CN117684063A - Vanadium alloy and preparation and application thereof - Google Patents
Vanadium alloy and preparation and application thereof Download PDFInfo
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- CN117684063A CN117684063A CN202311593961.3A CN202311593961A CN117684063A CN 117684063 A CN117684063 A CN 117684063A CN 202311593961 A CN202311593961 A CN 202311593961A CN 117684063 A CN117684063 A CN 117684063A
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- 229910000756 V alloy Inorganic materials 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 132
- 239000001257 hydrogen Substances 0.000 claims abstract description 132
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 125
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 40
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims description 106
- 229910045601 alloy Inorganic materials 0.000 claims description 105
- 238000003723 Smelting Methods 0.000 claims description 81
- 238000010438 heat treatment Methods 0.000 claims description 35
- 230000006698 induction Effects 0.000 claims description 33
- 238000001816 cooling Methods 0.000 claims description 32
- 238000003860 storage Methods 0.000 claims description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005086 pumping Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000010521 absorption reaction Methods 0.000 abstract description 50
- 239000013078 crystal Substances 0.000 abstract description 9
- 238000001994 activation Methods 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 25
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- 239000000843 powder Substances 0.000 description 22
- 230000008569 process Effects 0.000 description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 13
- 239000002994 raw material Substances 0.000 description 11
- 238000007873 sieving Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 150000004678 hydrides Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 239000000725 suspension Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 4
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- XSQMSOYAHMZLJC-UHFFFAOYSA-N [Cr].[Ti].[V] Chemical compound [Cr].[Ti].[V] XSQMSOYAHMZLJC-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a vanadium alloy, a preparation method and application thereof, wherein the chemical formula of the vanadium alloy is (FeV) a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represents V, ti, cr, W atoms, a is 90 or 95, x is 22-40, y is 20-46, z is 8-27, n/m is 0.3-3.5, and m=100-x-y-z-n; w is one or more of transition metal element and rare earth element, and the crystal form of the vanadium alloy is changed by element allocation, and the problems of incomplete hydrogen release, poor hydrogen absorption and release kinetic performance and short cycle life of the vanadium alloy at normal temperature and normal pressure are solved.
Description
Technical Field
The invention relates to the technical field of hydrogen storage materials, in particular to a vanadium alloy and preparation and application thereof.
Background
The vanadium (V) -based solid solution hydrogen storage alloy has a BCC structure, the theoretical hydrogen absorption amount can reach 3.8 percent (mass fraction), which is far greater than that of AB5 type and AB type hydrogen storage alloys, and the hydrogen can be quickly and reversibly absorbed and released at normal temperature, which is very beneficial to the application of the practical hydrogen storage industry.
In the related art, more researches are carried out on vanadium-based alloy, for example, chinese invention patent with patent number 202110036762.7 discloses a titanium-chromium-vanadium hydrogen storage alloy, a preparation method and application thereof, and the patent mainly aims at the problems of poor activation performance and low hydrogen storage amount of the material and improves the hydrogen storage amount and activation performance of the alloy through element allocation.
However, the alloy prepared by the method can only release a part of hydrogen reversibly at normal temperature and normal pressure, and has poor hydrogen absorption and desorption kinetics, and has great influence on the hydrogen supply amount of a hydrogen storage device; in addition, the vanadium-based alloy can have attenuation phenomenon after long-term cycle life test, so that the hydrogen storage performance is reduced, the total hydrogen storage amount of the hydrogen storage device is seriously influenced, and the application of the vanadium-based hydrogen storage alloy in the industrial field is restricted.
Therefore, in order to solve the problems of the prior art, there is a need for a high cycle life vanadium alloy and a preparation method thereof, which are used for solving the problems of incomplete hydrogen release, poor hydrogen absorption and release kinetics, difficult preparation method, high cost and rapid life decay after long-term cycle hydrogen charging and releasing of the existing vanadium hydrogen storage alloy at normal temperature and normal pressure.
Disclosure of Invention
In view of the above, the application provides a vanadium alloy and preparation and application thereof, which are used for simultaneously solving the problems of incomplete hydrogen release, poor hydrogen absorption and release kinetic performance and short cycle life of the vanadium alloy at normal temperature and normal pressure.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a vanadium-based alloy having the formula (FeV a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represents V, ti, cr, W atoms, a is 90 or 95, x is 22-40, y is 20-46, z is 8-27, n/m is 0.3-3.5, and m=100-x-y-z-n; w is one or more of transition metal element and rare earth element.
Preferably, W comprises one or more of Fe, mn, ni, pd, zr.
In a second aspect, the present application provides a method for preparing a vanadium-based alloy, comprising the steps of:
s1, mixing FeV according to the proportion a Pre-smelting V, ti and Cr to obtain a mixture;
s2, mixing the mixture with W element in a vacuum state, introducing inert gas to perform electrified smelting, and forming in a die to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, and then cooling and crushing to obtain the vanadium alloy.
Preferably, the vacuum state is achieved by: the reaction vessel of the mixture is subjected to primary vacuum pumping treatment, the vacuum degree of the reaction vessel is 8Pa or less, and then is subjected to secondary vacuum pumping treatment, and the vacuum degree of the reaction vessel is 0.01Pa or less.
Preferably, the voltage of the electrified melting is 450-550V and the current is 200-300A.
Preferably, the temperature of the high-frequency induction heat treatment is 1350-1550 ℃ and the time is 1-5h.
Preferably, the cooling mode is liquid nitrogen cooling.
Preferably, the grain size of the vanadium-based alloy is 20-100 mesh.
Preferably, after the cooling step, a step of removing the oxide layer is further included.
In a third aspect, the present application provides an application of a vanadium-based alloy in the field of hydrogen storage.
The beneficial effects of this application are as follows:
1. the method changes the crystal form of the vanadium alloy through element allocation, and the obtained vanadium alloy has the characteristics of high hydrogen absorption and desorption rate, high hydrogen charging and desorption kinetic performance and large hydrogen storage amount;
2. the activation performance of the vanadium alloy is improved by adding W (transition element and rare earth element), the activation can be completed by circularly charging and discharging hydrogen for a plurality of times in a short time, the activation time of the vanadium alloy is greatly shortened, on the other hand, the hydrogen discharging temperature of beta-phase hydride is influenced, hydrogen stored in the alloy is easier to release, the hydrogen discharging capability at normal temperature and normal pressure is improved, the stability of the hydride is effectively reduced, a hydrogen absorbing platform is flatter, the cycle stability of the vanadium alloy is improved, and the cycle life is prolonged;
3. according to the method, on the basis of alloy proportion and addition of transition elements and rare earth elements, a high-frequency induction smelting method is adopted, so that elements of the vanadium alloy are fused more uniformly, the synergistic effect of the added elements and main elements is fully exerted, the structural stress of the vanadium alloy is eliminated by combining a liquid nitrogen rapid cooling technology, the component segregation is reduced, the diffusion rate of hydrogen atoms is improved, the hydrogen absorption and desorption process is accelerated, and better hydrogen charging and desorption kinetic performance is shown;
4. the control capability of the vanadium alloy on hydrogen adsorption and release is improved through the temperature and time allocation in the high-frequency induction smelting method, so that the effective hydrogen release amount of each cycle of hydrogen charging and releasing is improved, the cycle life of the vanadium alloy is greatly prolonged, and the vanadium alloy is almost free from attenuation after the vanadium alloy is charged and released for a plurality of times;
5. according to the method, the heat-treated vanadium alloy is subjected to quick cooling treatment, so that the alloy is changed into a single BCC phase structure from a two-phase structure, meanwhile, the lattice constant of the alloy is increased along with the increase of the quick quenching cooling speed, the platform pressure of a hydrogen absorption and desorption platform of the alloy can be effectively reduced, the hydrogen desorption amount of the alloy is increased, and meanwhile, more interfaces are exposed on the surface of the alloy by matching with a crushing process, so that the activation process of the vanadium alloy is accelerated by doping the alloy with different meshes in the control range of the meshes, and the improvement of the hydrogen absorption and desorption amount of the vanadium alloy is promoted;
6. the maximum hydrogen absorption amount of the vanadium alloy with the high cycle life is more than or equal to 3.87wt%, the maximum hydrogen discharge amount is more than or equal to 3.11wt%, and the attenuation rate after 50 cycles of life is only 6.9%.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The present application provides a vanadium-based alloy having the chemical formula (FeV a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represents V, ti, cr, W atoms, a is 90 or 95, x is 22-40, y is 20-46, z is 8-27, n/m is 0.3-3.5, and m=100-x-y-z-n; w is one or more of transition metal element and rare earth element. The purity of each element raw material in the alloy component is more than 99.9 percent.
