CN102443730A - Hydrogen storage alloy - Google Patents
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- CN102443730A CN102443730A CN2010105104780A CN201010510478A CN102443730A CN 102443730 A CN102443730 A CN 102443730A CN 2010105104780 A CN2010105104780 A CN 2010105104780A CN 201010510478 A CN201010510478 A CN 201010510478A CN 102443730 A CN102443730 A CN 102443730A
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Abstract
The invention relates to a hydrogen storage alloy, which is a high-entropy alloy and has a molecular formula general formula of CouFevMnwTixVyZrz. The hydrogen storage alloy is an alloy material without rare earth elements and has a single C14 laves phase structure, in addition, the structure is stable, and in addition, high hydrogen storage and hydrogen release capability and high room temperature hydrogen storage quantity are realized in normal temperature and normal pressure work environment. The hydrogen storage alloy can be widely applied to hydrogen storage, heat storage, heat pumping, hydrogen purification and isotope separation and is used in the fields of secondary batteries, fuel batteries and the like, in addition, pollution gas harmful to the earth cannot be produced, and the hydrogen storage alloy belongs to a green environment-friendly energy source with great development potential.
Description
Technical field
The present invention relates to a kind of hydrogen storage alloy that does not have REE, particularly a kind of have the stable alloy structure and high suction hydrogen/the put hydrogen storage alloy of Hydrogen Energy power and hydrogen-storage amount arranged at normal temperatures.
Background technology
Because many harm that the ignition of energy dilemma and the method for use of the existing energy cause the earth; The exploitation of green energy resource just becomes the development project of being gazed at most; Can be under most economical situation such as how; Use natural hydrogen energy source, sun power, give birth to mass-energy source, underground heat, the damp silicon energy etc., can not pollute the energy and the method for threat, all receive extensive studies environment.
Hydrogen is the third-largest chemical element of standing stock on the earth, when it burns, can generate the heat of 140 kilojoule/kilograms (kJ/kg), and hydrogen is except having the good advantage of efficiency of combustion; Its products of combustion is not for causing the water of any pollution; Thereby become very powerful and exceedingly arrogant green energy resource, wherein nickel metal hydride battery is because having reserve of electricity reaches the high advantage of stability greatly, so each field is when selecting the energy for use; Nickel metal hydride battery also enjoys to be gazed at, the emphasis R&D direction when especially becoming the exploitation Hydrogen Fuel-cell Vehicles; But hydrogen is because have inflammableness; Therefore be that the energy is when generating electricity with hydrogen; The security of hydrogen storage just becomes an important problem; Hydrogenate (hydride) because have low price, safe, can not produce greenhouse gases, high unit storage capacity and absorb/disengage the characteristic of hydrogen easily, and be considered to be excellent hydrogen storage material.
High-entropy alloy (high-entropy alloy; HEA) be the material of extensively being noted in recent years; It is to comprise at least five kinds of elements; And with every kind of atoms of elements number per-cent (atomic percent) between 5 to 35%; At high temperature with after mutual uniform mixing of the state of liquid phase and the cooling; Generation has the alloy hydrogen storage material of high entropy and the low gloomy Gibbs free energy of lucky cloth characteristic, compare with general conventional alloys, high-entropy alloy have simple microstructure, easily form nano level prepared product, thermostability high, have good extension or compression property, hardness high, have remarkable electrically and the advantage of magnetic; But the metallic element of being selected for use when forming this kind alloy material, the ratio etc. of adding metallic element all can or be inhaled hydrogen/put hydrogen usefulness to produce great effect to the storage hydrogen of alloy, therefore essential optimizing condition when seeking alloy and using.
Summary of the invention
In order to reach the optimized hydrogen storage property of hydrogen storage alloy and to strengthen its application, the invention provides and a kind ofly utilize vacuum arc melting (vacuum arc remelting, VAM) the casting attitude high-entropy alloy that is prepared from of mode also can be heat-treated in case of necessity.
