CN112762715B - Preparation device and preparation method of Mg-C nano composite hydrogen storage material - Google Patents
Preparation device and preparation method of Mg-C nano composite hydrogen storage material Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 239000001257 hydrogen Substances 0.000 title claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 63
- 239000011232 storage material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000010453 quartz Substances 0.000 claims abstract description 88
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000011777 magnesium Substances 0.000 claims abstract description 80
- 239000007789 gas Substances 0.000 claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 51
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 28
- 229910052786 argon Inorganic materials 0.000 claims abstract description 22
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 23
- 238000011010 flushing procedure Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RWDBMHZWXLUGIB-UHFFFAOYSA-N [C].[Mg] Chemical compound [C].[Mg] RWDBMHZWXLUGIB-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- -1 hydrogen Chemical class 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B17/00—Furnaces of a kind not covered by any of groups F27B1/00 - F27B15/00
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0078—Composite solid storage mediums, i.e. coherent or loose mixtures of different solid constituents, chemically or structurally heterogeneous solid masses, coated solids or solids having a chemically modified surface region
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D11/00—Arrangement of elements for electric heating in or on furnaces
- F27D11/06—Induction heating, i.e. in which the material being heated, or its container or elements embodied therein, form the secondary of a transformer
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D5/00—Supports, screens or the like for the charge within the furnace
- F27D5/0068—Containers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D7/00—Forming, maintaining or circulating atmospheres in heating chambers
- F27D7/02—Supplying steam, vapour, gases or liquids
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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
- Y02E60/32—Hydrogen storage
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- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
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Abstract
本发明公开了一种Mg‑C纳米复合储氢材料的制备装置和制备方法，Mg‑C纳米复合储氢材料的制备装置，包括一个管式炉系统，管式炉内设有石英管，石英管内部设有一个石墨套管用于放置镁，在石英管上靠近气体出口的一侧外套有电感线圈，电感线圈连接有射频电源，石墨套管内放置镁的位置与套有电感线圈的位置之间为产品收集区域；Mg‑C纳米复合储氢材料的制备方法，包括以下步骤：在石墨套管内放入镁，使用氩气冲洗石英管；石英管内通入氩气—烃类气体—氢气的混合气体；启动管式炉系统，加热石英管，使石墨套管内产生镁的蒸气；启动射频电源，烃类气体分解产生碳，产品收集区域处实现镁与碳的均匀复合，形成Mg‑C纳米复合储氢材料。
The invention discloses a preparation device and a preparation method of a Mg-C nano-composite hydrogen storage material. The preparation device of the Mg-C nano-composite hydrogen storage material comprises a tubular furnace system. The tubular furnace is provided with a quartz tube, and the quartz There is a graphite sleeve inside the tube for placing magnesium, an inductance coil is sheathed on the side of the quartz tube near the gas outlet, and the inductance coil is connected with a radio frequency power supply. is the product collection area; the preparation method of the Mg-C nanocomposite hydrogen storage material includes the following steps: putting magnesium into the graphite sleeve, flushing the quartz tube with argon; introducing a mixture of argon-hydrocarbon gas-hydrogen into the quartz tube gas; start the tube furnace system, heat the quartz tube, and generate magnesium vapor in the graphite sleeve; start the radio frequency power supply, the hydrocarbon gas is decomposed to generate carbon, and the uniform composite of magnesium and carbon is realized in the product collection area to form Mg-C nanocomposite hydrogen storage material.
Description
Technical Field
The invention belongs to the technical field of hydrogen storage, and particularly relates to a preparation device and a preparation method of a Mg-C nano composite hydrogen storage material.
Background
The metal Mg is an important hydrogen storage material, the hydrogen absorption and desorption kinetics of the metal Mg can be effectively improved by reducing the size of the metal Mg, but the melting point of the magnesium is lower, and the performance is reduced because nano particles are easy to agglomerate in the process of repeatedly absorbing and desorbing hydrogen. The Mg and the carbon form a nano composite system, the carbon material has good thermal stability, light weight and strong heat and electric conductivity, and can effectively inhibit the agglomeration of the Mg and improve the hydrogen storage performance of the magnesium.
The preparation of the nano material of the magnesium metal is very difficult. Mg has good ductility, and small particles are difficult to obtain by a simple mechanical crushing method; meanwhile, the chemical property is very active, the cost of synthesizing the magnesium and carbon nano composite structure by a chemical method is very high, and the operation is very complex. The synthesis of the magnesium-carbon nano composite material is more difficult.
One method that has been reported to be effective in the preparation of Mg/C nanocomposites is the arc process. In patent CN102233435B, a method for preparing Mg/C nanocomposites by plasma arc evaporation of metallic magnesium in a mixture of argon and acetylene is reported, wherein the magnesium particle size is about 40 nm. Patent CN109928360A uses a plasma arc and a resistance heating stage to heat a catalyst ingot and a magnesium block, respectively, to produce carbon-coated magnesium-based composite nanoparticles having a magnesium particle size of less than 20nm and containing a metal catalyst (V, Nb, Ti, Zr, Co, Ni, Al or Mn). However, the high-temperature arc reaction device is complex, the energy consumption in the preparation process is high, and a control method for the Mg/C ratio and the particle size is lacked.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation device and a preparation method of a Mg-C nano composite hydrogen storage material, which solve the problems of high synthesis difficulty of a magnesium-C nano composite material, complex high-temperature arc reaction device and high energy consumption in the preparation process.
In order to achieve the purpose, the preparation device of the Mg-C nano composite hydrogen storage material comprises a tube furnace system, wherein a quartz tube is arranged in the tube furnace, a gas inlet and a gas outlet are respectively arranged on two sides of the quartz tube, a graphite sleeve is arranged in the quartz tube, raw material metal magnesium is placed in the graphite sleeve, an inductance coil is sleeved outside one side, close to the gas outlet, of the quartz tube, the inductance coil is connected with a radio frequency power supply, and a product collection area is arranged between the position, in which the raw material metal magnesium is placed, of the graphite sleeve and the position, in which the inductance coil is sleeved.
Further, a pump is connected to a gas outlet of the quartz tube and used for adjusting the pressure in the quartz tube, and a valve is arranged between the gas outlet of the quartz tube and the pump.
Preferably, the number of turns of the inductance coil is 1-10 turns.
The invention also provides a preparation method of the Mg-C nano composite hydrogen storage material by utilizing the preparation device of the Mg-C nano composite hydrogen storage material, which comprises the following steps:
(1) placing raw material metal magnesium into the graphite sleeve of the quartz tube, introducing argon through a gas inlet of the quartz tube, and flushing the quartz tube for 2-3 times by using the argon;
(2) introducing mixed gas of argon, hydrocarbon gas and hydrogen through a gas inlet of the quartz tube to maintain the pressure in the quartz tube between 10 and 200 Pa;
(3) starting the tube furnace system, heating the quartz tube to the set temperature of 400-;
(4) and when the temperature reaches a set temperature, starting the radio frequency power supply, wherein the radio frequency power supply generates glow discharge in the quartz tube through the inductance coil, the radio frequency power of the radio frequency power supply is 20-500W, and the reaction time is 20min-4h, so that the Mg-C nano composite hydrogen storage material with a uniform nano composite structure is formed in the product collection area.
Further, in the step (2), the volume percentage of argon in the mixed gas of argon-hydrocarbon gas-hydrogen gas is 50-95%, the volume percentage of hydrocarbon gas is 1-50%, and the volume percentage of hydrogen is 0-20%.
Preferably, in the step (2), the volume percentage of argon in the mixed gas of argon-hydrocarbon gas-hydrogen gas is 80-90%; the volume percentage of the hydrocarbon gas is 2-10%; the volume percentage of the hydrogen is 0-5%.
Preferably, in step (2), the pressure of the tube furnace system is maintained between 50 and 100 Pa.
Preferably, in the step (3), the quartz tube is heated to the set temperature of 550 ℃ and 650 ℃, and the temperature rise speed in the tube furnace system is controlled to be 10-20 ℃/min.
Preferably, in the step (4), the rf power of the rf power source is 100-.
And (5) stopping heating, turning off the radio frequency power supply when the temperature of the tube furnace system is reduced to 450 ℃, introducing argon through a gas inlet of the quartz tube to increase the system pressure to normal pressure after the tube furnace system is cooled to room temperature, opening the tube furnace system, taking out the graphite sleeve in the quartz tube, and collecting the Mg-C nano composite hydrogen storage material deposited in the graphite sleeve.
The preparation device and the preparation method of the Mg-C nano composite hydrogen storage material have the following beneficial effects:
1. the Mg and the C are effectively compounded uniformly, the Mg particles are reduced, the hydrogen absorption kinetics of the Mg can be effectively improved, and the product Mg-C nano composite hydrogen storage material has better performance in the fields of hydrogen storage and other energy storage.
2. The proportion of Mg and C in the Mg-C nano composite structure and the particle size of Mg can be flexibly controlled.
3. The preparation method of the Mg-C nano composite hydrogen storage material greatly reduces the temperature and the energy consumption.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for producing a Mg-C nanocomposite hydrogen storage material as a product in this example 1.
FIG. 2 is an X-ray diffraction pattern of the product Mg-C nanocomposite hydrogen storage material of example 1.
FIG. 3 is a scanning electron micrograph of the product Mg-C nanocomposite hydrogen storage material of example 1.
FIG. 4 is a TEM photograph of the Mg-C nanocomposite hydrogen storage material of the product obtained in example 1.
FIG. 5 is a high resolution TEM photograph of the Mg-C nanocomposite hydrogen storage material of the product of this example 1.
FIG. 6 shows the product Mg-C nanocomposite Hydrogen storage Material of example 1, which is converted to MgH after absorbing hydrogen2X-ray diffraction pattern of (a).
In the figure: 1. a quartz tube; 2. a tube furnace system; 3. an inductor coil; 4. a radio frequency power supply; 5. a graphite sleeve; 6. magnesium; 7. a product collection area; 8. a gas inlet; 9. and a gas outlet.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the technical field better understand the scheme of the present invention.
The invention discloses a preparation device and a preparation method of a Mg-C nano composite hydrogen storage material, which are used for preparing the Mg-C nano composite hydrogen storage material at a milder temperature, wherein in the mixed atmosphere of argon gas, hydrocarbon gas and hydrogen gas at low pressure, the air pressure is controlled to be less than 200Pa, magnesium 6 is thermally evaporated to generate magnesium vapor, simultaneously glow discharge is carried out to decompose the hydrocarbon gas to generate carbon, the thermal evaporation of the magnesium 6 and the plasma decomposition of the hydrocarbon gas are combined to obtain the Mg-C nano composite hydrogen storage material in one step, the particle size of the magnesium 6 can be controlled, and the hydrogen storage performance of the Mg-C nano composite hydrogen storage material is improved.
As shown in figure 1, a Mg-C nano composite hydrogen storage material preparation device comprises a tube furnace system 2, a quartz tube 1 is arranged in the tube furnace system 2, a gas inlet 8 for introducing a mixed gas of argon-hydrocarbon gas-hydrogen gas and a gas outlet 9 for introducing the mixed gas are arranged on the quartz tube 1, the gas inlet 8 side of the quartz tube 1 is the upstream of the quartz tube 1, the gas outlet 9 side of the quartz tube 1 is the downstream of the quartz tube 1, a mechanical pump is connected at the gas outlet 9 of the quartz tube 1, a valve is arranged between the gas outlet 9 of the quartz tube 1 and the mechanical pump and used for vacuumizing the quartz tube 1 or adjusting the pressure in the quartz tube 1 to be maintained in a required range, a graphite sleeve 5 is arranged in the quartz tube 1 and used for placing metal magnesium 6 in the graphite sleeve 5, the metal magnesium 6 can be magnesium blocks, magnesium grains, magnesium strips or magnesium powder and other different forms, an inductance coil 3 which is inductively coupled is sleeved outside one side of the quartz tube 1 close to the outlet, the number of turns of the inductance coil 3 is 1-10, the inductance coil 3 is connected with a radio frequency power supply 4, the radio frequency power supply 4 generates glow discharge inside the quartz tube 1 through the inductance coil 3, the glow of plasma can reach the central position of the quartz tube 1 where metal magnesium is placed, and a downstream product collecting area 7 is arranged between the position of the graphite sleeve 5 where the metal magnesium 6 is placed and the position where the inductance coil 3 is sleeved.
The preparation method of the Mg-C nano composite hydrogen storage material comprises the following steps:
1. flushing the quartz tube 1, adding raw material metal Mg, placing the raw material metal Mg in a graphite sleeve 5 of the quartz tube 1, vacuumizing the quartz tube 1 through a gas outlet 9 of the quartz tube 1 by using a mechanical pump, introducing argon through a gas inlet of the quartz tube 1, and flushing the quartz tube 1 for 2-3 times by using the argon;
2. the mixed gas is introduced into the quartz tube 1, the mixed gas of argon, hydrocarbon gas and hydrogen is introduced through the gas inlet of the quartz tube 1, and a valve between the quartz tube 1 and the mechanical pump is adjusted, so that the whole pressure of the tube furnace system 2 is maintained between 10 and 200Pa, preferably between 50 and 100 Pa. Wherein the hydrocarbon gas may be any gas containing only C and H, preferably CH4And C2H2. The volume percentage of argon in the mixed gas of argon-hydrocarbon gas-hydrogen is between 50% and 95%, and the preferred proportion is between 80% and 90%; the volume percentage of the hydrocarbon gas is between 1% and 50%, and the preferred proportion is between 2% and 10%; the hydrogen is present in a proportion of 0 to 20% by volume, preferably 0 to 5%.
