CN118026153A - Porous carbon material with directionally arranged nanopores and preparation method and application thereof - Google Patents
Porous carbon material with directionally arranged nanopores and preparation method and application thereof Download PDFInfo
- Publication number
- CN118026153A CN118026153A CN202410425460.2A CN202410425460A CN118026153A CN 118026153 A CN118026153 A CN 118026153A CN 202410425460 A CN202410425460 A CN 202410425460A CN 118026153 A CN118026153 A CN 118026153A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- carbon material
- pore
- nanopores
- metal nanowire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 44
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 7
- 239000002070 nanowire Substances 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 42
- 239000010426 asphalt Substances 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000006185 dispersion Substances 0.000 claims description 35
- 230000005291 magnetic effect Effects 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 28
- 238000003763 carbonization Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 19
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 230000005294 ferromagnetic effect Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000004939 coking Methods 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims 4
- 239000011295 pitch Substances 0.000 claims 2
- 239000011301 petroleum pitch Substances 0.000 claims 1
- 238000005019 vapor deposition process Methods 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000077 silane Inorganic materials 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 5
- 239000002210 silicon-based material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 13
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012761 high-performance material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000005292 diamagnetic effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a porous carbon material with directionally arranged nanopores, and a preparation method and application thereof, and belongs to the technical field of porous carbon material preparation. The porous carbon material prepared by the invention has a pore structure of a micropore and mesopore combined structure, the pore path length completely penetrates through the porous carbon particle body, and the micropores and mesopores are arranged in an oriented manner along the length direction of the pore path. Compared with the carbon material with random distribution of the conventional pores, the carbon material with the special structure provided by the invention is easier for silane gas to enter the pores when being used for further preparing silicon carbon materials by chemical vapor deposition, and is beneficial for the silane gas to be decomposed and deposited in the pores at high temperature. Meanwhile, the holes are arranged in an oriented manner along the length direction of the pore canal, and the pore canal completely penetrates through the porous carbon material body, so that the resistance of the silane gas diffusing in the material is smaller, the efficiency is higher, and the preparation time of the carbon-silicon material is obviously shortened.
Description
Technical Field
The invention belongs to the technical field of porous carbon material preparation, and particularly relates to a porous carbon material with directional arrangement of nano holes, and a preparation method and application thereof.
Background
The porous carbon material is widely applied to gas separation, water purification, heterogeneous catalytic carrier materials, high-performance thermal field materials and the like due to the unique surface characteristics and structures, and meanwhile, the porous carbon material gradually shows wide application prospects in the fields of high-performance materials for lithium ion batteries, high-performance materials for sodium ion batteries and other new energy materials. At present, research on a technical route of a silicon-carbon material for depositing nano-scale silicon particles by a chemical vapor deposition method by taking a porous carbon material as a carrier has increased or decreased heat, but the porous carbon material has the defects of poor controllability of a pore structure, poor uniformity and the like, so that the consistency of the silicon-carbon material is poor, and market popularization faces a plurality of challenges and use risks.
Through searching, related patent publication on porous carbon materials is disclosed, for example, the method adopted in the patent document with the Chinese patent publication number of CN106587003A is as follows: firstly synthesizing ordered mesoporous silica pore canal, then coating a carbon-containing material layer in the pore canal, achieving the structural strength required by the self-supporting of the carbon material pore canal through the repeated coating of the carbon material layer, finally removing silicon oxide through dehydrogenation at medium and high temperature (850 ℃) and HF soaking, and the like, so as to obtain a final product.
For another example, in the patent document of CN113929470a, natural wood is treated at high temperature to form a porous carbon material template, and the required components of the silicon nitride ceramic are subjected to carbothermal reduction nitridation reaction and high-temperature liquid phase sintering on the template to obtain anisotropic porous silicon nitride ceramic with directional nano-array arrangement, but the biomass porous carbon material has the outstanding problems of non-adjustable pore structure and size, poor source stability and the like.
For another example, in the patent document of CN114456603a, a heat conducting material is prepared by using magnetic field to induce and arrange carbon fibers, and is a non-porous material, which cannot be applied to the application field of preparing silicon-carbon materials by vapor deposition.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects that the existing porous carbon material has a pore structure and the size and the duty ratio of the porous carbon material are not adjustable, and provides a porous carbon material with aligned nano pores, which is mainly used as a porous carbon carrier for preparing a silicon carbon material by a vapor deposition method.