Hydrogen storage alloy of the present invention has Co
uFe
vMn
wTi
xV
yZr
zThe molecular formula general formula, wherein 0.5≤u≤2.0,0.5≤v≤2.5,0.5≤w≤2.0,0.5≤x≤2.5,0.4≤y≤3.0 and 0.4≤z≤3.0 are represented with atom number per-cent, the Co composition is between 9.0 to 28.6, all the other compositions are between 14.3 to 18.2; Or the Fe composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the Mn composition is between 9.0 to 28.6, and all the other compositions are between 14.3 to 18.2; Or the Ti composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the V composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the Zr composition is between 7.5 to 37.5, and all the other compositions are between 12.5 to 18.5; Therefore, this hydrogen storage alloy is a kind of non-equimolar alloy material, has the structure of single C14 Laves phase; And Stability Analysis of Structures; Can under the Working environment of normal temperature and pressure, have and inhale hydrogen and the ability of putting hydrogen, and " Wasserstoffatoms is to the alloy atom sum weight percent ratio (H/M value) " of high " expression hydrogen-storage amount "; Here, the per-cent ratio of microcrith and alloy atom gross weight (H/M value) expression hydrogen-storage amount.
Hydrogen storage alloy of the present invention can be widely used in storing hydrogen, thermmal storage, heat pump Pu, hydrogen purifying and separation of isotopes, and is used for fields such as secondary cell and fuel cell.
Description of drawings
Fig. 1 is all alloying constituent distribution range synoptic diagram of hydrogen storage alloy of the present invention;
Fig. 2 A is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy before carrying out the test of pressure composition isothermal curve that the present invention contains different titanium contents;
Fig. 2 B is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy after carrying out the test of pressure composition isothermal curve that the present invention contains different titanium contents;
Fig. 3 be hydrogen storage alloy of the present invention under differing temps, the graph of a relation of the hydrogen storage alloy hydrogen-absorbing ability of different titanium contents;
Fig. 4 A is the pressure composition isothermal curve figure of hydrogen storage alloy in the time of 25 ℃ that the present invention contains different titanium contents;
Fig. 4 B is the pressure composition isothermal curve figure of hydrogen storage alloy in the time of 80 ℃ that the present invention contains different titanium contents;
Fig. 5 A is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy before carrying out the test of pressure composition isothermal curve that the present invention contains different content of vanadium;
Fig. 5 B is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy after carrying out the test of pressure composition isothermal curve that the present invention contains different content of vanadium;
Fig. 6 be hydrogen storage alloy of the present invention under differing temps, the graph of a relation of the hydrogen storage alloy hydrogen-absorbing ability of different content of vanadium;
Fig. 7 A is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy before carrying out the test of pressure composition isothermal curve that the present invention contains different content of vanadium;
Fig. 7 B is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy after carrying out the test of pressure composition isothermal curve that the present invention contains different content of vanadium;
Fig. 8 be hydrogen storage alloy of the present invention under differing temps, the graph of a relation of the hydrogen storage alloy hydrogen-absorbing ability of different content of vanadium;
Fig. 9 A is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy before carrying out the test of pressure composition isothermal curve that the present invention contains different manganese content;
Fig. 9 B is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy after carrying out the test of pressure composition isothermal curve that the present invention contains different manganese content;
Figure 10 be hydrogen storage alloy of the present invention under differing temps, the graph of a relation of the hydrogen storage alloy hydrogen-absorbing ability of different manganese content;
Figure 11 A is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy before carrying out the test of pressure composition isothermal curve that the present invention contains different cobalt content;
Figure 11 B is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy after carrying out the test of pressure composition isothermal curve that the present invention contains different cobalt content;
Figure 12 be hydrogen storage alloy of the present invention under differing temps, the graph of a relation of the hydrogen storage alloy hydrogen-absorbing ability of different cobalt content;
Figure 13 A is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy before carrying out the test of pressure composition isothermal curve that the present invention contains different iron levels;
Figure 13 B is the X-ray diffraction collection of illustrative plates of hydrogen storage alloy after carrying out the test of pressure composition isothermal curve that the present invention contains different iron levels;
Figure 14 be hydrogen storage alloy of the present invention under differing temps, the graph of a relation of the high entropy hydrogen storage alloy hydrogen-absorbing ability of different iron levels.
