CN106410210B - A kind of preparation method of metal hydride/nano carbon composite material - Google Patents

A kind of preparation method of metal hydride/nano carbon composite material Download PDF

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CN106410210B
CN106410210B CN201610928164.XA CN201610928164A CN106410210B CN 106410210 B CN106410210 B CN 106410210B CN 201610928164 A CN201610928164 A CN 201610928164A CN 106410210 B CN106410210 B CN 106410210B
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孙大林
吴飞龙
方方
宋云
李永涛
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Fudan University
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    • H—ELECTRICITY
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    • 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
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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
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Abstract

The invention belongs to technical field of nanometer material preparation, specially a kind of preparation method of metal hydride/nano carbon composite material.The method of the present invention is using naphthalene as reaction media, dissolved alkali metal is formed to the precursor liquid of naphthalide in tetrahydrofuran, then alkali metal hydride/nano carbon composite material is made by the solvent-thermal method under hydrogen atmosphere, and multi-element metal hydride/nano carbon composite material can be synthesized further with other hydride reactions.The present invention provides a kind of low cost, high efficiency, method economic and environment-friendly, universality is strong to prepare metal hydride/nano carbon composite material.

Description

A kind of preparation method of metal hydride/nano carbon composite material
Technical field
The invention belongs to technical field of nanometer material preparation, and in particular to a kind of metal hydride/nano carbon composite material Preparation method.
Background technique
As energy crisis is got worse with what is polluted, exploitation cleans reproducible energy-storage system and has become global concern Focus.Hydrogen Energy because its with energy density height, cleanliness without any pollution, it is from a wealth of sources the advantages that and receive significant attention.[1,2] Efficiently, safety, economic hydrogen storage technology is the key that Hydrogen Energy scale application for exploitation.Relative to other hydrogen storage materials, MgH2, NaAlH4The advantages that equal metal hydrides are at low cost due to high with hydrogen content, resourceful.However, the reality of metal hydride The problems such as border application is but faced with hydrogen discharging temperature height, and hydrogen desorption kinetics are slow.[3] a series of research work show metal hydride Object with nano-carbon material is compound that its desorption temperature can be effectively reduced, enhance its hydrogen desorption kinetics, such as: work as NaAlH4Confinement in When mesoporous carbon, NaAlH at 180 DEG C4It can release the hydrogen of 4.8wt% in 30min, and pure NaAlH4It can only release 0.4 wt%[4]。
On the other hand, energy-storage system of the lithium ion battery as another highly effective and safe, is similarly subjected to extensively in recent years Concern.[5] metal hydride also can be applied to the negative electrode material of lithium ion battery.[6,7] MgH2, NaAlH4Equal metallic hydrogens The advantages such as compound has specific capacity high for lithium ion battery negative material, and operating voltage is low, have biggish application potential.So And metal hydride during embedding de- lithium there is volume expansion is big and poorly conductive this two large problems, cause its capacity fast Speed decaying.[8,9] are conducive to increase its electric conductivity the study found that metal hydride is supported on nano-carbon material, alleviate it Volume expansion, thus improve embedding de- lithium cyclical stability significantly, such as: the MgH being supported 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 improve its hydrogen storage and storage lithium performance, due to gold significantly Belong to hydride easily to decompose and there is high chemical activity (Yi Yushui, oxygen reaction), at present metal hydride/Nano Carbon The preparation method of material is only three kinds following:
(1) mixture of mechanical ball mill metal hydride and nano-carbon material.[11,12] this method is although easy to operate, But metal hydride is easily reunited in mechanical milling process, it is difficult to nano pore, gap into nano-carbon material, therefore should Method difficulty realizes metal hydride and the dispersion of nano-carbon material at the nanoscale；
(2) by metal hydride using solution or melt impregnation to the gap of nano-carbon material, in duct.[13,14] On the one hand, this method universality is poor, can only can dissolve to part or the metal hydride of low melting point is effective, such as NaAlH4, And it may not apply to MgH2, NaH, NaMgH3, LiNa2AlH6,Na3AlH6Equal hydride.On the other hand, due to nano-carbon material with The solution of hydride or the wellability of melt are poor, cause this method load efficiency low, the portative metal hydride content of institute It is low；