The vanadium alloy element combination under the system can reduce the affinity of hydrogen atoms and vanadium alloy, even if the valence bond force between the hydrogen atoms and the vanadium alloy is weakened, the lower temperature is needed for hydrogen desorption, the problem that the existing vanadium hydrogen storage alloy is not thorough in hydrogen desorption at normal temperature and normal pressure can be solved, and secondly, the hydrogen atoms in the beta phase can be transferred from octahedral gaps to tetrahedral gaps through the element collocation and the proportioning of the system alloy, so that the lattice structure is subjected to phase transformation, the diffusion rate of the hydrogen atoms in a lattice is accelerated, the hydrogen absorption and desorption kinetic performance is improved, and the cycle stability of the vanadium alloy is improved.
The W element in the system alloy is a transition metal element or a rare earth element, the addition of the W element can obviously influence the hydrogen release temperature of beta-phase hydride, so that hydrogen stored in the alloy is easier to release, the hydrogen release capacity at normal temperature and normal pressure is improved, the occupied capacity of hydrogen atoms in crystal lattices in the hydrogen absorption process is enhanced, the fermi level state density is influenced, the stability of the hydride is effectively reduced, a hydrogen absorption platform is flatter, the addition of the rare earth element can shorten the activation time of the vanadium alloy, the activation is completed after the alloy absorbs and releases hydrogen in a short period of circulation at normal temperature and normal pressure, and the total hydrogen absorption and release amount is not influenced.
Preferably, W comprises one or more of Fe, mn, ni, pd, zr.
The application provides a preparation method of vanadium alloy, which comprises the following steps:
s1, mixing FeV according to the proportion a Pre-smelting V, ti and Cr to obtain a mixture;
s2, mixing the mixture with W element in a vacuum state, introducing inert gas to perform electrified smelting, and forming in a die to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, and then cooling and crushing to obtain the vanadium alloy.
Specifically, the preparation method of the vanadium alloy comprises the following steps:
s1, mixing FeV according to the proportion a Weighing the powder of V, ti and Cr serving as main elements, putting the powder into a feeder, adding raw materials layer by adopting a rotary layering method, smelting for the first time by adding one raw material, and obtaining a mixture after all the main elements are pre-smelted; the smelting mode of the step S1 can be one of an induction smelting method, a suspension smelting method and a consumable arc smelting method;
s2, carrying out vacuumizing treatment on a smelting furnace in two steps, adding the mixture after pre-smelting into a crucible, electrifying and carrying out secondary smelting, namely electrifying smelting, wherein the process comprises the steps of adding W element according to a proportion, introducing inert gas in the smelting process, keeping constant current after all metal powder is smelted, continuing smelting, gradually reducing the current to 0, repeating electrifying smelting steps for 2-3 times, and finally casting the smelted alloy into a mould for forming to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, introducing water into a crucible coil, rapidly cooling, polishing an oxide layer on the surface of the crucible coil after cooling, crushing the treated alloy by an oil press, crushing the alloy by a grinder, and sieving the crushed alloy powder by different sieving devices to obtain vanadium alloy; the vanadium alloy is put into a sealed container containing inert gas for preservation.
In the present application, the vacuum state is achieved by the following steps: the reaction vessel of the mixture is subjected to primary vacuum pumping treatment, the vacuum degree of the reaction vessel is 8Pa or less, and then is subjected to secondary vacuum pumping treatment, and the vacuum degree of the reaction vessel is 0.01Pa or less.
In some embodiments, the voltage of the electrified melting is 450-550V, the current is 200-300A, and the melting time is 50-90s.
