CN101332976B - Method for preparing Li-Mg-N-H hydrogen-storing material - Google Patents
Method for preparing Li-Mg-N-H hydrogen-storing material Download PDFInfo
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- CN101332976B CN101332976B CN2008100632985A CN200810063298A CN101332976B CN 101332976 B CN101332976 B CN 101332976B CN 2008100632985 A CN2008100632985 A CN 2008100632985A CN 200810063298 A CN200810063298 A CN 200810063298A CN 101332976 B CN101332976 B CN 101332976B
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Abstract
The invention discloses a method for preparing Li-Mg-N-H hydrogen storage material. The mixture of the nitride or amino-compound of Li and Mg, the nitride or amino-compound of Mg is loaded in a stainless steel tank and evenly blended by a mechanical mixing or mechanical ball milling way; the evenly blended mixture is loaded in a sintering furnace, the sintering furnace is vacuumized or charged with inert gases and is heated to the temperature range from 250 to 350 DEG C for heat preservation and then the Li-Mg-N-H hydrogen storage material is obtained; the Li-Mg-N-H hydrogen storage material is loaded into a ball milling tank and undergoes ball milling process on a ball mill, and the grain diameter of the sample powder processed with ball milling is smaller than 100nm. The preparation method has simple operation, easy control and low cost. The Li-Mg-N-H prepared and processed by the invention has high hydrogen storage capacity, low working temperature and high speed of hydrogen absorbing and discharging and good reversibility, thus being the hydrogen storage material with excellent performance and being suitable for the storage and transportation of hydrogen.
Description
Technical field
The present invention relates to hydrogen storage material, especially a kind of preparation method of novel Li-Mg-N-H hydrogen storage material.
Background technology
Hydrogen is described as the green energy resource carrier of 21 century owing to its aboundresources, efficiency of combustion height, pollution-free.Adopt the defeated hydrogen of hydrogen storage material storage, safe and efficient, use cost is low, therefore receives much concern.The hydrogen storage material of practicability must satisfy that hydrogen-storage density is big, speed for hydrogen absorbing and releasing is fast, working temperature is moderate, the high requirement of security.With the on-board hydrogen source system, the target that international energy federation (IEA) proposes hydrogen storage material is the quality hydrogen-storage density greater than 5%, the volume hydrogen-storage density is greater than 50kg H for fuel cell
2/ m
3, hydrogen discharging temperature is lower than 150 ℃, and cycle life is above 1000 times.Have the hydride hydrogen-storing material now or, perhaps, be difficult to satisfy the needs of practicability because working temperature is higher because hydrogen-storage density is on the low side.Therefore, press for research and development novel high-performance hydrogen storage material.
In recent years, a brand-new field [P.Chen of novel high-capacity hydrogen storage material has been started in the discovery of light metal nitrogen hydride hydrogen-storing material, Z.T.Xiong, J.Z.Luo, J.Y.Lin, K.L.Tan, Nature, 2002,420:302.], the reversible storage that fracture and the reconstruction of this system material by the N-H key realized hydrogen.The reversible hydrogen storage amount of the Li-Mg-N-H hydrogen storage system of being developed is up to 5.5wt%[Z.T.Xiong, G.T.Wu, J.J.Hu, P.Chen, Advanced Materials, 2004,16:1522; W.F.Luo, J.Alloys Compd., 2004,381:284.], thereby caused people's common concern.But the preparation of Li-Mg-N-H hydrogen storage system is all from Mg (NH at present
2)
2With 2LiH or LiNH
2And MgH
2Set out, above-mentioned synthetic method is owing to adopt metal hydride LiH and MgH
2As starting material, cause the cost of material higher.In addition, utilize aforesaid method synthetic Li-Mg-N-H hydrogen storage material also to exist and put shortcomings such as the hydrogen working temperature is higher, cyclical stability is relatively poor.This shows that in order further to improve the hydrogen storage property of Li-Mg-N-H, reduce its cost, the novel method that develops low-cost raw material preparing Li-Mg-N-H hydrogen storage material is extremely urgent.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Li-Mg-N-H hydrogen storage material.
The preparation method of Li-Mg-N-H hydrogen storage material comprises the steps:
1) under the condition of secluding air, the mixture of the nitride of the nitride of Li or amides and Mg, Mg or amides packed into is placed with the stainless cylinder of steel of abrading-ball;
2) mode of employing mechanically mixing or mechanical ball milling, make the nitride of Li or nitride or the amides uniform mixing of amides and Mg, Mg, the weight ratio of abrading-ball and sample is (10-100): 1, and rotating speed is 30-550rpm, carries out under vacuum, inert atmosphere, ammonia atmosphere or nitrogen atmosphere;
3) under the condition of secluding air, the mixture of the nitride of the nitride of the Li that mixes or amides and Mg, Mg or amides is packed in the sintering oven;
4) sintering oven is vacuumized, directly feeds rare gas element or sintering oven is vacuumized back feeding rare gas element in sintering oven, inert gas pressure is 0.1-5atm, and flow velocity is 10-300mL/min;
5) sintering oven is heated to 250-350 ℃ temperature range, soaking time is 2-60h, obtains the Li-Mg-N-H hydrogen storage material;
6) under the condition of secluding air, the Li-Mg-N-H hydrogen storage material packed into is placed with the ball grinder of abrading-ball, and ratio of grinding media to material is (10-100): 1;
7) carry out ball-milling processing on ball mill, the ball milling time is 2-100h, and sample is in vacuum or inert atmosphere protection, and the particle diameter of sample powder is less than 100nm behind the ball milling.
The nitride of the nitride of described Li or amides and Mg, Mg or the mixture of amides composition are respectively Li
3N and Mg (NH
2)
2, Li
3N and Mg, Li
3N and Mg
3N
2, LiNH
2And Mg, LiNH
2And Mg
3N
2, LiNH
2And Mg (NH
2)
2, Li
3N, LiNH
2And Mg, Li
3N, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg (NH
2)
2, Li
3N, Mg and Mg (NH
2)
2, Li
3N, Mg and Mg
3N
2, LiNH
2, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg
3N
2, LiNH
2, Mg
3N
2And Mg (NH
2)
2, wherein the ratio of mixture makes that the atomic ratio of Li and Mg is 1.9～2.5.
The nitride of the nitride of described Li or amides and Mg, Mg or amides mix on powder machine, planetary ball mill or the oscillatory type ball mill at automation and carry out mechanically mixing or mechanical ball milling.The abrading-ball that described mechanically mixing or mechanical ball milling adopt is Stainless Steel Ball, zirconia ball or agate ball.
Li in the nitride of the nitride of described Li or amides and Mg, Mg or the mixture of amides
3N and Mg (NH
2)
2, LiNH
2And Mg, LiNH
2And Mg
3N
2, LiNH
2And Mg (NH
2)
2, Li
3N, LiNH
2And Mg, Li
3N, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg (NH
2)
2, Li
3N, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg
3N
2, LiNH
2, Mg
3N
2And Mg (NH
2)
2, adopting vacuum, inert atmosphere, ammonia atmosphere or nitrogen atmosphere during ball milling, described inert atmosphere is nitrogen atmosphere, argon atmospher or helium-atmosphere.
Li in the nitride of the nitride of described Li or amides and Mg, Mg or the mixture of amides
3N and Mg, Li
3N and Mg
3N
2, Li
3N, Mg and Mg
3N
2, adopt ammonia atmosphere or nitrogen atmosphere during ball milling;
Described sintering oven is vacuum type, atmosphere formula or vacuum atmosphere formula sintering oven, and atmosphere formula or vacuum atmosphere formula sintering oven are equipped with the air valve door.The used rare gas element of sintering is nitrogen, argon gas or helium.
The ball milling of described Li-Mg-N-H hydrogen storage material is to carry out on planetary ball mill or oscillatory type ball mill, and the rotating speed of planetary ball mill is 100-550rpm.Described ball milling inert atmosphere is nitrogen, argon gas or helium.
The ratio of grinding media to material of described Li-Mg-N-H hydrogen storage material is 60: 1, and rotational speed of ball-mill is 550rpm, and the ball milling time is 36h, and the particle diameter of sample powder is 10-100nm behind the ball milling.
Adopt the Li-Mg-N-H hydrogen storage material of the present invention's preparation, hydrogen-storage amount remains on more than the 5wt%, suction is put the hydrogen working temperature and is reduced by 30%, speed for hydrogen absorbing and releasing is obviously accelerated, and cyclical stability significantly improves, and abundant raw materials of the present invention is easy to get, cost is lower, preparation process is simple to operate, is easy to control, helps the industrialization of this technology.
Description of drawings
Fig. 1 is with Li
3N-Mg (NH
2)
2The X-ray diffraction spectrum of the Li-Mg-N-H sample for preparing for the starting material sintering;
Fig. 2 is with LiNH
2-Mg
3N
2-Mg (NH
2)
2The infrared spectra of the Li-Mg-N-H sample that obtains for raw material preparing;
Fig. 3 is with LiNH
2-Mg
3N
2The X-ray diffraction spectrum of the Li-Mg-N-H sample that obtains for raw material preparing;
Fig. 4 is with Li
3N-Mg-Mg
3N
2The X ray collection of illustrative plates of the Li-Mg-N-H sample that obtains for raw material preparing;
Fig. 5 is with Li
3N-LiNH
2-Mg (NH
2)
2The infrared spectra of the Li-Mg-N-H sample that obtains for raw material preparing;
Fig. 6 is the suction hydrogen curve comparison diagram of the Li-Mg-N-H sample for preparing of the Li-Mg-N-H sample that prepared by the present invention and traditional method;
Fig. 7 be the Li-Mg-N-H sample for preparing of the present invention put the hydrogen curve with temperature;
Fig. 8 is the hydrogen desorption kinetics comparison diagram after 1 circulation of the Li-Mg-N-H sample for preparing of the Li-Mg-N-H sample that prepared by the present invention and traditional method.
Embodiment
Nitride (Li with Li
3N) or amides (LiNH
2) with the nitride (Mg of Mg, Mg
3N
2) or amides (Mg (NH
2)
2) press the certain mol proportion mixing, form Li
3N and Mg (NH
2)
2, Li
3N and Mg, Li
3N and Mg
3N
2, LiNH
2And Mg, LiNH
2And Mg
3N
2, LiNH
2And Mg (NH
2)
2, Li
3N, LiNH
2And Mg, Li
3N, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg (NH
2)
2, Li
3N, Mg and Mg (NH
2)
2, Li
3N, Mg and Mg
3N
2, LiNH
2, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg
3N
2, LiNH
2, Mg
3N
2And Mg (NH
2)
2Mixture, then mixture is carried out mechanically mixing or mechanical ball milling respectively under corresponding atmosphere, ratio of grinding media to material is (10-100): 1.The mixture of sintered compound after evenly prepares the Li-Mg-N-H hydrogen storage material in vacuum or inert atmosphere, and it is carried out X-ray diffraction and Infrared spectroscopy.Under vacuum or inert atmosphere protection, the Li-Mg-N-H sample that sintering is prepared carries out mechanical ball milling processing, the structure of specimen and hydrogen storage property.Because sample easily reacts with the oxygen G﹠W, all sample weighings and sample transfer are all carried out in the glove box that is filled with high-purity argon gas or nitrogen, wherein in the glove box content of oxygen and water less than 50ppm.
The X ray diffracting data of sample is collected on Japan Rikagu D/MAX-RA of science diffractometer, and the infrared spectrum characterization of sample carries out on Bruker Vector 22 infrared test instrument.
The suction of sample is put the hydrogen behavior and is carried out in temperature programmed control desorption system, and the hydrogen storage property test is carried out on the gaseous state performance test apparatus.For putting the hydrogen test, before the test, reactive system is evacuated to 10 earlier
-2Atm.For inhaling the hydrogen test, the initial hydrogen pressure of system is 80atm, inhales to put the hydrogen process and use AI-708P type programmed temperature control instrument to be heated to relevant temperature with the heating rate of 2 ℃/min by room temperature.Hydrogen pressure, program temperature and the thermopair observed temperature of automatic record reactive system are over time in the experimentation.
Embodiment 1
In the glove box that is full of Ar gas, with Li
3N and Mg (NH
2)
2, LiNH
2And Mg, LiNH
2And Mg (NH
2)
2, LiNH
2, Mg and Mg (NH
2)
2Respectively by 2: 3,1.95: 1, the mixed in molar ratio of 2: 1 and 2.5: 0.5: 0.5, the stainless cylinder of steel of packing into and can seal adopts argon shield, mixes on the powder machine at automation and carries out mechanically mixing, ratio of grinding media to material 40: 1, rotating speed 90rpm, mixing time 8h.The mixture that mixes under the condition of secluding air, is put into atmosphere formula sintering oven, adopt the nitrogen gas stream protection, nitrogen pressure 2atm, flow velocity 100mL/min, the sample sintering temperature is 250 ℃, soaking time 36h carries out sintering and prepares the Li-Mg-N-H hydrogen storage material.The mol ratio of biased sample and mixing thereof, sintering preparation condition are listed in table 1.Sample to the sintering preparation carries out X-ray diffraction test discovery, and sample presents Li
2MgN
2H
2Diffracting spectrum.What Fig. 1 was exemplary has provided with Li
3N-Mg (NH
2)
2The X-ray diffraction spectrum of the Li-Mg-N-H sample for preparing for the starting material sintering.As can be seen from the figure, sample diffraction peak more sharp-pointed, peak width at half height is less, illustrates that its crystallinity is good.
In the glove box that is full of Ar gas, with mol ratio 2.05: 1 LiNH
2And Mg (NH
2)
2Mixture is packed into and is had the ball grinder of opening-closing valve, and after ball grinder forvacuum, on planetary ball mill, carry out ball milling and mix, ratio of grinding media to material 55: 1, rotating speed is 550rpm, the ball milling time is 6h.Then, mixture is put into atmosphere formula sintering oven under the condition of secluding air, adopts the nitrogen gas stream protection, nitrogen pressure 1.6atm, and flow velocity 70mL/min, the sample sintering temperature is 280 ℃, soaking time 30h, sintering prepare the Li-Mg-N-H hydrogen storage material.The mixed sintering preparation parameter of sample is also listed in table 1.Sintering prepares the X-ray diffraction test shows of sample, and product mainly comprises Li
2MgN
2H
2Phase.
Embodiment 3
In being full of the glove box of nitrogen, with mol ratio 2: 0.1: 0.7 LiNH
2And Mg
3N
2And Mg (NH
2)
2The stainless cylinder of steel that mixture is packed into and can be sealed adopts nitrogen protection, mixes on the powder machine at automation and carries out mechanically mixing, ratio of grinding media to material 80: 1, rotating speed 60rpm, mixing time 12h.Then the mixture that mixes be not exposed under the airborne condition, is being transferred to the vacuum type sintering oven, adopting and vacuumize protection, vacuum tightness is 10
-2-10
-6Atm, the sample sintering temperature is 300 ℃, soaking time 24h, sintering prepare the Li-Mg-N-H hydrogen storage material.The mixing of sample, sintering preparation condition are also listed in table 1.Sintered sample is carried out examination of infrared spectrum, Figure 2 shows that with LiNH
2-Mg
3N
2-Mg (NH
2)
2The infrared spectra of the Li-Mg-N-H sample that obtains for raw material preparing.As can be seen from the figure, at wave number 2400-3600cm
-1In the scope, has only a N-H vibration at 3176cm
-1Near can being detected, this is a typical imino-thing Li
2MgN
2H
2Vibration absorption peak.
In the glove box that is full of Ar gas, with mol ratio 6: 1 LiNH
2And Mg
3N
2The stainless cylinder of steel that mixture is packed into and can be sealed adopts argon shield, carries out ball milling and mix ratio of grinding media to material 50: 1, mixing time 6h on the oscillatory type ball mill.The mixture that mixes under the condition of secluding air, is put into atmosphere formula sintering oven, adopt the helium flow protection, helium pressure 0.2atm, flow velocity 30mL/min, the sample sintering temperature is 315 ℃, soaking time 16h, sintering prepare the Li-Mg-N-H hydrogen storage material.Sample to the sintering preparation carries out the X-ray diffraction test, Figure 3 shows that sintering prepares the X ray collection of illustrative plates of sample.Can find that from figure sample presents the Li of mixed structure
2MgN
2H
2Diffracting spectrum.
In the glove box that is full of Ar gas, mol ratio was respectively 2: 3.02,2.2: 1,2.1: 1,6.05: 1,1: 1: 2, the Li of 2.2: 1: 2 and 2: 0.4: 0.2
3N and Mg, Li
3N and Mg
3N
2, LiNH
2And Mg, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg, Li
3N, Mg and Mg
3N
2, LiNH
2, Mg and Mg
3N
2Mixture pack into and have the ball grinder of opening-closing valve, after ball grinder forvacuum, charge into the ammonia of 8atm, on planetary ball mill, carry out ball milling and mix, ratio of grinding media to material 100: 1, rotating speed is 500rpm, the ball milling time is 24h.Then, the mixture that mixes is put into vacuum atmosphere formula sintering oven under the condition of secluding air, at first after the forvacuum; the protection of employing nitrogen gas stream, nitrogen pressure 1.5atm, flow velocity 50mL/min; the sample sintering temperature is 320 ℃, and soaking time 12h, sintering prepare the Li-Mg-N-H hydrogen storage material.The mol ratio of biased sample and mixed sintering preparation parameter thereof are listed in table 1.The sample of sintering preparation carries out the X-ray diffraction test.Figure 4 shows that with Li
3N-Mg-Mg
3N
2The X ray collection of illustrative plates of the Li-Mg-N-H sample that obtains for raw material preparing.Can find that from figure sample also presents Li
2MgN
2H
2Diffracting spectrum.
Embodiment 6
In the glove box that is full of Ar gas, with Li
3N, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg (NH
2)
2, Li
3N, Mg and Mg (NH
2)
21: 3: 1 in molar ratio respectively; 1.2: mixed in 3: 1 and 2.05: 1: 2; biased sample packed into have the ball grinder of opening-closing valve; ball grinder is forvacuum at first; charge into the hydrogen shield of 30atm then, on planetary ball mill, carry out ball milling and mix ratio of grinding media to material 60: 1; rotating speed is 400rpm, and the ball milling time is 36h.Ball milling finishes, and the mixture that mixes be not exposed under the airborne condition, puts into atmosphere formula sintering oven; the protection of employing argon gas stream, argon pressure 0.5atm, flow velocity 40mL/min; the sample sintering temperature is 350 ℃, and soaking time 6h, sintering prepare the Li-Mg-N-H hydrogen storage material.The mol ratio of biased sample and mixing thereof, sintering parameter are listed in table 1.Sample behind the sintering carries out examination of infrared spectrum.Figure 5 shows that with Li
3N-LiNH
2-Mg (NH
2)
2The infrared spectra of the Li-Mg-N-H sample that obtains for raw material preparing.As can be seen from the figure, one at 3171cm
-1Near N-H vibration absorption peak can be detected, and this should be imino-thing Li
2Mg
2N
2H
2The eigen vibration absorption peak.
The mole of table 1 different mixtures when mixes, the sintering preparation condition
| Sample | Mol ratio | Hybrid mode | Hybrid protection atmosphere | Ratio of grinding media to material | Rotating speed (rev/min) | Mixing time (hour) | The sintering protective atmosphere | Sintering temperature (degree centigrade) | Sintering time (hour) | |
| Li 3N-Mg(NH 2) 2 | 2∶3 | Mechanically mixing | Ar | 40∶1 | 90 | 8 | |
250 | 36 | |
| Li
3N- |
2∶3.02 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| Li 3N-Mg 3N 2 | 2.2∶1 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| LiNH 2-Mg | 1.95∶1 | Mechanically mixing | Ar | 40∶1 | 90 | 8 | |
250 | 36 | |
| LiNH 2-Mg | 2.1∶1 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| LiNH 2-Mg 3N 2 | 6∶1 | | Ar | 50∶1 | 6 | He | 315 | 16 | ||
| LiNH 2-Mg 3N 2 | 6.05∶1 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| LiNH 2-Mg(NH 2) 2 | 2∶1 | Mechanically mixing | Ar | 40∶1 | 90 | 8 | |
250 | 36 | |
| LiNH 2-Mg(NH 2) 2 | 2.05∶1 | Planetary type ball-milling | Vacuum | 55∶1 | 550 | 6 | N 2 | 280 | 30 | |
| Li 3N-LiNH 2-Mg | 1∶1∶2 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| Li 3N-LiNH 2- Mg 3N 2 | 1∶3∶1 | Planetary type ball- | H | 2 | 60∶1 | 400 | 36 | Ar | 350 | 6 |
| Li 3N-LiNH 2- Mg(NH 2) 2 | 1.2∶3∶1 | Planetary type ball- | H | 2 | 60∶1 | 400 | 36 | Ar | 350 | 6 |
| Li 3N-Mg- Mg(NH 2) 2 | 2.05∶1∶2 | Planetary type ball- | H | 2 | 60∶1 | 400 | 36 | Ar | 350 | 6 |
| Li 3N-Mg- Mg 3N 2 | 2.2∶1∶2 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| LiNH 2-Mg- Mg(NH 2) 2 | 2.5∶0.5∶ 0.5 | Mechanically mixing | Ar | 40∶1 | 90 | 8 | |
250 | 36 | |
| LiNH 2-Mg- Mg 3N 2 | 2∶0.4∶0.2 | Planetary type ball- | NH | 3 | 100∶1 | 500 | 24 | N 2 | 320 | 12 |
| LiNH 2-Mg 3N 2- Mg(NH 2) 2 | 2∶0.1∶0.7 | Mechanically mixing | |
80∶1 | 60 | 12 | Vacuum | 300 | 24 |
Embodiment 7
Be full of in the glove box of argon gas, the Li-Mg-N-H hydrogen storage material for preparing among the embodiment 1 is packed in the ball grinder, sample adopts the oscillatory type ball mill to carry out ball-milling processing under argon shield.The weight ratio of sample and abrading-ball is 40: 1, and the ball milling time is 6-36h.The hydrogen sucking function of sample the results are shown in table 2 behind the test ball milling.As can be seen from the table, sample can realize inhaling hydrogen behind the ball milling in 50-150 ℃ scope, and hydrogen has reflected that all above 5wt% it has good hydrogen sucking function.
The hydrogen storage property of the partial L i-Mg-N-H sample of sintering preparation behind table 2 ball milling
| Sample | The ball milling time | Inhale hydrogen begin temperature (degree centigrade) | Hydrogen (weight percent) |
| Li 3N-Mg(NH 2) 2 | 6 | 150 | 5.1 |
| LiNH 2-Mg | 12 | 130 | 5.2 |
| LiNH 2-Mg(NH 2) 2 | 18 | 90 | 5.3 |
| LiNH 2-Mg-Mg(NH 2) 2 | 36 | 50 | 5.3 |
Embodiment 8
In being full of the glove box of nitrogen, the Li-Mg-N-H hydrogen storage material for preparing among embodiment 2, embodiment 3 and the embodiment 4 to be packed in the ball grinder, sample adopts the oscillatory type ball mill to carry out ball-milling processing under nitrogen protection.The weight ratio of sample and abrading-ball is 60: 1.The hydrogen sucking function of sample behind the test ball milling.
Comparative example 1
In being full of the glove box of nitrogen, with Mg (NH
2)
2Mix by 1: 2 mol ratio with LiH, in the ball grinder of packing into, sample adopts the oscillatory type ball mill to carry out ball-milling processing under nitrogen protection.The weight ratio of sample and abrading-ball is 60: 1.Its hydrogen sucking function is tested at first dehydrogenation of sample then behind the ball milling.
Figure 6 shows that respectively the suction hydrogen curve of the Li-Mg-N-H for preparing according to embodiment 8 and comparative example 1.As can be seen from the figure, adopt the hydrogen of the Li-Mg-N-H of the present invention's preparation can reach 5.0wt%, inhale the hydrogen starting temperature and only be 50 ℃, inhale the hydrogen temperature and obviously reduce.
Embodiment 9
In being full of the glove box of argon gas, the Li-Mg-N-H hydrogen storage material for preparing among the embodiment 5 is packed in the ball grinder, on planetary ball mill, carry out ball-milling processing, sample adopts argon shield, ratio of grinding media to material 100: 1, rotating speed is 400rpm.Sample is inhaled hydrogen at first at low temperatures behind the ball milling, tests its hydrogen discharging performance then.Figure 7 shows that the hydrogen behavior of putting that sample raises with temperature.As can be seen from the figure, the initial hydrogen discharging temperature of sample is about 120 ℃, and total hydrogen desorption capacity can reach 5.0wt%.
In being full of the glove box of argon gas, the Li-Mg-N-H hydrogen storage material for preparing among the embodiment 6 packed into to be had in the ball grinder of opening-closing valve, and ball grinder vacuumizes then, carries out ball-milling processing on planetary ball mill, ratio of grinding media to material 80: 1, and rotating speed is 550rpm.Sample is inhaled hydrogen at first at low temperatures behind the ball milling, tests its hydrogen desorption kinetics performance then.
Comparative example 2
In being full of the glove box of argon gas, with Mg (NH
2)
2Mix by 1: 2 mol ratio with LiH, packing into has in the ball grinder of opening-closing valve, and ball grinder vacuumizes then, carries out ball-milling processing on planetary ball mill, ratio of grinding media to material 80: 1, and rotating speed is 550rpm.Sample at first carries out single step of releasing hydrogen, inhales the hydrogen circulation behind the ball milling, then the hydrogen desorption kinetics performance of sample behind the test suction hydrogen.
Figure 8 shows that the hydrogen desorption kinetics comparison curves of embodiment 10 and comparative example 2 prepared samples.As can be seen from the figure, sample obviously improves the hydrogen desorption kinetics performance of Li-Mg-N-H hydrogen storage material in working cycle of the present invention's preparation in the example 2 than comparing.
Claims (10)
1. the preparation method of a Li-Mg-N-H hydrogen storage material is characterized in that comprising the steps:
1) under the condition of secluding air, the mixture of the nitride of the nitride of Li or amides and Mg, Mg or amides packed into is placed with the stainless cylinder of steel of abrading-ball;
2) mode of employing mechanically mixing or mechanical ball milling, make the nitride of Li or nitride or the amides uniform mixing of amides and Mg, Mg, the weight ratio of abrading-ball and sample is (10-100): 1, and rotating speed is 30-550rpm, carries out under vacuum, inert atmosphere, ammonia atmosphere or nitrogen atmosphere;
3) under the condition of secluding air, the mixture of the nitride of the nitride of the Li that mixes or amides and Mg, Mg or amides is packed in the sintering oven;
4) sintering oven is vacuumized, directly feeds rare gas element or sintering oven is vacuumized back feeding rare gas element in sintering oven, inert gas pressure is 0.1-5atm, and flow velocity is 10-300mL/min;
5) sintering oven is heated to 250-350 ℃ temperature range, soaking time is 2-60h, obtains the Li-Mg-N-H hydrogen storage material;
6) under the condition of secluding air, the Li-Mg-N-H hydrogen storage material packed into is placed with the ball grinder of abrading-ball, and ratio of grinding media to material is (10-100): 1;
7) carry out ball-milling processing on ball mill, the ball milling time is 2-100h, and sample is in vacuum or inert atmosphere protection, and the particle diameter of sample powder is less than 100nm behind the ball milling;
The nitride of the nitride of described Li or amides and Mg, Mg or the mixture of amides composition are respectively Li
3N and Mg (NH
2)
2, Li
3N and Mg, Li
3N and Mg
3N
2, LiNH
2And Mg
3N
2, LiNH
2And Mg (NH
2)
2, Li
3N, LiNH
2And Mg, Li
3N, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg (NH
2)
2, Li
3N, Mg and Mg (NH
2)
2, Li
3N, Mg and Mg
3N
2, LiNH
2, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg
3N
2, LiNH
2, Mg
3N
2And Mg (NH
2)
2, wherein the ratio of mixture makes that the atomic ratio of Li and Mg is 1.9～2.5.
2. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1 is characterized in that the nitride of described Li or nitride or the amides of amides and Mg, Mg carry out mechanically mixing or mechanical ball milling on automation mixed powder machine, planetary ball mill or oscillatory type ball mill.
3. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 2 is characterized in that the abrading-ball that described mechanically mixing or mechanical ball milling adopt is Stainless Steel Ball, zirconia ball or agate ball.
4. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1 is characterized in that the Li in the mixture of the nitride of the nitride of described Li or amides and Mg, Mg or amides
3N and Mg (NH
2)
2, LiNH
2And Mg
3N
2, LiNH
2And Mg (NH
2)
2, Li
3N, LiNH
2And Mg, Li
3N, LiNH
2And Mg
3N
2, Li
3N, LiNH
2And Mg (NH
2)
2, Li
3N, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg (NH
2)
2, LiNH
2, Mg and Mg
3N
2, LiNH
2, Mg
3N
2And Mg (NH
2)
2, adopting vacuum, inert atmosphere, ammonia atmosphere or nitrogen atmosphere during ball milling, described inert atmosphere is nitrogen atmosphere, argon atmospher or helium-atmosphere.
5. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1 is characterized in that the Li in the mixture of the nitride of the nitride of described Li or amides and Mg, Mg or amides
3N and Mg, Li
3N and Mg
3N
2, Li
3N, Mg and Mg
3N
2, adopt ammonia atmosphere or nitrogen atmosphere during ball milling.
6. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1 is characterized in that described sintering oven is vacuum type or atmosphere formula sintering oven, and atmosphere formula sintering oven is equipped with the air valve door; The used rare gas element of sintering is nitrogen, argon gas or helium.
7. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1 is characterized in that described sintering oven is a vacuum atmosphere formula sintering oven, and vacuum atmosphere formula sintering oven is equipped with the air valve door; The used rare gas element of sintering is nitrogen, argon gas or helium.
8. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1, the ball milling that it is characterized in that described Li-Mg-N-H hydrogen storage material carries out on planetary ball mill or oscillatory type ball mill, and the rotating speed of planetary ball mill is 100-550rpm.
9. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1 is characterized in that described ball milling inert atmosphere is nitrogen, argon gas or helium.
10. the preparation method of a kind of Li-Mg-N-H hydrogen storage material according to claim 1, the ratio of grinding media to material that it is characterized in that described Li-Mg-N-H hydrogen storage material is 60: 1, rotational speed of ball-mill is 550rpm, and the ball milling time is 36h, and the particle diameter of sample powder is 10-100nm behind the ball milling.
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| CN102153050A (en) * | 2011-02-24 | 2011-08-17 | 浙江大学 | Doped Li-Mg-N-H hydrogen storage material |
| CN103879956A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Metal ion modified nitrogen-containing organic compound for storing hydrogen |
| CN103539070B (en) * | 2013-11-12 | 2015-11-25 | 安泰科技股份有限公司 | A kind of high power capacity storage hydrogen material preparation method containing LiMgN |
| CN105039815B (en) * | 2015-08-20 | 2017-03-22 | 广西大学 | Preparation method of Mg-Li solid solution hydrogen storage material |
| CN107915203A (en) * | 2016-10-11 | 2018-04-17 | 中国科学院大连化学物理研究所 | The preparation method and complex hydride hydrogen storage material of complex hydride hydrogen storage material |
| CN107285275B (en) * | 2017-08-21 | 2019-07-26 | 北京理工大学 | The composite hydrogen storage material and preparation method thereof of boracic hydrogen amino |
| CN111689463A (en) * | 2020-06-09 | 2020-09-22 | 世能氢电科技有限公司 | LiNH2-metal amide/metal hydride composite hydrogen storage material and preparation method thereof |
| CN112062110A (en) * | 2020-08-14 | 2020-12-11 | 浙江工业大学 | Method for synthesizing binary metal amino compound |
| CN112110426B (en) * | 2020-08-20 | 2022-06-03 | 浙江工业大学 | Method for synthesizing amino lithium potassium by mechanical ball milling |
| CN112079331B (en) * | 2020-08-20 | 2022-06-03 | 浙江工业大学 | Synthesis method of metal-nitrogen-hydrogen system hydrogen storage material |
| CN114380275A (en) * | 2022-01-27 | 2022-04-22 | 安泰科技股份有限公司 | LiNH-containing material2Mg-Mg composite hydrogen storage material and preparation method thereof |
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