CN103449361B - 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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CN103449361B
CN103449361B CN201210181590.3A CN201210181590A CN103449361B CN 103449361 B CN103449361 B CN 103449361B CN 201210181590 A CN201210181590 A CN 201210181590A CN 103449361 B CN103449361 B CN 103449361B
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coc
ball
lialh
storage material
hydrogen storage
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CN103449361A (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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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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-CoC) 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-CoC) composite hydrogen storage material and preparation method thereof; Specifically with CoCo [Ni (EDTA)] 24H 2the coated Ni-Co bimetal nano particles (Ni-CoC) of carbon of O to be precursor power diameter be 4-6nm.Be that catalyzer is by itself and LiAlH with Ni-CoC 4carry out compound, obtained LiAlH 4composite hydrogen storage material can show good hydrogen discharging performance at a lower temperature.
Background technology
LiAlH 4because of the theoretical hydrogen storage capability (10.6wt%) that it is higher, be considered to one of most potential hydrogen storage material.LiAlH 4dehydrogenation have three step process: 3LiAlH 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) and (3)
Because the decomposition temperature of formula (3) is too high, be generally not considered.In recent years, most study concentrate on improvement formula (1) and formula (2) decomposition temperature and dynamic performance on.Current report concentrates on ball milling and admixed with additives aspect, and wherein the method for admixed with additives is one 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 large quantity research has been carried out to Ni doping, but the disadvantage of Ni doping has a large amount of hydrogen to release because high reactivity causes in mechanical milling process, thus cause 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) studies for the doping agent of carbon material at present, and hydrogen storage property report comparison in difference is large.Viswanathan study group reaches 6.8wt%(L.H.Kumar by after LiAlH4 and 5wt% carbon nanofiber ball milling at 135 ° of below C hydrogen desorption capacities, B.Viswanathan and S.S.Murthy, Int.J.Hydrogen Energy, 2008,33,366-373).And hydrogen discharging temperature initial after LiAlH4 and 5wt% Single Walled Carbon Nanotube ball milling is 80 ° of C(M.Ismail by Y. Zhao, Y.Zhao, X.Yu, A.Ranbar and S.Dou, J.Hydrogen Energy 2011,36,3593-3599).But, so far there are no about carbon-clad metal nano particle catalysis LiAlH 4relevant report.
Reduce LiAlH 4desorption temperature, make system hydrogen-storage amount reach DOE requirement, be a urgent problem simultaneously.So we are based on the catalysis superiority of bimetal nano particles, with CoCo [Ni (EDTA)] 24H 2o is precursor synthesis Ni-CoC nanoparticle, effectively improves LiAlH 4hydrogen discharging performance.
Summary of the invention
The object of the invention is to prepare the coated bimetal nano particles of carbon, 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:
The preparation method of the coated bimetal nano particles of carbon, 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), is warming up to 450 ~ 700 ° of C with the temperature rise rate of 1 ~ 5 ° of C/min, keeps 2 ~ 10 hours, in argon gas atmosphere, cool to room temperature at 450 ~ 700 ° of C.
By coated for carbon Ni-Co bimetal nano particles (Ni-CoC) to LiAlH 4carried out compound research, carried out hydrogen discharging performance test to described matrix material, specific operation process is:
(1) in glove box by LiAlH 4with Ni-CoC according to a certain ratio (10:0 ~ 7:1) weigh sample, sample total amount is 0.5g, pours into and is equipped with in the 100mL ball grinder of 8 ~ 20 10mm Stainless Steel Balls, by ball grinder seal after take out from glove box.
(2) be loaded into by ball grinder on planetary ball mill QM-3SP2, setting Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) carry out ball milling.Again ball grinder is put into glove box after ball milling terminates, sample is taken out stand-by.
(3) get appropriate amount of sample (100mg ~ 300mg) and carry out thermogravimetric analysis.Adopt U.S. Cahn Thermax500 hot high pressure balance, Ar gas carrier gas flux controls at 1.7%(~ 145mL/min), first system is vacuumized ventilation after dress sample, temperature rise rate is 2 ° of C/min.
Tool of the present invention has the following advantages:
(1) CoCo [Ni (EDTA)] with orderly single crystal structure is adopted 24H 2o is presoma, and prepared the coated Ni-Co bimetal nano particles (Ni-CoC) of carbon that diameter is 4-6nm, particle granules is less, have extraordinary uniformly dispersed, effectively prevent the reunion condensation of metal, the preparation technology of this invention is simple, easy to operate.
(2) LiAlH is effectively improved 4hydrogen storage property.When the doping of catalyst n i-CoC 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 and improves significantly, by present the minimum hydrogen discharging temperature of report metal hydride.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the coated Ni-Co bimetal nano particles (Ni-CoC) of carbon of specific embodiments of the invention 1.
Fig. 2 is the HRTEM figure of the coated Ni-Co bimetal nano particles (Ni-CoC) of carbon of specific embodiments of the invention 1.
Fig. 3 is the LiAlH of the doping 0wt%Ni-CoC of specific embodiments of the invention 2 4tGA(2 ° of C/min) curve;
Fig. 4 is the LiAlH of the doping 1wt%Ni-CoC of specific embodiments of the invention 3 4tGA(2 ° of C/min) curve;
Fig. 5 is the LiAlH of the doping 5wt%Ni-CoC of specific embodiments of the invention 4 4tGA(2 ° of C/min) curve;
Fig. 6 is the LiAlH of the doping 10wt%Ni-CoC of 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, prepared by 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, 180 DEG C of crystallization 1 day in synthesis baking oven, after being cooled to room temperature, by product 100ml deionized water filtration washing, 50 DEG C of dried in vacuo overnight, 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), 450 ~ 700 ° of C are warming up to the temperature rise rate of 1 ~ 5 ° of C/min, keep 2 ~ 10 hours at 450 ~ 700 ° of C, in argon gas atmosphere, cool to room temperature, obtain the coated Ni-Co bimetal nano particles (Ni-CoC) of carbon that diameter is 4-6nm.
Embodiment 2
LiAlH is taken in glove box 4(0.5g), pour into and be equipped with in the 100mL ball grinder of 8 ~ 20 10mm Stainless Steel Balls, take out from glove box after ball grinder is sealed; Be loaded into by ball grinder on planetary ball mill QM-3SP2, setting Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) carry out ball milling.Again ball grinder is put into glove box after ball milling terminates, get appropriate amount of sample (100mg ~ 300mg) and carry out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balance, Ar gas carrier gas flux controls at 1.7%(~ 145mL/min), first system is vacuumized ventilation after 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
LiAlH is taken in glove box 4(0.495g) and Ni-CoC(0.05g), pour into and be equipped with in the 100mL ball grinder of 8 ~ 20 10mm Stainless Steel Balls, by ball grinder seal after take out from glove box; Be loaded into by ball grinder on planetary ball mill QM-3SP2, setting Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) carry out ball milling.Again ball grinder is put into glove box after ball milling terminates, get appropriate amount of sample (100mg ~ 300mg) and carry out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balance, Ar gas carrier gas flux controls at 1.7%(~ 145mL/min), first system is vacuumized ventilation after 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
LiAlH is taken in glove box 4(0.475g) and Ni-CoC(0.025g), pour into and be equipped with in the 100mL ball grinder of 8 ~ 20 10mm Stainless Steel Balls, by ball grinder seal after take out from glove box; Be loaded into by ball grinder on planetary ball mill QM-3SP2, setting Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) carry out ball milling.Again ball grinder is put into glove box after ball milling terminates, get appropriate amount of sample (100mg ~ 300mg) and carry out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balance, Ar gas carrier gas flux controls at 1.7%(~ 145mL/min), first system is vacuumized ventilation after 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
By LiAlH in glove box 4(0.45g) and Ni-CoC(0.05g) proportioning weigh sample, pour into and be equipped with in the 100mL ball grinder of 8 ~ 20 10mm Stainless Steel Balls, by ball grinder seal after take out from glove box; Be loaded into by ball grinder on planetary ball mill QM-3SP2, setting Ball-milling Time (0.2 ~ 2h) and rotating speed (200 ~ 500r/min) carry out ball milling.Again ball grinder is put into glove box after ball milling terminates, get appropriate amount of sample (100mg ~ 300mg) and carry out thermogravimetric analysis.Adopt U.S. Cahn Thermax 500 hot high pressure balance, Ar gas carrier gas flux controls at 1.7%(~ 145mL/min), first system is vacuumized ventilation after 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-CoC composite hydrogen storage material, is characterized in that: adopt the CoCo [Ni (EDTA)] with orderly single crystal structure 24H 2o is presoma, has prepared by high-temperature sintering process the carbon coated Ni-Co metal nanoparticle Ni-CoC that diameter is 4-6nm; Ball milled is adopted to prepare LiAlH 4/ carbon coated Ni-Co metal nanoparticle Ni-CoC composite hydrogen storage material, wherein LiAlH 4with Ni-CoC mass ratio 100:1 ~ 7:1.
2. LiAlH described in a claim 1 4the preparation method of/carbon-clad metal nano particle Ni-CoC composite hydrogen storage material, is characterized in that: the CoCo [Ni (EDTA)] adopting orderly single crystal structure 24H 2o is presoma, has prepared by high-temperature sintering process the carbon coated Ni-Co metal nanoparticle Ni-CoC that diameter is 4-6nm; Ball milled is adopted to prepare LiAlH 4/ carbon coated Ni-Co metal nanoparticle Ni-CoC composite hydrogen storage material, wherein LiAlH 4with Ni-CoC mass ratio 100:1 ~ 7:1.
3. the preparation method of composite hydrogen storage material according to claim 2, is characterized in that:
Its preparation and operating process are:
(1) by CoCo [Ni (EDTA)] 24H 2o is placed in tube furnace, and adopt argon gas atmosphere, gas flow rate is 150 ~ 400mL/min, with the temperature rise rate of 1 ~ 5 DEG C/min from room temperature to 450 ~ 700 DEG C, keeps 2 ~ 10 hours, in argon gas atmosphere, cool to room temperature at 450 ~ 700 DEG C;
(2) in glove box by LiAlH 4weigh sample according to a certain ratio with Ni-CoC, pour in the ball grinder that particle diameter 5-10mm Stainless Steel Ball is housed, take out from glove box after ball grinder is sealed;
Be loaded into by ball grinder on planetary ball mill, setting Ball-milling Time 0.2 ~ 2h and rotating speed 200 ~ 500r/min carries out ball milling; Again ball grinder is put into glove box after ball milling terminates, sample is taken out, obtains product.
4. the preparation method of composite hydrogen storage material according to claim 3, is characterized in that:
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. the preparation method of composite hydrogen storage material according to claim 3, 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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