3. Starting the tube furnace, heating the quartz tube 1 to a set temperature, controlling the temperature rise speed at 5-100 ℃/min, preferably 10-20 ℃/min, and reaching the set temperature, wherein the set temperature is 400-.
4. Starting a radio frequency power supply 4 to generate the Mg-C nano composite hydrogen storage material, starting the radio frequency power supply 4 when the set temperature is reached, wherein the radio frequency power supply 4 generates glow discharge inside the quartz tube 1 through an inductance coil 3, so that the glow of plasma can reach the central position of the metal magnesium 6 placed in the graphite sleeve 5, the radio frequency is 13.56MHz, the radio frequency power is 20-500W, and the preferred power is 100-150W, so that hydrocarbon gas in the mixed gas is decomposed to generate carbon. Mg vapor and hydrocarbon gas are mixed and enter a downstream product collecting area 7, the downstream temperature of the quartz tube 1 is lower than the center of the quartz tube 1 in the tube furnace, the magnesium vapor reaches the product collecting area 7 to be condensed, the preferable deposition temperature area at the product collecting area 7 is 400-500 ℃, meanwhile, the hydrocarbon gas is decomposed to generate carbon, the carbon and the condensed magnesium vapor directly form a nano compound to be deposited, and the uniform compounding of Mg and the carbon is effectively realized because the magnesium vapor and the hydrocarbon gas are very uniformly mixed in a gas phase, so that the Mg-C nano compound hydrogen storage material with a very uniform nano compound structure can be formed, the particle size of Mg is reduced, the hydrogen absorption kinetics of Mg in the Mg-C nano compound hydrogen storage material can be effectively improved, the Mg has better performance in the fields of hydrogen storage and other energy storage, and the reaction time is 20min-4h, the preferred time is 60-120 min.
5. Stopping heating, turning off the radio frequency power supply 4 when the temperature of the tube furnace is reduced to below 450 ℃, introducing argon gas through a gas inlet 8 of the quartz tube 1 to increase the system pressure to normal pressure after the tube furnace is cooled to room temperature, opening the tube furnace, taking out the graphite sleeve 5 in the quartz tube 1, and collecting the product Mg-C nano composite hydrogen storage material deposited in the graphite sleeve 5.
The preparation method of the Mg-C nano-composite hydrogen storage material can conveniently regulate and control the proportion of Mg and carbon and the particle size of Mg in the Mg-C nano-composite hydrogen storage material, because the Mg and the carbon are generated independently, the faster the metal magnesium is gasified, the higher the proportion of Mg in Mg-C is, so that the proportion of hydrocarbon gas in the mixed gas is increased, or the radio frequency power of the radio frequency power supply 4 is increased, and the content of carbon in Mg-C can be increased. Compared with other preparation methods such as high-temperature electric arc and the like, the preparation method of the Mg-C nano composite hydrogen storage material has the advantages that the temperature and the energy consumption are greatly reduced.
Example 1
The preparation of the Mg-C nano composite hydrogen storage material comprises the following steps:
1. placing a graphite sleeve 5 with the inner diameter of 2.5cm into a quartz tube 1 with the inner diameter of 3cm, flushing the quartz tube 1, placing a magnesium strip with the purity of 99% into the graphite sleeve 5 and the magnesium strip being 0.80g, cutting the magnesium strip into a rectangle with the length of 2cm and the width of 0.5cm, placing the quartz tube 1 into a tube furnace, enabling the position of the magnesium strip to be just positioned at the central position of the tube furnace, sleeving an induction coil 3 outside the quartz tube 1, arranging the induction coil 3 at the downstream of the quartz tube 1, vacuumizing the quartz tube 1 to 0.1Pa through a gas outlet 9 of the quartz tube 1 by using a mechanical pump, introducing argon gas to 1kPa through a gas inlet of the quartz tube 1, vacuumizing to 0.1Pa again, repeating for 3 times, flushing the quartz tube 1 for 3 times by using the argon gas, and removing oxygen and water vapor in the system;
2. mixed gas is introduced into the quartz tube 1, and Ar-C is introduced through a gas inlet of the quartz tube 12H2-H2Wherein the flow rate of Ar is 80cm in a standard state3/min，C2H2The flow rate of (2) is 12cm in a standard state3/min，H2The flow rate of (2) is 8cm in a standard state3Min, standard state 1 atmosphere and at 25 ℃, the valve between the quartz tube 1 and the mechanical pump is adjusted to maintain the overall pressure of the tube furnace system 2 between 80 Pa.
