pressure of the hydrogen absorbing/releasing platform is obviously increased. In comparative example 3, the B-side non-hydrogen-occluding element contained Cu and not Al, and the hysteresis coefficient and the absolute values of the hydrogen occlusion/desorption heat contents were higher than those of examples 1 to 4. In comparative example 4, the content of Cr is too low, the content of Mn is too high, the hysteresis coefficient and the absolute value of the hydrogen absorption/desorption heat change are higher than those of examples 1 to 4, and the hydrogen absorption/desorption plateau is too low. In comparative example 4, the content of Cr is too high, the content of Mn is too low, the hysteresis coefficient, the gradient of the hydrogen desorption plateau and the absolute values of the hydrogen absorption/desorption heat changes are all higher than those in examples 1 to 4, and the hydrogen absorption/desorption plateau pressure is too high.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. A titanium-chromium-manganese hydrogen storage alloy is characterized by comprising the following components in formula (1):
Ti x Zr y Cr 1-a-b-c Mn z V a Al b M c (1)
wherein x is more than or equal to 0.7 and less than 0.85, y is more than 0.1 and less than or equal to 0.3, x + y is 1, and x/y is more than or equal to 9 and more than or equal to 2; z is 1.0; a is more than 0 and less than or equal to 0.2, b is more than 0 and less than or equal to 0.3, and c is more than 0 and less than or equal to 0.2;
wherein M is Si;
wherein x, y, z, a, b and c represent the atomic ratio of each element, respectively.
2. The Ti-Cr-Mn hydrogen storage alloy according to claim 1, wherein y is 0.15< y.ltoreq.0.3.
3. The Ti-Cr-Mn hydrogen storage alloy according to claim 1, wherein 0.6. ltoreq.1-a-b-c. ltoreq.0.9.
4. The Ti-Cr-Mn hydrogen storage alloy according to claim 1, wherein x/y is 5. gtoreq.2.
5. The Ti-Cr-Mn hydrogen storage alloy according to claim 1, wherein 0< c.ltoreq.0.15.
6. The Ti-Cr-Mn hydrogen storage alloy according to claim 1, wherein 0.63. ltoreq.1-a-b-c. ltoreq.0.85.
7. The Ti-Cr-Mn hydrogen storage alloy according to claim 1, wherein b is 0.005. ltoreq. b.ltoreq.0.2.
8. The Ti-Cr-Mn hydrogen storage alloy according to any one of claims 1 to 7, wherein the Ti-Cr-Mn hydrogen storage alloy has a composition represented by the following formula:
Ti 0.7 Zr 0.3 Cr 0.75 Mn 1.0 V 0.1 Al 0.05 Si 0.1 。
9. the method for preparing the titanium-chromium-manganese-based hydrogen storage alloy according to any one of claims 1 to 8, comprising the steps of:
smelting a metal raw material with the composition shown in the formula (1) under the protection of inert gas and under the condition that the relative vacuum degree is-0.01 to-0.1 MPa, and then cooling and forming; and repeatedly smelting for 2-5 times to obtain the titanium-chromium-manganese hydrogen storage alloy.
10. Use of the titanium chromium manganese-based hydrogen storage alloy according to any one of claims 1 to 8 for the production of hydrogen compressors and/or hydrogen storage tanks.
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