Description of reference numerals: in an embodiment of the present invention, all alloys that contains 1.0 mol ratios are all equal, i.e. A2=B3=C3=D4=E4=F2.These moles alloy is the non-index alloy that waits the mole alloy of different metal conversion content in the related alloy system.
A1-contains the high entropy hydrogen storage alloy of 0.5 mol ratio titanium; A2-contains the high entropy hydrogen storage alloy of 1.0 mol ratio titaniums; A3-contains the high entropy hydrogen storage alloy of 1.5 mol ratio titaniums; A4-contains the high entropy hydrogen storage alloy of 2.0 mol ratio titaniums; A5-contains the high entropy hydrogen storage alloy of 2.5 mol ratio titaniums; B1 contains the high entropy hydrogen storage alloy of 0.4 mol ratio zirconium; B2-contains the high entropy hydrogen storage alloy of 0.7 mol ratio zirconium; B3-contains the high entropy hydrogen storage alloy of 1.0 mol ratio zirconiums; B4-contains the high entropy hydrogen storage alloy of 1.3 mol ratio zirconiums; B5-contains the high entropy hydrogen storage alloy of 1.7 mol ratio zirconiums; B6-contains the high entropy hydrogen storage alloy of 2.0 mol ratio zirconiums; B7-contains the high entropy hydrogen storage alloy of 2.3 mol ratio zirconiums; B8-contains the high entropy hydrogen storage alloy of 2.6 mol ratio zirconiums; B9-contains the high entropy hydrogen storage alloy of 3.0 mol ratio zirconiums; C1-contains the high entropy hydrogen storage alloy of 0.4 mol ratio vanadium; C2-contains the high entropy hydrogen storage alloy of 0.7 mol ratio vanadium; C3-contains the high entropy hydrogen storage alloy of 1.0 mol ratio vanadium; C4-contains the high entropy hydrogen storage alloy of 1.3 mol ratio vanadium; C5-contains the high entropy hydrogen storage alloy of 1.7 mol ratio vanadium; C6-contains the high entropy hydrogen storage alloy of 2.0 mol ratio vanadium; C7-contains the high entropy hydrogen storage alloy of 2.3 mol ratio vanadium; C8-contains the high entropy hydrogen storage alloy of 2.6 mol ratio vanadium; C9-contains the high entropy hydrogen storage alloy of 3.0 mol ratio vanadium; D1-contains the high entropy hydrogen storage alloy of 0 mol ratio manganese; D2-contains the high entropy hydrogen storage alloy of 0.5 mol ratio manganese; D3-contains the high entropy hydrogen storage alloy of 0.75 mol ratio manganese; D4-contains the high entropy hydrogen storage alloy of 1.0 mol ratio manganese; D5-contains the high entropy hydrogen storage alloy of 1.25 mol ratio manganese; D6-contains the high entropy hydrogen storage alloy of 1.5 mol ratio manganese; D7-contains the high entropy hydrogen storage alloy of 2.0 mol ratio manganese; E1-contains the high entropy hydrogen storage alloy of 0 mol ratio cobalt; E2-contains the high entropy hydrogen storage alloy of 0.5 mol ratio cobalt; E3-contains the high entropy hydrogen storage alloy of 0.75 mol ratio cobalt; E4-contains the high entropy hydrogen storage alloy of 1.0 mol ratio cobalts; E5-contains the high entropy hydrogen storage alloy of 1.25 mol ratio cobalts; E6-contains the high entropy hydrogen storage alloy of 1.5 mol ratio cobalts; E7-contains the high entropy hydrogen storage alloy of 2.0 mol ratio cobalts; F1-contains the high entropy hydrogen storage alloy of 0.5 mol ratio iron; F2-contains the high entropy hydrogen storage alloy of 1.0 mol ratio iron; F3-contains the high entropy hydrogen storage alloy of 1.25 mol ratio iron; F4-contains the high entropy hydrogen storage alloy of 1.5 mol ratio iron; F5-contains the high entropy hydrogen storage alloy of 2.0 mol ratio iron; F6-contains the high entropy hydrogen storage alloy of 2.5 mol ratio iron; 1-25 ℃ of suction hydrogen efficiency curve down; 2-80 ℃ of suction hydrogen efficiency curve down; 3-150 ℃ of suction hydrogen efficiency curve down.