In addition, the invention also provides a preparation method and application of the porous carbon material, and the prepared porous carbon material with micropores and mesopores arranged in an oriented manner along the length direction of the pore canal can be effectively used in the application field of preparing the silicon carbon material by a vapor deposition method.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
In one aspect, the present invention provides a porous carbon material with aligned nanopores, and a photograph thereof is shown in fig. 1. The porous carbon material with the special structure provided by the invention is used for preparing the silicon carbon material by chemical vapor deposition, silane gas is easier to enter the pores, and the silane gas is decomposed at high temperature and deposited in the pores. Meanwhile, the holes are arranged in an oriented manner along the length direction of the pore canal, and the pore canal completely penetrates through the porous carbon material body, so that the resistance of the silane gas diffusing in the material is smaller, the efficiency is higher, and the preparation time of the carbon-silicon material is obviously shortened.
As a further improvement of the invention, the granularity of the porous carbon material is 5-15 um, the granularity range is controlled, the comprehensive performance of the porous carbon material is better, and when the granularity is too small, namely: when the granularity is less than 5um, the compaction performance of the porous carbon material is low, and the volume energy density of the silicon carbon material is low; meanwhile, the porous carbon material has a large specific surface area, and excessive Li + is consumed for SEI film formation, so that the initial coulombic efficiency is low. And when the particles are too large, i.e.: the granularity is larger than 15um, so that the diffusion distance of silane gas in the particle is increased and the deposition efficiency is low when the silicon-carbon material is prepared. Meanwhile, the particle size of the silicon-carbon material after silicon is deposited by a gas phase method is large, the diffusion distance of Li + in the particle is increased, the diffusion resistance of Li + is increased, the polarization is increased, and the rate capability of the material is reduced.
As a further improvement of the invention, the pore size distribution range of the porous carbon material is 0.5-10 nm, the micropore volume ratio is 60-90%, the mesopore volume ratio is 10-40%, wherein the pore size is 2-50 nm as mesopores, the pore size is less than 2nm (excluding 2 nm) as micropores, and the prepared silicon carbon material has higher strength by regulating and controlling the pore volume ratio of the micropores and mesopores, so that more silane gas is more hopefully deposited in the micropores when the silane gas is deposited, thereby effectively improving the stress resistance of the carbon silicon material. The mesopores are mainly used for providing a gas molecule cracking channel, micropores promote adsorption and cracking of gas molecules, and reasonable micropores and medium Kong Zhanbi can enable silane gas molecules to have higher diffusion rate and improve deposition efficiency on one hand and enable porous carbon particles to have more silane deposition active sites on the other hand.
Secondly, the invention provides a preparation method of the porous carbon material, which comprises the following steps:
step one, asphalt is dissolved in a dispersion liquid to form an asphalt solution;
Step two, adding the ferromagnetic or antimagnetic metal nanowires into the asphalt solution in the step one, and performing ultrasonic dispersion for 5-20 minutes to obtain a dispersion liquid;
Step three, the dispersion liquid obtained in the step two is placed in a non-magnetic container and placed in a magnetic field, and meanwhile the non-magnetic container is heated to 420-460 ℃, and the temperature is kept for 4-6 hours, so that the dispersion liquid is converted into solid from liquid;
fourthly, placing the solid obtained in the third step into a box-type carbonization furnace, heating to 850-950 ℃, and preserving heat for 3-5 hours to finish primary carbonization shaping of the solid;
Step five, crushing the primary carbide obtained in the step four to enable the particle size D50 of carbide particles to be 6-16 um;
step six, adding carbide particles obtained in the step five into acid liquor, performing ultrasonic dispersion for 8-12 minutes, then performing microwave heating for 2-4 hours, taking out solids, and washing with water until the pH value is 3.0-5.0;
And step seven, placing the solid washed in the step six in a box-type carbonization furnace, heating to 1300-1500 ℃, preserving heat for 5-10 hours, finishing secondary carbonization, cooling to normal temperature, and taking out to obtain the porous carbon material with the aligned nano holes.
According to the invention, through the optimization design of the preparation process, the porous carbon material meeting the conditions of the invention is prepared, the positions and the sizes of the holes of the porous carbon material can be effectively controlled, and meanwhile, the porous carbon material with the holes arranged in a directional manner along the length direction of the pore canal is produced.
