CN100457954C - High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof - Google Patents

High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof Download PDF

Info

Publication number
CN100457954C
CN100457954C CNB200710117709XA CN200710117709A CN100457954C CN 100457954 C CN100457954 C CN 100457954C CN B200710117709X A CNB200710117709X A CN B200710117709XA CN 200710117709 A CN200710117709 A CN 200710117709A CN 100457954 C CN100457954 C CN 100457954C
Authority
CN
China
Prior art keywords
alloy
amorphous
preparation
helium
type hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CNB200710117709XA
Other languages
Chinese (zh)
Other versions
CN101078094A (en
Inventor
张羊换
赵栋梁
王新林
李平
庞在广
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Iron and Steel Research Institute
Original Assignee
Central Iron and Steel Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central Iron and Steel Research Institute filed Critical Central Iron and Steel Research Institute
Priority to CNB200710117709XA priority Critical patent/CN100457954C/en
Publication of CN101078094A publication Critical patent/CN101078094A/en
Application granted granted Critical
Publication of CN100457954C publication Critical patent/CN100457954C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

This patent belongs to hydrogen storage alloy technology field, and it provides a kind of Mg2Ni type hydrogen storage alloy amorphous zonal material and the method to prepare it. The chemical formula of this amorphous zonal material is Mg20-xLaxNi10-yZry. In the formula: 0.5<=x<=10, 0<=y<=5. The preparation method of the above amorphous zonal material is as following (1)To weigh material according to the chemical formula Mg20-xLaxNi10-yZry. (2) To melt the raw material, which has been weighed, and Mg20-xLaxNi10-yZry alloy can be obtained. (3) To make it into Mg2Ni type hydrogen storage alloy fast quenched thin strip, the thickness of which is between 20 and 35 mu m, and the breadth of which is between 1and 20mm, according to fast quenching blast strip technology. The Mg2Ni type hydrogen storage alloy amorphous zonal material in this patent owns high electrochemistry capability and favorable stability to season hydrogen cycle. The preparation technology is stable and easy to operate, the efficiency of it is high, and it is suitable to produce in batches, the thickness of the amorphous zonal material prepared by the method is uniform and the length of it is continuous.