3. Starting the tube furnace, heating the quartz tube 1 to the set temperature of 650 ℃, controlling the temperature rise speed at 20 ℃/min, and generating Mg steam in the graphite sleeve 5.
4. Starting the radio frequency power supply 4 to generate the Mg-C nano composite hydrogen storage material, starting the radio frequency power supply 4 when the set temperature is 650 ℃, adjusting the radio frequency power to 130W, enabling the radio frequency power supply 4 to generate glow discharge in the quartz tube 1 through the inductance coil 3, enabling the glow of the plasma to reach the central position of the metal magnesium 6 placed in the graphite sleeve 5, and enabling the hydrocarbon gas in the mixed gas to be decomposed to generate carbon. Mg vapor and hydrocarbon gas are mixed and enter a downstream product collecting area 7, the downstream temperature of the quartz tube 1 is lower than the center of the quartz tube 1 in the tube furnace, magnesium vapor reaches the product collecting area 7 to be condensed, meanwhile, the hydrocarbon gas is decomposed to generate carbon, and the carbon and the condensed magnesium vapor directly form a nano compound to be deposited, and the reaction time is controlled to be 60 min.
5. Stopping heating, turning off the radio frequency power supply 4 when the temperature of the tube furnace is reduced to 450 ℃, introducing argon gas through a gas inlet 8 of the quartz tube 1 to increase the system pressure to 1 atmosphere at normal pressure after the tube furnace is cooled to room temperature, opening the tube furnace, taking out the graphite sleeve 5 in the quartz tube 1, and collecting the product Mg-C nano composite hydrogen storage material deposited in the graphite sleeve 5. And weighing the residual magnesium strips, wherein the residual magnesium strips are 0.22g, collecting products at the position 8-11cm away from the magnesium strip, wherein the appearance of the products is black loose powder, the corresponding deposition temperature is 480-520 ℃, and collecting 0.34g of the Mg-C nano composite hydrogen storage material.
The product Mg-C nano composite hydrogen storage material is subjected to X-ray diffraction analysis, as shown in figure 2, the result shows that the main product is metal magnesium and a small amount of MgH is contained2As a result, no diffraction peak was observed for carbon, indicating that carbon was amorphous. Elemental analysis showed 72.6% and 25.8% by mass of Mg and C, respectively, with the remaining masses being H and O. As shown in fig. 3 and 4, a scanning electron microscope and a transmission electron microscope show that the sample presents the appearance of a bent short nanotube, the diameter of the tube is about 100nm, as shown in fig. 5, a high-resolution transmission electron microscope can see the bent graphite lamellar structure and the lattice fringes of metal magnesium, which shows that the nanotube is a composite structure formed by Mg nanocrystalline and amorphous carbon, and the structural characterization shows that the Mg-C nano composite hydrogen storage material is obtained by the method.
The Mg-C nano composite hydrogen storage material obtained by heating under 4MPa of hydrogen can convert Mg in the Mg-C nano composite hydrogen storage material into MgH2As shown in fig. 6, no diffraction peak was observed for carbon, indicating that carbon is still amorphous carbon.
By changing parameters such as evaporation temperature of metal magnesium, components of mixed gas (particularly C and H ratio) and radio frequency power, Mg-C composite materials with different components can be obtained, the shapes of the Mg-C composite materials are also different, and the Mg and the amorphous carbon have crystalline compositions.
The inventive concept is explained in detail herein using specific examples, which are given only to aid in understanding the core concepts of the invention. It should be understood that any obvious modifications, equivalents and other improvements made by those skilled in the art without departing from the spirit of the present invention are included in the scope of the present invention.
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| CN102148368A (en) * | 2011-02-24 | 2011-08-10 | 宁波工程学院 | Preparation method of lithium ion battery anode composite material and special device thereof |
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