(3) with di-n-butyl magnesium, the organic metal such as ethyl-lithium as raw material, born by the mode for first passing through solution dipping It is loaded on nano-carbon material, then is hydrogenated to metal hydride.[15] this method is due to using organic metal as raw material, Preparation cost is high, and a large amount of byproduct of reaction (organic matter of complicated multichain) overlays on hydride surface and is difficult to remove.In addition, by In the method use solution dipping methods, therefore load efficiency is low.
In conclusion a kind of low cost newly developed, high efficiency, universality is strong, and can realize metal hydride and nano-sized carbon Compound preparation method has very important significance material at the nanoscale.
Bibliography
[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.Nanoscale 2014, 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.。
Summary of the invention
The present invention for overcome the deficiencies in the prior art, provides 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 at 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 provided by the invention is under high pressure hydrogen atmosphere to naphthalene The precursor liquid of Base Metal carries out solvent thermal reaction, specific steps are as follows:
(1) alkali metal particles and naphthalene are dissolved into tetrahydrofuran by the molar ratio of 1:3~1:1,0.5~15mg/ is made The naphthalide precursor liquid of ml；
(2) nano-carbon material is added in above-mentioned precursor liquid according to 0.05~600mg/ml ratio, then encloses height Reaction kettle is pressed, and is passed through 0.5~4.5 MPa hydrogen, then container is maintained 90~200 DEG C of temperature by ultrasound 10~90 minutes It descends and is stirred continuously hydrogenation 6~48 hours, then be cooled to room temperature；Reaction product tetrahydrofuran eccentric cleaning, drying obtain alkali gold Belong to hydride/nano carbon composite material；Waste liquid is through being distilled to recover tetrahydrofuran and naphthalene；
(3) alkali metal hydride/nano carbon composite material made from rubs with other metal hydride powders according to hydride You mix than 1:3~3:1, and 1~48 hour ball milling is carried out under protective atmosphere, and multi-element metal hydride/Nano Carbon is made Material.
In step 1, the alkali metal particles can be selected from any one in Li, Na, K.
In step 2, the carbon nanomaterial is selected from graphene, single-walled carbon nanotube, multi-walled carbon nanotube, carbon nanometer Stick, carbon nanocoils, carbon nanometer rod, any one in carbon fiber；The alkali metal hydride is in LiH, NaH, KH Any one.
In step 3, other described metal hydride powders can be selected from LiH, NaH, KH, AlH3、CaH2、MgH2、 LiAlH4、NaAlH4In any one；The protective atmosphere can be selected from H2Gas, Ar gas, any one in He gas；It is described Multi-element metal hydride can be selected from NaMgH3, LiAlH4、NaAlH4、LiNa2AlH6、Na3AlH6、Li3AlH6In it is any one Kind.
The technical principle of the method for the present invention is:
When the temperature of precursor liquid is more than boiling point (66 DEG C) of tetrahydrofuran, precursor liquid is in gas-liquid mixed state, Surface tension declines rapidly, can penetrate into the gap of the nano-carbon material being difficult to enter under room temperature, in duct；At the same time, naphthalene The activity that metal is reacted with hydrogen enhances significantly, can equably nucleating growth goes out alkali metal hydride in gap, duct Nano particle realizes that alkali metal hydride and nano-carbon material are compound at the nanoscale.In further synthesis multi-element metal hydrogen During compound/nano carbon composite material, nano-carbon material prevents the multi-element metal hydride generated as physical isolation medium Reunion is grown up, so that the metal hydride nano particle generated is evenly dispersed on nano-carbon material carrier.
The good effect of the method for the present invention is:
1. the raw material that this method uses only include alkali metal, hydrogen, tetrahydrofuran, naphthalene is common industrial former material Material, and tetrahydrofuran and the separable recycling of naphthalene, no waste liquid/object discharge, therefore this method low production cost, it is economic and environment-friendly；
2. maximum temperature needed for this method is only 200 DEG C, maximum pressure is only 4.5 MPa, is all in the industrial production It is easily achieved, required reaction kettle, centrifuge etc. is industrial common device, and easy to operate, therefore this method It is high-efficient, it can be applied to large-scale industrial production；
3. this method can prepare LiH, NaH, KH, NaMgH3, LiNa2AlH6, Na3AlH6, Li3AlH6Equal metal hydrides with The composite material of nano-carbon material, universality are strong.Hydride is dispersed in nanometer with form of nanoparticles in the composite On carbon carrier, content, pattern and distribution etc. can regulate and control according to experiment condition further progress.
Detailed description of the invention
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 the circulation of/graphene composite material.
Fig. 6 is synthesized Na3AlH6The X ray diffracting spectrum of/single-walled carbon nanotube composite material.
Specific embodiment
Preparation method of the invention is described in detail below in conjunction with example and attached drawing.
The preparation of embodiment 1:NaH/graphene composite material
