Cerium-containing lanthanum-yttrium-nickel hydrogen storage alloy, method for producing the same, and use of cerium

Abstract

The application discloses a cerium-containing lanthanum-yttrium-nickel hydrogen storage alloy, a preparation method thereof and a use of cerium. The lanthanum-yttrium-nickel hydrogen storage alloy has a composition shown in formula (I): La m Ce p Y 6‑m‑p Ni 21‑q Mn q (I); wherein, the value range of m is 0.1-2, the value range of p is 0.1-2, and the value range of q is 0.1-1; wherein, m represents a molar fraction of La, p represents a molar fraction of Ce, 6-m-p represents a molar fraction of Y, 21-q represents a molar fraction of Ni, and q represents a molar fraction of Mn. The lanthanum-yttrium-nickel hydrogen storage alloy has a relatively high hydrogen release platform pressure.

Description

TECHNICAL FIELD

[0001] The present application relates to a cerium-containing lanthanum-yttrium-nickel hydrogen storage alloy, a preparation method thereof and a use of cerium. BACKGROUND

[0002] Safe and efficient storage and transportation of hydrogen is a difficult point in the development and application of hydrogen energy. The superlattice AB 3-3.8 The La-Mg-Ni rare earth hydrogen storage alloy of type AB

[0003] CN117012943A discloses a hydrogen storage alloy comprising the following components by weight: nickel 36-51 parts, manganese 7-12 parts, aluminum 0.9-3 parts, copper 5.5-13.0 parts, yttrium 0-1.5 parts, zirconium 0-0.5 parts, lanthanum 12-24 parts, cerium 6-20 parts, praseodymium 0-0.4 parts, and neodymium 0-0.3 parts. The hydrogen storage alloy has a low hydrogen release plateau pressure.

[0004] CN115992319A discloses a rare earth hydrogen storage alloy with a chemical composition of RE x Ca y Ni d-a-b Mn a M b ; wherein 0.5≤x≤0.9, 0.1≤y≤0.5, and x+y=1; 0.05≤a≤0.35, 0≤b≤0.3, 4.5≤d≤5.5, 4.68≤d-a-b≤4.95; wherein RE is selected from one or more of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and must contain La and Ce; wherein M is selected from one or more of Cu, Sn, V, Ti, Zr, Cr, Zn, Mo, and Si; wherein x, y, a, b, and d-a-b represent the mole fraction of each element, respectively. The hydrogen storage alloy is not an A2B7 type hydrogen storage alloy.

[0005] CN114703400A discloses an A5B 19 type rare earth-yttrium-nickel hydrogen storage alloy with a composition as shown below: RE x Y 3-x Ni y M z; wherein Y is yttrium element, Ni is nickel element, RE is selected from one or more of La, Ce, Pr, Nd, Sm and Gd elements, and M is selected from one or more of Mn, Al, Cu, Fe and Co; wherein x, 3-x, y and z respectively represent the molar coefficients of RE, Y, Ni and M; wherein 0.75 < x < 1.2, 0.55 < z < 1.4 and 11.0 < y + z < 12.0. The hydrogen storage alloy is an A5B 19 type hydrogen storage alloy. SUMMARY

[0006] Therefore, one object of the present application is to provide a cerium-containing lanthanum-yttrium-nickel hydrogen storage alloy with a high hydrogen release plateau pressure. Further, the hydrogen storage alloy has a high hydrogen storage capacity ratio at 0.1 MPa or above. Still further, the hydrogen storage alloy has a high reversible hydrogen storage capacity. Another object of the present application is to provide a preparation method of the above-mentioned cerium-containing lanthanum-yttrium-nickel hydrogen storage alloy. Still another object of the present application is to provide a use of cerium.

[0007] The above technical objects are achieved by the following technical solutions.

[0008] In one aspect, the present application provides a cerium-containing lanthanum-yttrium-nickel hydrogen storage alloy, which has a composition as shown in formula (I):

[0009] La m Ce p Y 6-m-p Ni 21-q Mn q (I);

[0010] wherein the value range of m is 0.1-2, the value range of p is 0.1-2, and the value range of q is 0.1-1.

