CN101323918A - Preparation of light hydrogen occluding alloy - Google Patents

Abstract

The invention provides a method for preparing light hydrogen-storage alloy, pertaining to the technical field of hydrogen-storage alloy materials. The light hydrogen-storage alloy is Ca-Mg-Ni or La-Mg-Ni series; the preparation method of the light hydrogen-storage alloy comprises the steps that: first, magnetic levitation melting of raw materials is carried out according to the mixture ratio of the alloy; the alloy after being melted is ground into alloy powder of 100 meshes in a glove box; then ball milling is carried out to the alloy powder in a mill pot full of argon gas for 24 to 48 hours, thus obtaining amorphous alloy powder; the amorphous alloy powder is put into a stainless grinding apparatus with constant pressure and then manufactured into a green compact with Phi 13 multiplied 3mm; the green compact is put into a ceramic combustion boat, and then undergoes anneal in a common vacuum annealing furnace; after annealing, a single-phase Ca-Mg-Ni or La-Mg-Ni hydrogen-storage alloy is obtained. The method is mainly used for preparing light Ca-Mg-Ni or La-Mg-Ni hydrogen-storage alloys with high yield and further improving the hydrogen-storage performance of the alloys.

Description

A kind of preparation method of light hydrogen occluding alloy

Technical field

The invention belongs to the hydrogen storage material technical field, be specifically related to a kind of preparation method of light hydrogen occluding alloy.

Background technology

Along with world energy sources crisis and environmental degradation, Hydrogen Energy more and more is subjected to people's attention as a kind of novel clean energy.Extremely pay attention to various countries with the hydrogen storage material that Hydrogen Technology is of close concern to each other, people have carried out extensive studies at composition design, crystalline structure, hydrogen storage property and the aspects such as mechanism and technology of preparing of hydrogen storage material.Wherein composition design and technology of preparing are again the keys of good hydrogen storage alloy development and utilization.The target of hydrogen storage material development is to explore the hydrogen storage material of new generation of hydrogen storage capability height, good combination property.Therefore, light hydrogen occluding alloy becomes present research focus, and wherein Ca-Mg-Ni system and La-Mg-Ni are that alloy is considered to one of the most promising light hydrogen occluding alloy [K.Kadir, T.Sakai, I.Uehara, J Alloys Compd., 302 (2000) 112.].Because Ca-Mg-Ni system and La-Mg-Ni are alloy solution to be produced inevitably when solidifying and is separated, so by smelting method for preparing Ca-Mg-Ni system and La-Mg-Ni is the characteristics that there is heterogeneous coexistence in alloy, thereby the low hydrogen storage capability [T.Z.Si that has reduced alloy of storage hydrogen principal phase content in the alloy, Q.A.Zhang, N.Liu, Int J Hydrogen Energy, 33 (2008) 1729].Based on this, people are alloy by sintering synthetic Ca-Mg-Ni system and La-Mg-Ni mainly, for avoiding the influence to alloying constituent of Ca, La and Mg melting loss of elements, adopt 6～10 atmospheric Ar during sintering ₂Protect, but productive rate is still lower and the agglomerating plant investment is high.This shows that preparation difficulty has had a strong impact on Ca-Mg-Ni system and La-Mg-Ni is the development and the application of storage hydrogen of alloy.

Since the Lu Ke academician of the Chinese Academy of Sciences becomes crystal phase Ni with amorphous Ni-P alloy band in low temperature (610K) crystallization first ₃Since the P, amorphous crystallization method is widely applied to the preparation [C.A.Schuh, T.G.Nieh, Acta Mater, 51 (2003) 87] of magneticsubstance, superconducting material and structure nano material.Yet the related scientific research report that is equipped with hydrogen storage material about amorphous crystallization legal system is less.Ca-Mg-Ni system and La-Mg-Ni base hydrogen storage alloy are easy to obtain non-crystaline amorphous metal by the ball milling mechanical alloying, therefore, can obtain the Ca-Mg-Ni system and the La-Mg-Ni base hydrogen storage alloy of high yield fully by rational amorphous crystallization process control.

Summary of the invention

At existing Ca-Mg-Ni system and La-Mg-Ni is the problem that exists in the light hydrogen occluding alloy technology of preparing, the invention provides a kind of preparation method of light hydrogen occluding alloy, and this light hydrogen occluding alloy is that Ca-Mg-Ni system or La-Mg-Ni alloy system comprise AB ₂, AB ₃And A ₂B ₇Type (A=Ca, Mg or La, Mg or Ca, La, Mg, B=Ni) alloy.

Preparation method's concrete steps of a kind of light hydrogen occluding alloy provided by the present invention are as follows:

(1) takes by weighing a certain amount of Ca, La, Mg and Ni raw material by alloying constituent, the purity of raw material all is not less than 99.0wt.%, wherein the scaling loss that Ca, La and Mg element are added 4～6wt.%, 1～2wt.% and 8～10wt.% respectively adopts magnetic levitation melting stove molten alloy then;

(2) place glove box to grind to form 100 purpose powdered alloys the prepared molten alloy of step (1), then this powdered alloy is put into ball grinder, charge into the 1atm argon gas in this ball grinder, ball milling 24～48h obtains amorphous powdered alloy, wherein ratio of grinding media to material is 10: 1～20: 1, and drum's speed of rotation is 200～300rpm;

(3) make step (2) to such an extent that amorphous powdered alloy is put into the stainless steel grinding tool, in pressurize under the 30Mpa pressure after 30 seconds, be pressed into the green compact of φ 13 * 3mm, the gained green compact are put into pottery to be burnt behind the boat conventional vacuum annealing furnace annealing 10 hours, 400～600 ℃ of annealing temperatures obtain single-phase Ca-Mg-Ni system or La-Mg-Ni base hydrogen storage alloy after the annealing.

The invention has the beneficial effects as follows:

1, can overcome that smelting process and sintering process prepare Ca-Mg-Ni system and La-Mg-Ni is the low shortcoming of alloy productive rate, removing the small amounts beyond the region of objective existence through the alloy of this method preparation is the single-phased alloy compound substantially;

2, can prepare Ca-Mg-Ni system and La-Mg-Ni is that the system of light hydrogen occluding alloy is wide, comprises AB ₂, AB ₃And A ₂B ₇The type alloy;

3, to prepare facility investment few for this method, and the preparation technology of alloy is simple, and cost is low.

Description of drawings

Fig. 1 Ca ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy magnetic levitation melting, amorphous and crystallization sample.

Fig. 2 (CaMg) Ni ₂(AB ₂Type) X-ray diffractogram of alloy magnetic levitation melting, amorphous and crystallization sample.

Fig. 3 (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy magnetic levitation melting, amorphous and crystallization sample.

Wherein: Fig. 1 (a) is Ca ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy magnetic levitation melting sample.

Fig. 1 (b) is Ca ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy amorphous sample.

Fig. 1 (c) is Ca ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy crystallization sample.

Fig. 2 (a) is (CaMg) Ni ₂(AB ₂Type) X-ray diffractogram of alloy magnetic levitation melting sample.

Fig. 2 (b) is (CaMg) Ni ₂(AB ₂Type) X-ray diffractogram of alloy amorphous sample.

Fig. 2 (c) is (CaMg) Ni ₂(AB ₂Type) X-ray diffractogram of alloy crystallization sample.

Fig. 3 (a) is (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy magnetic levitation melting sample.

Fig. 3 (b) is (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy amorphous sample.

Fig. 3 (c) is (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy crystallization sample.

Embodiment:

Embodiment 1:

Metal Ca grain, purity are 99.0%; Metal M g powder, purity 99.7%, granularity 200 orders; Metal Ni sheet purity is 99.9%.Press Ca ₂MgNi ₉The alloy molecular formula takes by weighing a certain amount of feed metal (Ca and Mg are added suitable scaling loss), and magnetic levitation melting obtains polyphase alloy 2 times under 18KW power, and alloy phase is (CaMg) Ni ₃, (CaMg) Ni ₂(CaMg) ₂Ni ₇(Fig. 2 (a) Ca ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy magnetic levitation melting sample).Put into stainless cylinder of steel after in mortar molten alloy being ground to form 100 orders, stainless steel is potted in that argon shield ball milling 48 hours (ratio of grinding media to material is 10: 1) obtains non-crystaline amorphous metal (Fig. 2 (b) Ca in the planetary ball mill ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy amorphous sample).Amorphous powdered alloy 30MPa pressurize in the stainless steel grinding tool is pressed into φ 13 * 3mm green compact after 30 seconds; Green compact are put into pottery to be burnt behind the boat in 550 ℃ of annealing of conventional vacuum annealing furnace 10 hours.Annealing back sample is except that minute quantity CaO, and other is single-phase Ca ₂MgNi ₉Alloy, Fig. 2 (c) is Ca ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy crystallization sample.

Embodiment 2:

Metal Ca grain, purity are 99.0%; Metal M g powder, purity 99.7%, granularity 200 orders; Metal Ni sheet purity is 99.9%.By (CaMg) Ni ₂The alloy molecular formula takes by weighing a certain amount of feed metal (Ca and Mg are added suitable scaling loss), and magnetic levitation melting obtains polyphase alloy 2 times under 18KW power, and alloy phase is (CaMg) Ni ₂, Ca ₂Ni ₇And MgNi ₂(Fig. 3 (a) is Ni (CaMg) ₂(AB ₂Type) X-ray diffractogram of alloy magnetic levitation melting sample).Put into stainless cylinder of steel after in mortar molten alloy being ground to form 100 orders, stainless steel is potted in the planetary ball mill argon shield ball milling 48 hours (ratio of grinding media to material is 10: 1) and obtains non-crystaline amorphous metal (Fig. 3 (b) is Ni (CaMg) ₂(AB ₂Type) X-ray diffractogram of alloy amorphous sample).Amorphous powdered alloy 30 MPa pressurizes in the stainless steel grinding tool are pressed into φ 13 * 3mm green compact after 30 seconds; Green compact are put into pottery to be burnt behind the boat in 550 ℃ of annealing of conventional vacuum annealing furnace 10 hours.Annealing back sample is except that minute quantity CaO, and other is single-phase (CaMg) Ni ₂Alloy, Fig. 3 (c) are (CaMg) Ni ₂(AB ₂Type) X-ray diffractogram of alloy crystallization sample.

Embodiment 3:

Metal Ca grain, purity are 99.0%; Metal La piece, purity are 99.5%; Metal M g powder, purity 99.7%, granularity 200 orders; Metal Ni sheet purity is 99.9%.By (CaLa) ₂MgNi ₉The alloy molecular formula takes by weighing a certain amount of feed metal (Ca, La and Mg are added suitable scaling loss), and magnetic levitation melting obtains polyphase alloy 2 times under 18KW power, and alloy phase is (CaLa) ₂MgNi ₉, (CaMg) ₂Ni ₇And CaNi ₂(Fig. 3 (a) (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy magnetic levitation melting sample).Put into stainless cylinder of steel after in mortar molten alloy being ground to form 100 orders, stainless steel is potted in the planetary ball mill argon shield ball milling 48 hours (ratio of grinding media to material is 10: 1) and obtains non-crystaline amorphous metal (Fig. 3 (b) (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy amorphous sample).Amorphous powdered alloy 30MPa pressurize in the stainless steel grinding tool is pressed into φ 13 * 3mm green compact after 30 seconds; Green compact are put into pottery to be burnt behind the boat in 580 ℃ of annealing of conventional vacuum annealing furnace 10 hours.Outside the sample depolarization small amount of N i of annealing back, other is single-phase (CaLa) ₂MgNi ₉Alloy, Fig. 3 (c) is (CaLa) ₂MgNi ₉(AB ₃Type) X-ray diffractogram of alloy crystallization sample.

Claims (1)

1, a kind of preparation method of light hydrogen occluding alloy is characterized in that: described light hydrogen occluding alloy is Ca-Mg-Ni OrLa-Mg-Ni alloy, described light hydrogen occluding alloy are AB ₂Or AB ₃Or A ₂B ₇Type, wherein A=Ca, Mg or La, Mg or Ca, La, Mg, B=Ni, the preparation method of described light hydrogen occluding alloy is specific as follows:

(1) takes by weighing a certain amount of Ca, La, Mg and Ni raw material by alloying constituent, the purity of raw material all is not less than 99.0wt.%, wherein the scaling loss that Ca, La and Mg element are added 4～6wt.%, 1～2wt.% and 8～10wt.% respectively adopts magnetic levitation melting stove molten alloy then;

(2) place glove box to grind to form 100 purpose powdered alloys the prepared molten alloy of step (1), then this powdered alloy is put into ball grinder, charge into the 1atm argon gas in this ball grinder, ball milling 24～48h obtains amorphous powdered alloy, wherein ratio of grinding media to material is 10: 1～20: 1, and drum's speed of rotation is 200～300rpm;

(3) make step (2) to such an extent that amorphous powdered alloy is put into the stainless steel grinding tool, in pressurize under the 30Mpa pressure after 30 seconds, be pressed into the green compact of φ 13 * 3mm, the gained green compact are put into pottery to be burnt behind the boat conventional vacuum annealing furnace annealing 10 hours, 400～600 ℃ of annealing temperatures obtain single-phase Ca-Mg-Ni system or La-Mg-Ni base hydrogen storage alloy after the annealing.

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