In inert atmosphere glove box, the naphthalene of the metal Na and 8g of 1g are put into the tetrahydrofuran of 500ml, persistently stirred 12h is mixed, metal Na and naphthalene are completely dissolved, naphthalene sodium precursor liquid is made.Precursor liquid is transferred in reaction kettle, is added simultaneously The graphene of 0.5g is passed through hydrogen to 3MPa pressure.After reaction kettle ultrasound 30min, it is transferred in oil bath pan, it is lasting to stir And 130 DEG C are gradually heated to, it is down to room temperature naturally after keeping the temperature 12h.Through filtering or centrifugal treating, and 2 are cleaned with tetrahydrofuran ~3 times, NaH/ graphene composite material can be obtained after dry.The X-ray diffractogram of synthesized NaH/ graphene composite material Spectrum and transmission electron microscope image difference are as illustrated in fig. 1 and 2.Fig. 1 shows that this method is successfully prepared NaH.It is visible big in Fig. 2 NaH nanometer rods/particle that amount diameter is about 150 nm is equably supported on graphene, illustrates that this preparation method can realize alkali gold Belong to hydride and carbon nanomaterial at the nanoscale compound.
Embodiment 2:LiNa2AlH6The preparation and its electrochemical lithium storage characteristic of/graphene composite material
NaH/ graphene composite material is prepared first, and detailed process is referring to example 1.In inert atmosphere glove box, by 1g Obtained NaH/ graphene composite material and 0.52g LiAlH4Powder mixing is fitted into ball grinder, in a hydrogen atmosphere Ball milling 36h, rotational speed of ball-mill are 400 revs/min, ratio of grinding media to material 30:1, and LiNa is made2AlH6/ graphene composite material, product X ray diffracting spectrum and transmission electron microscope image difference it is as shown in Figure 3 and Figure 4.Fig. 3 shows that this 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 realize multi-element metal hydride and nano-carbon material at the nanoscale compound.
Fig. 5 is the LiNa of synthesis2AlH6The electrochemical lithium storage cycle characteristics of/graphene composite material.In 100mA g-1It fills Under discharge current density, by 55 circulation after, LiNa2AlH6The specific capacity of/graphene composite material can still keep 404 mAh g-1, there is relatively stable embedding de- lithium performance, be a kind of negative electrode material with application potential.
Implement the preparation of example 3:NaH/ single-walled carbon nanotube composite material
In inert atmosphere glove box, the naphthalene of the metal Na and 7g of 0.75g are put into the tetrahydrofuran of 500ml, held Continuous stirring 12h, is completely dissolved metal Na and naphthalene, naphthalene sodium precursor liquid is made.Precursor liquid is transferred in reaction kettle, simultaneously The single-walled carbon nanotube of 0.45g is added, is passed through hydrogen to 4MPa pressure.After reaction kettle ultrasound 60min, it is transferred to oil bath pan It is interior, it persistently stirs and is gradually heated to 170 DEG C, be down to room temperature naturally after keeping the temperature 48h.Through filtering or centrifugal treating, and with four Hydrogen furans cleans 2~3 times, and NaH/ single-walled carbon nanotube composite material can be obtained after dry.
Implement example 4:Na3AlH6The preparation of/single-walled carbon nanotube composite material
NaH/ single-walled carbon nanotube composite material is prepared first, and detailed process is referring to example 3.In inert atmosphere glove box It is interior, by the NaAlH of the obtained NaH/ single-walled carbon nanotube composite material and 0.713g of 1g4Powder mixing is packed into ball grinder In, ball milling 18h, rotational speed of ball-mill are 300 revs/min, ratio of grinding media to material 40:1 under an argon atmosphere, and Na is made3AlH6/ single wall carbon is received The X ray diffracting spectrum of mitron composite material, product is as shown in Figure 6.Fig. 6 shows that this method successfully synthesizes Na3AlH6/ mono- Wall carbon nano-tube composite material.
Implement the preparation of example 5:LiH/ carbon fibre composite
In inert atmosphere glove box, the naphthalene of the metal Li and 8g of 0.35g are put into the tetrahydrofuran of 500ml, held Continuous stirring 10h, is completely dissolved metal Li and naphthalene, naphthalene lithium precursor liquid is made.Precursor liquid is transferred in reaction kettle, simultaneously The carbon fiber of 0.5g is added, is passed through hydrogen to 1MPa pressure.It after reaction kettle ultrasound 90min, is transferred in oil bath pan, continues It stirs and is gradually heated to 120 DEG C, be down to room temperature naturally afterwards for 24 hours in heat preservation.It is and clear with tetrahydrofuran through filtering or centrifugal treating It washes 3 times, LiH/ carbon fibre composite can be obtained after dry.
Implement the preparation of example 6:KH/ multi-wall carbon nano-tube composite material
In inert atmosphere glove box, the naphthalene of the metal K and 4g of 0.5g are put into the tetrahydrofuran of 200ml, continued 10h is stirred, metal Li and naphthalene are completely dissolved, naphthalene potassium precursor liquid is made.Precursor liquid is transferred in reaction kettle, is added simultaneously The multi-walled carbon nanotube for entering 0.7g is passed through hydrogen to 1.5MPa pressure.After reaction kettle ultrasound 20min, it is transferred to oil bath pan It is interior, it persistently stirs and is gradually heated to 90 DEG C, be down to room temperature naturally after keeping the temperature 7h.Through filtering or centrifugal treating, and use tetrahydro Furans cleans 3 times, and KH/ multi-wall carbon nano-tube composite material can be obtained after dry.