In some embodiments, the high frequency induction heat treatment is performed at a temperature of 1350-1550 ℃ for a time of 1-5 hours. The high-frequency induction heat treatment method aims at homogenizing the components of the vanadium alloy to obtain finer vanadium alloy particles, eliminating the structural stress of the vanadium alloy, reducing the component segregation, improving the cyclical stability of the vanadium alloy, reducing the hydrogen absorption amount of the alloy due to the fact that the lattice strain of the vanadium alloy is influenced by the fact that the heat treatment temperature is too high or too low, and changing the hydrogen absorption and release platform pressure due to the fact that the size of final grains of the vanadium alloy is influenced by the length of the heat treatment time. It is noted that the induction heating heat treatment can be classified into 5 types of ultrahigh frequency, high frequency, superaudio frequency, intermediate frequency and power frequency according to the frequency of alternating current, the current frequency used for the high frequency induction heating heat treatment is usually 200-300 khz, and the depth of the heating layer is 0.5-2 mm.
In some embodiments, the cooling mode is liquid nitrogen cooling, and the liquid nitrogen cooling can realize rapid cooling, the rapid cooling can change the two-phase structure of the alloy into a single BCC phase structure, and meanwhile, the lattice constant of the alloy also increases along with the increase of the rapid quenching cooling speed, and the hydrogen absorption and desorption platform characteristics of the alloy are obviously improved, so that the hydrogen desorption amount of the alloy is increased.
In some embodiments, the vanadium-based alloy has a particle size of 20-100 mesh, and to produce more crystal lattices and interfaces, the grain size is reduced, the activation performance is improved, and the hydrogen storage capacity and cycle life are improved.
In some embodiments, after the cooling step, an oxide layer removal step is also included.
The application provides application of vanadium alloy in the field of hydrogen storage.
The present application is further illustrated by the following detailed description.
Example 1
A vanadium alloy having the chemical formula (FeV) a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represent the atomic number of V, ti, cr, W, a has the values of 90, x=22, y=43, z=8, n/m=0.8, m=100-x-y-z-n, respectively; w is Ni.
The preparation method of the vanadium alloy comprises the following steps:
s1, mixing FeV according to the proportion 90 Weighing the powder of V, ti and Cr serving as main elements, putting the powder into a feeder, adding raw materials layer by adopting a rotary layering method, smelting for the first time by adding one raw material, and obtaining a mixture after all the main elements are pre-smelted; the smelting mode of the step S1 can be one of an induction smelting method, a suspension smelting method and a consumable arc smelting method;
s2, carrying out primary vacuumizing treatment on the smelting furnace, enabling the vacuum degree of the smelting furnace to reach 8Pa, and carrying out secondary vacuumizing treatment, and enabling the vacuum degree of the smelting furnace to reach 0.01Pa; charging the pre-smelted mixture into a crucible, and electrifying to carry out secondary smelting: adding W element according to a proportion, introducing inert gas in the smelting process, and keeping constant current after all metal powder is smelted, wherein the electrified smelting voltage is 450V, the current is 200A, continuing smelting, gradually reducing the current to 0, repeating the electrified smelting step for 3 times, and finally casting the smelted alloy in a mould for forming to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, wherein the temperature of the high-frequency induction heat treatment is 1350 ℃ and the time is 4 hours, introducing water into a crucible coil, performing rapid liquid nitrogen cooling, polishing an oxide layer on the surface after cooling, crushing the treated alloy by an oil press, crushing the alloy by a grinder, and sieving the crushed alloy powder by a 50-mesh sieving device to obtain vanadium alloy; the vanadium alloy is put into a sealed container containing inert gas for preservation.
Example 2
A vanadium alloy having the chemical formula (FeV) a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represent the atomic number of V, ti, cr, W, a has the values of 95, x=39, y=20, z=8, n/m=1.2, m=100-x-y-z-n, respectively; w is Zr.
The preparation method of the vanadium alloy comprises the following steps:
s1, mixing FeV according to the proportion 95 Weighing the powder of V, ti and Cr serving as main elements, putting the powder into a feeder, adding raw materials layer by adopting a rotary layering method, smelting for the first time by adding one raw material, and obtaining a mixture after all the main elements are pre-smelted; the smelting mode of the step S1 can be one of an induction smelting method, a suspension smelting method and a consumable arc smelting method;
s2, carrying out primary vacuumizing treatment on the smelting furnace, enabling the vacuum degree of the smelting furnace to reach 7Pa, and carrying out secondary vacuumizing treatment, and enabling the vacuum degree of the smelting furnace to reach 0.01Pa; charging the pre-smelted mixture into a crucible, and electrifying to carry out secondary smelting: adding W element according to a proportion, introducing inert gas in the smelting process, and keeping constant current after all metal powder is smelted, wherein the electrified smelting voltage is 550V, the current is 300A, continuing smelting, gradually reducing the current to 0, repeating the electrified smelting step for 2-3 times, and finally casting the smelted alloy in a mould for forming to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, wherein the temperature of the high-frequency induction heat treatment is 1400 ℃, the time is 3 hours, and the crucible coil is filled with water and is subjected to rapid liquid nitrogen cooling, the oxidation layer on the surface is polished after cooling, the treated alloy is crushed by an oil press, and the crushed alloy powder is sieved by a 40-mesh sieving device to obtain vanadium alloy; the vanadium alloy is put into a sealed container containing inert gas for preservation.
