CN103449361A - LiAlH4/carbon-coated metal nanoparticle (Ni-Co@C) composite hydrogen storage material and preparation method thereof - Google Patents

LiAlH4/carbon-coated metal nanoparticle (Ni-Co@C) composite hydrogen storage material and preparation method thereof Download PDF

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CN103449361A
CN103449361A CN2012101815903A CN201210181590A CN103449361A CN 103449361 A CN103449361 A CN 103449361A CN 2012101815903 A CN2012101815903 A CN 2012101815903A CN 201210181590 A CN201210181590 A CN 201210181590A CN 103449361 A CN103449361 A CN 103449361A
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carbon
ball
storage material
hydrogen storage
lialh
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CN103449361B (en
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孙立贤
焦成丽
张箭
徐芬
司晓亮
赵梓名
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a LiAlH4/carbon-coated metal nanoparticle (Ni-Co@C) composite hydrogen storage material and a preparation method thereof. Carbon-coated Ni-Co bimetal nanoparticles (Ni-Co@C) with a uniform diameter of 4-6nm are prepared by taking CoCo(Ni(EDTA))2.4H2O as a precursor through a high-temperature sintering method; Ni-Co@C is taken as a catalyst for compounding with LiAlH4, so that the hydrogen desorption temperature of a LiAlH4 system is greatly reduced; when the doping amount of the catalyst is 1wt%, the hydrogen desorption temperature is reduced to 43 DEG C and the hydrogen desorption amount achieves 7.3wt%; and when the doping amount of the catalyst is 10wt%, the hydrogen desorption temperature achieves 36 DEG C for the first time. The catalyst (Ni-Co@C) prepared by the method disclosed by the invention has great uniform dispersion, and the prepared LiAlH4 composite hydrogen storage material can show good hydrogen desorption performance at relatively low temperature.

Description

LiAlH 4/ carbon-clad metal nano particle (Ni-Co@C) composite hydrogen storage material and preparation method thereof
Technical field
The present invention relates to a kind of LiAlH 4/ carbon-clad metal nano particle (Ni-Co@C) composite hydrogen storage material and preparation method thereof; Specifically with CoCo[Ni (EDTA)] 24H 2o is that presoma has prepared the carbon that diameter is 4-6nm and coats Ni-Co bimetal nano particles (Ni-Co@C).Take Ni-Co@C as catalyzer by itself and LiAlH 4carry out compound, the LiAlH made 4composite hydrogen storage material can show good hydrogen discharging performance at lower temperature.
Background technology
LiAlH 4because of its higher theoretical hydrogen storage capability (10.6wt%), be considered to one of most potential hydrogen storage material.LiAlH 4dehydrogenation three step process: 3LiAlH are arranged 4→ Li 3alH 6+ 2Al+3H 2(5.3wt%H 2, 150-175 ° of C) and (1) Li 3alH 6→ 3LiH+Al+3/2H 2(2.6wt%H 2, 180-220 ° of C) and (2) LiH+Al → LiAl+1/2H 2(2.7wt%H 2, 400 ° of C) (3)
Because the decomposition temperature of formula (3) is too high, generally be not considered.In recent years, most research concentrates on the decomposition temperature and dynamic performance of improvement formula (1) and formula (2).Current report concentrates on ball milling and admixed with additives aspect, and wherein the method for admixed with additives is of most study, and the additive of report has at present: Ti, Fe, Ni, Al, Al 3ti, Al 3fe, TiF 3, AlCl 3, VBr, TiH 2and carbon material.Wherein to Ni, large quantity research has been carried out in doping, but the disadvantage of Ni doping is to have a large amount of hydrogen to emit because high reactivity causes in mechanical milling process, thereby causes greatly reducing of hydrogen-storage amount.(M.Resan, M.D.Hampton, J.K.Lomness and D.K.Slattery, Int.J.Hydrogen Energy, 2005,30,1413-1416), at present for the doping agent research of carbon material, hydrogen storage property report diversity ratio is larger.Viswanathan study group will reach 6.8wt%(L.H.Kumar at 135 ° of following hydrogen desorption capacities of C after LiAlH4 and 5wt% carbon nanofiber ball milling, B.Viswanathan and S.S.Murthy, and Int.J.Hydrogen Energy, 2008,33,366-373).And Y. Zhao is 80 ° of C(M.Ismail by initial hydrogen discharging temperature after LiAlH4 and 5wt% Single Walled Carbon Nanotube ball milling, Y.Zhao, X.Yu, A.Ranbar and S.Dou, J.Hydrogen Energy 2011,36,3593-3599).But so far there are no relevant for carbon-clad metal nano particle catalysis LiAlH 4relevant report.
Reduce LiAlH 4desorption temperature, make the system hydrogen-storage amount reach the DOE requirement simultaneously, be a urgent problem.So our catalysis superiority based on bimetal nano particles, with CoCo[Ni (EDTA)] 24H 2o has been precursor synthesis Ni-Co@C nanoparticle, improved LiAlH effectively 4hydrogen discharging performance.
Summary of the invention
The objective of the invention is to prepare carbon and coat bimetal nano particles, by itself and LiAlH 4carry out compound and improve LiAlH 4hydrogen storage property.
For achieving the above object, the technical solution used in the present invention is:
Carbon coats the preparation method of bimetal nano particles, and concrete preparation process is:
By CoCo[Ni (EDTA)] 24H 2o is placed in tube furnace, adopts argon gas atmosphere (gas flow rate is 150 ~ 400mL/min), with the temperature rise rate of 1 ~ 5 ° of C/min, is warming up to 450 ~ 700 ° of C, at 450 ~ 700 ° of C, keeps 2 ~ 10 hours, cools to room temperature in argon gas atmosphere.
Carbon is coated to Ni-Co bimetal nano particles (Ni-Co@C) to LiAlH 4carried out compound research, described matrix material is carried out to the hydrogen discharging performance test, specific operation process is:
(1) in glove box by LiAlH 4with Ni-Co@C (10:0 ~ 7:1) weighing sample according to a certain ratio, the sample total amount is 0.5g, pours in the 100mL ball grinder that 8 ~ 20 10mm Stainless Steel Balls are housed, and will after the ball grinder sealing, from glove box, take out.
(2) ball grinder is loaded into to planetary ball mill QM-3SP2 above, sets Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) and carry out ball milling.Ball milling is put into glove box by ball grinder after finishing again, sample is taken out stand-by.
(3) get appropriate sample (100mg ~ 300mg) and carry out thermogravimetric analysis.Adopt U.S. Cahn Thermax500 hot high pressure balance, Ar gas carrier gas flux is controlled at 1.7%(～145mL/min), first system is vacuumized to ventilation after the dress sample, temperature rise rate is 2 ° of C/min.
The present invention has following advantage:
(1) adopt the CoCo[Ni (EDTA) with orderly single crystal structure] 24H 2o is presoma, and the carbon that to have prepared diameter be 4-6nm coats Ni-Co bimetal nano particles (Ni-Co@C), and the particle particle is less, have extraordinary uniformly dispersed, the reunion that has effectively prevented metal is condensed, and the preparation technology of this invention is simple, easy to operate.
(2) effectively improved LiAlH 4hydrogen storage property.When the doping of catalyst n i-Co@C is 1wt%, initial hydrogen discharging temperature is down to 43 ° of C, and hydrogen desorption capacity reaches 7.3wt%; When the doping of catalyzer is 10wt%, hydrogen discharging temperature reaches 36 ° of C first, and its hydrogen discharging performance has significantly and to improve, by present the minimum hydrogen discharging temperature of report metal hydride.
The accompanying drawing explanation
The carbon that Fig. 1 is specific embodiments of the invention 1 coats the XRD spectra of Ni-Co bimetal nano particles (Ni-Co@C).
The carbon that Fig. 2 is specific embodiments of the invention 1 coats the HRTEM figure of Ni-Co bimetal nano particles (Ni-Co@C).
The LiAlH of the doping 0wt%Ni-Co@C that Fig. 3 is specific embodiments of the invention 2 4tGA(2 ° of C/min) curve;
The LiAlH of the doping 1wt%Ni-Co@C that Fig. 4 is specific embodiments of the invention 3 4tGA(2 ° of C/min) curve;
The LiAlH of the doping 5wt%Ni-Co@C that Fig. 5 is specific embodiments of the invention 4 4tGA(2 ° of C/min) curve;
The LiAlH of the doping 10wt%Ni-Co@C that Fig. 6 is specific embodiments of the invention 5 4tGA(2 ° of C/min) curve.
Embodiment
Presoma CoCo[Ni (EDTA)] 24H 2o is with reference to F.Sapina, E.Coronado, D.Beltran, R.Burriel, J.Am.Chem.Soc.1991, the preparation of 113,7940-7944 method.Its preparation process is: take 0.56g Co (NO 3) 26H 2o, 0.57g Ni (NO 3) 26H 2o is dissolved in the mixing solutions of 15mL water and methyl alcohol, and after fully stirring, in synthetic baking oven, 180 ℃ of crystallization are 1 day, and after being cooled to room temperature, by 100ml deionized water filtration washing for product, 50 ℃ of vacuum-dryings are spent the night, and obtain target product.
Embodiment 1
By CoCo[Ni (EDTA)] 24H 2o is placed in tube furnace, adopt argon gas atmosphere (gas flow rate is 150 ~ 400mL/min), temperature rise rate with 1 ~ 5 ° of C/min is warming up to 450 ~ 700 ° of C, at 450 ~ 700 ° of C, keep 2 ~ 10 hours, cool to room temperature in argon gas atmosphere, the carbon that to have obtained diameter be 4-6nm coats Ni-Co bimetal nano particles (Ni-Co@C).
Embodiment 2
Take LiAlH in glove box 4(0.5g), pour in the 100mL ball grinder that 8 ~ 20 10mm Stainless Steel Balls are housed, will take out from glove box after the ball grinder sealing; Ball grinder is loaded into to planetary ball mill QM-3SP2 upper, sets Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) and carry out ball milling.Ball milling is put into glove box by ball grinder after finishing again, gets appropriate sample (100mg ~ 300mg) and carries out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balances, Ar gas carrier gas flux is controlled at 1.7%(~ 145mL/min), first system is vacuumized to ventilation after the dress sample, temperature rise rate is 2 ° of C/min.Initial hydrogen discharging temperature is 139 ° of C, and total hydrogen desorption capacity is 7.6wt%.
Embodiment 3
Take LiAlH in glove box 4(0.495g) with Ni-Co@C(0.05g), pour in the 100mL ball grinder that 8 ~ 20 10mm Stainless Steel Balls are housed, will after the ball grinder sealing, from glove box, take out; Ball grinder is loaded into to planetary ball mill QM-3SP2 upper, sets Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) and carry out ball milling.Ball milling is put into glove box by ball grinder after finishing again, gets appropriate sample (100mg ~ 300mg) and carries out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balances, Ar gas carrier gas flux is controlled at 1.7%(~ 145mL/min), first system is vacuumized to ventilation after the dress sample, temperature rise rate is 2 ° of C/min.Initial hydrogen discharging temperature is 43 ° of C, and total hydrogen desorption capacity is up to 7.3wt%.
Embodiment 4
Take LiAlH in glove box 4(0.475g) with Ni-Co@C(0.025g), pour in the 100mL ball grinder that 8 ~ 20 10mm Stainless Steel Balls are housed, will after the ball grinder sealing, from glove box, take out; Ball grinder is loaded into to planetary ball mill QM-3SP2 upper, sets Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) and carry out ball milling.Ball milling is put into glove box by ball grinder after finishing again, gets appropriate sample (100mg ~ 300mg) and carries out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balances, Ar gas carrier gas flux is controlled at 1.7%(~ 145mL/min), first system is vacuumized to ventilation after the dress sample, temperature rise rate is 2 ° of C/min.Initial hydrogen discharging temperature is 34 ° of C, and total hydrogen desorption capacity is up to 5.9wt%.
Embodiment 5
In glove box by LiAlH 4(0.45g) and Ni-Co@C(0.05g) proportioning weighing sample, pour in the 100mL ball grinder that 8 ~ 20 10mm Stainless Steel Balls are housed, will ball grinder from glove box, take out after sealing; Ball grinder is loaded into to planetary ball mill QM-3SP2 upper, sets Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) and carry out ball milling.Ball milling is put into glove box by ball grinder after finishing again, gets appropriate sample (100mg ~ 300mg) and carries out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balances, Ar gas carrier gas flux is controlled at 1.7%(~ 145mL/min), first system is vacuumized to ventilation after the dress sample, temperature rise rate is 2 ° of C/min.Initial hydrogen discharging temperature is 36 ° of C, and total hydrogen desorption capacity is 3.7wt%.

Claims (5)

1. a LiAlH 4/ carbon-clad metal nano particle (Ni-Co@C) composite hydrogen storage material is characterized in that: adopt CoCo[Ni (EDTA)] 24H 2o is presoma, by high-temperature sintering process, has prepared the carbon-clad metal nano particle (Ni-Co@C) that diameter is 4-6nm; Adopt ball milled to prepare LiAlH 4/ carbon-clad metal nano particle (Ni-Co@C) composite hydrogen storage material.
2. the described LiAlH of claim 1 4the preparation method of/carbon-clad metal nano particle (Ni-Co@C) composite hydrogen storage material is characterized in that: adopt CoCo[Ni (EDTA)] 24H 2o is presoma, by high-temperature sintering process, has prepared the carbon-clad metal nano particle (Ni-Co@C) that diameter is 4-6nm; Adopt ball milled to prepare LiAlH 4/ carbon-clad metal nano particle (Ni-Co@C) composite hydrogen storage material.
3. according to the described composite hydrogen storage material of claim 1 or 2, it is characterized in that:
Its preparation and operating process are:
(1) by CoCo[Ni (EDTA)] 24H 2o is placed in tube furnace, adopts argon gas atmosphere, and gas flow rate is 150 ~ 400mL/min, with the temperature rise rate of 1 ~ 5 ° of C/min, from room temperature, is warming up to 450 ~ 700 ° of C, at 450 ~ 700 ° of C, keeps 2 ~ 10 hours, cools to room temperature in argon gas atmosphere;
(2) in glove box by LiAlH 4with Ni-Co@C weighing sample according to a certain ratio, LiAlH 4with Ni-Co@C mass ratio 100:1 ~ 7:1, pour in the ball grinder that particle diameter 5-10mm Stainless Steel Ball is housed, will after the ball grinder sealing, from glove box, take out;
Ball grinder is loaded on planetary ball mill, sets Ball-milling Time 0.2 ~ 2h and rotating speed 200 ~ 500r/min and carry out ball milling; Ball milling is put into glove box by ball grinder after finishing again, and sample is taken out, and obtains product.
4. composite hydrogen storage material according to claim 3 is characterized in that:
The sample total amount is 0.2-0.5g, and sample is poured in the 100mL ball grinder that 8 ~ 20 particle footpath 5-10mm Stainless Steel Balls are housed.
5. composite hydrogen storage material according to claim 3, it is characterized in that: planetary ball mill is planetary ball mill QM-3SP2.
CN201210181590.3A 2012-06-04 2012-06-04 LiAlH4/carbon-coated metal nanoparticle (Ni-Co@C) composite hydrogen storage material and preparation method thereof Expired - Fee Related CN103449361B (en)

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CN110217756A (en) * 2019-06-28 2019-09-10 桂林电子科技大学 A kind of preparation method and application of the aluminum-based composite hydrogen manufacturing material of carbon load bismuth

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CN101289161A (en) * 2007-04-20 2008-10-22 中国科学院大连化学物理研究所 Method for preparing hydrogen-storing material

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Title
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110217756A (en) * 2019-06-28 2019-09-10 桂林电子科技大学 A kind of preparation method and application of the aluminum-based composite hydrogen manufacturing material of carbon load bismuth

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