Zirconium-containing hydrogen storage alloy, method for producing the same, and use of zirconium

Abstract

A hydrogen storage alloy containing zirconium, a method for producing the same and use of zirconium are disclosed. The hydrogen storage alloy has a content of A2B7 phase > 50 wt% and a composition as shown in formula (I): La m RE n Y p Zr q Ni a Mn b A c (I); wherein RE is selected from one or more of Ce, Pr, Nd, Sm and Gd; A is selected from one or more of Al, V, Cu, Fe and Co; wherein m, n, p, q, a, b and c represent the mole fraction of each element, respectively; m is in the range of 0.5-3, n is in the range of 0-2, p is in the range of 1-4, q is in the range of 0.2-2.5, a is in the range of 19-20.5, b is in the range of 0.4-1.2, and c is in the range of 0-0.5. The hydrogen storage alloy has a high hydrogen desorption plateau pressure.

Description

TECHNICAL FIELD

[0001] The present application relates to a zirconium-containing hydrogen storage alloy, a production method thereof and the use of zirconium. BACKGROUND

[0002] Rare earth hydrogen storage alloys have the advantages of fast hydrogen absorption and desorption speed, small hysteresis, easy activation, and resistance to poisoning, and are widely used. LaNi5 hydrogen storage alloy has a small hydrogen storage capacity, and La-Mg-Ni hydrogen storage alloy is prone to explosion during manufacturing. Although La-Y-Ni hydrogen storage alloy overcomes the shortcomings of LaNi5 hydrogen storage alloy and La-Mg-Ni hydrogen storage alloy, it has a low hydrogen absorption and desorption plateau pressure.

[0003] CN111471894A discloses a doped A5B 19 type samarium-containing hydrogen storage alloy having a chemical composition of RE a Sm b Ni c Mn x Al y M z Zr u Ti v . a, b, c, x, y, z, u and v respectively represent the mole fractions of RE, Sm, Ni, Mn, Al, M, Zr and Ti; RE is selected from one or more of rare earth metal elements, but not Sm; M is selected from one or more of Fe, Sn, Cr, Zn, V, W, Cu, Mo and Si elements; the hydrogen storage alloy does not contain Mg; a>0, b>0.1, a+b=3; 13>c+x+y+z≥11, 4≥x+y>0, 3≥z≥0, 3≥u+v>0. The hydrogen storage alloy is A5B 19 type.

[0004] CN116024459A discloses a superlattice rare earth hydrogen storage material having a chemical formula of A a Ce b Y c Ni x Mn y B z , A is one or more selected from La, Pr, Nd, Gd, or Sm containing La, B is one or more of Al, Cu, Fe, Zn, Co, Si, Zr, Ti, 40wt%≤(A,Y,Ce)2(Ni,Mn,B)7 phase content≤70wt%, 20wt%≤(A,Y,Ce)5(Ni,Mn,B) 19 phase content≤60wt%. The rare earth hydrogen storage material has a low hydrogen desorption plateau pressure.

[0005] CN110714139A discloses a rare earth-nickel-based hydrogen storage alloy material, which has a chemical composition of C 1-x- y Sm x Y y Ni z-a-b Al a D b ; wherein 0.2≤x≤0.8, 0≤y<0.5, 3.4≤z≤3.6, 0.1≤a≤0.4, 0≤b≤0.15, C is one or two or more of La, Ce, Pr, Nd, Gd, Zr, Ti, and D is one or two or more of Co, Mn, Cu, V, Fe, Zn, W, Si. The hydrogen storage alloy has a low hydrogen release platform pressure. SUMMARY

[0006] Therefore, one object of the present application is to provide a zirconium-containing hydrogen storage alloy having a high hydrogen release platform pressure. Further, the hydrogen storage alloy has a high reversible hydrogen storage capacity. Still further, the hydrogen storage alloy has a high hydrogen storage amount ratio above 0.1 MPa. Another object of the present application is to provide a production method of the above-mentioned zirconium-containing hydrogen storage alloy. Still another object of the present application is to provide a use of zirconium. The above technical objects are achieved by the following technical solutions.

[0007] In one aspect, the present application provides a zirconium-containing hydrogen storage alloy, which has a content of A2B7 phase > 50wt%, and has a composition as shown in formula (I):

[0008] La m RE n Y p Zr q Ni a Mn b A c (I);

[0009] wherein RE is selected from one or more of Ce, Pr, Nd, Sm and Gd; A is selected from one or more of Al, V, Cu, Fe and Co;

[0010] wherein m, n, p, q, a, b and c respectively represent the mole fraction of each element; m has a value range of 0.5-3, n has a value range of 0-2, p has a value range of 1-4, q has a value range of 0.2-2.5, a has a value range of 19-20.5, b has a value range of 0.4-1.2, and c has a value range of 0-0.5.

[0011] According to the hydrogen storage alloy of the present application, preferably, the hydrogen storage alloy contains a Co5Zr phase.

[0012] According to the hydrogen storage alloy of the present application, preferably, m+n+p+q=6, a+b+c=21.

[0013] According to the hydrogen storage alloy of the present application, preferably, the RE is Ce, and n is in the range of 0.5-1.5.

[0014] According to the hydrogen storage alloy of the present application, preferably, c=0.

[0015] According to the hydrogen storage alloy of the present application, preferably, the hydrogen storage alloy does not contain Mg, Ca, Ba, Na and K.

[0016] According to the hydrogen storage alloy of the present application, preferably, the reversible hydrogen storage capacity of the hydrogen storage alloy is ≥1.4wt%, the hydrogen release plateau pressure of the hydrogen storage alloy is ≥0.3MPa, and the hydrogen storage amount of the hydrogen storage alloy at 0.1MPa or above accounts for ≥85%.

[0017] According to the hydrogen storage alloy of the present application, preferably, the hydrogen storage alloy has a composition as shown in one of the following:

[0018] La2Y2Zr2Ni 20.2 Mn 0.8 ;

[0019] La2Y 2.5 Zr 1.5 Ni 20.2 Mn 0.8 ;

[0020] La2Y3ZrNi 20.2 Mn 0.8 ;

[0021] La2Y 3.5 Zr 0.5 Ni 20.2 Mn 0.8 ;

[0022] La2CeY 1.5 Zr 1.5 Ni 20.2 Mn 0.8 ;

[0023] La2CeY2ZrNi 20.2 Mn 0.8 ;

[0024] La2CeY 2.5 Zr 0.5 Ni 20.2 Mn 0.8 ;

[0025] LaCeY2Zr2Ni 20.2 Mn 0.8 ;

[0026] LaCeY 2.5 Zr 1.5 Ni 20.2 Mn 0.8 ;

[0027] LaCeY3ZrNi 20.2 Mn 0.8 ;

[0028] LaCeY 3.5 Zr 0.5 Ni 20.2 Mn 0.8 。

[0029] In another aspect, the present application provides a production method of the above-mentioned hydrogen storage alloy, comprising the following steps: melting raw materials for forming the hydrogen storage alloy in an inert atmosphere to form an alloy liquid; then rapidly quenching the alloy liquid into alloy pieces; annealing the alloy pieces, and then crushing to obtain the hydrogen storage alloy.

[0030] In still another aspect, the present application provides a use of zirconium in improving the hydrogen desorption plateau pressure of a hydrogen storage alloy, characterized in that the amount of the zirconium is 0.2-2.5 mole fraction.

[0031] The hydrogen storage alloy comprises 0.5-3 mole fraction of La, 0-2 mole fraction of RE, 1-4 mole fraction of Y, 19-20.5 mole fraction of Ni, 0.4-1.2 mole fraction of Mn and 0-0.5 mole fraction of A.

[0032] The RE is selected from one or more of Ce, Pr, Nd, Sm and Gd; and the A is selected from one or more of Al, V, Cu, Fe and Co.

[0033] In the present application, the La and / or Y on the A side of the hydrogen storage alloy is replaced by an appropriate amount of Zr, and the Ni on the B side of the hydrogen storage alloy is replaced by an appropriate amount of Mn, and the elements on the A side and the elements on the B side cooperate with each other to improve the hydrogen desorption plateau pressure of the hydrogen storage alloy. Controlling the amounts of the elements in the hydrogen storage alloy of the present application to appropriate amounts can make the hydrogen storage alloy have a high hydrogen desorption plateau pressure, a reversible hydrogen storage capacity and a hydrogen storage amount at 0.1 MPa or above accounting for a high proportion. DETAILED DESCRIPTION

[0034] The present application will be further described below in conjunction with specific examples, but the scope of protection of the present application is not limited thereto.

[0035] <Hydrogen storage alloy containing zirconium>

[0036] In the hydrogen storage alloy containing zirconium of the present application, the content of A2B7 phase is >50wt%, and has a composition as shown in formula (I):

[0037] Lam RE n Y p Zr q Ni a Mn b A c (I)

[0038] The zirconium-containing hydrogen storage alloy of the present application does not contain alkali metals and alkaline earth metals. The alkali metals are, for example, Li, Na, K, and the like. The alkaline earth metals are, for example, Be, Mg, Ca, Sr, Ba, and the like. In some embodiments, the hydrogen storage alloy of the present application consists only of La, RE, Y, Zr, Ni, Mn, and A, and of course, can contain some unavoidable impurities.

[0039] In the hydrogen storage alloy of the present application, the content of the A2B7 phase is > 50 wt%; preferably, the content of the A2B7 phase is > 60 wt%. In some embodiments, the content of the A2B7 phase is > 65 wt%. In other embodiments, the content of the A2B7 phase is > 70 wt%. In still other embodiments, the content of the A2B7 phase is > 75 wt%. The A2B7 phase can be a Ce2Ni7 phase.

[0040] In the hydrogen storage alloy of the present application, Zr is added to the A side, thereby forming a Co5Zr phase in the hydrogen storage alloy of the present application.

[0041] The hydrogen storage alloy of the present application includes a Ce2Ni7 phase, a Ce5Co 19 phase, and a Co5Zr phase.

[0042] La represents a rare earth element lanthanum. m represents the mole fraction of La. m has a value in the range of 0.5 to 3; preferably, m has a value in the range of 1 to 2.5. In some embodiments, m satisfies 1 < m < 1.5. In other embodiments, m satisfies 2 < m < 2.2.

[0043] RE represents a rare earth element. RE is selected from one or more of Ce, Pr, Nd, Sm, and Gd. Preferably, RE is Ce.

[0044] n represents the mole fraction of RE. n has a value in the range of 0 to 2. In some embodiments, n = 0. In other embodiments, n satisfies 0.5 < n < 1.5; preferably, n satisfies 1 < n < 1.2.

[0045] Y represents a rare earth element yttrium. p represents the mole fraction of Y. p has a value in the range of 1 to 4; preferably, p has a value in the range of 1.5 to 3.5. In some embodiments, p satisfies 2 < p < 3. In other embodiments, p satisfies 2.5 < p < 2.7.

[0046] Zr represents a metal element zirconium. q represents a mole fraction of Zr. q has a value in a range from 0.2 to 2.5; preferably, q has a value in a range from 0.5 to 2. In some embodiments, q satisfies 0.8 ≤ q ≤ 1. In other embodiments, q satisfies 1.5 ≤ q ≤ 1.7.

[0047] In the present application, m + n + p + q = 6.

[0048] Ni represents a metal element nickel. a represents a mole fraction of Ni. a has a value in a range from 19 to 20.5; preferably, a has a value in a range from 19.5 to 20.3; more preferably, a has a value in a range from 20 to 20.2.

[0049] Mn represents a metal element manganese. b represents a mole fraction of Mn. b has a value in a range from 0.4 to 1.2; preferably, b has a value in a range from 0.6 to 1; more preferably, b has a value in a range from 0.8 to 0.9.

[0050] A represents a metal element. A is selected from one or more of Al, V, Cu, Fe, and Co. In some embodiments, A is Al. In other embodiments, A is V.

[0051] c represents a mole fraction of A. c has a value in a range from 0 to 0.5. In some embodiments, c is 0. In other embodiments, c has a value in a range from 0.1 to 0.2.

[0052] In the present application, a + b + c = 21.

[0053] In some embodiments, the hydrogen storage alloy of the present application has a composition shown in one of the following:

[0054] La2Y2Zr2Ni 20.2 Mn 0.8 ;

[0055] La2Y 2.5 Zr 1.5 Ni 20.2 Mn 0.8 ;

[0056] La2Y3ZrNi 20.2 Mn 0.8 ;

[0057] La2Y 3.5 Zr 0.5 Ni 20.2 Mn 0.8 ;

[0058] La2CeY 1.5 Zr 1.5 Ni 20.2 Mn0.8 ;

[0059] La2CeY2ZrNi 20.2 Mn 0.8 ;

[0060] La2CeY 2.5 Zr 0.5 Ni 20.2 Mn 0.8 ;

[0061] LaCeY2Zr2Ni 20.2 Mn 0.8 ;

[0062] LaCeY 2.5 Zr 1.5 Ni 20.2 Mn 0.8 ;

[0063] LaCeY3ZrNi 20.2 Mn 0.8 ;

[0064] LaCeY 3.5 Zr 0.5 Ni 20.2 Mn 0.8 .

[0065] The hydrogen storage alloy of the present application has a high hydrogen release plateau pressure. The hydrogen release plateau pressure is ≥0.3 MPa; preferably, the hydrogen release plateau pressure is ≥0.4 MPa; more preferably, the hydrogen release plateau pressure is ≥0.5 MPa; most preferably, the hydrogen release plateau pressure is ≥0.6 MPa.

[0066] The hydrogen storage alloy of the present application has a high reversible hydrogen storage capacity. The reversible hydrogen storage capacity is ≥1.4 wt%; preferably, the reversible hydrogen storage capacity is ≥1.5 wt%; more preferably, the reversible hydrogen storage capacity is ≥1.6 wt%.

[0067] The hydrogen storage alloy of the present application has a high proportion of hydrogen storage capacity above 0.1 MPa. The proportion of hydrogen storage capacity above 0.1 MPa is ≥85 wt%; preferably, the proportion of hydrogen storage capacity above 0.1 MPa is ≥87 wt%; more preferably, the proportion of hydrogen storage capacity above 0.1 MPa is ≥90 wt%.

[0068] <Method for producing a hydrogen storage alloy containing zirconium>

[0069] The method for producing a hydrogen storage alloy containing zirconium of the present application comprises the following steps: melting raw materials for forming a hydrogen storage alloy in an inert atmosphere to form an alloy liquid; then rapidly quenching the alloy liquid into an alloy sheet; annealing the alloy sheet, then crushing to obtain a hydrogen storage alloy.

[0070] The raw materials for forming the hydrogen storage alloy are prepared according to the composition of the hydrogen storage alloy. The raw materials can be metal elements or alloys.

[0071] The annealing can be performed in an inert atmosphere. Preferably, the gas providing the inert atmosphere is selected from one or more of nitrogen, argon, and helium. The annealing process conditions are as follows: heating from room temperature to 700-900°C, preferably 750-850°C, at a heating rate of 5-15°C / min, preferably 8-12°C / min; then heating to 1000-1200°C, preferably 1050-1100°C, at a heating rate of 1-10°C / min, preferably 3-7°C / min, and holding for 10-20h, preferably 13-17h; and then cooling to room temperature. Preferably, the cooling is performed by furnace cooling after holding.

[0072] The pulverization can be performed in an inert atmosphere. Preferably, the gas providing the inert atmosphere is selected from one or more of nitrogen, argon, and helium. The pulverization can be performed by a combination of mechanical crushing and grinding. The mechanical crushing can be performed first, followed by the grinding.

[0073] <Use of zirconium>

[0074] The present application finds that the addition of appropriate zirconium element in the hydrogen storage alloy can improve the hydrogen release plateau pressure of the hydrogen storage alloy. Therefore, the present application provides a use of zirconium in improving the hydrogen release plateau pressure of the hydrogen storage alloy.

[0075] The amount of zirconium is 0.2-2.5 mole fraction. The amount of zirconium can be represented by q, the unit of q is mole fraction, and the range of q is as described above.

[0076] The hydrogen storage alloy of the present application comprises La, RE, Y, Ni, Mn, and A. The hydrogen storage alloy does not contain alkali metals and alkaline earth metals. The alkali metals are, for example, Li, Na, K, etc. The alkaline earth metals are, for example, Be, Mg, Ca, Sr, Ba, etc.

[0077] In the hydrogen storage alloy of the present application, the content of La is 0.5-3 mole fraction. The content of La can be represented by m, the unit of m is mole fraction, and the range of m is as described above.

[0078] In the hydrogen storage alloy of the present application, RE is selected from one or more of Ce, Pr, Nd, Sm, and Gd. In some embodiments, RE is Ce.

[0079] The content of RE is 0-2 mole fraction. The content of RE can be represented by n, the unit of n is mole fraction, and the range of n is as described above.

[0080] In the hydrogen storage alloy of the present application, the content of Y is 1-4 mole fraction. The content of Y can be represented by p, the unit of p is mole fraction, and the range of p is as described above.

[0081] In the hydrogen storage alloy of the present application, the content of Ni is 19-20.5 mole fraction. The content of Ni can be expressed by a, the unit of a is mole fraction, and the range of a is as described above.

[0082] In the hydrogen storage alloy of the present application, the content of Mn is 0.4-1.2 mole fraction. The content of Mn can be expressed by b, the unit of b is mole fraction, and the range of b is as described above.

[0083] In the hydrogen storage alloy of the present application, A is selected from one or more of Al, V, Cu, Fe and Co.

[0084] The content of A is 0-0.5 mole fraction. The content of A can be expressed by c, the unit of c is mole fraction, and the range of c is as described above.

[0085] Examples 1 to 11

[0086] The raw materials were provided according to the hydrogen storage alloy composition shown in Table 1. The raw materials were melted in a medium-frequency induction melting furnace in the presence of inert gas to form an alloy liquid. The alloy liquid was rapidly quenched into an alloy sheet.

[0087] The alloy sheet was heated in an argon atmosphere from room temperature to 800℃ at a heating rate of 10℃ / min, then heated to 1050℃ at a heating rate of 5℃ / min, and kept at 1050℃ for 16h. After the heat preservation, the alloy sheet was cooled to room temperature in the furnace to obtain an annealed alloy sheet.

[0088] The annealed alloy sheet was mechanically broken in an argon atmosphere, and then ground to obtain a zirconium-containing hydrogen storage alloy.

[0089] The composition of the hydrogen storage alloy and the performance of the hydrogen storage alloy are shown in Table 1.

[0090] Experimental Examples

[0091] 1. The phase composition and the content of the main phase of the hydrogen storage alloy were determined according to the XRD diffraction pattern. The XRD diffraction pattern was obtained by using hydrogen storage alloy powder with a particle size of less than 200 mesh as the sample and using an X’Pert PRO powder X-ray diffractometer (Cu target, Kα ray) as the measuring instrument. The test conditions were as follows: power was 40kV×40mA, step size was 0.01°, dwell time was 30s, and scanning range was 10-80°. According to the obtained XRD diffraction pattern, the hydrogen storage alloy of the present application was composed of Ce2Ni7 phase, Ce5Co 19 phase and Co5Zr phase, wherein the Ce2Ni7 phase was the main phase. The mass content of the main phase (Ce2Ni7 phase) was obtained by Rietveld refinement of the XRD diffraction pattern using Maud software, as shown in Table 1.

[0092] 2. The hydrogen storage performance of the hydrogen storage alloy is obtained according to a P-C-T curve. The test method of the P-C-T curve is as follows: preparation of the test sample: 1.5-1.7 g of the hydrogen storage alloy with a particle size of less than 100 mesh is vacuumized at 300℃ for 30 min, and the test sample is obtained after being cooled to room temperature. The test temperature is 40℃. The test equipment is a Sievelts device. According to the P-C-T curve, the reversible hydrogen storage capacity, the hydrogen release platform pressure and the proportion of the hydrogen storage amount above 0.1 MPa are obtained, as shown in Table 1.

[0093] Table 1

[0094]

[0095]

[0096] It can be known from Examples 1-4, Examples 5-7 and Examples 8-11 that the hydrogen release platform pressure of the hydrogen storage alloy increases with the increase of the Zr content, but the reversible hydrogen storage capacity decreases. The content of Zr in the range of the present application can make the hydrogen storage alloy have both high reversible hydrogen storage capacity and hydrogen release platform pressure.

[0097] The present application is not limited to the above-mentioned embodiments, and any modification, improvement and replacement conceived by those skilled in the art without departing from the essential content of the present application falls within the scope of the present application.

Claims

1. A hydrogen storage alloy containing zirconium, characterized by, The A2B7 phase content of which is >50wt%, and has a composition as shown in formula (I): La m RE n Y p Zr q Ni a Mn b A c (I); RE is selected from one or more of Ce, Pr, Nd, Sm and Gd; A is selected from one or more of Al, V, Cu, Fe and Co; m, n, p, q, a, b and c represent the mole fraction of each element respectively; m is in the range of 0.5-3, n is in the range of 0-2, p is in the range of 1-4, q is in the range of 0.2-2.5, a is in the range of 19-20.5, b is in the range of 0.4-1.2, and c is in the range of 0-0.5; m+n+p+q=6, and a+b+c=21; The reversible hydrogen storage capacity of the hydrogen storage alloy is ≥1.4wt%, the hydrogen release plateau pressure of the hydrogen storage alloy is ≥0.3MPa, and the hydrogen storage amount ratio of the hydrogen storage alloy at 0.1MPa or above is ≥85%.

2. The hydrogen storage alloy according to claim 1, characterized by The hydrogen storage alloy contains a Co5Zr phase.

3. The hydrogen storage alloy according to claim 1, characterized by The RE is Ce, and n is in the range of 0.5-1.

5.

4. The hydrogen storage alloy according to claim 1, wherein c=0。 5. The hydrogen storage alloy according to claim 1, wherein The hydrogen storage alloy does not contain Mg, Ca, Ba, Na and K.

6. The hydrogen storage alloy according to any one of claims 1 to 5, characterized by, The hydrogen storage alloy has a composition as shown in one of the following: La2Y2Zr2Ni 20.2 Mn 0.8 ; La2Y 2.5 Zr 1.5 Ni 20.2 Mn 0.8 ; La2Y3ZrNi 20.2 Mn 0.8 ; La2Y 3.5 Zr 0.5 Ni 20.2 Mn 0.8 ; La2CeY 1.5 Zr 1.5 Ni 20.2 Mn 0.8 ; La2CeY2ZrNi 20.2 Mn 0.8 ; La2CeY 2.5 Zr 0.5 Ni 20.2 Mn 0.8 ; LaCeY2Zr2Ni 20.2 Mn 0.8 ; LaCeY 2.5 Zr 1.5 Ni 20.2 Mn 0.8 ; LaCeY3ZrNi 20.2 Mn 0.8 ; LaCeY 3.5 Zr 0.5 Ni 20.2 Mn 0.8 .

7. The method of producing a hydrogen storage alloy according to any one of claims 1 to 6, characterized by, The method comprises the following steps: The raw materials for forming the hydrogen storage alloy are smelted in an inert atmosphere to form an alloy liquid, and then the alloy liquid is rapidly quenched into alloy pieces; the alloy pieces are annealed, then crushed to obtain the hydrogen storage alloy.

8. Use of zirconium in improving the hydrogen release plateau pressure of a hydrogen storage alloy, characterized in that, The hydrogen storage alloy is composed of 0.5-3 moles of La, 0-2 moles of RE, 1-4 moles of Y, 19-20.5 moles of Ni, 0.4-1.2 moles of Mn, 0-0.5 moles of A and 0.2-2.5 moles of zirconium; the sum of the mole fractions of La, RE, Y and Zr is 6, and the sum of the mole fractions of Ni, Mn and A is 21; RE is selected from one or more of Ce, Pr, Nd, Sm and Gd; A is selected from one or more of Al, V, Cu, Fe and Co; The reversible hydrogen storage capacity of the hydrogen storage alloy is ≥1.4wt%, the hydrogen release plateau pressure of the hydrogen storage alloy is ≥0.3MPa, and the hydrogen storage amount ratio of the hydrogen storage alloy at 0.1MPa or above is ≥85%.

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