Example 3
A vanadium alloy having the chemical formula (FeV) a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represent the atomic number of V, ti, cr, W, a has the values of 90, x=26, y=46, z=20, n/m=0.6, m=100-x-y-z-n, respectively; w is Mn.
The preparation method of the vanadium alloy comprises the following steps:
s1, mixing FeV according to the proportion 95 Weighing the powder of V, ti and Cr serving as main elements, putting the powder into a feeder, adding raw materials layer by adopting a rotary layering method, smelting for the first time by adding one raw material, and obtaining a mixture after all the main elements are pre-smelted; the smelting mode of the step S1 can be one of an induction smelting method, a suspension smelting method and a consumable arc smelting method;
s2, carrying out primary vacuumizing treatment on the smelting furnace, enabling the vacuum degree of the smelting furnace to reach 8Pa, and carrying out secondary vacuumizing treatment, and enabling the vacuum degree of the smelting furnace to reach 0.01Pa; charging the pre-smelted mixture into a crucible, and electrifying to carry out secondary smelting: adding W element according to a proportion, introducing inert gas in the smelting process, and keeping constant current after all metal powder is smelted, wherein the voltage of electrified smelting is 500V, the current is 250A, continuing smelting, gradually reducing the current to 0, repeating the electrified smelting step for 3 times, and finally casting the smelted alloy in a mould for forming to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, wherein the temperature of the high-frequency induction heat treatment is 1550 ℃ and the time is 1h, introducing water into a crucible coil, performing rapid liquid nitrogen cooling, polishing an oxide layer on the surface after cooling, crushing the treated alloy by an oil press, crushing the alloy by a grinder, and sieving the crushed alloy powder by a 80-mesh sieving device to obtain vanadium alloy; the vanadium alloy is put into a sealed container containing inert gas for preservation.
Example 4
A vanadium alloy having the chemical formula (FeV) a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m respectively represent the atomic number of V, ti, cr, W, a has a value of 90, x=40, y=23. z=27, n/m=1.5, m=100-x-y-z-n; w is Ni.
The preparation method of the vanadium alloy comprises the following steps:
s1, mixing FeV according to the proportion 95 Weighing the powder of V, ti and Cr serving as main elements, putting the powder into a feeder, adding raw materials layer by adopting a rotary layering method, smelting for the first time by adding one raw material, and obtaining a mixture after all the main elements are pre-smelted; the smelting mode of the step S1 can be one of an induction smelting method, a suspension smelting method and a consumable arc smelting method;
s2, carrying out primary vacuumizing treatment on the smelting furnace, enabling the vacuum degree of the smelting furnace to reach 8Pa, and carrying out secondary vacuumizing treatment, and enabling the vacuum degree of the smelting furnace to reach 0.01Pa; charging the pre-smelted mixture into a crucible, and electrifying to carry out secondary smelting: adding W element according to a proportion, introducing inert gas in the smelting process, and keeping constant current after all metal powder is smelted, wherein the electrified smelting voltage is 550V, the current is 300A, continuing smelting, gradually reducing the current to 0, repeating the electrified smelting step for 3 times, and finally casting the smelted alloy in a mould for forming to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, wherein the temperature of the high-frequency induction heat treatment is 1350 ℃ and the time is 5 hours, introducing water into a crucible coil, performing rapid liquid nitrogen cooling, polishing an oxide layer on the surface after cooling, crushing the treated alloy by an oil press, crushing the alloy by a grinder, and sieving the crushed alloy powder by a 20-mesh sieving device to obtain vanadium alloy; the vanadium alloy is put into a sealed container containing inert gas for preservation.
Example 5
A vanadium-based alloy was the same as in example 1, except that x=40, y=20, z=10, n/m=2, and m=100-x-y-z-n.
Example 6
A vanadium-based alloy was the same as in example 1, except that x=25, y=22, z=13, n/m=1, and m=100-x-y-z-n.
Comparative example 1
A vanadium-based alloy was the same as in example 1, except that z=3.
Comparative example 2
A vanadium-based alloy was the same as in example 1, except that z=30.
Comparative example 3
A vanadium alloy was the same as in example 1, except that n/m=0.2.
Comparative example 4
A vanadium alloy was the same as in example 1, except that n/m=4.0.
Comparative example 5
The vanadium alloy was the same as in example 2, except that in step S2, the primary vacuum treatment was performed on the melting furnace to a vacuum degree of 10Pa, and the secondary vacuum treatment was performed to a vacuum degree of 0.05Pa.
Comparative example 6
A vanadium alloy was prepared in the same manner as in example 3, except that the high-frequency induction heat treatment was conducted at 1200 ℃.
Comparative example 7
A vanadium alloy was prepared in the same manner as in example 3 except that the high-frequency induction heat treatment was conducted at 1700 ℃.
Comparative example 8
A vanadium alloy was prepared in the same manner as in example 3, except that the high-frequency induction heat treatment was conducted for 20 minutes.
Comparative example 9
A vanadium alloy was prepared in the same manner as in example 3, except that the high-frequency induction heat treatment was conducted for 8 hours.
Comparative example 10
A vanadium alloy was prepared in the same manner as in example 4, except that the voltage for melting by energization was 300V and the current was 100A.
Comparative example 11
A vanadium alloy was prepared in the same manner as in example 4, except that the voltage for melting by energization was 800V and the current was 300A.
Comparative example 12
A vanadium-based alloy was the same as in example 5 except that the pulverized alloy powder was sieved by a 10-mesh sieving apparatus.
Comparative example 13
A vanadium-based alloy was the same as in example 5 except that the pulverized alloy powder was sieved by a 200-mesh sieving device.
Comparative example 14
A vanadium alloy was prepared in the same manner as in example 6, except that the liquid nitrogen cooling was changed to cold water cooling.
Evaluation test
The vanadium-based alloys of examples 1 to 6 and comparative examples 1 to 14 were subjected to performance test, and the results are shown in Table 1.
Maximum hydrogen absorption amount: the vanadium alloy absorbs hydrogen to a saturated value in the first period (first week) of completing activation under the pressure and the temperature of hydrogen;
maximum hydrogen discharge amount: the vanadium alloy starts to release hydrogen to the testing value after the end in the first period (first week) of completing activation under the stop pressure and the temperature;
number of activation cycles: the vanadium alloy is subjected to one activation cycle from the initial state without hydrogen absorption and desorption, until the maximum hydrogen absorption amount of the vanadium alloy is higher than or close to the theoretical hydrogen absorption amount of the vanadium alloy material, the activation is considered to be completed, and the cycle number of the activation is the activation cycle.
Cyclic decay rate: the value obtained by subtracting the residual hydrogen amount under the cut-off pressure from the maximum hydrogen absorption amount in each period of the vanadium alloy is the effective hydrogen release amount, and the value obtained by dividing the difference between the effective hydrogen release amount in the previous period and the effective hydrogen release amount in the next period by the effective hydrogen release amount in the first period after the initial activation is the cyclic attenuation rate.
Hydrogen absorption kinetics time: the vanadium alloy starts from the end of the last period of hydrogen release to the whole time that the next period of hydrogen absorption reaches saturation.
In the test process, the hydrogen charging pressure is 5-8MPa, the hydrogen discharging cut-off pressure range is 0.1-0.25 MPa, the hydrogen absorption temperature is 273-293K, and the hydrogen discharging temperature is 298-323K.
Table 1 test results
As can be seen from comparison of comparative examples 1 and 2 with example 1, too low content of Ti element can lead to higher hydrogen release temperature of vanadium alloy compared with example 1 under the system formula, thereby reducing the hydrogen release amount of vanadium alloy, leading to incomplete hydrogen release, even affecting the hydrogen release rate, showing poor hydrogen release kinetics, mainly because the content of Ti element can cause the hydrogen release temperature of beta-phase hydride, and because the beta-phase needs higher hydrogen release temperature, the addition of Ti element changes the hydrogen release temperature of beta-phase hydride and also changes the stability of beta-phase hydride; the too high content of Ti element can lead to the reduction of the platform pressure of the vanadium alloy compared with the embodiment 1 under the system formula, namely, the hydrogen release is incomplete under the condition of certain hydrogen release cut-off pressure, the hydrogen release amount is less than the embodiment 1, in addition, the too high content of Ti element is unfavorable for the stability of hydride in the hydrogen absorption process, the hydrogen absorption amount is less, the main reason is that the too high content of Ti element leads to higher interfacial energy between different elements and density difference between the two, segregation is generated in smelting, the hydride in the hydrogen absorption process is in an unstable state, and the hydrogen absorption amount is reduced.
As can be seen from comparison of comparative examples 3 and 4 with example 1, the ratio of Cr to W is too low, the hydrogen absorption and reversible hydrogen storage of the alloy are greatly reduced, and the hydrogen absorption and desorption rate is also slow, mainly because the excessive addition of W makes the alloy phase not uniform, inhibits the nature of V, ti and other elements, and leads to poor hydrogen absorption and desorption performance; the ratio of Cr to W element is too high, the alloy has hydrogen charging and discharging performance after activation inoculation for a long time at room temperature, the activation period is long, and the cycle performance is poor, because the W element is too low, the vanadium alloy does not have the effect of catalytic acceleration in the activation process, the energy barrier between the alloy and hydrogen combination cannot be reduced, the activation performance is poor, and the hydrogen absorbing and discharging circularity is vivid.
As is clear from comparison of comparative example 5 and example 2, in comparative example 5, the maximum hydrogen charge amount of the vanadium alloy is found to be lower in the test, the effective hydrogen discharge amount is also less, the attenuation is found to be faster after several times of cyclic hydrogen charging and discharging, and the hydrogen storage performance is reduced because the two times of vacuumizing parameters do not reach the required parameters. The main reason is that the process is not carried out according to the technology, so that the surface of the vanadium alloy gathers and adsorbs some carbon and oxygen elements in the smelting process, and the residual carbon and oxygen elements cover the surface of the vanadium alloy, so that the combined adsorption of hydrogen atoms and the alloy is blocked, the hydrogen absorption amount of the alloy is seriously reduced, and the aim of re-use cannot be achieved even after shorter cyclic charging and discharging.
As can be seen from comparison of comparative examples 6 and 7 with example 3, when the high-frequency induction heat treatment temperature is too low, the hydrogen absorption amount of the alloy is low, the effective hydrogen storage amount is also low, and several times of cycle life tests show that the attenuation rate is higher than that of example three, mainly because the too low heat treatment temperature enables the crystal lattice in the vanadium alloy to be converted from one phase to the other phase, so that hydrogen atoms are transferred from octahedral gaps to tetrahedral gaps, the hydrogen absorption amount of the alloy is reduced, and the cycle life of the alloy is naturally influenced; when the high-frequency induction heat treatment temperature is too high, the alloy has lower hydrogen absorption and desorption amount and lower effective hydrogen storage amount, and the attenuation rate is higher than that of the third embodiment through several times of cycle life tests. The main reason is that the lattice constant of the alloy is abnormal due to the higher heat treatment temperature, so that the difficulty of adsorption and separation of hydrogen atoms and the alloy is increased, and the hydrogen absorption and desorption amount of the alloy is reduced.
As can be seen from comparison of comparative examples 8 and 9 with example 3, when the high-frequency induction heat treatment time is shorter, the first-week hydrogen absorption amount of the vanadium alloy prepared by the process is lower, the cycle attenuation rate is higher, and the main reasons are that the insufficient heat treatment time can cause the lack of uniformity of components of the vanadium alloy, and the uniformity of the distribution of each element in the alloy is not high, so that the generation of hydrogen absorption and hydrogen release phase change is influenced, the first-week hydrogen absorption amount is lower, and the cycle attenuation rate is higher; when the high-frequency induction heat treatment time is longer, the effective hydrogen release amount of the vanadium alloy prepared by the process is lower, the cycle performance is also poor compared with that of the third embodiment, and the vanadium alloy shows higher attenuation rate. The main reason is that the alloy crystal grains are coarsened by long-time heat treatment, and the crystal boundary is partially melted, so that the crystal boundary is too weak, thereby affecting the absorption and release capacity of the alloy to hydrogen atoms and causing poor hydrogen storage performance.
As can be seen from comparison of comparative examples 10 and 11 with example 4, the lower voltage and current in the smelting process causes uneven surface, more protrusions, long activation period of the alloy, and slower hydrogen absorption rate, and poorer hydrogen absorption and desorption kinetics, mainly because the lower smelting voltage and current cause elements such as gap impurity C, O in the alloy not to be controlled to the minimum, and the impurity elements exist in the vanadium alloy formed by smelting, thus the alloy has poorer activation performance and slower hydrogen absorption rate; the high voltage and current in the smelting process cause the poor performance of the alloy after smelting, the slow hydrogen absorption and desorption rate and the long activation period are shown, and the main reasons are that the high smelting voltage and current influence the occupying positions of hydrogen atoms in the solid solution alloy, and the different occupying positions influence the diffusion rate of the hydrogen atoms, so the hydrogen absorption and desorption performance is poor.
As can be seen from comparison of comparative examples 12 and 13 with example 5, the reasonable mesh number arrangement allows favorable chain reaction to occur in the activation process, i.e., after partial activation, the alloy quickly drives the other part to activate, thereby accelerating the activation process, and further exhibiting better hydrogen charging and discharging performance and longer cycle life.
As can be seen from the comparison between comparative example 14 and example 6, the maximum hydrogen absorption of the vanadium alloy prepared in comparative example 14 is small at room temperature, and the attenuation rate of hydrogen absorption and desorption is large after several cycles, mainly because water cooling is slow cooling, the vanadium alloy has poor kinetic performance of hydrogen absorption and desorption due to the fact that the components in the alloy structure segregate due to large temperature difference between the inner and outer parts after the surface is contacted with the inner part of the water, the grain size and the grain boundary size in the forming process are affected, the diffusion rate of hydrogen atoms in alloy crystal lattice is reduced, and the hydrogen absorption rate is slow.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A vanadium alloy, characterized in that the chemical formula is (FeV a ) x V y Ti z Cr n W m The method comprises the steps of carrying out a first treatment on the surface of the Wherein a represents FeV a X, y, z, n, m represents V, ti, cr, W atoms, a is 90 or 95, x is 22-40, y is 20-46, z is 8-27, n/m is 0.3-3.5, and m=100-x-y-z-n; w is one or more of transition metal element and rare earth element.
2. The vanadium-based alloy according to claim 1, wherein W comprises one or more of Fe, mn, ni, pd, zr.
3. A method for producing the vanadium-based alloy according to any one of claims 1 to 2, comprising the steps of:
s1, mixing FeV according to the proportion a Pre-smelting V, V, ti, cr to obtain a mixture;
s2, mixing the mixture with W element in a vacuum state, introducing inert gas to perform electrified smelting, and forming in a die to obtain a formed alloy;
s3, performing high-frequency induction heat treatment on the formed alloy, and then cooling and crushing to obtain the vanadium alloy.
4. A method of manufacturing according to claim 3, wherein the vacuum state is achieved by: the reaction vessel of the mixture is subjected to primary vacuum pumping treatment, the vacuum degree of the reaction vessel is 8Pa or less, and then is subjected to secondary vacuum pumping treatment, and the vacuum degree of the reaction vessel is 0.01Pa or less.
5. A method of manufacture according to claim 3 wherein the power-on smelting is at a voltage of 450-550V and a current of 200-300A.
6. The method according to claim 3, wherein the high-frequency induction heat treatment is carried out at 1350-1550 ℃ for 1-5 hours.
7. A method of manufacture according to claim 3, wherein the cooling is by liquid nitrogen cooling.
8. The method according to claim 3, wherein the vanadium-based alloy has a particle size of 20 to 100 mesh.
9. The method of claim 3, further comprising a step of removing an oxide layer after the cooling step.
10. Use of a vanadium-based alloy according to any one of claims 1-2 in the field of hydrogen storage.
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