In the second step, the diameter of the metal nanowire is 5-50 nm, and the diameter of the metal nanowire is controlled so as to conveniently regulate and control the pore diameter of the hole, thereby realizing the controllable production of the pore diameter of the porous carbon material, and specifically, the diameter of the added metal nanowire and the addition quantity thereof meet the following requirements in actual production:
The diameter of the metal nanowire is 5 nm-20 nm, the metal nanowire contains 5nm and does not contain 20nm, and the addition quantity accounts for 60% -90%;
the diameter of the metal nanowire is 20-50 nm, the metal nanowire comprises 20nm and 50nm, and the addition amount accounts for 10-40%.
The invention can design the sizes and the duty ratio of the micropores and the mesopores by regulating the diameters and the addition quantity of the metal nanowires, and can effectively regulate the structure of the porous carbon material so as to prepare the porous carbon material with controllable pore structure and size and better uniformity. During preparation, the two metal nanowires with the diameters are added, and the carbonization temperature setting of the porous carbon material is matched, so that the pores shrink to a certain extent in the carbonization process, and the porous carbon material meeting the pore structure requirement of the invention can be effectively ensured to be prepared.
Meanwhile, the length of the metal nanowire is controlled to be 40-100 mu m, the length is designed to be larger than the diameter of the crushed porous carbon particles, so that on one hand, through-type pore channels can be formed, and on the other hand, the metal nanowire is conveniently dissolved out by acid liquor.
In addition, the weight ratio of the metal nanowire to the asphalt solution is 1 (1-5), and the metal nanowire is controlled within the range, so that more holes are formed due to the fact that the metal nanowire is too much, the hole walls between adjacent holes are thinner due to the fact that the silicon deposition is not excessive, the particle strength is poor due to the fact that the holes are too much, the compaction density of the silicon-carbon material is reduced due to the fact that the holes are too much, the volume energy density of the material is reduced, and further application is difficult. And too few metal nanowires are introduced, so that fewer holes are formed, more active sites cannot be provided for chemical vapor deposition silane, the deposition amount of silicon is small, and the prepared silicon-carbon negative electrode material has the problem of low gram capacity.
In the second step, the metal nanowire is selected from iron nanowire or nickel nanowire.
As a further improvement of the invention, in the third step, the applied magnetic field strength is 0.01-10 Tesla, the quality of the prepared product can be effectively ensured through the optimized selection of the magnetic field strength, and when the magnetic field strength is controlled to be lower, the metal nanowires can not be aligned, so that the aligned pore structure can not be prepared. When the magnetic field intensity is controlled to be too high, the metal nano wires are excessively magnetized, and the effects of controlling the pore structure distribution and adjusting the pore size are difficult to achieve. In addition, the magnetic field is applied in the direction perpendicular or parallel to the surface of the solution in the non-magnetic container.
As a further improvement of the invention, in the first step, the asphalt is petroleum asphalt, the coking temperature is less than or equal to 450 ℃, the ratio of the asphalt to the dispersion liquid is 2 (1-2), and the asphalt and the metal nano wires can be uniformly mixed under the ratio. When the dispersion liquid is too much, the interaction between the dispersants is enhanced, asphalt particles cannot be effectively dispersed, and the particles are easily precipitated. When the dispersion liquid is too small, asphalt particles cannot be effectively dispersed, so that asphalt particles are agglomerated and cannot be uniformly dispersed. The dispersion liquid adopts a mixture of water, N-methyl pyrrolidone (NMP) and a surfactant, and the water, the N-methyl pyrrolidone (NMP) and the surfactant are mixed according to the mass ratio of 50:50:1.
In the sixth step, the volume ratio of carbide particles to acid liquor is 1 (1-3), wherein the acid liquor is mixed acid of two or more of dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid and phosphoric acid, and mixed metal nanowires are removed by adding acid liquor into the carbide particles, so that holes are formed conveniently.
Thirdly, the porous carbon material is prepared by using the porous carbon material prepared by the method for preparing the silicon carbon material by using a vapor deposition method.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, the metal nanowire is introduced into asphalt, and the cross section area, the length and the introduction amount of the metal nanowire are regulated and controlled, and the metal nanowire is matched with the magnetic field treatment, so that the porous carbon material with uniform pore structure and the pore path length of 'fully penetrating' the porous carbon particle body is prepared, and the pores are arranged in an oriented manner along the length direction of the pore path, and are used as carriers for producing silicon carbon materials.