Description

A kind of high capacity Mg 2Ni type hydrogen storing alloy amorphous band and preparation method thereof
Technical field
The invention belongs to the storage alloy material for hydrogen technical field, a kind of high capacity Mg particularly is provided 2Ni type hydrogen storing alloy amorphous band and preparation method thereof.
Background technology
Characteristics such as that Magnuminium has is in light weight, storage hydrogen density height, aboundresources are to be known as the hydrogen storage material that has very big application and development prospect most at present.Mg particularly 2Ni type hydrogen-storage alloy has high theoretical electrochemistry capacity (reaching 999mAh/g), but the Mg of crystalline state 2The Ni alloy does not at room temperature almost have the ability of reversible hydrogen adsorption and desorption.Method with mechanical alloying can obtain amorphous Mg 2The Ni powder is improved the storage hydrogen dynamic performance of alloy significantly.But the preparation efficiency of mechanical alloying is very low, and the powder size of acquisition does not meet the service requirements of Ni-MH battery, and the electrochemistry cyclical stability extreme difference of alloy can not satisfy the requirement of practicability far away.In addition, very easily oxidation and other chemical property of alloy is reduced of the ultrafine powder that obtains of mechanical alloying.Have both at home and abroad and prepare Mg with quick-quenching method 2The report of the alloy amorphous thin slice of Ni, the composition of its alloy mainly are to add Mm, Y, and rare earth elements such as Nd, but all do not form the uniform successive amorphous ribbon of thickness, mainly be that the composition design and the spray technology of alloy is not well mated.
Summary of the invention
The object of the present invention is to provide a kind of amorphous Mg with high electrochemistry capacitance and good seasoning hydrogen cyclical stability 2Ni type hydrogen-storage alloy thin band material, and stable preparation process, easy to operate, the efficient height is fit to mass production; Preparation thickness is even, the fast quenching spray band method of length successive amorphous ribbon material.
According to above-mentioned purpose, the technical scheme principle of work of integral body of the present invention is:
At the composition design aspect of alloy, with the Mg in the La part instead of alloy, with the Ni in the Zr part instead of alloy.Because in rare earth element, La has maximum atomic radius and hydrogen-absorbing ability.Adding La, can to increase in the alloy between element atomic radius poor, in the amorphous formation ability that improves alloy, do not reduce the hydrogen of alloy as far as possible; The effect that adds Zr is similar to La, and Zr itself has very strong amorphous formation ability, and simultaneously, Zr still inhales protium.Total thought is under the prerequisite that guarantees the formation amorphous, does not reduce the hydrogen-absorbing ability of alloy as far as possible.
According to above-mentioned purpose and principle of work, the concrete technical scheme of the present invention is:
This high capacity Mg 2Ni type hydrogen storing alloy amorphous band chemical formula is Mg 20-xLa xNi 10-yZr y, in its formula: 0.5≤x≤10,0≤y≤5.
Prepare above-mentioned high capacity Mg 2The concrete steps of the method for Ni type hydrogen storing alloy amorphous band are:
(1) presses chemical formula Mg 20-xLa xNi 10-yZr yWeighing; In its formula: 0.5≤x≤10,0≤y≤5;
(2) starting material that weigh up are heated to fusion, obtain Mg 20-xLa xNi 10-yZr yAlloy, its Heating temperature are 1000-1500 ℃, and the fusion environment is 1 * 10 -2To 5 * 10 -3The vacuum tightness of Pa, or the 0.01 helium shielding gas to the 0.1MPa negative pressure kept 1-5 minute under melting condition; Alloy with fusing is poured in the water cooled copper mould then, obtains the as cast condition mother alloy ingot;
(3) fast quenching spray band technology: place the bottom to have in the silica tube of slit on the ingot casting of above-mentioned steps (2) preparation; be heated to molten state once more; utilize the pressure of shielding gas helium that it is sprayed from the silica tube slit; continuous injection is on the smooth surface with 20-40m/s linear rate copper roller rotating; in the helium protective atmosphere, adopt the cooling rate of 5-2000 ℃/s to be cooled to room temperature; form thickness between 20-35 μ m, width is between 1-20mm, and length is greater than the Mg of 10m 2The fast quenching amorphous strip of Ni type hydrogen-storage alloy.
Type of heating described in the above-mentioned steps (2) comprises: arc melting or induction heating melting.
Fast quenching type of heating described in the above-mentioned steps (3) comprises: with radio frequency heating or the resistive heating of 50-245kHz.
Amorphous Mg of the present invention 2Ni type hydrogen-storage alloy thin band material compared with prior art has the advantage of high electrochemistry capacitance and good circulation seasoning stabilized hydrogen, and stable preparation process, and is easy to operate, the efficient height, be fit to mass production, the amorphous ribbon material thickness of preparation has evenly, length successive advantage.
Above-mentioned advantage is specific as follows:
The volatilization loss of MAGNESIUM METAL has been avoided in the gas shiled that adds helium when 1, using the medium-frequency induction furnace melting basically, has guaranteed to meet the Mg of design component mole proportioning 2Ni type hydrogen-storage alloy.
2, compare with mechanical alloying, production efficiency of the present invention is higher, and the electrochemistry cyclical stability that obtains amorphous alloy is higher.Mainly be because alloy is the continuous band with non-crystal structure, improved the corrosion resistance nature of alloy in alkaline electrolyte.
3, stable preparation process of the present invention is easy to operate, and the efficient height is fit to mass production.
4, the even length successive of the thickness amorphous ribbon of the present invention's preparation satisfies the needs that prepare " sandwich style " laminar electrodes.
Description of drawings
Fig. 1 is fast quenching Mg of the present invention 2The XRD diffraction spectra of Ni type hydrogen-storage alloy.
Embodiment
Embodiment 1:
Choose the bulk metal magnesium of purity 〉=99.8%, metallic nickel, lanthanoid metal.Press chemical formula Mg 18La 2Ni 10Chemical dosage ratio weigh.Take by weighing MAGNESIUM METAL 369.6g, metallic nickel 405.8g, lanthanoid metal 224g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, vacuumizes about 40 minutes to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.04MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 20mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 30m/s, and obtaining length is greater than 10m, and thickness is about 30 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 2:
Preparation consists of: Mg 16La 4Ni 10Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 279.4g, metallic nickel 383.2g, lanthanoid metal 380.8g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, vacuumizes about 40 minutes to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.04MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 20mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 20m/s, and obtaining length is greater than 10m, and thickness is about 30 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 3:
Preparation consists of: Mg 14La 6Ni 10Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 212.6g, metallic nickel 333.4g, lanthanoid metal 569g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, vacuumizes about 40 minutes to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.04MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 25mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 30m/s, and obtaining length is greater than 10m, and thickness is about 30 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 4:
Preparation consists of: Mg 16La 4Ni 9.5Zr 0.5Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 276.4g, metallic nickel 360.3g, lanthanoid metal 376.9g, metal zirconium 29.5g prepares amorphous material according to the method for embodiment 1, and different is that the silica tube bottom slit that adopts is of a size of 0.05mm * 10mm.The XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1, and the electrochemical hydrogenation and dehydrogenation performance with simulated battery has been tested alloy the results are shown in Table 1.
Embodiment 5:
Preparation consists of: Mg 16La 4Ni 9Zr 1Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 273.5g, metallic nickel 337.8g, lanthanoid metal 373g, metal zirconium 58.3g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, vacuumizes about 40 minutes to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.04MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 10mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 30m/s, and obtaining length is greater than 10m, and thickness is about 26 μ m, and width is the strip of 10mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 6:
Preparation consists of: Mg 16La 4Ni 8.5Zr 1.5Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 270.7g, metallic nickel 315.7g, lanthanoid metal 369.2g, metal zirconium 86.6g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, vacuumizes about 40 minutes to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.05MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 20mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 25m/s, and obtaining length is greater than 10m, and thickness is about 29 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 7:
Preparation consists of: Mg 16La 4Ni 8Zr 2Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 267.9g, metallic nickel 294.1g, lanthanoid metal 365.4g, metal zirconium 114.2g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, is evacuated to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.04MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 20mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 20m/s, and obtaining length is greater than 10m, and thickness is 34 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 8:
Preparation consists of: Mg 19.5La 0.5Ni 9Zr 1Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 448.3g, metallic nickel 454.3g, lanthanoid metal 62.7g, metal zirconium 78.4g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, is evacuated to vacuum tightness 4.8 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.03MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 25mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 25m/s, and obtaining length is greater than 10m, and thickness is 32 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 9:
Preparation consists of: Mg 10La 10Ni 7Zr 3Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 115.4g, metallic nickel 177.3g, lanthanoid metal 629.5g, metal zirconium 118.1g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, is evacuated to vacuum tightness 4.8 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.05MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 10mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 30m/s, and obtaining length is greater than 10m, and thickness is 30 μ m, and width is the strip of 10mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Embodiment 10:
Preparation consists of: Mg 12La 8Ni 5Zr 5Mg 2The hydrogen storing alloy amorphous attitude band of Ni type; Take by weighing MAGNESIUM METAL 149g, metallic nickel 136.3g, lanthanoid metal 542.1g, metal zirconium 211.9g places the magnesia crucible that makes medium-frequency induction furnace, builds bell then, is evacuated to vacuum tightness 5 * 10 -3More than the Pa, charge into helium shielding gas to air pressure again and reach the 0.05MPa negative pressure, adjusting power is 4.5kW, and temperature is controlled at 650 ℃, makes metal M g fusing, regulates power then to 25kW, and temperature is controlled at 1000 ℃, makes the fusing of metallic nickel and lanthanum.Melting of metal finishes, and keeps 5 minutes under melting condition, at last liquation is poured into ingot mould, when injecting ingot mould, power regulation is arrived 8.2kW.Come out of the stove after 20 minutes in cooling under the helium protective atmosphere.
It is the silica tube that 30mm, bottom have slit that the about 100g of cast alloy bar is put into diameter, and slit is of a size of 0.05mm * 25mm; Radio frequency with 245 kilohertzs is heated to fusion, and under the helium-atmosphere protection, heating power is 1-15kW; At helium pressure is under the 1.05atm molten alloy to be ejected on the water-cooled copper roller surface that linear resonance surface velocity is 20m/s, and obtaining length is greater than 10m, and thickness is 26 μ m, and width is the strip of 20mm homogeneous; Analyze the chemical ingredients of its amorphous band then, the XRD test result shows that alloy has non-crystal structure, the results are shown in Figure 1; The electrochemistry capacitance and the cyclical stability of alloy have been tested, result such as table 1.
Table 1 heterogeneity Mg 2The electrochemistry storage hydrogen capacity and the cyclical stability of Ni hydrogen-storage alloy
Figure C20071011770900111
( *Journal?of?Power?Sources?87(2000)118-124)
C 60, max-when charging or discharging current density is 60mA/g, the maximum discharge capacity of alloy (mAh/g);
S 50/100=C 100,50/ C 100, max* 100%, C wherein 100,50For charging or discharging current density is 100mA/g, the loading capacity of the 50th circulation time; C 100, maxMaximum discharge capacity when being 100mA/g for charging or discharging current density.
The continuously even band of using the present invention's preparation has satisfied the requirement of preparation " sandwich style laminar electrodes ", aspect chemical property, the suction hydrogen dynamic performance and the cyclical stability that have more excellent electrochemical properties, particularly alloy than the close material of composition of mechanical alloying method preparation significantly improve.

Claims (4)

1, a kind of high capacity Mg 2Ni type hydrogen storing alloy amorphous band, the chemical formula that it is characterized in that this amorphous band is Mg 20-xLa xNi 10-yZr y, in its formula: 0.5≤x≤10,0≤y≤5.
2, a kind of high capacity Mg 2The preparation method of Ni type hydrogen storing alloy amorphous band is characterized in that, these method concrete steps are:
(1) presses chemical formula Mg 20-xLa xNi 10-yZr yWeighing; In its formula: 0.5≤x≤10,0≤y≤5;
(2) starting material that weigh up are heated to fusion, obtain Mg 20-xLa xNi 10-yZr yAlloy, its Heating temperature are 1000-1500 ℃, and the fusion environment is 1 * 10 -2To 5 * 10 -3The vacuum tightness of Pa, or the 0.01 helium shielding gas to the 0.1MPa negative pressure kept 1-5 minute under melting condition; Alloy with fusing is poured in the water cooled copper mould then, obtains the as cast condition mother alloy ingot;
(3) fast quenching spray band technology: place the bottom to have in the silica tube of slit on the ingot casting of above-mentioned steps (2) preparation; be heated to molten state once more; utilize the pressure of shielding gas helium that it is sprayed from the silica tube slit; continuous injection is on the smooth surface with 20-40m/s linear rate copper roller rotating; in the helium protective atmosphere, adopt the cooling rate of 5-2000 ℃/s to be cooled to room temperature; form thickness between 20-35 μ m, the Mg of width between 1-20mm 2The fast quenching amorphous strip of Ni type hydrogen-storage alloy.
3, preparation method according to claim 2 is characterized in that: the type of heating described in the step (2) comprises: arc melting or induction heating melting.
4, preparation method according to claim 2 is characterized in that: the fast quenching type of heating described in the step (3) comprises: with radio frequency heating or the resistive heating of 50-245kHz.
CNB200710117709XA 2007-06-22 2007-06-22 High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof Active CN100457954C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200710117709XA CN100457954C (en) 2007-06-22 2007-06-22 High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200710117709XA CN100457954C (en) 2007-06-22 2007-06-22 High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101078094A CN101078094A (en) 2007-11-28
CN100457954C true CN100457954C (en) 2009-02-04

Family

ID=38905755

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200710117709XA Active CN100457954C (en) 2007-06-22 2007-06-22 High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof

Country Status (1)

Country Link
CN (1) CN100457954C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101985710A (en) * 2010-09-03 2011-03-16 燕山大学 Multiphase Mg-RE-Ni hydrogen storage alloy

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101845563B (en) * 2010-03-23 2011-06-01 广西大学 Preparation method for improving hydrogen storage performance of AB2C9 La-Mg-Ni-based alloy
CN101985726A (en) * 2010-10-22 2011-03-16 南京航空航天大学 Amorphous hydrogen storage alloy
CN103074529A (en) * 2012-10-16 2013-05-01 西北工业大学 Magnesium-nickel-yttria hydrogen storage alloy thin belt and preparation method thereof
CN103088277B (en) * 2012-12-31 2016-01-20 中南大学 A kind of raising Mg 2the method of Ni type hydrogen-storage alloy performance and device
CN103173656A (en) * 2013-03-08 2013-06-26 燕山大学 Composite additive for improving hydrogen storage performance of Mg2Ni based hydrogen storage alloy
CN103498089B (en) * 2013-09-27 2015-11-04 内蒙古科技大学 A kind of fuel cell high capacity hydrogen storage alloy and preparation method thereof
CN103643178B (en) * 2013-12-09 2016-04-13 内蒙古科技大学 Nanocrystalline-amorhigh-capacity high-capacity hydrogen storage electrode alloy and preparation method thereof
CN103682285B (en) * 2013-12-12 2016-03-23 内蒙古科技大学 Ni-MH battery high capacity hydrogen storage electrode metal and preparation method thereof
CN103938052B (en) * 2014-01-16 2016-09-21 内蒙古科技大学 High capacity hydrogen storage electrode metal and preparation method thereof
CN103741004B (en) * 2014-01-28 2015-09-16 内蒙古科技大学 CoS 2high capacity hydrogen storage alloy of catalysis and preparation method thereof
CN113699469A (en) * 2021-08-27 2021-11-26 广东省国研科技研究中心有限公司 High-thermal-stability magnesium-based amorphous micron hydrogen storage filament and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269572A (en) * 1998-03-24 1999-10-05 Japan Metals & Chem Co Ltd Production of amorphous magnesium-nickel base hydrogen storage alloy
CN1563453A (en) * 2004-04-01 2005-01-12 桂林电子工业学院 rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method
US20050139566A1 (en) * 2002-01-29 2005-06-30 Yoshino Kogyosho Co., Ltd. Biaxially oriented, blown-molded bottles and preform thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11269572A (en) * 1998-03-24 1999-10-05 Japan Metals & Chem Co Ltd Production of amorphous magnesium-nickel base hydrogen storage alloy
US20050139566A1 (en) * 2002-01-29 2005-06-30 Yoshino Kogyosho Co., Ltd. Biaxially oriented, blown-molded bottles and preform thereof
CN1563453A (en) * 2004-04-01 2005-01-12 桂林电子工业学院 rEXmGYnI4-zAz alloy of storing hydrogen and uncrystallized preparation method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Mg-Ni基非晶/纳米晶贮氢合金的研究新进展. 黄林军.中国稀土学报，第23卷. 2005
Mg-Ni基非晶/纳米晶贮氢合金的研究新进展. 黄林军.中国稀土学报，第23卷. 2005 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101985710A (en) * 2010-09-03 2011-03-16 燕山大学 Multiphase Mg-RE-Ni hydrogen storage alloy
CN101985710B (en) * 2010-09-03 2012-03-14 燕山大学 Multiphase Mg-RE-Ni hydrogen storage alloy

Also Published As

Publication number Publication date
CN101078094A (en) 2007-11-28

Similar Documents

Publication Publication Date Title
CN100457954C (en) High capacity Mg2Ni-type hydrogen storing alloy amorphous band and preparation method thereof
CN103165873B (en) A kind of power battery hydrogen storage electrode alloy and preparation method thereof
CN104593651B (en) A kind of Mg-Ti-RE-Ni base hydrogen-storing alloy and preparation method thereof
CN101597711B (en) Rare earth-magnesium-transition metal base hydrogen storage metal preparation method
CN100478466C (en) Method for preparing RE-Mg-Ni-M series hydrogen storage alloy
CN103695753A (en) High-capacity RE-Mg-Ni-Co based hydrogen storage alloy and preparation method thereof
CN103667837A (en) Nanometer TiF3 catalyzed high-volume hydrogen-storing alloy and preparation method thereof
CN101906545A (en) Preparation method of Mg-contained hydrogen storage alloy
CN111118341A (en) Rare earth-samarium-nickel type hydrogen storage alloy, negative electrode, battery and preparation method
CN103633339B (en) A kind of nano Ce O 2high power capacity RE-Mg-Ni base hydrogen-storing alloy of catalysis and preparation method thereof
CN107099724B (en) The preparation method of nanometer titanium trifluoride catalysis Mg-RE-Ni-Al-Ti-Co base hydrogen-storing alloy
CN103031481A (en) Quasicrystal complex phase hydrogen storage alloy containing magnesium, titanium, vanadium and nickel and preparation method thereof
CN108588521A (en) A kind of high capacity Mg-Cu-Ni ternary hydrogen-storage alloys and preparation method thereof
CN102834538B (en) Hydrogen absorbing alloy, hydrogen absorbing alloy electrode and secondary cell
CN108097947A (en) A kind of high capacity Mg-Zn-Ni ternary hydrogen-storage alloys and preparation method thereof
CN103498089B (en) A kind of fuel cell high capacity hydrogen storage alloy and preparation method thereof
CN107338381B (en) The hydrogen-storage alloy and preparation method thereof that fuel cell graphene is catalyzed
CN108247040A (en) Nano-oxide catalyst coats the in-situ synthesis of hydrogen storing alloy composite material
CN103647063B (en) Hydrogen storage electrode alloy for Ni-MH secondary battery and preparation method thereof
CN103938052B (en) High capacity hydrogen storage electrode metal and preparation method thereof
CN103682288B (en) Hydrogen storage electrode alloy for Ni-MH battery and preparation method thereof
CN107385300B (en) LaCl3The preparation method of the high capacity hydrogen storage alloy powder of catalysis
CN105671405A (en) Low-temperature high-capacity Mg-RE-Ni-based A2B-type hydrogen storage alloy and preparation method thereof
CN105463256A (en) Hydrogen storage alloy for nickel-metal hydride battery and manufacturing method of hydrogen storage alloy
CN106756355B (en) Fuel cell stores hydrogen intermediate alloy, hydrogen storage material and preparation method with Mg-Sn-Ni ternary

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant