CN102418018A - Nano-magnesium-based hydrogen storage material and preparation method thereof - Google Patents
Nano-magnesium-based hydrogen storage material and preparation method thereof Download PDFInfo
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- CN102418018A CN102418018A CN201110363698XA CN201110363698A CN102418018A CN 102418018 A CN102418018 A CN 102418018A CN 201110363698X A CN201110363698X A CN 201110363698XA CN 201110363698 A CN201110363698 A CN 201110363698A CN 102418018 A CN102418018 A CN 102418018A
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 134
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 134
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000011777 magnesium Substances 0.000 title claims abstract description 79
- 239000011232 storage material Substances 0.000 title claims abstract description 62
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 49
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 238000005049 combustion synthesis Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 166
- 239000000843 powder Substances 0.000 claims description 80
- 229910052759 nickel Inorganic materials 0.000 claims description 77
- 229910052799 carbon Inorganic materials 0.000 claims description 75
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 16
- 238000009413 insulation Methods 0.000 claims description 16
- 239000002048 multi walled nanotube Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 7
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 3
- 238000003701 mechanical milling Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000011161 development Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 2
- 230000018044 dehydration Effects 0.000 abstract 2
- 238000006297 dehydration reaction Methods 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000004845 hydriding Methods 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 238000007306 functionalization reaction Methods 0.000 description 12
- 238000003795 desorption Methods 0.000 description 11
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000001996 bearing alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a nano-magnesium-based hydrogen storage material and a preparation method thereof. The preparation method comprises the following steps of: firstly, preparing by adopting a chemical method to obtain various nickel-carried carbon powder; uniformly mixing magnesium powder and the nickel-carried carbon powder by using ultrasound and drying to obtain magnesium/nickel-carried carbon powder; secondly, preparing a magnesium-based hydrogen storage material from the magnesium/nickel-carried carbon powder by adopting a hydriding combustion synthesis process; and ball milling the obtained magnesium-based hydrogen storage material under the protection of hydrogen gas or argon gas atmosphere to finally obtain the nano-magnesium-based hydrogen storage material. The hydrogen absorption amount of the prepared nano-magnesium-based hydrogen storage material at the temperature of 373K within 100s reaches 5.62 percent by weight; and the initial dehydration temperature of samples is reduced below 400K. The nano-magnesium-based hydrogen storage material has excellent low-temperature hydrogen storage performance; and according to the nano-magnesium-based hydrogen storage material, the hydrogen absorption performance at low temperature is improved, the initial dehydration temperature is effectively reduced and the practical development of the magnesium-based hydrogen storage material is promoted.
Description
Technical field
The present invention relates to a kind of nano Mg base hydrogen storage material and preparation method thereof, particularly a kind of nano Mg base hydrogen storage material that has better low-temp reversible hydrogen storage property and preparation method thereof.
Background technology
At present the pollutent carbonic acid gas that discharges of industrial energy, carbon monoxide, sulfurous gas, oxynitride etc. make environmental degradation, and traditional energy coal, oil etc. are also exhausted day by day, and people press for the novel continuable clean energy of research and development.Hydrogen Energy is the secondhand energy of human future ideality, and its development and application is significant to solving energy dilemma and environmental pollution.The important step that hydrogen storage technology is used as Hydrogen Energy has obtained paying attention to widely in recent years.
Utilizing hydrogen storage alloy storage hydrogen is an important hydrogen storage technology, and hydrogen storage alloy has advantage such as hydrogen-storage density height, safety and stability and receives broad research, mainly contains rare earth system, zirconium titanium system, magnesium and is and hydrogen storage alloy such as vanadium system.Magnesium is that alloy is little owing to its density, cost is low, pollution-free and hydrogen storage capability is high receives extensive favor (MgH
2Hydrogen-storage amount reaches 7.6wt.%), however it inhales the hydrogen desorption kinetics poor-performing, and it is higher to inhale hydrogen discharging temperature, particularly under the 523-573K temperature, just can put hydrogen and suppress its application and development.Existing research shows (Ref:SimaAminorroaya et al, International Journal of Hydrogen Energy 35 (2010) 4144-4153; Ye Luo et al, Scripta Materialia 56 (2007) 765-768), through in magnesium-base hydrogen storage material, adding carbon nanotube and catalyzer, can reduce product to a certain extent and inhale hydrogen discharging temperature, improve product and inhale the hydrogen desorption kinetics performance.Although through unremitting effort, the suction hydrogen temperature of Mg base hydrogen bearing alloy can be reduced to 373K, and it is still not ideal enough to inhale the hydrogen desorption kinetics performance; Alloy need just begin dehydrogenation more than the 473K temperature in addition, and desorption temperature is still higher.The product that the patented claim of application number 200910028197.9 is mentioned is this breadboard stage achievement in research, and the hydrogen of product under the 373K temperature is 5.1wt.%, and initial hydrogen discharging temperature is reduced to 423K.
Summary of the invention
The object of the present invention is to provide a kind of further nano Mg base hydrogen storage material of reduction of better low-temp reversible hydrogen storage property, especially initial desorption temperature that has; Another object of the present invention provides the preparation method of above-mentioned nano Mg base hydrogen storage material.
Technical scheme of the present invention is: a kind of nano Mg base hydrogen storage material, and it is characterized in that the per-cent of the shared nano Mg base hydrogen storage material of its component and each component gross weight is respectively: magnesium is 80%-89%, and it is 11%-20% that carbon carries nickel; Preferably magnesium is 83%-87%, and it is 13%-17% that carbon carries nickel.
Preferred above-mentioned carbon carries the content of nickel in the nickel, and to account for the per-cent that carbon carries the nickel gross weight be 20%-80%; Wherein preferred carbon is a kind of in multi-wall carbon nano-tube pipe powder, carbon nanofiber powder or the active carbon powder.
The present invention also provides the preparation method of above-mentioned nano Mg base hydrogen storage material, and its concrete steps are following:
A. carbon dust is put into HNO
3In, through 140-180 ℃ of backflow 4-8 hour, the cooling back was washed till neutral and oven dry with deionized water;
B. the carbon dust and the Ni (NO that oven dry in the steps A are obtained
3)
26H
2O mixes, and joins in the ethanol reagent and dries behind the ultrasonic mixing; Powder after the oven dry was calcined 3-5 hour in 350-450 ℃ argon gas atmosphere, in 400-500 ℃ hydrogen atmosphere, reduced 3-5 hour then, naturally cooling obtains carbon and carries nickel by powder;
C. will account for per-cent that magnesium powder and carbon carries the nickel by powder gross weight and be the per-cent that accounts for gross weight for preparing among magnesium powder and the step B of 80%-89% mixes for 11%-20% carbon carries nickel by powder; Join in the acetone reagent and dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder;
D. magnesium/the carbon that obtains among the step C being carried nickel by powder, to carry out hydrogenation burning synthetic, obtains pulverous magnesium-base hydrogen storage material;
E. through the above-mentioned magnesium-base hydrogen storage material of powerful mechanical ball milling, obtain the nano Mg base hydrogen storage material.
Reflux temperature is 150-170 ℃ among the preferred steps A, and return time is 5-7 hour.Ni (NO among the preferred steps B
3)
26H
2The add-on of O is to be controlled to make carbon and carry the content of nickel in the nickel by powder to account for the per-cent that carbon carries the nickel gross weight be 20%-80%.The argon gas atmosphere calcining temperature is 380-420 ℃ among the preferred steps B; The hydrogen atmosphere reduction temperature is 430-470 ℃.
The hydrogenation combustion synthesis process parameter that adopts among the preferred steps D is: the magnesium/carbon behind the mixing is carried the hydrogen atmosphere reactor drum that nickel by powder places pressure 1-2MPa; Be warmed up to 500-600 ℃ of insulation 0.5-2 hour; Be cooled to 300-350 ℃ of insulation 3-5 hour then; Last cooling naturally prepares magnesium-base hydrogen storage material.
Use planetary high-energy ball mill that magnesium-base hydrogen storage material is carried out powerful mechanical ball milling among the preferred steps E, mechanical milling process is under hydrogen or the argon gas atmosphere protection, 1-50 hour ball milling time, rotating speed 300-500rpm, ball-to-powder weight ratio 10: 1-50: 1.
The present invention also can directly carry out mechanical ball milling with carbon dust and nickel powder and prepare carbon and carry nickel by powder.
Above raw materials market is all on sale.The present invention does not have particular requirement to magnesium powder, nickelous nitrate, nickel powder, carbon dust and concentrated nitric acid, all can implement.(particle diameter 50～100nm), carbon dust (purity＞98%) and concentrated nitric acid (mass concentration 69%), the nano Mg base hydrogen storage material hydrogen storage property that obtains is better for preferably magnesium powder (particle diameter＜74 μ m), nickelous nitrate (analytical pure), nickel powder.
The present invention also provides above-mentioned nano Mg base hydrogen storage material, in the accumulating of hydrogen or hydrogen fuel cell, uses.
Beneficial effect:
1. adopt the nano Mg base hydrogen storage material of the inventive method preparation to have the high reactivity characteristics.At first we use chemical method to prepare carbon and carry nickel, and in hydrogenation burning building-up process, the magnesium gas-migration carries the surface of nickel and generates Mg to carbon
2NiH
4, and the carbon nano-structured Mg that limited effectively
2NiH
4Particulate is grown up, thereby has improved the hydrogen storage property of product.
2. prepared nano Mg base hydrogen storage material has excellent low temperature and inhales the hydrogen dynamic performance, and under 373K, the hydrogen in the 100s reaches 5.62wt.%; The initial desorption temperature of sample is reduced to below the 400K.
3. prepared nano Mg base hydrogen storage material can be used for the accumulating or the hydrogen fuel cell of hydrogen.
Description of drawings
Fig. 1: 85Mg-xNi-yMWNTs (x/y=3/12,6/9,9/6,12/3) sample, in the 373K temperature, the suction hydrogen kinetic curve under the 3MPa hydrogen pressure (MWNTs is a multi-walled carbon nano-tubes, the digitized representation mass percent of element front, down together).
Fig. 2: the carbon that add to carry the nickel amount among the Mg of different mass and be 60wt.% carries the nickel sample, in the 373K temperature, and the suction hydrogen kinetic curve under the 3MPa hydrogen pressure.
Fig. 3: 85Mg-xNi-yMWNTs (x/y=3/12,6/9,9/6,12/3) sample, amount of dehydrogenation and temperature relation curve in the temperature-rise period.Average temperature rise rate is 20K/min.
Fig. 4: the carbon that add to carry the nickel amount among the Mg of different mass and be 60wt.% carries the nickel sample, amount of dehydrogenation and temperature relation curve in the temperature-rise period.Average temperature rise rate is 20K/min.
Embodiment
Through embodiment the present invention is elaborated below.
The carbon nanofiber powder is put into dense HNO
3In, through 140 ℃ of backflows 8 hours, the cooling back was washed till neutral with deionized water and dries, and obtains functionalization carbon nanofiber powder.With 0.3g functionalization carbon nanofiber powder and 6g Ni (NO
3)
26H
2O (per-cent that the content of nickel accounts for carbon and nickel gross weight is 80%) joins in the ethanol reagent, dries behind the ultrasonic mixing; Powder after the oven dry was calcined 3 hours in 450 ℃ argon gas atmosphere, in 500 ℃ hydrogen atmosphere, reduced 3 hours then, naturally cooling obtains carbon and carries nickel by powder.Get 8.5g magnesium powder and 1.5g carbon and carry nickel by powder and place acetone reagent, dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder.Magnesium/carbon is carried nickel by powder, and to carry out hydrogenation burning synthetic, and in hydrogenation burning building-up process, magnesium/carbon carries nickel by powder and under the 2MPa hydrogen atmosphere, is warmed up to 600 ℃ of insulations 2 hours, is cooled to 350 ℃ of insulations 5 hours then, lowers the temperature naturally at last, obtains magnesium-base hydrogen storage material.
Get 2g hydrogenation burning synthetic magnesium-base hydrogen storage material and put into ball grinder, ball milling is 50 hours under the 0.1MPa argon gas atmosphere, and rotating speed is 300rpm, and ball-to-powder weight ratio is 10: 1, obtains final nano Mg base hydrogen storage material.The nano Mg base hydrogen storage material of preparing, hydrogen all can reach capacity in 100s under 373K, 473K and 523K.And under 373K, hydrogen can reach 5.30wt.% in the 100s.
The multi-wall carbon nano-tube pipe powder is put into dense HNO
3In, through 140 ℃ of backflows 6 hours, the cooling back was washed till neutral with deionized water and dries, and obtains functionalization multi-wall carbon nano-tube pipe powder.With 0.6g functionalization multi-wall carbon nano-tube pipe powder and 4.5g Ni (NO
3)
26H
2O (per-cent that the content of nickel accounts for carbon and nickel gross weight is 60%) joins in the ethanol reagent, dries behind the ultrasonic mixing; Powder after the oven dry was calcined 4 hours in 400 ℃ argon gas atmosphere, in 450 ℃ hydrogen atmosphere, reduced 4 hours then, naturally cooling obtains carbon and carries nickel by powder.8.5g magnesium powder and 1.5g carbon are carried nickel by powder place acetone reagent, dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder.Magnesium/carbon is carried nickel by powder, and to carry out hydrogenation burning synthetic, and in hydrogenation burning building-up process, magnesium/carbon carries nickel by powder and under the 2MPa hydrogen atmosphere, is warmed up to 580 ℃ of insulations 1 hour, is cooled to 340 ℃ of insulations 4 hours then, lowers the temperature naturally at last, obtains magnesium-base hydrogen storage material.
Get 2g hydrogenation burning synthetic magnesium-base hydrogen storage material and put into ball grinder, ball milling is 10 hours under the 0.1MPa hydrogen atmosphere, and rotating speed is 400rpm, and ball-to-powder weight ratio is 30: 1, obtains final nano Mg base hydrogen storage material.The nano Mg base hydrogen storage material of preparing, the hydrogen that under 373K, 473K and 523K, all can in 100s, reach capacity, and the hydrogen under 373K reaches 5.62wt.%; The initial desorption temperature of sample is reduced to below the 400K.Experimental result is seen Fig. 1,3.
Embodiment 3
The multi-wall carbon nano-tube pipe powder is put into dense HNO
3In, through 140 ℃ of backflows 7 hours, the cooling back was washed till neutral with deionized water and dries, and obtains functionalization multi-wall carbon nano-tube pipe powder.With 0.78g functionalization multi-wall carbon nano-tube pipe powder and 2.6g Ni (NO
3)
26H
2O (per-cent that the content of nickel accounts for carbon and nickel gross weight is 40%) joins in the ethanol reagent, dries behind the ultrasonic mixing; Powder after the oven dry was calcined 5 hours in 380 ℃ argon gas atmosphere, in 470 ℃ hydrogen atmosphere, reduced 5 hours then, naturally cooling obtains carbon and carries nickel by powder.8.7g magnesium powder and 1.3g carbon are carried nickel by powder place acetone reagent, dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder.Magnesium/carbon is carried nickel by powder, and to carry out hydrogenation burning synthetic, and in hydrogenation burning building-up process, magnesium/carbon carries nickel by powder and under the 2MPa hydrogen atmosphere, is warmed up to 560 ℃ of insulations 1 hour, is cooled to 330 ℃ of insulations 3 hours then, lowers the temperature naturally at last, obtains magnesium-base hydrogen storage material.
Get 2g hydrogenation burning synthetic magnesium-base hydrogen storage material and put into ball grinder, ball milling is 20 hours under the 0.1MPa argon gas atmosphere, and rotating speed is 400rpm, and ball-to-powder weight ratio is 20: 1, obtains final nano Mg base hydrogen storage material.The material hydrogen that under 373K, 473K and 523K, can both in 100s, reach capacity, and the hydrogen under 373K reaches 5.50wt.%; The initial desorption temperature of sample is 400K.
Active carbon powder is put into dense HNO
3In, through 180 ℃ of backflows 4 hours, the cooling back was washed till neutral with deionized water and dries, and obtains the functionalization active carbon powder.With 0.88g functionalization active carbon powder and 11gNi (NO
3)
26H
2O (per-cent that the content of nickel accounts for carbon and nickel gross weight is 20%) joins in the ethanol reagent, dries behind the ultrasonic mixing; Powder after the oven dry was calcined 5 hours in 350 ℃ argon gas atmosphere, in 400 ℃ hydrogen atmosphere, reduced 4 hours then, naturally cooling obtains carbon and carries nickel by powder.Get 8.9g magnesium powder and 1.1g carbon and carry nickel by powder and place acetone reagent, dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder.Magnesium/carbon is carried nickel by powder, and to carry out hydrogenation burning synthetic; In hydrogenation burning building-up process, magnesium/carbon carries nickel by powder and under the 1MPa hydrogen atmosphere, is warmed up to 500 ℃ of insulations 0.5 hour, is cooled to 300 ℃ of insulations 3 hours then; Last cooling naturally obtains magnesium-base hydrogen storage material.
Get 2g hydrogenation burning synthetic magnesium-base hydrogen storage material and put into ball grinder, ball milling is 1 hour under the 0.1MPa hydrogen atmosphere, and rotating speed is 500rpm, and ball-to-powder weight ratio is 50: 1, obtains final nano Mg base hydrogen storage material.Material is under 373K, and the hydrogen in the 100s reaches 5.41wt.%; The initial desorption temperature of sample is 410K.
The multi-wall carbon nano-tube pipe powder is put into dense HNO
3In, through 140 ℃ of backflows 6 hours, the cooling back was washed till neutral with deionized water and dries, and obtains functionalization multi-wall carbon nano-tube pipe powder.With 0.8g functionalization multi-wall carbon nano-tube pipe powder and 6.0g Ni (NO
3)
26H
2O (per-cent that the content of nickel accounts for carbon and nickel gross weight is 60%) joins in the ethanol reagent, dries behind the ultrasonic mixing; Powder after the oven dry was calcined 4 hours in 400 ℃ argon gas atmosphere, in 450 ℃ hydrogen atmosphere, reduced 4 hours then, naturally cooling obtains carbon and carries nickel by powder.8.0g magnesium powder and 2.0g carbon are carried nickel by powder place acetone reagent, dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder.Magnesium/carbon is carried nickel by powder, and to carry out hydrogenation burning synthetic, and in hydrogenation burning building-up process, magnesium/carbon carries nickel by powder and under the 2MPa hydrogen atmosphere, is warmed up to 580 ℃ of insulations 1 hour, is cooled to 340 ℃ of insulations 4 hours then, lowers the temperature naturally at last, obtains magnesium-base hydrogen storage material.
Get 2g hydrogenation burning synthetic magnesium-base hydrogen storage material and put into ball grinder, ball milling is 10 hours under the 0.1MPa hydrogen atmosphere, and rotating speed is 400rpm, and ball-to-powder weight ratio is 30: 1, obtains final nano Mg base hydrogen storage material.The nano Mg base hydrogen storage material of preparing, the hydrogen that under 373K, 473K and 523K, all can in 100s, reach capacity, and the initial desorption temperature of sample also is reduced to below the 400K.Experimental result is seen Fig. 2,4.
The multi-wall carbon nano-tube pipe powder is put into dense HNO
3In, through 170 ℃ of backflows 5 hours, the cooling back was washed till neutral with deionized water and dries, and obtains functionalization multi-wall carbon nano-tube pipe powder.With 0.34g functionalization multi-wall carbon nano-tube pipe powder and 6.8g Ni (NO
3)
26H
2O (per-cent that the content of nickel accounts for carbon and nickel gross weight is 80%) joins in the ethanol reagent, dries behind the ultrasonic mixing; Powder after the oven dry was calcined 3 hours in 400 ℃ argon gas atmosphere, in 460 ℃ hydrogen atmosphere, reduced 4 hours then, naturally cooling obtains carbon and carries nickel by powder.8.3g magnesium powder and 1.7g carbon are carried nickel by powder place acetone reagent, dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder.Magnesium/carbon is carried nickel by powder, and to carry out hydrogenation burning synthetic; In hydrogenation burning building-up process, magnesium/carbon carries nickel by powder and under the 1.5MPa hydrogen atmosphere, is warmed up to 540 ℃ of insulations 2 hours, is cooled to 340 ℃ of insulations 5 hours then; Last cooling naturally obtains magnesium-base hydrogen storage material.
Get 2g hydrogenation burning synthetic magnesium-base hydrogen storage material and put into ball grinder, ball milling is 10 hours under the 0.1MPa hydrogen atmosphere, and rotating speed is 300rpm, and ball-to-powder weight ratio is 30: 1, obtains final nano Mg base hydrogen storage material.The nano Mg base hydrogen storage material of preparing, the hydrogen that under 373K, 473K and 523K, all can in 100s, reach capacity, and the hydrogen in the 100s reaches 5.48wt.% under 373K; The initial desorption temperature of sample is reduced to below the 400K.
Claims (9)
1. nano Mg base hydrogen storage material, it is characterized in that the per-cent of the shared nano Mg base hydrogen storage material of its component and each component gross weight is respectively: magnesium is 80%-89%, and it is 11%-20% that carbon carries nickel.
2. nano Mg base hydrogen storage material according to claim 1, it is characterized in that the per-cent of the shared nano Mg base hydrogen storage material of its component and each component gross weight is: magnesium is 83%-87%, and it is 13%-17% that carbon carries nickel.
3. nano Mg base hydrogen storage material according to claim 1, it is characterized in that carrying the content of nickel in the nickel by described carbon, to account for the per-cent that carbon carries the nickel gross weight be 20%-80%; Wherein carbon is a kind of in multi-wall carbon nano-tube pipe powder, carbon nanofiber powder or the active carbon powder.
4. method for preparing nano Mg base hydrogen storage material as claimed in claim 1, its concrete steps are following:
A. carbon dust is put into HNO
3In, through 140-180 ℃ of backflow 4-8 hour, the cooling back was washed till neutral and oven dry with deionized water;
B. the carbon dust and the Ni (NO that oven dry in the steps A are obtained
3)
26H
2O mixes, and joins in the ethanol reagent and dries behind the ultrasonic mixing; Powder after the oven dry was calcined 3-5 hour in 350-450 ℃ argon gas atmosphere, in 400-500 ℃ hydrogen atmosphere, reduced 3-5 hour then, naturally cooling obtains carbon and carries nickel by powder;
C. will account for per-cent that magnesium powder and carbon carries the nickel by powder gross weight and be the per-cent that accounts for gross weight for preparing among magnesium powder and the step B of 80%-89% mixes for 11%-20% carbon carries nickel by powder; Join in the acetone reagent and dry behind the ultrasonic mixing, obtain magnesium/carbon and carry nickel by powder;
D. magnesium/the carbon that obtains among the step C being carried nickel by powder, to carry out hydrogenation burning synthetic, obtains pulverous magnesium-base hydrogen storage material;
E. through the above-mentioned magnesium-base hydrogen storage material of powerful mechanical ball milling, obtain the nano Mg base hydrogen storage material.
5. method according to claim 4 is characterized in that reflux temperature is 150-170 ℃ in the steps A, and return time is 5-7 hour.
6. method according to claim 4 is characterized in that Ni (NO among the step B
3)
26H
2The add-on of O is to be controlled to make carbon and carry the content of nickel in the nickel by powder to account for the per-cent that carbon carries the nickel gross weight be 20%-80%.
7. method according to claim 4; It is characterized in that the hydrogenation combustion synthesis process parameter that adopts among the step D is: the magnesium/carbon behind the mixing is carried the hydrogen atmosphere reactor drum that nickel by powder places pressure 1-2MPa; Be warmed up to 500-600 ℃ of insulation 0.5-2 hour; Be cooled to 300-350 ℃ of insulation 3-5 hour then, last cooling naturally prepares magnesium-base hydrogen storage material.
8. method according to claim 4; It is characterized in that using in the step e planetary high-energy ball mill that magnesium-base hydrogen storage material is carried out powerful mechanical ball milling, mechanical milling process is under hydrogen or the argon gas atmosphere protection, 1-50 hour ball milling time; Rotating speed 300-500rpm, ball-to-powder weight ratio 10: 1-50: 1.
9. use in the accumulating of hydrogen or hydrogen fuel cell like claim 1 described nano Mg base hydrogen storage material for one kind.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN105586519A (en) * | 2015-12-21 | 2016-05-18 | 安泰科技股份有限公司 | High-performance nano magnesium-based hydrogen storage material and preparation method thereof |
| CN105597779A (en) * | 2015-12-21 | 2016-05-25 | 安泰科技股份有限公司 | Composite material with nano-nickel particles and nano-palladium particles on graphene and preparation method of composite material |
| CN106637932A (en) * | 2016-11-15 | 2017-05-10 | 复旦大学 | Method for preparing hydrogen storage material, i.e., magnesium-nickel (Mg-Ni) alloy nanofiber |
| CN106784737A (en) * | 2017-02-10 | 2017-05-31 | 淄博君行电源技术有限公司 | Capacitor type Ni-MH power cell spherical hydrogen-storage alloy and preparation method thereof |
| CN108118227A (en) * | 2017-11-09 | 2018-06-05 | 广德宝达精密电路有限公司 | Nano-magnesium-based hydrogen storage material for high-energy solid battery and preparation method thereof |
| CN108455523A (en) * | 2018-02-05 | 2018-08-28 | 安泰科技股份有限公司 | Mg(BH4)2- xCNTs system hydrogen storage materials and preparation method thereof |
| CN108941610A (en) * | 2018-09-19 | 2018-12-07 | 西京学院 | A method of hydrogen storage magnesium-nickel alloy nanometer powder is prepared based on polyol process |
| CN110182759A (en) * | 2019-06-05 | 2019-08-30 | 浙江大学 | Bamboo-like carbon nano tubes load MgH2Nano-particles reinforcement hydrogen storage material and preparation method thereof |
| CN111515380A (en) * | 2020-05-11 | 2020-08-11 | 安泰科技股份有限公司 | High-capacity magnesium-based composite hydrogen storage material and preparation method thereof |
| CN114411028A (en) * | 2022-01-21 | 2022-04-29 | 徐州工程学院 | Trace nickel composite layered magnesium composite material and preparation method and application thereof |
| CN115636390A (en) * | 2022-12-01 | 2023-01-24 | 世能氢电科技有限公司 | Magnesium-based composite hydrogen storage material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785844A (en) * | 2014-01-13 | 2014-05-14 | 上海交通大学 | Nano-structure block magnesium material and preparation method thereof |
| CN105586519A (en) * | 2015-12-21 | 2016-05-18 | 安泰科技股份有限公司 | High-performance nano magnesium-based hydrogen storage material and preparation method thereof |
| CN105597779A (en) * | 2015-12-21 | 2016-05-25 | 安泰科技股份有限公司 | Composite material with nano-nickel particles and nano-palladium particles on graphene and preparation method of composite material |
| CN106637932A (en) * | 2016-11-15 | 2017-05-10 | 复旦大学 | Method for preparing hydrogen storage material, i.e., magnesium-nickel (Mg-Ni) alloy nanofiber |
| CN106784737A (en) * | 2017-02-10 | 2017-05-31 | 淄博君行电源技术有限公司 | Capacitor type Ni-MH power cell spherical hydrogen-storage alloy and preparation method thereof |
| CN108118227A (en) * | 2017-11-09 | 2018-06-05 | 广德宝达精密电路有限公司 | Nano-magnesium-based hydrogen storage material for high-energy solid battery and preparation method thereof |
| CN108455523A (en) * | 2018-02-05 | 2018-08-28 | 安泰科技股份有限公司 | Mg(BH4)2- xCNTs system hydrogen storage materials and preparation method thereof |
| CN108941610A (en) * | 2018-09-19 | 2018-12-07 | 西京学院 | A method of hydrogen storage magnesium-nickel alloy nanometer powder is prepared based on polyol process |
| CN108941610B (en) * | 2018-09-19 | 2021-07-16 | 西京学院 | Method for preparing hydrogen storage magnesium-nickel alloy nano powder based on polyol method |
| CN110182759A (en) * | 2019-06-05 | 2019-08-30 | 浙江大学 | Bamboo-like carbon nano tubes load MgH2Nano-particles reinforcement hydrogen storage material and preparation method thereof |
| CN111515380A (en) * | 2020-05-11 | 2020-08-11 | 安泰科技股份有限公司 | High-capacity magnesium-based composite hydrogen storage material and preparation method thereof |
| CN111515380B (en) * | 2020-05-11 | 2022-04-29 | 安泰科技股份有限公司 | High-capacity magnesium-based composite hydrogen storage material and preparation method thereof |
| CN114411028A (en) * | 2022-01-21 | 2022-04-29 | 徐州工程学院 | Trace nickel composite layered magnesium composite material and preparation method and application thereof |
| CN114411028B (en) * | 2022-01-21 | 2022-09-20 | 徐州工程学院 | Trace nickel composite layered magnesium composite material and preparation method and application thereof |
| CN115636390A (en) * | 2022-12-01 | 2023-01-24 | 世能氢电科技有限公司 | Magnesium-based composite hydrogen storage material and preparation method thereof |
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