2) When the porous carbon material is used as a carrier for preparing a negative electrode material, the defect of low efficiency of chemical vapor deposition silane existing in the prior conventional porous carbon material can be effectively solved, the directional arrangement and penetrating structure of the porous carbon material has high deposition efficiency, the number of required holes can be reduced under the condition of the same silicon deposition amount (the silicon deposition amount is corresponding to the capacity of the material), and the thickness of the hole walls of adjacent holes can be increased, so that the particle strength of the porous carbon material is increased, the expansion of the silicon material is effectively inhibited, and the cycle performance of the silicon carbon material is improved.
3) The preparation method of the porous carbon material provided by the invention is convenient for regulating and controlling the pore diameter and distribution of the pores, is simple to operate, has high production efficiency, saves energy and is high-efficiency, and suitable for industrial production.
Drawings
FIG. 1 is a photograph of a porous carbon material prepared in example 1 of the present invention;
FIG. 2 is a flow chart of the preparation of the porous carbon material of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments.
Example 1
As shown in fig. 2, the overall preparation flow of the porous carbon material of the present invention is shown, and the preparation method of the porous carbon material of the present embodiment specifically includes the following steps:
step one, asphalt is prepared from the following components in percentage by weight: dispersion = 2:1.5, asphalt is dissolved in the dispersion to form an asphalt solution;
Adding the ferromagnetic iron nanowire into the asphalt solution in the first step, and performing ultrasonic dispersion for 10 minutes to obtain a dispersion liquid, wherein the iron nanowire and the asphalt solution are added according to the weight ratio of 1:3, and the diameter of the iron nanowire and the addition amount of the iron nanowire are as follows: the adding quantity with the diameter of 15nm accounts for 70 percent, the adding quantity with the diameter of 40nm accounts for 30 percent, and the length of the iron nanowire is 60um;
Thirdly, placing the dispersion liquid obtained in the second step in a non-magnetic container, and placing the non-magnetic container in a magnetic field, wherein the strength of the applied magnetic field is 5 Tesla, the application direction of the magnetic field is vertical to the surface of the solution in the container, and meanwhile, heating the container to 450 ℃, and preserving the temperature for 5 hours, so that the dispersion liquid is converted into solid from liquid;
step four, placing the solid obtained in the step three in a box-type carbonization furnace, heating to 900 ℃, and preserving heat for 4 hours to finish primary carbonization shaping of the solid;
step five, crushing the primary carbide obtained in the step four to enable the particle size D50 of the carbide to be 5-8 um;
Step six, adding carbide particles obtained in the step five into the mixed acid liquid of the dilute hydrochloric acid and the dilute nitric acid, controlling the volume ratio of the carbide particles to the acid liquid to be 1:2, performing ultrasonic dispersion for 10 minutes, heating for 3 hours by microwaves, taking out solids, and washing with water to pH4.0;
And step seven, placing the solid washed in the step six in a box-type carbonization furnace, heating to 1400 ℃, preserving heat for 7 hours, completing secondary carbonization, cooling to normal temperature, and taking out to obtain the porous carbon material with the aligned nano holes, wherein the photo is shown in figure 1.
Comparative example 1
A porous carbon material of the comparative example was prepared as follows:
Uniformly mixing coal tar pitch, silicon dioxide nanospheres and KOH according to the mass ratio of 1:1:3, performing ultrasonic dispersion and magnetic stirring, and drying to obtain a mixture;
Carbonizing the mixture for 1h at 800 ℃ in inert gas atmosphere, and cooling the carbonized mixture to room temperature;
and thirdly, mixing the carbonized product with 20% hydrofluoric acid according to a mass ratio of 1:5, magnetically stirring for 4 hours, performing suction filtration, washing with distilled water to be neutral, and drying to obtain the porous carbon material.
Comparative example 2
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the diameter of the iron nanowire and the addition amount thereof are as follows: the addition amount of 2nm in diameter was 70% and the addition amount of 4nm in diameter was 30%.
Comparative example 3
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the diameter of the iron nanowire and the addition amount thereof are as follows: the addition amount of 55nm in diameter was 70% and the addition amount of 60nm in diameter was 30%.
Comparative example 4
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the length of the iron nanowire was 30um.
Comparative example 5
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the weight ratio of the metal nanowires to the asphalt solution is 1:0.5.
Comparative example 6
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the weight ratio of the metal nanowires to the asphalt solution is 1:6.
Comparative example 7
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the iron nanowires were directly added to the asphalt (not mixed with the dispersion) for ultrasonic dispersion.