Embodiment
Below in conjunction with embodiment the present invention is described further, it should be understood that these embodiment only are used for the purpose of illustration, never limit protection scope of the present invention.
Hydrogen storage alloy of the present invention has Co
uFe
vMn
wTi
xV
yZr
zThe molecular formula general formula, wherein 0.5≤u≤2.0,0.5≤v≤2.5,0.5≤w≤2.0,0.5≤x≤2.5,0.4≤y≤3.0 and 0.4≤z≤3.0 are represented with atom number per-cent, the Co composition is between 9.0 to 28.6, all the other compositions are between 14.3 to 18.2; Or the Fe composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the Mn composition is between 9.0 to 28.6, and all the other compositions are between 14.3 to 18.2; Or the Ti composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the V composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the Zr composition is between 7.5 to 37.5, and all the other compositions are between 12.5 to 18.5.。
Embodiment 1: the preparation method that hydrogen storage alloy of the present invention is common, also can use reciprocity preparation method, like machine-alloying.
Hydrogen storage alloy of the present invention is to use vacuum arc melting furnace (vacuum arc remelter; VAM) by pure metal bulk melting and casting; Manufacture alloy, it is that each pure metal is placed on the cooling copper crucible, and open vacuum pump (vacuum pump) makes pressure reach 2 * 10 subsequently
-2Behind the holder ear (torr), the vacuum pump valve is shut, repeated to feed argon gas and make pressure be maintained at 200torr for several times; When guaranteeing in the stove that oxygen partial pressure is enough low, just feed and be lower than the 1 atmospheric argon gas and the electric arc that ignites, with Metal Melting to molten soup shape; To dissolve even stirring of metal of soup shape with electric arc after, stop electric current, with the alloy turn-over; The remelt of laying equal stress on refining step treats that alloy cools off the back fully and takes out for several times.
Embodiment 2: the influence of different titaniums (Ti) metal content
As shown in Figure 1, for understanding special metal under the situation of different mol ratio,, be under the situation of fixing other metal content for the influence of hydrogen storage alloy characteristic, adjust single indivedual special metal content, for example, and in the present embodiment, promptly with Co
uFe
vMn
wTi
xV
yZr
zMolecular formula be general formula, coefficients such as u, v, w, y and z are fixed as 1, with via adjustment x value (CoFeMnTi
xVZr, 0.5≤x≤2.5) understand of the influence of titanium metal content to the hydrogen storage alloy characteristic.
Shown in Fig. 2 to 4; The content mobility scale of titanium metal is set in 0.5≤x≤2.5; Or with atom number percentage ratio (atomic percent) expression, the composition of Ti is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; And carry out crystal, microstructure, suction hydrogen kinetics and inhale hydrogen and put the ability test of hydrogen, wherein label A1 to A5 representes that respectively the mol ratio of titanium metal in the hydrogen storage alloy is 0.5,1.0,1.5,2.0 and 2.5.In X-ray diffraction collection of illustrative plates, can find out; This hydrogen storage alloy has the C14-Laves phase; And lattice is increased and crest is produced to right-hand displacement, this is because the atomic diameter of titanium metal, than other atoms metal mean diameter in the alloy big due to.Under differing temps (25 ℃ and 80 ℃), hydrogen storage alloy is reaching 90% o'clock of maximum hydrogen, the needed time (t0.9); Can increase with titanium metal content; Tailing off gradually becomes big more gradually, and under lower temperature (25 ℃), reach t0.9 also needs the long time; In pressure composition isothermal curve (hereinafter to be referred as PCI) is analyzed; Can find out under 25 ℃ and 80 ℃; When titanium metal content increases, because the avidity of hydrogen is promoted, so the microcrith of expression hydrogen-storage amount is to alloy atom sum weight percent ratio (hereinafter to be referred as the H/M value); Being all gradually increases, and the Wasserstoffatoms of maximum storage hydrogen quantity to alloy atom sum weight percent ratio (hereinafter to be referred as (H/M)
MaxValue) be all 1.8, and (H/M) under the low temperature
MaxValue is mostly than pyritous (H/M)
MaxValue is for big, and this meets inhales the theory that hydrogen act as thermopositive reaction, has only when the mol ratio of titanium metal is 2.5, and (H/M) value all has a declining tendency under the differing temps, and (H/M) under the high temperature
MaxValue is than cryogenic (H/M)
MaxValue is for big, possibly be because titanium metal content when too much, some segregations (segregation) phenomenon can occur, and at high temperature, occurs due to titanium metal separates out.Different titanium content alloys carry out PCI analyze before and after lattice parameter and cubical expansivity as shown in table 1.
Table 1
Embodiment 3: the influence of different zirconiums (Zr) metal content
Be the influence for the hydrogen storage alloy characteristic of the zirconium metal of understanding different mol ratio, as shown in Figure 1, under the situation of fixing other metal content, adjustment zirconium metal content is promptly with CoFeMnTiVZr
zMolecular formula; Conversion Zr composition, scope be in 0.4≤z≤3.0, or represent with atom number per-cent; The composition of Zr is between 7.5 to 37.5; All the other compositions and carry out crystal, microstructure, suction hydrogen kinetics and inhale hydrogen and put the ability test of hydrogen between 12.5 to 18.5, and wherein label B1 to B9 representes that respectively the mol ratio of zirconium metal in the hydrogen storage alloy is 0.4,0.7,1.0,1.3,1.7,2.0,2.3,2.6 and 3.0.As shown in Figure 5; By finding out in the X-ray diffraction collection of illustrative plates when the zirconium metal content increases; Titanium metal and zirconium metal lattice increased, therefore be moved to the left, so all can produce significantly influence to the lattice parameter (lattice constants) of hydrogenate at (110) crest; As shown in Figure 6 again, when the content of zirconium metal in the hydrogen storage alloy increases, can make the hydrogen-absorbing ability of hydrogen storage alloy improve, and when the temperature of effect environment reduces, also can promote the hydrogen-absorbing ability of hydrogen storage alloy.In addition; Carrying out to find that when the content of zirconium metal in the hydrogen storage alloy was 1.6 mol ratios, the lattice volume can be expanded 23.83% (as shown in table 2) when PCI analyzes; Make an explanation as if X-ray diffraction collection of illustrative plates that this result is arranged in pairs or groups; Just can explain to contain in the many hydrogen storage alloys of zirconium, still have many " remaining hydrogens ", therefore have good hydrogen-absorbing ability.Table 2 is carrying out PCI analysis front and back lattice parameter and cubical expansivity for the zirconium metal.
Table 2
Embodiment 4: the influence of different vanadium (V) metal content
Like Fig. 1, Fig. 7 and shown in Figure 8, be the influence of the vanadium metal of understanding different mol ratio for the hydrogen storage alloy characteristic, under the situation of fixing other metal content, adjustment vanadium metal content is promptly with CoFeMnTiV
yThe molecular formula of Zr; Conversion V composition, scope be in 0.5≤y≤2.5, or represent with atom number per-cent; The composition of V is between 9.0 to 33.3; All the other compositions and carry out crystal, microstructure, suction hydrogen kinetics and inhale hydrogen and put the ability test of hydrogen between 13.3 to 18.2, and wherein label C1 to C9 representes that respectively the mol ratio of vanadium metal in the hydrogen storage alloy is 0.4,0.7,1.0,1.3,1.7,2.0,2.3,2.6 and 3.0.In X-ray diffraction collection of illustrative plates, can find out; Hydrogen storage alloy can't increase because of the addition of vanadium metal; And each crest location in the X-ray diffraction collection of illustrative plates is produced significantly influence; This is because the atomic diameter of vanadium metal is all littler than titanium and zirconium metal, near alloy average atom diameter, therefore can not produce obviously influence (as shown in table 3) for the lattice size; And the hydrogen-absorbing ability of different vanadiumcontent alloys can't receive Influence of Temperature fully, but because of the synthetic enthalpy between vanadium metal and hydrogen is-37.4kJ/mol/H
2, so the many alloys of vanadiumcontent very come out hydrogen release easily.Table 3 is carrying out PCI analysis front and back lattice parameter and cubical expansivity for different vanadiumcontents in the hydrogen storage alloy.
Table 3
Embodiment 5: the influence of different manganese (Mn) content
To shown in Figure 10, be the influence for the hydrogen storage alloy characteristic of the manganese metal of understanding different mol ratio like Fig. 1, Fig. 9, under the situation of fixing other metal content, adjustment manganese metal content is promptly with CoFeMn
wThe molecular formula of TiVZr; Conversion Mn composition, scope be in 0.5≤w≤2.0, or represent with atom number per-cent; The composition of Mn is between 9.0 to 28.6; All the other compositions and carry out crystal, microstructure, suction hydrogen kinetics and inhale hydrogen and put the ability test of hydrogen between 14.3 to 18.2, and wherein label D1 to D7 representes that respectively the mol ratio of manganese metal in the hydrogen storage alloy is 0,0.5,0.75,1.0,1.25,1.5 and 2.0.When adding the manganese metal of different content in the hydrogen storage alloy; Also because the atomic diameter of manganese is less; So on X-ray diffraction collection of illustrative plates, do not produce the phenomenon of crest skew yet, in addition, as shown in table 4; Reach the required time of 90% maximum hydrogen mostly in 100 seconds, the maximum hydrogen of hydrogen storage alloy and maximum hydrogen desorption capacity then are respectively 1.94 and 1.39 weight percents.Table 4 is each item characteristic of different manganese contents under differing temps in the hydrogen storage alloy.
Table 4
Embodiment 6: the influence of different cobalt (Co) content
To shown in Figure 12, be the influence for the hydrogen storage alloy characteristic of the cobalt metal of understanding different mol ratio like Fig. 1, Figure 11, under the situation of fixing other metal content, adjustment cobalt metal content is promptly with Co
uThe molecular formula of FeMnTiVZr; Conversion Co composition, scope are represented with atom number per-cent in 0.5≤u≤2.0; The composition of Co is between 9.0 to 28.6; All the other compositions and carry out crystal, microstructure, suction hydrogen kinetics and inhale hydrogen and put the ability test of hydrogen between 14.3 to 18.2, and wherein label E1 to E7 representes that respectively the mol ratio of cobalt metal in the hydrogen storage alloy is 0,0.5,0.75,1.0,1.25,1.5 and 2.0.Add the cobalt metal of different content in the hydrogen storage alloy; Also less because of the atomic diameter of cobalt, thus the phenomenon of crest skew on X-ray diffraction collection of illustrative plates, do not produced yet, in addition; As shown in table 5; Reaching the required time meeting of 90% maximum hydrogen have evident difference because of the content of cobalt metal, and the content of cobalt metal can have influence on the suction hydrogen efficiency of hydrogen storage alloy in the therefore visible hydrogen storage alloy, and the maximum hydrogen of hydrogen storage alloy and maximum hydrogen desorption capacity reach 1.91 and 1.39 weight percents respectively.Table 5 is the different each item characteristics of cobalt amount under differing temps that contain in the hydrogen storage alloy.
Table 5
Embodiment 7: the influence of different iron (Fe) content
To shown in Figure 14, be the influence for the hydrogen storage alloy characteristic of the ferrous metal of understanding different mol ratio like Fig. 1, Figure 13, under the situation of fixing other metal content, the adjustment iron metal contents is promptly with CoFe
vThe molecular formula of MnTiVZr; Conversion Fe composition, scope be in 0.5≤v≤2.5, or represent with atom number per-cent; The composition of Fe is between 9.0 to 33.3; All the other compositions and carry out crystal, microstructure, suction hydrogen kinetics and inhale hydrogen and put the ability test of hydrogen between 13.3 to 18.2, and wherein label F1 to F6 representes that respectively the mol ratio of ferrous metal in the hydrogen storage alloy is 0.5,1.0,1.25,1.5,2.0 and 2.5.The ferrous metal that adds different content in the hydrogen storage alloy is also because the atomic diameter of iron is less; So on X-ray diffraction collection of illustrative plates, do not produce the phenomenon of crest skew yet; In addition; As shown in table 6, reach the required time of 90% maximum hydrogen to be easier at normal temperatures receive the content of ferrous metal in the hydrogen storage alloy and to influence, change iron metal contents and can make the maximum hydrogen of hydrogen storage alloy and maximum hydrogen desorption capacity reach 1.97 and 1.39 weight percents respectively.Table 6 is each item characteristic of different iron-holder under differing temps in the hydrogen storage alloy.
Table 6
In sum,, just can reach and make this hydrogen storage alloy under the Working environment of normal temperature and pressure, have the high hydrogen/put the ability of hydrogen and Chu Qing inhaled, make it have the potential quality that develops into the environmental protection energy through the content of each metal in the adjustment hydrogen storage alloy of the present invention.
The above is merely preferred embodiment of the present invention, only is illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and in spirit that claim of the present invention limited and scope, can carry out many changes to it, revise, in addition equivalent, but all will fall in protection scope of the present invention.
Claims (2)
1. hydrogen storage alloy, it has Co
uFe
vMn
wTi
xV
yZr
zThe molecular formula general formula, 0.5≤u≤2.0,0.5≤v≤2.5,0.5≤w≤2.0,0.5≤x≤2.5,0.4≤y≤3.0 and 0.4≤z≤3.0 wherein; Represent that with atom number per-cent the Co composition is between 9.0 to 28.6, all the other compositions are between 14.3 to 18.2; Or the Fe composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the Mn composition is between 9.0 to 28.6, and all the other compositions are between 14.3 to 18.2; Or the composition of Ti is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the V composition is between 9.0 to 33.3, and all the other compositions are between 13.3 to 18.2; Or the Zr composition is between 7.5 to 37.5, and all the other compositions are between 12.5 to 18.5.
2. hydrogen storage alloy as claimed in claim 1 is characterized in that, this hydrogen storage alloy is the C14-Laves phase.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451338A (en) * | 2014-12-03 | 2015-03-25 | 北京理工大学 | Cocrfenialcusi high-entropy alloy and preparation method thereof |
| CN106374116A (en) * | 2016-12-01 | 2017-02-01 | 上海电机学院 | High-entropy alloy composite coating on metal bipolar plate of fuel cell and process |
| CN109182875A (en) * | 2018-11-06 | 2019-01-11 | 中国工程物理研究院核物理与化学研究所 | A kind of single-phase reversible and anti-oxidant storage hydrogen high-entropy alloy and preparation method thereof |
| CN114293086A (en) * | 2021-12-30 | 2022-04-08 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Hydrogen storage high-entropy alloy and preparation method thereof |
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