[0011] wherein m represents the molar fraction of La, p represents the molar fraction of Ce, 6-m-p represents the molar fraction of Y, 21-q represents the molar fraction of Ni, and q represents the molar fraction of Mn.

[0012] According to the lanthanum-yttrium-nickel hydrogen storage alloy of the present application, preferably, the value range of m + p is 1.5-2.5.

[0013] According to the lanthanum-yttrium-nickel hydrogen storage alloy of the present application, preferably, the value range of 6-m-p is 3.5-4.5, and the value range of 21-q is 20-20.9.

[0014] According to the lanthanum-yttrium-nickel hydrogen storage alloy of the present application, preferably, the lanthanum-yttrium-nickel hydrogen storage alloy does not contain alkali metals and alkaline earth metals.

[0015] The lanthanum-yttrium-nickel-based hydrogen storage alloy according to the present application preferably consists of only the elements represented by formula (I) except for inevitable impurities.

[0016] The lanthanum-yttrium-nickel-based hydrogen storage alloy according to the present application preferably includes a Ce2Ni7 phase, a Ce5Co 19 phase, and a LaNi5 phase, and the content of the Ce2Ni7 phase is ≥ 75 wt%.

[0017] The lanthanum-yttrium-nickel-based hydrogen storage alloy according to the present application preferably has a Ce2Ni7 phase having a space group of P63 / mmc, an average length of an a-axis of a unit cell of an average length of a c-axis of a unit cell of

[0018] The lanthanum-yttrium-nickel-based hydrogen storage alloy according to the present application preferably has a composition represented by one of the following:

[0019] (1) La 0.2 Ce 1.8 Y4Ni 20.2 Mn 0.8 ;

[0020] (2) La 0.5 Ce 1.5 Y4Ni 20.2 Mn 0.8 ;

[0021] (3) La 0.8 Ce 1.2 Y4Ni 20.2 Mn 0.8 ;

[0022] (4) La 1.1 Ce 0.9 Y4Ni 20.2 Mn 0.8 ;

[0023] (5) La 1.4 Ce 0.6 Y4Ni 20.2 Mn 0.8 ;

[0024] (6) La 1.7 Ce 0.3 Y4Ni 20.2 Mn 0.8 ;

[0025] (7) La 1.1 Ce 0.9 Y4Ni 20.4 Mn 0.6 ;

[0026] (8)La 1.1 Ce 0.9 Y4Ni 20.6 Mn 0.4 .

[0027] In another aspect, the present application provides a preparation method of the lanthanum-yttrium-nickel-based hydrogen storage alloy, comprising the following steps:

[0028] The raw materials provided according to the composition of the lanthanum-yttrium-nickel-based hydrogen storage alloy are melted in an inert atmosphere, and then rapidly quenched into alloy sheets; the alloy sheets are annealed, and then crushed to obtain the lanthanum-yttrium-nickel-based hydrogen storage alloy containing cerium.

[0029] In still another aspect, the present application provides a use of cerium in improving the hydrogen release plateau pressure of a lanthanum-yttrium-nickel-based hydrogen storage alloy, the lanthanum-yttrium-nickel-based hydrogen storage alloy comprising La 0.1-2 mol parts, Y 3.5-4.5 mol parts, Ni 20-20.9 mol parts, and Mn 0.1-1 mol parts, and the amount of Ce in the lanthanum-yttrium-nickel-based hydrogen storage alloy being 0.1-2 mol parts.

[0030] The lanthanum-yttrium-nickel-based hydrogen storage alloy containing cerium of the present application is an A2B7 type La-Y-Ni superlattice hydrogen storage alloy. In the hydrogen storage alloy of the present application, La and / or Y on the A side are replaced by an appropriate amount of Ce, and Ni on the B side 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 release plateau pressure of the lanthanum-yttrium-nickel-based hydrogen storage alloy. In a preferred embodiment of the present application, the lanthanum-yttrium-nickel-based hydrogen storage alloy of the present application has a relatively high hydrogen release plateau pressure, a hydrogen storage capacity of 0.1 MPa or more, and a reversible hydrogen storage capacity. DETAILED DESCRIPTION

[0031] 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.