Comparative example 8
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: the ratio of bitumen to dispersion was 2:0.5.
Comparative example 9
A porous carbon material of this comparative example, which was produced by the same method as in example 1, was different from example 1 in that: and fifthly, crushing the carbide, controlling the particle size of the carbide to be 20-30 um, adding the carbide into acid liquor, performing ultrasonic dispersion, microwave heating and water washing to pH4.0, and finally performing secondary carbonization to obtain the porous carbon material.
Example 2
The preparation method of the porous carbon material of the embodiment comprises the following steps:
Step one, asphalt is prepared from the following components in percentage by weight: mixing the dispersion liquid=1:1, and dissolving asphalt in the dispersion liquid to form an asphalt solution;
Adding the ferromagnetic iron nanowire into the asphalt solution in the first step, and performing ultrasonic dispersion for 5 minutes to obtain a dispersion liquid, wherein the iron nanowire and the asphalt solution are added according to a weight ratio of 1:1; the diameter of the iron nanowire and the addition amount thereof are as follows: the adding quantity with the diameter of 19nm accounts for 60 percent, the adding quantity with the diameter of 50nm accounts for 40 percent, and the length of the iron nanowire is 100um;
Thirdly, placing the dispersion liquid obtained in the second step in a non-magnetic container, and placing the non-magnetic container in a magnetic field, wherein the strength of the applied magnetic field is 10 Tesla, the application direction of the magnetic field is vertical to the surface of the solution in the container, and meanwhile, heating the container to 420 ℃, and preserving the temperature for 5 hours, so that the dispersion liquid is converted into solid from liquid;
fourthly, placing the solid obtained in the third step into a box-type carbonization furnace, heating to 850 ℃, and preserving heat for 5 hours to finish primary carbonization shaping of the solid;
Step five, crushing the primary carbide obtained in the step four to ensure that the particle size D50 of the carbide is 12-16 um;
Step six, adding carbide particles obtained in the step five into the mixed acid liquid of the dilute hydrochloric acid and the dilute sulfuric acid, controlling the volume ratio of the carbide particles to the acid liquid to be 1:1, performing ultrasonic dispersion for 8 minutes, heating by microwaves for 2 hours, taking out solids, and washing by water to pH3.0;
And step seven, placing the solid washed in the step six in a box-type carbonization furnace, heating to 1500 ℃, preserving heat for 5 hours, finishing secondary carbonization, cooling to normal temperature, and taking out to obtain the porous carbon material with the directional arrangement of the nanopores.
Example 3
The preparation method of the porous carbon material of the embodiment comprises the following steps:
Step one, asphalt is prepared from the following components in percentage by weight: dispersion = 2:1.3 mixing, asphalt is dissolved in the dispersion to form an asphalt solution;
Adding the ferromagnetic nickel nanowires into the asphalt solution in the first step, and performing ultrasonic dispersion for 15 minutes to obtain a dispersion liquid, wherein the nickel nanowires and the asphalt solution are added according to a weight ratio of 1:1; the diameter of the nickel nanowire and the addition amount thereof are as follows: the addition quantity with the diameter of 10nm accounts for 90 percent, the addition quantity with the diameter of 50nm accounts for 10 percent, and the length of the nickel nanowire is 40um;
Thirdly, placing the dispersion liquid obtained in the second step in a non-magnetic container, and placing the non-magnetic container in a magnetic field, wherein the strength of the applied magnetic field is 3 Tesla, the application direction of the magnetic field is vertical to the surface of the solution in the container, and meanwhile, heating the container to 460 ℃, and preserving the temperature for 4 hours, so that the dispersion liquid is converted into solid from liquid;
step four, placing the solid obtained in the step three in a box-type carbonization furnace, heating to 950 ℃, and preserving heat for 4 hours to finish primary carbonization shaping of the solid;
Step five, crushing the primary carbide obtained in the step four to ensure that the particle size D50 of carbide particles is 10-15 um;
Step six, adding carbide particles obtained in the step five into mixed acid liquid of phosphoric acid and dilute nitric acid, controlling the volume ratio of the carbide particles to the acid liquid to be 1:3, performing ultrasonic dispersion for 12 minutes, heating by microwaves for 4 hours, taking out solids, and washing by water to pH5.0;
And step seven, placing the solid washed in the step six in a box-type carbonization furnace, heating to 1300 ℃, preserving heat for 10 hours, finishing secondary carbonization, cooling to normal temperature, and taking out to obtain the porous carbon material with the directional arrangement of the nanopores.
Example 4
The preparation method of the porous carbon material of the embodiment comprises the following steps:
Step one, asphalt is prepared from the following components in percentage by weight: mixing the dispersion liquid=2:1, and dissolving asphalt in the dispersion liquid to form an asphalt solution;
Adding the diamagnetic nickel nanowires into the asphalt solution in the first step, and performing ultrasonic dispersion for 20 minutes to obtain a dispersion liquid, wherein the nickel nanowires and the asphalt solution are added according to a weight ratio of 1:5; the diameter of the nickel nanowire and the addition amount thereof are as follows: the addition quantity with the diameter of 5nm accounts for 80 percent, the addition quantity with the diameter of 40nm accounts for 20 percent, and the length of the nickel nanowire is 60um;
Thirdly, placing the dispersion liquid obtained in the second step in a non-magnetic container, placing the non-magnetic container in a magnetic field, wherein the strength of the applied magnetic field is 0.01 tesla, the application direction of the magnetic field is vertical to the surface of the solution in the container, and simultaneously heating the container to 450 ℃, and preserving the heat for 6 hours, so that the dispersion liquid is converted into solid from liquid;
step four, placing the solid obtained in the step three in a box-type carbonization furnace, heating to 900 ℃, and preserving heat for 3 hours to finish primary carbonization shaping of the solid;
Step five, crushing the primary carbide obtained in the step four to enable the particle size D50 of the carbide to be 6-10 um;
step six, adding carbide particles obtained in the step five into the mixed acid liquid of the dilute hydrochloric acid and the phosphoric acid, controlling the volume ratio of the carbide particles to the acid liquid to be 1:2, performing ultrasonic dispersion for 10 minutes, heating by microwaves for 3 hours, taking out solids, and washing by water to pH4.0;
And step seven, placing the solid washed in the step six in a box-type carbonization furnace, heating to 1500 ℃, preserving heat for 5 hours, finishing secondary carbonization, cooling to normal temperature, and taking out to obtain the porous carbon material with the directional arrangement of the nanopores.
The porous carbon materials prepared in the above examples and comparative examples were subjected to performance tests, and specific test items are as follows:
1. specific surface area, pore volume and pore size distribution detection
The porous carbon material was taken and vacuum degassed in a sample tube at 150 ℃ for 4h. And testing the adsorption quantity of the porous carbon material to nitrogen under different pressures by using a microphone ASAP2460 full-automatic specific surface area analyzer until the adsorbate and the adsorption gas reach balance. At constant temperature, the relation between the gas adsorption capacity and the gas balance relative pressure is the adsorption isotherm. And the specific surface area, pore volume and pore diameter distribution of the sample are equivalently obtained by measuring the equilibrium adsorption quantity and utilizing a theoretical model.
2. Porous carbon material particle strength test
The particle strength of the porous carbon material was tested by nanoindenter Hysicron TI 950, reference standard JB/T12721-2016. Dispersing a porous carbon material in an epoxy resin curing agent, polishing by a polishing machine, applying pressure to a plurality of porous carbon particles by using a nano probe, monitoring the indentation depth of the surfaces of the particles, and calculating to obtain the strength of single particles.
The results of the above detection are shown in Table 1, respectively.
TABLE 1 detection results of porous carbon materials obtained in examples and comparative examples of the present invention
The porous carbon materials prepared in examples 1 to 4 and comparative examples 1 to 9 were used for vapor deposition to prepare silicon carbon materials, and the relevant process parameters and deposition times are shown in table 2:
TABLE 2 deposition results of silicon carbon materials prepared using the porous carbon materials obtained in the examples and comparative examples of the present invention
More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments that have been modified, omitted, e.g., combined, adapted, and/or substituted between the various embodiments, as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, definitions, will control. Where a rate, pressure, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range bounded by a list of upper and lower preferred values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1-50 should be understood to include any number, combination of numbers, or subranges selected from 1、2、3、4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19、20、21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38、39、40、41、42、43、44、45、46、47、48、49 or 50, and all fractional values between the integers described above, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1-50 can include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
Claims (10)
1. The preparation method of the porous carbon material with the directional arrangement of the nano holes is characterized by comprising the following steps of:
step one, asphalt is dissolved in a dispersion liquid to form an asphalt solution;
Step two, adding the ferromagnetic or antimagnetic metal nanowires into the asphalt solution in the step one, and performing ultrasonic dispersion for 5-20 minutes to obtain a dispersion liquid;
Step three, the dispersion liquid obtained in the step two is placed in a non-magnetic container and placed in a magnetic field, and meanwhile the container is heated to 420-460 ℃, and the temperature is kept for 4-6 hours, so that the dispersion liquid is converted into solid from liquid;
fourthly, placing the solid obtained in the third step in a carbonization furnace, heating to 850-950 ℃, and preserving heat for 3-5 hours to finish primary carbonization shaping of the solid;
Step five, crushing the primary carbide obtained in the step four to enable the particle size D50 of carbide particles to be 6-16 um;
step six, adding carbide particles obtained in the step five into acid liquor, performing ultrasonic dispersion for 8-12 minutes, then performing microwave heating for 2-4 hours, taking out solids, and washing with water until the pH value is 3.0-5.0;
And step seven, placing the solid washed in the step six in a carbonization furnace, heating to 1300-1500 ℃, preserving heat for 5-10 hours, finishing secondary carbonization, cooling to normal temperature, and taking out to obtain the porous carbon material with the aligned nano holes.
2. The method for preparing the porous carbon material with the directional arrangement of the nanopores, which is characterized in that in the second step, the diameter of the metal nanowire is 5-50 nm, the length of the metal nanowire is 40-100 um, the weight ratio of the metal nanowire to the asphalt solution is 1 (1-5), and the diameter of the added metal nanowire and the addition amount thereof meet the following conditions:
The diameter of the metal nanowire is 5 nm-20 nm, the metal nanowire contains 5nm and does not contain 20nm, and the addition quantity accounts for 60% -90%;
the diameter of the metal nanowire is 20-50 nm, the metal nanowire comprises 20nm and 50nm, and the addition amount accounts for 10-40%.
3. The method for preparing a porous carbon material with aligned nanopores according to claim 2, wherein in the second step, the metal nanowires are iron nanowires or nickel nanowires.
4. The method for preparing a porous carbon material with aligned nanopores according to claim 1, wherein in the third step, the applied magnetic field has a strength of 0.01 to 10 tesla, and the applied magnetic field is perpendicular or parallel to the surface of the solution in the nonmagnetic container.
5. The method for preparing a porous carbon material with aligned nanopores according to claim 1, wherein in the first step, the pitch is petroleum pitch, the coking temperature is less than or equal to 450 ℃, and the mass ratio of pitch to dispersion is 2 (1-2).
6. The method for preparing the porous carbon material with the directional arrangement of the nanopores, which is disclosed in claim 1, is characterized in that in the sixth step, the volume ratio of carbide particles to acid liquor is 1 (1-3), and the acid liquor is mixed acid of two or more of dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid and phosphoric acid.
7. The porous carbon nanomaterial with directional arrangement of nanopores, characterized in that the porous carbon nanomaterial prepared by the method of any one of claims 1 to 6 has a pore structure of a combined structure of micropores and mesopores, the pore path length of the porous carbon nanomaterial is 'fully penetrated' through the porous carbon particle body, and each micropore and each mesopore are directional arranged along the length direction of the pore path.
8. The porous carbon material with aligned nanopores according to claim 7, wherein the porous carbon material has a particle size of 5-15 um.
9. The porous carbon material with directional arrangement of nano holes according to claim 7, wherein the pore size distribution range is 0.5-10 nm, the micropore volume ratio is 60-90%, and the mesopore volume ratio is 10% -40%.
10. Use of a porous carbon nanomaterial with aligned nanopores, prepared by the method of any one of claims 1-6, in a vapor deposition process for preparing a silicon carbon material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410425460.2A CN118026153A (en) | 2024-04-10 | 2024-04-10 | Porous carbon material with directionally arranged nanopores and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410425460.2A CN118026153A (en) | 2024-04-10 | 2024-04-10 | Porous carbon material with directionally arranged nanopores and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118026153A true CN118026153A (en) | 2024-05-14 |
Family
ID=90995294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410425460.2A Pending CN118026153A (en) | 2024-04-10 | 2024-04-10 | Porous carbon material with directionally arranged nanopores and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118026153A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11116352A (en) * | 1997-10-15 | 1999-04-27 | Asahi Glass Co Ltd | Production of porous ceramic |
| US20130236816A1 (en) * | 2010-11-16 | 2013-09-12 | Korea Institute Of Energy Research | Method for producing porous carbon materials having mesopores and catalyst support for a fuel cell produced using same |
| US20160096334A1 (en) * | 2014-10-03 | 2016-04-07 | Massachusetts Institute Of Technology | Pore orientation using magnetic fields |
| CN111732102A (en) * | 2019-12-04 | 2020-10-02 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon material by ruthenium particle assisted etching in strong alkaline environment |
-
2024
- 2024-04-10 CN CN202410425460.2A patent/CN118026153A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11116352A (en) * | 1997-10-15 | 1999-04-27 | Asahi Glass Co Ltd | Production of porous ceramic |
| US20130236816A1 (en) * | 2010-11-16 | 2013-09-12 | Korea Institute Of Energy Research | Method for producing porous carbon materials having mesopores and catalyst support for a fuel cell produced using same |
| US20160096334A1 (en) * | 2014-10-03 | 2016-04-07 | Massachusetts Institute Of Technology | Pore orientation using magnetic fields |
| CN111732102A (en) * | 2019-12-04 | 2020-10-02 | 中国科学院上海硅酸盐研究所 | Method for preparing porous carbon material by ruthenium particle assisted etching in strong alkaline environment |
Non-Patent Citations (1)
| Title |
|---|
| WEN FUWANG: "Synergistic effect of nitrogen and oxygen dopants in 3D hierarchical porous carbon cathodes for ultra-fast zinc ion hybrid supercapacitors", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, 31 December 2023 (2023-12-31), pages 1029 - 1039 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Co-gelation synthesis of porous graphitic carbons with high surface area and their applications | |
| CN107265433A (en) | Three-dimensional porous nitrating carbon material and its preparation method and application | |
| WO2019095602A1 (en) | Method for preparing three-dimensional graphene fiber by means of thermal chemical vapor deposition, and use thereof | |
| CN103924172B (en) | A kind of preparation method of reinforced aluminum matrix composites | |
| CN107579214A (en) | A kind of method, its product and application that Si-C composite material is prepared using silicate glass as raw material | |
| CN108083261A (en) | Three-dimensional porous carbon material, three-dimensional porous nitrating carbon material, its preparation method and application | |
| Wang et al. | Dual template method to prepare hierarchical porous carbon nanofibers for high-power supercapacitors | |
| Zhao et al. | Facile synthesis of hierarchically porous carbons and their application as a catalyst support for methanol oxidation | |
| CN110902680A (en) | Method for preparing mesoporous carbon material by organic potassium catalytic activation of sodium lignosulfonate | |
| Wang et al. | Highly hydrophilic carbon dots' decoration on NiCo2O4 nanowires for greatly increased electric conductivity, supercapacitance, and energy density | |
| Ying et al. | Simple synthesis of semi-graphitized ordered mesoporous carbons with tunable pore sizes | |
| CN110451465B (en) | Sea urchin-shaped boron nitride nanosphere-nanotube hierarchical structure and preparation method thereof | |
| KR20210128176A (en) | Method for Preparing Graphene-Carbon Nanotube Composite | |
| CN118026153A (en) | Porous carbon material with directionally arranged nanopores and preparation method and application thereof | |
| Sun et al. | Nanowires Framework Supported Porous Lotus‐Carbon Anode Boosts Lithium‐Ion and Sodium‐Ion Batteries | |
| Zhu et al. | Improved thermal stability of melamine resin spheres and electrochemical properties of their carbon derivatives induced by F127 | |
| CN113066996B (en) | PEM fuel cell, gas diffusion layer porous carbon paper and preparation method thereof | |
| CN115513432A (en) | Silicon-carbon composite material, preparation method thereof, negative plate and lithium secondary battery | |
| CN112047322B (en) | Modified carbon microtube carbonized by silver willow and preparation method and application thereof | |
| CN108630942B (en) | Nitrogen-doped carbon foam negative electrode material and preparation method and application thereof | |
| CN110127660B (en) | Method for preparing porous carbon nanomaterial by microwaves | |
| CN113697807A (en) | Method for preparing capacitance carbon and circularly regenerating template by using chloride as template | |
| CN112919459A (en) | Method for preparing three-dimensional ordered microporous carbon at low temperature on large scale | |
| Guo et al. | Controllable synthesis of bowl-shaped porous carbon materials through didodecyldimethylammonium bromide for high performance supercapacitors | |
| Liao et al. | Porous hard carbon microtubes from renewable cotton as high-performance anode material for lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |