CN106410210A - Preparation method of metal hydride/nano carbon composite materials - Google Patents
Preparation method of metal hydride/nano carbon composite materials Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 229910052987 metal hydride Inorganic materials 0.000 title claims abstract description 37
- 150000004681 metal hydrides Chemical class 0.000 title claims abstract description 36
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 150000004678 hydrides Chemical class 0.000 claims abstract description 8
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims abstract description 7
- 150000008046 alkali metal hydrides Chemical class 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 239000002086 nanomaterial Substances 0.000 claims abstract description 4
- UKOVZLWSUZKTRL-UHFFFAOYSA-N naphthalid Chemical compound C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 239000003575 carbonaceous material Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 229910020828 NaAlH4 Inorganic materials 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- -1 alkali metal hydrogen Compound Chemical class 0.000 claims description 6
- 229910012375 magnesium hydride Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 229910010084 LiAlH4 Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000091 aluminium hydride Inorganic materials 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002073 nanorod Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of preparation of nano materials and particularly relates to a preparation method of metal hydride/nano carbon composite materials. The preparation method includes that naphthalene is taken as reaction media, alkali metal is dissolved in tetrahydrofuran to form precursor liquid of naphthalide, and the alkali metal hydride/nano carbon composite materials are prepared with a solvothermal method under hydrogen atmosphere and can be further reacted with other hydrides to be synthesized into multi-metal hydride/nano carbon composite materials. The preparation method is low in cost, high in efficiency, economical and environment friendly and high in universality.
Description
Technical field
The invention belongs to technical field of nanometer material preparation is and in particular to a kind of metal hydride/nano carbon composite material
Preparation method.
Background technology
Increasingly serious with pollute with energy crisis, exploitation is cleaned reproducible energy-storage system and is had become as global concern
Focus.Hydrogen Energy receives significant attention because it has the advantages of energy density height, cleanliness without any pollution, wide material sources.[1,2]
Exploitation is efficient, safety, and economic hydrogen storage technology is the key of Hydrogen Energy scale application.With respect to other hydrogen storage materials, MgH2,
NaAlH4Deng metal hydride due to having the advantages of hydrogen content height, low cost, aboundresources.However, the reality of metal hydride
Border application is but faced with the problems such as hydrogen discharging temperature is high, and hydrogen desorption kineticses are slow.[3] a series of research work show, by metal hydride
Thing is combined and can effectively reduce its desorption temperature with nano-carbon material, strengthens its hydrogen desorption kinetics, for example：Work as NaAlH4Confinement in
During mesoporous carbon, NaAlH at 180 DEG C4The hydrogen of 4.8wt% can be discharged in 30min, and pure NaAlH4Only can discharge
0.4 wt%[4].
On the other hand, lithium ion battery, as the energy-storage system of another kind of highly effective and safe, is similarly subjected to extensively in recent years
Concern.[5] metal hydride can also be applied to the negative material of lithium ion battery.[6,7] MgH2, NaAlH4Deng metallic hydrogen
Compound has specific capacity height, the low advantage of running voltage for lithium ion battery negative material, has larger application potential.So
And, metal hydride has during embedding de- lithium that volumetric expansion is big and this two large problems of poorly conductive, leads to its capacity fast
Speed decay.[8,9] research finds, metal hydride is supported on nano-carbon material and is conducive to increasing its electric conductivity, alleviate it
Volumetric expansion, thus significantly improve embedding de- lithium cyclical stability, such as：It is supported on the MgH on porous carbon2After 20 circulations
500 mAh g can also be discharged-1Specific capacity, and pure MgH2Specific capacity less than 100mAh g-1[10].
Although metal hydride/nano carbon composite material can significantly improve its hydrogen storage and storage lithium performance, due to gold
Belong to hydride easily to decompose and there is high chemism（Yi Yushui, oxygen reaction）, metal current hydride/Nano Carbon
Only following three kinds of the preparation method of material：
（1）Mechanical ball milling metal hydride and the mixture of nano-carbon material.[11,12] although the method is simple to operate,
Metal hydride easily occurs to reunite it is difficult to enter the nano pore of nano-carbon material, space, therefore the method in mechanical milling process
Difficulty realizes metal hydride and dispersion under nanoscale for the nano-carbon material；
（2）Metal hydride is utilized solution or melt impregnation to the space of nano-carbon material, in duct.[13,14] one sides
Face, the method universality is poor, part can only can be dissolved or the metal hydride of low melting point is effective, such as NaAlH4, and not
Can apply to MgH2, NaH, NaMgH3, LiNa2AlH6,Na3AlH6Deng hydride.On the other hand, due to nano-carbon material and hydrogenation
The wellability of the solution of thing or melt is poor, leads to the method load efficiency low, and the portative metal hydride content of institute is low；
（3）With di-n-butyl magnesium, the organic metal such as ethyl-lithium is carried on as raw material, the mode first passing through solution impregnation
On nano-carbon material, then it is hydrogenated to metal hydride.[15] the method, due to being used organic metal as raw material, is therefore prepared
High cost, and substantial amounts of byproduct of reaction（The Organic substance of complicated multichain）Overlay on hydride surface to be difficult to remove.Further, since should
Method employs solution dipping method, and therefore load efficiency is low.
In sum, a kind of low cost newly developed, high efficiency, universality is strong, and can achieve metal hydride and nano-sized carbon
The compound preparation method under nanoscale of material has very important significance.
List of references
[1] Schlapbach, L.; Züttel, A.Nature2001, 414, 353.
[2] Crabtree, G. W.; Dresselhaus, M. S.; Buchanan, M. V.Phys. Today2004,
57, 39.
[3] Staubitz, A.; Robertson, A. P. M.; Manners, I.Chem. Rev.2010, 110,
4079.
[4] Li, Y.; Zhou, G.; Fang, F.; Yu, X.; Zhang, Q.; Ouyang, L.; Zhu, M.;
Sun, D.Acta Mater.2011, 59, 1829.
[5] Goodenough, J. B.; Kim, Y.Chem. Mater.2010, 22, 587.
[6] Aymard, L.; Oumellal, Y.; Bonnet, J. P.Beilstein J. Nanotechnol.2015, 6, 1821.
[7] Oumellal, Y.; Rougier, A.; Nazri, G. A.; Tarascon, J. M.; Aymard, L.Nature Mater.2008, 7, 916.
[8] Brutti, S.; Mulas, G.; Piciollo, E.; Panero, S.; Reale, P.J. Mater. Chem.2012, 22, 14531.
[9] Teprovich, J. A.; Zhang, J.; Colón-Mercado, H.; Cuevas, F.; Peters,
B.; Greenway, S.; Zidan, R.; Latroche, M.J. Phys. Chem. C2015, 119, 4666.
[10] Oumellal, Y.; Zlotea, C.; Bastide, S.; Cachet-Vivier, C.; Leonel,
E.; Sengmany, S.; Leroy, E.; Aymard, L.; Bonnet, J. P.; Latroche, M.Nanoscale2014, 6, 14459.
[11] Xu, L.; Ge, Q.Int. J. Hydrogen Energy2013, 38, 3670.
[12] Liu, G.; Wang, Y.; Jiao, L.; Yuan, H.ACS Appl. Mater. Interfaces2014, 6, 11038.
[13] Adelhelm, P.; Gao, J.; Verkuijlen, M. H. W.; Rongeat, C.; Herrich,
M.; van Bentum, P. J. M.; Gutfleisch, O.; Kentgens, A. P. M.; de Jong, K. P.;
de Jongh, P. E.Chem. Mater.2010, 22, 2233.
[14] Zheng, S.; Fang, F.; Zhou, G.; Chen, G.; Ouyang, L.; Zhu, M.; Sun,
D.Chem. Mater. 2008, 20, 3954.
[15] Zlotea, C.; Oumellal, Y.; Hwang, S.-J.; Ghimbeu, C. M.; de Jongh, P.
E.; Latroche, M.J. Phys. Chem. C2015, 119, 18091..
Content of the invention
The present invention is in order to overcome the deficiencies in the prior art, there is provided a kind of system of metal hydride/nano carbon composite material
Preparation Method, enables metal hydride nano-particle to be evenly dispersed on nano-carbon material carrier, and has low cost, efficiency
Height, economic and environment-friendly, the features such as universality is strong.
The preparation method of metal hydride/nano carbon composite material that the present invention provides, is to naphthalene under high pressure hydrogen atmosphere
The precursor liquid of Base Metal carries out solvent thermal reaction, concretely comprises the following steps：
（1）Alkali metal particles and naphthalene are pressed 1：3～1：1 mol ratio is dissolved in oxolane, is obtained 0.5～15mg/ml's
Naphthalide precursor liquid；
（2）Nano-carbon material is added to above-mentioned precursor liquid according to 0.05～600mg/ml ratio, is then sealing in high pressure anti-
Answer kettle, and be passed through 0.5～4.5 MPa hydrogen, ultrasonic 10～90 minutes, at a temperature of then container being maintained 90～200 DEG C simultaneously
It is stirred continuously hydrogenation 6～48 hours, then be cooled to room temperature；Product oxolane eccentric cleaning, drying, obtain alkali metal hydrogen
Compound/nano carbon composite material；Waste liquid is through Distillation recovery oxolane and naphthalene；
（3）Prepared alkali metal hydride/nano carbon composite material and other metal hydride powder are according to hydride mol ratio
1:3～3:1 mixing, carries out 1～48 hour ball milling, prepared multi-element metal hydride/nano carbon composite material under protective atmosphere.
In step 1, described alkali metal particles are selected from any one in Li, Na, K.
In step 2, described carbon nanomaterial is selected from Graphene, SWCN, multi-walled carbon nano-tubes, carbon nanometer
Any one in rod, carbon nanocoils, carbon nanometer rod, carbon fiber；Described alkali metal hydride is selected from LiH, NaH, KH
Any one.
In step 3, other described metal hydride powder are selected from LiH, NaH, KH, AlH3、CaH2、MgH2、
LiAlH4、NaAlH4In any one；Described protective atmosphere is selected from H2Any one in gas, Ar gas, He gas；Described
Multi-element metal hydride be selected from NaMgH3, LiAlH4、NaAlH4、LiNa2AlH6、Na3AlH6、Li3AlH6In any one
Kind.
The know-why of the inventive method is：
The temperature of precursor liquid exceedes the boiling point of oxolane（66℃）When, precursor liquid is in gas-liquid mixed state, its surface
Tension force declines rapidly, can penetrate into the space of nano-carbon material being difficult under room temperature to enter, in duct；Meanwhile, naphthalide
Significantly strengthen with the activity that hydrogen reacts, can in space, duct equably nucleating growth go out the nanometer of alkali metal hydride
Granule, realizes alkali metal hydride compound under nanoscale with nano-carbon material.Synthesize further multi-element metal hydride/
During nano carbon composite material, nano-carbon material, as physical isolation medium, stops the multi-element metal hydride generating from being reunited
Grow up so that the metal hydride nano-particle generating is evenly dispersed on nano-carbon material carrier.
The good effect of the inventive method is：
1. the raw material that this method uses only comprises alkali metal, hydrogen, oxolane, naphthalene, is common industrial raw materials,
And oxolane and the separable recovery of naphthalene, no waste liquid/thing discharge, therefore this method low production cost, economic and environment-friendly；
2. the maximum temperature needed for this method is only 200 DEG C, and maximum pressure is only 4.5 MPa, is all easy in the industrial production
Realize, required reactor, centrifuge etc. is industrial common device, and simple to operate, therefore this method efficiency
Height, can be applicable to large-scale industrial production；
3. this method can prepare LiH, NaH, KH, NaMgH3, LiNa2AlH6, Na3AlH6, Li3AlH6Deng metal hydride and nanometer
The composite of material with carbon element, universality is strong.Hydride is dispersed in nano-sized carbon with form of nanoparticles and carries in the composite
On body, its content, pattern and distribution etc. can be regulated and controled further according to experiment condition.
Brief description
Fig. 1 is the X ray diffracting spectrum of synthesized NaH/ graphene composite material.
Fig. 2 is the transmission electron microscope image of synthesized NaH/ graphene composite material.
Fig. 3 is synthesized LiNa2AlH6The X ray diffracting spectrum of/graphene composite material.
Fig. 4 is synthesized LiNa2AlH6The transmission electron microscope image of/graphene composite material.
Fig. 5 is synthesized LiNa2AlH6The embedding de- lithium performance of circulation of/graphene composite material.
Fig. 6 is synthesized Na3AlH6The X ray diffracting spectrum of/SWCN composite.
Specific embodiment
The preparation method of the present invention is described in detail with accompanying drawing below in conjunction with example.
Embodiment 1：The preparation of NaH/graphene composite material
In inert atmosphere glove box, the naphthalene of metal Na and 8g of 1g is put in the oxolane of 500ml, continuously stirred
12h, makes metal Na and naphthalene be completely dissolved, prepared naphthalene sodium precursor liquid.Precursor liquid is transferred in reactor, is simultaneously introduced
The Graphene of 0.5g, is passed through hydrogen to 3MPa pressure.After ultrasonic for this reactor 30min, it is transferred in oil bath pan, continuously stirred
And it is gradually heating to 130 DEG C, naturally it is down to room temperature after insulation 12h.Through filtration or centrifugal treating, and clean 2 with oxolane
～3 times, after being dried, can get NaH/ graphene composite material.The X-ray diffractogram of synthesized NaH/ graphene composite material
Spectrum and transmission electron microscope image are respectively as illustrated in fig. 1 and 2.Fig. 1 shows that the method is successfully prepared NaH.Visible big in Fig. 2
NaH nanometer rods/granule that amount diameter is about 150 nm is equably supported on Graphene, illustrates that this preparation method can achieve alkali gold
Belong to hydride compound under nanoscale with carbon nanomaterial.
Embodiment 2：LiNa2AlH6The preparation of/graphene composite material and its electrochemical lithium storage characteristic
Prepare NaH/ graphene composite material first, detailed process is with reference to example 1.In inert atmosphere glove box, by the institute of 1g
Prepared NaH/ graphene composite material and the LiAlH of 0.52g4Powder mixing loads in ball grinder, ball milling in a hydrogen atmosphere
36h, rotational speed of ball-mill is 400 revs/min, and ratio of grinding media to material is 30:1, prepared LiNa2AlH6/ graphene composite material, the X of its product penetrates
Ray diffraction diagram spectrum and transmission electron microscope image are respectively as shown in Figure 3 and Figure 4.Fig. 3 shows that the method can synthesize
LiNa2AlH6.Fig. 4 can be seen that LiNa2AlH6The diameter of nano-particle is about 25 nm, and it is uniformly coated with graphite
Alkene, illustrates that this preparation method can achieve that multi-element metal hydride and nano-carbon material are compound under nanoscale.
Fig. 5 is the LiNa of synthesis2AlH6The electrochemical lithium storage cycle characteristics of/graphene composite material.In 100mA g-1Fill
Under discharge current density, through 55 circulation after, LiNa2AlH6The specific capacity of/graphene composite material still can keep 404
mAh g-1, there is relatively stable embedding de- lithium performance, be a kind of negative material with application potential.
Implement example 3：The preparation of NaH/ SWCN composite
In inert atmosphere glove box, the naphthalene of metal Na and 7g of 0.75g is put in the oxolane of 500ml, persistently stirs
Mix 12h, so that metal Na and naphthalene is completely dissolved, prepared naphthalene sodium precursor liquid.Precursor liquid is transferred in reactor, is simultaneously introduced
The SWCN of 0.45g, is passed through hydrogen to 4MPa pressure.After ultrasonic for this reactor 60min, it is transferred in oil bath pan,
Continuously stirred and be gradually heating to 170 DEG C, naturally it is down to room temperature after insulation 48h.Through filtration or centrifugal treating, and use tetrahydrochysene furan
Mutter cleaning 2～3 times, after being dried, can get NaH/ SWCN composite.
Implement example 4：Na3AlH6The preparation of/SWCN composite
Prepare NaH/ SWCN composite first, detailed process is with reference to example 3.In inert atmosphere glove box, will
The obtained NaH/ SWCN composite of 1g and the NaAlH of 0.713g4Powder mixing loads in ball grinder, in argon
Ball milling 18h under gas atmosphere, rotational speed of ball-mill is 300 revs/min, and ratio of grinding media to material is 40:1, prepared Na3AlH6/ SWCN is combined
Material, the X ray diffracting spectrum of its product is as shown in Figure 6.Fig. 6 shows that the method successfully synthesizes Na3AlH6/ single
Pipe composite.
Implement example 5：The preparation of LiH/ carbon fibre composite
In inert atmosphere glove box, the naphthalene of metal Li and 8g of 0.35g is put in the oxolane of 500ml, persistently stirs
Mix 10h, so that metal Li and naphthalene is completely dissolved, prepared naphthalene lithium precursor liquid.Precursor liquid is transferred in reactor, is simultaneously introduced
The carbon fiber of 0.5g, is passed through hydrogen to 1MPa pressure.After ultrasonic for this reactor 90min, it is transferred in oil bath pan, continuously stirred
And it is gradually heating to 120 DEG C, naturally it is down to room temperature after insulation 24h.Through filtration or centrifugal treating, and clean 3 with oxolane
Secondary, can get LiH/ carbon fibre composite after being dried.
Implement example 6：The preparation of KH/ multi-wall carbon nano-tube composite material
In inert atmosphere glove box, the naphthalene of metal K and 4g of 0.5g is put in the oxolane of 200ml, continuously stirred
10h, makes metal Li and naphthalene be completely dissolved, prepared naphthalene potassium precursor liquid.Precursor liquid is transferred in reactor, is simultaneously introduced
The multi-walled carbon nano-tubes of 0.7g, is passed through hydrogen to 1.5MPa pressure.After ultrasonic for this reactor 20min, it is transferred in oil bath pan,
Continuously stirred and be gradually heating to 90 DEG C, naturally it is down to room temperature after insulation 7h.Through filtration or centrifugal treating, and use oxolane
Cleaning 3 times, can get KH/ multi-wall carbon nano-tube composite material after being dried.
Claims (6)
1. a kind of preparation method of metal hydride/nano carbon composite material is it is characterised in that be to naphthalene under high pressure hydrogen atmosphere
The precursor liquid of Base Metal carries out solvent thermal reaction, concretely comprises the following steps：
（1）Alkali metal particles and naphthalene are pressed 1：3～1：1 mol ratio is dissolved in oxolane, is obtained 0.5～15mg/ml's
Naphthalide precursor liquid；
（2）Nano-carbon material is added to above-mentioned precursor liquid according to 0.05～600mg/ml ratio, is then sealing in high pressure anti-
Answer kettle, and be passed through 0.5～4.5 MPa hydrogen, ultrasonic 10～90 minutes, at a temperature of then container being maintained 90～200 DEG C simultaneously
It is stirred continuously hydrogenation 6～48 hours, then be cooled to room temperature；Product oxolane eccentric cleaning, drying, obtain alkali metal hydrogen
Compound/nano carbon composite material；Waste liquid is through Distillation recovery oxolane and naphthalene；
（3）Prepared alkali metal hydride/nano carbon composite material and other metal hydride powder are according to hydride mol ratio
1:3～3:1 mixing, carries out 1～48 hour ball milling, prepared multi-element metal hydride/nano carbon composite material under protective atmosphere.
2. preparation method according to claim 1 is it is characterised in that step（1）Described in alkali metal be selected from Li, Na, K
In any one.
3. preparation method according to claim 1 and 2 is it is characterised in that step（2）Described in carbon nanomaterial be selected from
Any one in Graphene, SWCN, multi-walled carbon nano-tubes, carbon nano rod, carbon nanocoils, carbon nanometer rod, carbon fiber
Kind.
4. preparation method according to claim 3 is it is characterised in that step（2）Described in alkali metal hydride be
Any one in LiH, NaH, KH.
5. the preparation method according to claim 1,2 or 4 is it is characterised in that step（3）Described in other metal hydrides
Thing powder is selected from LiH, NaH, KH, AlH3、CaH2、MgH2、LiAlH4、NaAlH4In any one；Described protective atmosphere choosing
From H2Any one in gas, Ar gas, He gas.
6. preparation method according to claim 5 is it is characterised in that step（3）Described in multi-element metal hydride be
NaMgH3、LiAlH4、NaAlH4、LiNa2AlH6、Na3AlH6、Li3AlH6In any one.
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| CN116569281A (en) * | 2020-12-15 | 2023-08-08 | 罗伯特·博世有限公司 | Method for producing a conductive conductor bundle comprising at least one carbon conductor |
| CN116583917A (en) * | 2020-12-15 | 2023-08-11 | 罗伯特·博世有限公司 | Method for producing an electrically conductive carbon conductor in the form of a carbon structure |
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| CN116583917A (en) * | 2020-12-15 | 2023-08-11 | 罗伯特·博世有限公司 | Method for producing an electrically conductive carbon conductor in the form of a carbon structure |
| CN116902911A (en) * | 2023-07-13 | 2023-10-20 | 京氢未来新能源科技(北京)有限公司 | MgH supported by carbon fiber 2 Composite material and preparation method thereof |
| CN116902911B (en) * | 2023-07-13 | 2024-01-30 | 京氢未来新能源科技(北京)有限公司 | MgH supported by carbon fiber 2 Composite material and preparation method thereof |
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