Claims (6)

1. a kind of preparation method of metal hydride/nano carbon composite material, which is characterized in that be under high pressure hydrogen atmosphere to naphthalene The precursor liquid of Base Metal carries out solvent thermal reaction, specific steps are as follows:
(1) alkali metal particles and naphthalene are dissolved into tetrahydrofuran by the molar ratio of 1:3~1:1, are made 0.5~15mg/ml's Naphthalide precursor liquid；
(2) nano-carbon material is added in above-mentioned precursor liquid according to 0.05~600mg/ml ratio, it is anti-then encloses high pressure Kettle is answered, and is passed through 0.5~4.5 MPa hydrogen, ultrasound 10~90 minutes, at a temperature of container is then maintained 90~200 DEG C simultaneously It is stirred continuously hydrogenation 6~48 hours, then is cooled to room temperature；Reaction product tetrahydrofuran eccentric cleaning, drying, obtain alkali metal hydrogen Compound/nano carbon composite material；Waste liquid is through being distilled to recover tetrahydrofuran and naphthalene；
(3) alkali metal hydride/nano carbon composite material made from and other metal hydride powders are according to hydride molar ratio 1:3~3:1 mixing, carries out 1~48 hour ball milling under protective atmosphere, and multi-element metal hydride/nano carbon composite material is made.
2. preparation method according to claim 1, which is characterized in that alkali metal as described in step (1) is selected from Li, Na, K In any one.
3. preparation method according to claim 1 or 2, which is characterized in that nano-carbon material described in step (2) is selected from Graphene, single-walled carbon nanotube, multi-walled carbon nanotube, carbon nano rod, any one in carbon fiber.
4. preparation method according to claim 3, which is characterized in that alkali metal hydride described in step (2) is Any one in LiH, NaH, KH.
5. preparation method according to claim 1,2 or 4, which is characterized in that other metal hydrides described in step (3) Object powder is selected from LiH, NaH, KH, AlH3、CaH2、MgH2、LiAlH4、NaAlH4In any one；The protective atmosphere choosing From H2Gas, Ar gas, any one in He gas.
6. preparation method according to claim 5, which is characterized in that multi-element metal hydride described in step (3) is NaMgH3、LiAlH4、NaAlH4、LiNa2AlH6、Na3AlH6、Li3AlH6In any one.
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