[0032] <La-Y-Ni hydrogen storage alloy containing Ce>

[0033] The lanthanum-yttrium-nickel-based hydrogen storage alloy containing cerium of the present application has a composition as shown in formula (I):

[0034] La m Ce p Y 6-m-p Ni 21-q Mn q (I)

[0035] The yttrium-nickel-based hydrogen storage alloy of the present application does not contain alkali metals and alkaline earth metals. Examples of alkali metals include but are not limited to lithium, sodium, and potassium. Examples of alkaline earth metals include but are not limited to beryllium, magnesium, calcium, strontium, and barium. In certain embodiments, the lanthanum-yttrium-nickel-based hydrogen storage alloy containing cerium of the present application is composed only of the elements shown in formula (I) except for inevitable impurities.

[0036] m represents the mole fraction of La. La represents the lanthanum element. m has a value ranging from 0.1 to 2. In some embodiments, m has a value ranging from 0.2 to 0.5. In other embodiments, m has a value ranging from 1 to 1.5; preferably, 1.1 to 1.3.

[0037] p represents the mole fraction of Ce. Ce represents the cerium element. p has a value ranging from 0.1 to 2. In some embodiments, p has a value ranging from 1.5 to 1.8. In other embodiments, p has a value ranging from 0.7 to 1.3; preferably, 0.9 to 1.1.

[0038] In the present application, m + p has a value ranging from 1.5 to 2.5; preferably, 1.8 to 2.3; more preferably, 2 to 2.1.

[0039] 6 - m - p represents the mole fraction of Y. Y represents the yttrium element. The content of Y can be determined by m and p. 6 - m - p has a value ranging from 3.5 to 4.5; preferably, 3.8 to 4.3; more preferably, 4 to 4.1.

[0040] 21 - q represents the mole fraction of Ni. Ni represents the nickel element. The content of Ni can be determined by q. 21 - q has a value ranging from 20 to 20.9. In some embodiments, 21 - q has a value ranging from 20.2 to 20.4. In other embodiments, 21 - q has a value ranging from 20.6 to 20.7.

[0041] q represents the mole fraction of Mn. Mn represents the manganese element. q has a value ranging from 0.1 to 1. In some embodiments, q has a value ranging from 0.6 to 0.8. In other embodiments, q has a value ranging from 0.3 to 0.4.

[0042] In some embodiments, the cerium-containing lanthanum-yttrium-nickel series hydrogen storage alloy has a composition shown in one of the following:

[0043] (1) La 0.2 Ce 1.8 Y4Ni 20.2 Mn 0.8 ;

[0044] (2) La 0.5 Ce 1.5 Y4Ni 20.2 Mn 0.8 ;

[0045] (3) La 0.8 Ce 1.2 Y4Ni 20.2 Mn 0.8 ;

[0046] (4) La 1.1 Ce 0.9 Y4Ni 20.2 Mn 0.8 ;

[0047] (5) La 1.4 Ce 0.6 Y4Ni 20.2 Mn 0.8 ;

[0048] (6) La 1.7 Ce 0.3 Y4Ni 20.2 Mn 0.8 ;

[0049] (7) La 1.1 Ce 0.9 Y4Ni 20.4 Mn 0.6 ;

[0050] (8) La 1.1 Ce 0.9 Y4Ni 20.6 Mn 0.4 .

[0051] The Ce-containing lanthanum yttrium nickel series hydrogen storage alloy of the present application contains a Ce2Ni7 phase, a Ce5Co 19 phase and a LaNi5 phase. In some embodiments, the Ce-containing lanthanum yttrium nickel series hydrogen storage alloy consists of a Ce2Ni7 phase, a Ce5Co 19 phase and a LaNi5 phase.

[0052] The content of the Ce2Ni7 phase can be ≥ 75 wt%. In some embodiments, the content of the Ce2Ni7 phase is ≥ 80 wt%. In other embodiments, the content of the Ce2Ni7 phase is ≥ 85 wt%.

[0053] The content of the Ce2Ni7 phase can be ≤ 90 wt%. In some embodiments, the content of the Ce2Ni7 phase is ≤ 85 wt%. In other embodiments, the content of the Ce2Ni7 phase is ≤ 82 wt%.

[0054] The space group of the Ce2Ni7 phase is P63 / mmc. The average length of the a axis of the unit cell is The average length of the c axis is

[0055] The hydrogen desorption plateau pressure of the Ce-containing lanthanum yttrium nickel series hydrogen storage alloy of the present application is greater than or equal to 0.25 MPa; preferably, greater than or equal to 0.5 MPa; more preferably, greater than or equal to 0.65 MPa.

[0056] The reversible hydrogen storage capacity of the Ce-containing lanthanum-yttrium-nickel hydrogen storage alloy is greater than or equal to 1.5wt%; preferably, greater than or equal to 1.6wt%; more preferably, greater than or equal to 1.65wt%.

[0057] The hydrogen storage amount of the Ce-containing lanthanum-yttrium-nickel hydrogen storage alloy of the present application at 0.1MPa is greater than or equal to 89wt%; preferably, greater than or equal to 92wt%; more preferably, greater than or equal to 95wt%.

[0058] Preparation method of Ce-containing lanthanum-yttrium-nickel hydrogen storage alloy

[0059] The preparation method of the Ce-containing lanthanum-yttrium-nickel hydrogen storage alloy of the present application comprises the following steps: smelting raw materials provided according to the composition of the lanthanum-yttrium-nickel hydrogen storage alloy in an inert atmosphere, and then rapidly quenching into alloy sheets; annealing the alloy sheets, and then crushing to obtain the Ce-containing lanthanum-yttrium-nickel hydrogen storage alloy.

[0060] The smelting can be carried out in a medium-frequency induction smelting furnace.

[0061] The annealing can be carried out in an inert atmosphere. Preferably, the gas providing the inert atmosphere is selected from one or more of nitrogen, argon, and helium.

[0062] The annealing process conditions are as follows: heating from room temperature to 700-900℃, preferably 750-850℃, at a heating rate of 5-15℃ / min, preferably 8-12℃ / min; then heating to 1000-1200℃, preferably 1050-1100℃, at a heating rate of 1-10℃ / min, preferably 3-7℃ / min, and holding for 10-20h, preferably 13-17h; after holding, cooling to room temperature, preferably, after holding, cooling to room temperature in the furnace.

[0063] The crushing can be carried out in an inert atmosphere. Preferably, the gas providing the inert atmosphere is selected from one or more of nitrogen, argon, and helium.

[0064] The crushing can be carried out in a combination of mechanical crushing and grinding. The mechanical crushing can be carried out first, and then the grinding.

[0065] Use of cerium

[0066] The present application finds that adding appropriate cerium elements in the lanthanum-yttrium-nickel hydrogen storage alloy can improve the hydrogen release platform pressure of the lanthanum-yttrium-nickel hydrogen storage alloy. Therefore, the present application provides a use of cerium in improving the hydrogen release platform pressure of the lanthanum-yttrium-nickel hydrogen storage alloy.

[0067] The lanthanum-yttrium-nickel-based hydrogen storage alloy contains La, Y, Ni and Mn. Preferably, the lanthanum-yttrium-nickel-based hydrogen storage alloy does not contain alkali metals and alkaline earth metals. Examples of alkali metals include, but are not limited to, lithium, sodium, potassium. Examples of alkaline earth metals include, but are not limited to, beryllium, magnesium, calcium, strontium, barium. In some embodiments, the lanthanum-yttrium-nickel-based hydrogen storage alloy consists only of the above elements, except for inevitable impurities.

[0068] In the lanthanum-yttrium-nickel-based hydrogen storage alloy of the present application, the content of La is 0.1-2 moles. In some embodiments, the content of La is 0.2-0.5 moles. In other embodiments, the content of La is 1-1.5 moles; preferably, 1.1-1.3 moles.

[0069] In the lanthanum-yttrium-nickel-based hydrogen storage alloy of the present application, the content of Y is 3.5-4.5 moles; preferably, 3.8-4.3 moles; more preferably, 4-4.1 moles.

[0070] In the lanthanum-yttrium-nickel-based hydrogen storage alloy of the present application, the content of Ni is 20-20.9 moles. In some embodiments, the content of Ni is 20.2-20.4 moles. In other embodiments, the content of Ni is 20.6-20.7 moles.

[0071] In the lanthanum-yttrium-nickel-based hydrogen storage alloy of the present application, the content of Mn is 0.1-1 moles. In some embodiments, the content of Mn is 0.6-0.8 moles. In other embodiments, the content of Mn is 0.3-0.4 moles.

[0072] In the lanthanum-yttrium-nickel-based hydrogen storage alloy of the present application, the content of Ce is 0.1-2 moles. In some embodiments, the content of Ce is 1.5-1.8 moles. In other embodiments, the content of Ce is 0.7-1.3 moles; preferably, 0.9-1.1 moles.

[0073] Examples 1 to 8 and Comparative Examples 1 to 2

[0074] The raw materials provided according to the composition of the lanthanum-yttrium-nickel-based hydrogen storage alloy shown in Table 1 were melted in an inert atmosphere, and then rapidly quenched into alloy pieces. The melting was performed in a medium-frequency induction melting furnace. The alloy pieces were annealed in an argon atmosphere; then, mechanical crushing was performed first, followed by grinding in an argon atmosphere, to obtain a lanthanum-yttrium-nickel-based hydrogen storage alloy containing cerium. The annealing process conditions are as follows: from room temperature, the temperature was raised to 800℃ at a temperature raising rate of 10℃ / min; then, the temperature was raised to 1050℃ at a temperature raising rate of 5℃ / min, and the temperature was kept at 1050℃ for 16h; after the temperature keeping, the furnace was cooled to room temperature.

[0075] Table 1

[0076] No. La-Y-Ni-based hydrogen storage alloy composition Example 1 La 0.2 Ce 1.8 Y4Ni 20.2 Mn 0.8 <!-- 4 -->]]> Example 2 La 0.5 Ce 1.5 Y4Ni 20.2 Mn 0.8 ]]> Example 3 La 0.8 Ce 1.2 Y4Ni 20.2 Mn 0.8 ]]> Example 4 La 1.1 Ce 0.9 Y4Ni 20.2 Mn 0.8 ]]> Example 5 La 1.4 Ce 0.6 Y4Ni 20.2 Mn 0.8 ]]> Example 6 La 1.7 Ce 0.3 Y4Ni 20.2 Mn 0.8 ]]> Example 7 La 1.1 Ce 0.9 Y4Ni 20.4 Mn 0.6 ]]> Example 8 La 1.1 Ce 0.9 Y4Ni 20.6 Mn 0.4 ]]> Comparative Example 1 La2Y4Ni 20.2 Mn 0.8 ]]> Comparative Example 2 Ce2Y4Ni 20.2 Mn 0.8 ]]>

[0077] Experimental Example

[0078] 1. Phase composition and main phase content:

[0079] Test sample: alloy powder with particle size less than 200 mesh in lanthanum-yttrium-nickel hydrogen storage alloy.

[0080] Test instrument: X'Pert PRO powder X-ray diffractometer (Cu target, K alpha ray) is adopted.

[0081] Test condition: power is 40kV*40mA, step length is 0.01°, each step stays for 30s, and scanning range is 10-80°.

[0082] According to the X-ray diffraction spectrum, the lanthanum-yttrium-nickel hydrogen storage alloy containing cerium of the application is composed of Ce2Ni7 phase, Ce5Co 19 phase and LaNi5 phase.

[0083] The mass content of the main phase (Ce2Ni7 phase) is obtained by Rietveld refinement of the X-ray diffraction spectrum by using Maud software, as shown in Table 2.

[0084] 2. Reversible hydrogen storage capacity, hydrogen release plateau pressure and hydrogen storage amount ratio above 0.1MPa:

[0085] 1.5-1.7g of hydrogen storage alloy with particle size less than 100 mesh is taken, vacuumized at 300℃ for 30min, so that the hydrogen storage alloy is fully activated, and after cooling to room temperature, P-C-T curve test is carried out at 40℃ by using Sievelts device. According to the P-C-T curve test, the reversible hydrogen storage capacity, hydrogen release plateau pressure and hydrogen storage amount ratio above 0.1MPa are obtained, as shown in Table 2.

[0086] Table 2

[0087]

[0088] It can be known by comparing examples 1-8 that the content of La, Ce and Mn has important influence on the hydrogen release plateau pressure of the lanthanum-yttrium-nickel hydrogen storage alloy, and appropriate content of La, Ce and Mn can significantly improve the hydrogen release plateau pressure. Setting the content of La, Ce and Mn in a specific range can make the lanthanum-yttrium-nickel hydrogen storage alloy have higher hydrogen release plateau pressure, hydrogen storage amount ratio above 0.1MPa and reversible hydrogen storage capacity.

[0089] It can be known by comparing examples 1-6 and comparative examples 1-2 that the hydrogen storage alloy without adding La or Ce cannot have higher hydrogen storage capacity, hydrogen release plateau pressure and hydrogen storage amount ratio above 0.1MPa.

[0090] The present application is not limited to the above-described embodiments, and any modification, improvement, replacement that can be 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 cerium-containing lanthanum yttrium nickel-based hydrogen storage alloy, characterized by, The lanthanum-yttrium-nickel hydrogen storage alloy has a composition as shown in formula (I) Composition: La m Ce p Y 6-m-p Ni 21-q Mn q (I) wherein m is in the range of 1-1.3, p is in the range of 0.7-1.1, 6-m-p is in the range of 4-4.3, and q is in the range of 0.4-0.8; wherein m represents the mole fraction of La, p represents the mole fraction of Ce, 6-m-p represents the mole fraction of Y, 21-q represents the mole fraction of Ni, and q represents the mole fraction of Mn; The lanthanum yttrium nickel series hydrogen storage alloy includes Ce2Ni7 phase, Ce5Co 19 phase and LaNi5 phase, and the content of the Ce2Ni7 phase is ≥75 wt%. The Ce2Ni7 phase has a space group of P63 / mmc, and the average length of the a axis of the unit cell is The average length of the c axis is 2. The lanthanum yttrium nickel-based hydrogen storage alloy according to claim 1, characterized by, m+p is in the range of 1.8-2.

3.

3. The lanthanum yttrium nickel-based hydrogen storage alloy according to claim 1, characterized by, 6-m-p is in the range of 4-4.1, and 21-q is in the range of 20.2-20.

6.

4. The lanthanum yttrium nickel-based hydrogen storage alloy according to claim 1, characterized by, The lanthanum-yttrium-nickel hydrogen storage alloy does not contain alkali metals and alkaline earth metals.

5. The lanthanum yttrium nickel-based hydrogen storage alloy according to claim 1, characterized by, Except for inevitable impurities, the lanthanum-yttrium-nickel hydrogen storage alloy is composed of only the elements shown in formula (I).

6. The lanthanum yttrium nickel-based hydrogen storage alloy according to any one of claims 1 to 5, characterized by, The lanthanum-yttrium-nickel hydrogen storage alloy has a composition as shown in one of the following: (1) La 1.1 Ce 0.9 Y4Ni 20.2 Mn 0.8 ; (2) La 1.1 Ce 0.9 Y4Ni 20.4 Mn 0.6 ; (3) La 1.1 Ce 0.9 Y4Ni 20.6 Mn 0.4 .

7. The method of producing a lanthanum yttrium nickel-based hydrogen storage alloy according to any one of claims 1 to 6, characterized by, The method comprises the following steps: The raw materials provided according to the composition of the lanthanum-yttrium-nickel hydrogen storage alloy are smelted in an inert atmosphere, and then rapidly quenched into alloy sheets; the alloy sheets are annealed, and then crushed to obtain the lanthanum-yttrium-nickel hydrogen storage alloy containing Ce.

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