CN117819548A - Carbon material with parallel slit holes and preparation method and application thereof - Google Patents
Carbon material with parallel slit holes and preparation method and application thereof Download PDFInfo
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- CN117819548A CN117819548A CN202410233855.2A CN202410233855A CN117819548A CN 117819548 A CN117819548 A CN 117819548A CN 202410233855 A CN202410233855 A CN 202410233855A CN 117819548 A CN117819548 A CN 117819548A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000007833 carbon precursor Substances 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000002028 Biomass Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 8
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- 230000003213 activating effect Effects 0.000 claims abstract description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
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- 238000010438 heat treatment Methods 0.000 claims description 20
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- 238000001816 cooling Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 241000219000 Populus Species 0.000 claims description 12
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 5
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 3
- 241000018646 Pinus brutia Species 0.000 claims description 3
- 235000011613 Pinus brutia Nutrition 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 description 36
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 34
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- 239000003792 electrolyte Substances 0.000 description 7
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- 239000002006 petroleum coke Substances 0.000 description 7
- 239000006183 anode active material Substances 0.000 description 6
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- 239000013081 microcrystal Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 240000006394 Sorghum bicolor Species 0.000 description 1
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- 239000002149 hierarchical pore Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon material with parallel slit holes, and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, carbonizing a biomass precursor with lignin content higher than 30% at a preset temperature to form a carbon precursor; step 2, dry-mixing a carbon precursor and solid alkali in proportion, wherein the mass ratio of the solid alkali to the carbon precursor is more than 0.4 and less than or equal to 1, then activating and pore-forming under the protection of protective gas at a preset temperature, and pickling and drying after the reaction is finished to obtain porous carbon; and 3, utilizing chemical vapor deposition to shrink the pore openings of the porous carbon, and finally obtaining the carbon material with parallel slit pores. The carbon material with parallel slit holes has higher average working potential of a platform and good safety performance and power characteristics.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a carbon material with parallel slit holes, and a preparation method and application thereof.
Background
When the carbonaceous anode material is used as the anode of a sodium ion battery, the potential of a platform is too low and is very close to the potential of 0V, and 0V is the potential of sodium metal precipitation, so that under the condition of high current density or low temperature, the low potential platform of hard carbon can reach 0V very rapidly due to the increase of polarization, thus sodium metal precipitation is caused, the membrane of the battery is easy to be pierced by sodium metal, and the safety problem of serious short circuit and fire is caused.
In the prior art, in order to improve the average working potential of a hard carbon low potential platform, the safety performance and the power characteristic are improved, and the following two modes are probably available:
1. the number of hard carbon holes is increased, surface defects are enriched, the capacity of a slope section is increased, the capacity of a part of platforms is abandoned, the safety can be improved, but the voltage window is reduced, and the energy density of the sodium ion battery is seriously reduced;
2. in the preparation process of the material, molecules and ions with certain sizes are introduced into the layered stacked material, the interlayer spacing of the material is widened, the ion transmission capacity in the material is improved, the overall overpotential of the material is reduced, and the platform voltage is optimized. Its advantages are simple process, high cost and low stability of material structure.
Disclosure of Invention
The invention aims to provide a carbon material with parallel slit holes, which aims at the problem that the potential of a platform is too low when a carbon-containing anode material in the prior art is used as a sodium ion battery anode.
It is another object of the present invention to provide a method for preparing the carbon material.
It is another object of the present invention to provide the use of said carbon material in a negative electrode of a battery.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a method for preparing a carbon material having parallel slit holes, comprising the steps of:
step 1, carbonizing a biomass precursor with lignin content higher than 30% at a preset temperature to form a carbon precursor;
step 2, dry-mixing the carbon precursor obtained in the step 1 with solid alkali in proportion, wherein the mass ratio of the solid alkali to the carbon precursor is more than 0.4 and less than or equal to 1, then activating and pore-forming under the protection of protective gas at a preset temperature, and pickling and drying after the reaction is finished to obtain porous carbon;
and 3, shrinking the pore opening of the porous carbon obtained in the step 2 by utilizing chemical vapor deposition to finally obtain the carbon material with parallel slit pores.
In the above technical scheme, the preset temperature in the step 1 is 400-600 ℃, when the temperature is too high, the biomass precursor is excessively graphitized to form long Cheng Danmo microcrystals, the smaller interlayer spacing causes sodium compounds or potassium compounds with NaOH or KOH in the activation process of the step 2, the microcrystals are not easy to be subjected to intercalation etching, the difficulty of pore forming is increased, when the temperature is too low, a large number of polymers in the microcrystals are not depolymerized and condensed yet, and a large number of tar is generated in the activation process to influence pore forming.
In the above technical solution, the carbonization time in the step 1 is 60-120min, and the carbonization is performed under the protection of a protective gas, and preferably, the protective gas is nitrogen or argon.
In the above technical scheme, the particle size of the biomass precursor in the step 1 is 10-20 meshes, the contact between the solid alkali and the carbon precursor is uneven due to the overlarge particle size, and the structural collapse in the activation process is caused due to the overlarge particle size.
In the above technical scheme, the biomass precursor in the step 1 is poplar, pine, chaff, plant straw or walnut shell, and the solid alkali is NaOH or KOH.
In the above technical scheme, the predetermined temperature in the step 2 is 800-900 ℃, when the temperature is too high, the etching degree is severe, wedge-shaped holes or cylindrical holes with the hole web diameter larger than 1nm are formed, when the temperature is too low, the etching degree is low, the number of parallel slit holes is not abundant, and the platform capacity is small.
In the above technical scheme, the time for activating and pore-forming in the step 2 is 120-240min, too long time can lead to high activation degree, wedge-shaped pores or cylindrical pores with the pore web diameter larger than 1nm are formed, and too short time can lead to insufficient activation, and the number of the pores is small.
In the technical scheme, in the step 2, the acid liquor with the hydrogen ion concentration of 0.5-2.0mol/L is used for washing, the drying temperature is 100-120 ℃, and the drying time is 24-48h.
In the above technical solution, in the step 3, the specific steps of chemical vapor deposition are as follows: and (3) placing the porous carbon obtained in the step (2) into a tube furnace, introducing 10-100ml/min of protective gas, then heating to 700-1100 ℃, introducing 10-100ml/min of carbon source gas, closing the carbon source gas after the deposition reaction is finished, and cooling to room temperature.
In the above technical scheme, the carbon source gas is methane, ethane, propane, ethylene, acetylene, benzene, toluene or xylene.
In the above technical solution, the shielding gas is nitrogen or argon.
In the technical scheme, the time of the deposition reaction is 60-1440min.
In the technical scheme, the heating and cooling speeds are 5-10 ℃/min.
In another aspect of the invention, the carbon material with parallel slit holes prepared by the preparation method is characterized in that the diameter of the hole web of the parallel slit holes is smaller than 1nm, the diameter of the orifice of the parallel slit holes is smaller than 0.364nm, and the specific surface area of the carbon material with parallel slit holes obtained by nitrogen adsorption and desorption test cannot be measured, which indicates that the diameter of the orifice of the carbon material with parallel slit holes is smaller than 0.364nm of the diameter of nitrogen molecules.
In another aspect of the invention, the use of the carbon material in a negative electrode of a battery is also included.
In another aspect of the invention, the battery anode comprises an anode active material, a conductive agent and a binder, wherein the anode active material is the carbon material with parallel slit holes; the conductive agent is SUPER-P, KS-6, conductive graphite, carbon nanotube, graphene, carbon fiber VGCF, acetylene black or ketjen black; the adhesive is PVDF, CMC, SBR, PTFE, SA, PAA or PAN.
In another aspect of the invention, a battery is also included, comprising a positive electrode, a negative electrode of the battery, and an electrolyte;
the active material of the positive electrode is transition metal layered oxide, sodium polyanion compound, prussian blue or Prussian white.
The electrolyte comprises an organic solvent and sodium salt, wherein the organic solvent comprises EC, PC, DMC, DEC, EMC, EA, FEC or VC; the sodium salt comprises NaClO 4 、NaPF 6 、NaBF 4 NaFSI or naffsi.
Compared with the prior art, the invention has the beneficial effects that:
1. the precursor of the invention selects a biomass precursor with lignin content higher than 30%, and as the biomass precursor is a soft carbon precursor, the size of the pre-carbonized microcrystal is larger, and carbon layers in the microcrystal are orderly stacked in parallel, thereby providing good conditions for forming parallel slit holes with size smaller than 1nm by solid alkali intercalation etching;
2. the mass ratio of the solid alkali to the carbon precursor is controlled to be more than 0.4 and less than or equal to 1, so that a large number of parallel slit holes below 1nm can be formed, if the ratio is increased, the hole shape can be changed, the holes are converted into wedge-shaped holes or cylindrical holes with increased hole wall curvature, the holes are not beneficial to the potential of a lifting platform, and if the ratio is too small, the parallel slit holes are too few, and the capacity of the carbon material is too low;
3. the carbon material with parallel slit holes obtained by the preparation method has higher average working potential of a platform, specifically 65-72 mV, and has good safety performance and power characteristics.
Drawings
Fig. 1 is a TEM of the porous carbon obtained in example 1.
Fig. 2 is a TEM of the carbon material with parallel slit holes obtained in example 1.
Fig. 3 is a first-turn charge-discharge curve of the sodium-ion battery of example 1.
Fig. 4 is an enlarged first-round charge-discharge curve (the potential at the midpoint of plateau capacity is taken as the average operating potential) of the sodium-ion battery of example 1.
Fig. 5 is a graph of the rate performance of the sodium ion battery of example 1.
Fig. 6 is a TEM of the porous carbon material D obtained in comparative example 1.
Fig. 7 is a first-turn charge-discharge curve of the sodium-ion battery of comparative example 1.
Fig. 8 is an enlarged first-round charge-discharge curve (the potential at the midpoint of plateau capacity is taken as the average operating potential) of the sodium-ion battery of comparative example 1.
Fig. 9 is a graph of the rate performance of the sodium ion battery of comparative example 1.
Fig. 10 is a TEM of the porous carbon material D obtained in comparative example 2.
Fig. 11 is a first-turn charge-discharge curve of the sodium-ion battery of comparative example 2.
Fig. 12 is an enlarged first-turn charge-discharge curve (the potential at the midpoint of plateau capacity is taken as the average operating potential) of the sodium-ion battery of comparative example 2.
Fig. 13 is a graph of the rate performance of the sodium ion battery of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A carbon material having parallel slit holes, prepared by the method of:
step 1, crushing poplar to 10-20 meshes, putting the crushed poplar into a tube furnace, and carbonizing the poplar in a nitrogen atmosphere at 400 ℃ for 60min to obtain a carbon precursor;
step 2, the mass ratio of the carbon precursor obtained in the step 1 to NaOH is 1:1, mixing to obtain a mixture A, placing the mixture A in a tube furnace protected by nitrogen atmosphere, introducing nitrogen at a flow rate of 100ml/min, heating to 800 ℃ at a heating rate of 5 ℃/min and maintaining for 3 hours, then performing programmed cooling at a cooling rate of 5 ℃/min to obtain a mixture B, immersing a product cooled to a temperature close to room temperature in an acid solution with a hydrogen ion concentration of 1mol/L for 5 times, washing for 30 minutes each time, drying the obtained product at a temperature of 105 ℃ under normal pressure, and recording as porous carbon;
and 3, placing the porous carbon in a tubular furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the condition of continuously introducing nitrogen with a flow rate of 100ml/min, introducing mixed gas of carbon source gas and nitrogen with a mass ratio of 1:2 into the furnace after the furnace temperature is stable for 60min, and performing program cooling at a cooling rate of 10 ℃/min after introducing the mixed gas for 120min to obtain the carbon material with parallel slit holes (the hole web diameter is smaller than 1 nm).
The TEM of the porous carbon obtained in step 2 of this example is shown in fig. 1, and it can be seen that the graphite crystallites in the porous carbon are all stacked in a flat shape, and the gaps between the crystallites are parallel slit holes smaller than 1 nm.
The TEM of the carbon material with parallel slit holes obtained in step 3 of this embodiment is shown in fig. 2, and the microstructure before and after the hole shrinkage is not significantly changed, the hole web diameter of the parallel slit holes is smaller than 1nm, the hole internal structure is not affected by the hole shrinkage, and the hole web diameter remains unchanged.
The carbon material with parallel slit holes obtained by the embodiment is used for assembling a sodium ion battery, and the preparation process is as follows:
carbon material with parallel slit holes is used as anode active material, vinylidene fluoride (PVDF) is used as binder, and acetylene black is used as conductive agent according to the mass ratio of 90:5:5Uniformly mixing the materials in NMP (N-methyl pyrrolidone) solvent, coating the materials into an electrode film, drying the electrode film in a vacuum drying oven at 120 ℃ for 12 hours, and rolling and blanking the electrode film to obtain a negative electrode plate; adopts a metal sodium sheet as a counter electrode, and the electrolyte is 1M NaClO 4 in diglyme=1:1 is electrolyte, the negative electrode plate is assembled into a 2032 button battery in a glove box, and the electrochemical performance of the button battery is tested.
The first charge-discharge curve of the sodium ion battery provided in example 1 is shown in fig. 3, and shows a reversible specific capacity (based on the mass of the anode active material) of 470mAh/g and a first coulombic efficiency of 87% at a current density of 50 mA/g.
The enlarged first-turn charge-discharge curve of the sodium ion battery provided in example 1 is shown in fig. 4, and it can be seen from the graph that the average operating potential of the platform section is high, at 70mV.
The rate performance graph of the sodium ion battery provided in example 1 is shown in fig. 5, and it can be seen that the material has excellent power characteristics, and the capacity retention rate at 4C is still 70%.
In addition, the biomass precursor in the embodiment is replaced by pine, chaff, sorghum straw, corn straw or walnut shell, and the sodium ion battery is assembled, so that the similar platform average working potential, rate performance, power characteristics and capacity are shown.
Example 2
Except that the mass ratio of NaOH to carbon precursor in the step 2 is changed to 0.8:1, the rest conditions are identical to those in the example 1, the specific capacity of the sodium ion battery 0.1C obtained in the example is 443mAh/g, the initial coulomb efficiency is 88%, the average platform potential is 72mV, and the capacity retention rate is 75% at 4C.
Example 3
Except that the temperature of activation pore-forming in the step 2 was changed to 900 ℃, the conditions were the same as in the example 1, the specific capacity of the sodium ion battery 0.1C was 460mAh/g, the initial coulomb efficiency was 85%, the average plateau potential was 65mV, and the capacity retention rate at 4C was still 70%.
Example 4
Except that the pre-carbonization temperature in the step 1 is changed to 600 ℃, the conditions are consistent with those in the example 1, the specific capacity of the sodium ion battery 0.1C is 452mAh/g, the initial coulombic efficiency is 87%, the average platform potential is 68mV, and the capacity retention rate is 72% at 4C.
Example 5
Except that the time for activating pore-forming in the step 2 was changed to 240min, the other conditions were the same as in example 1, the specific capacity of the sodium ion battery 0.1C was 475mAh/g, the initial coulombic efficiency was 87%, the average plateau potential was 68mV, and the capacity retention rate at 4C was still 70%.
Example 6
Except that the chemical vapor deposition temperature in step 3 was changed to 700 ℃, the conditions were the same as in example 1, the specific capacity of the sodium ion battery 0.1C was 450mAh/g, the initial coulomb efficiency was 86%, the average plateau potential was 70mV, and the capacity retention rate at 4C was 68%.
Example 7
Except that the chemical vapor deposition temperature in step 3 was changed to 1100 ℃, the conditions were the same as in example 1, the specific capacity of the sodium ion battery 0.1C was 463mAh/g, the initial coulomb efficiency was 88%, the average plateau potential was 70mV, and the capacity retention rate at 4C was still 72%.
Comparative example 1
Compared with example 1, the comparative example replaces poplar with petroleum coke, and the rest parameter conditions are consistent with example 1 by taking petroleum coke as a precursor.
A method for preparing a porous carbon material, comprising the steps of:
step 1, crushing petroleum coke to 10-20 meshes, putting the crushed petroleum coke into a tube furnace, and carbonizing the crushed petroleum coke in a nitrogen atmosphere at 400 ℃ for 60min to obtain a petroleum coke-based carbon precursor;
step 2, mixing the petroleum coke-based carbon precursor obtained in the step 1 with alkali (NaOH) according to the mass ratio of 1:1, mixing to obtain a mixture A; placing the mixture A in a tube furnace protected by nitrogen atmosphere, introducing nitrogen at a flow rate of 100ml/min, heating to 800 ℃ at a heating rate of 5 ℃/min and keeping for 3 hours, and then performing programmed cooling at a cooling rate of 5 ℃/min to obtain a mixture B; immersing the product cooled to nearly room temperature in acid solution with the hydrogen ion concentration of 1mol/L for 5 times and 30 minutes each time, and drying the obtained product at 105 ℃ under normal pressure, and recording the product as a product C;
step 3, cvd process: placing the product C in a tubular furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the condition of continuously introducing nitrogen with a flow rate of 100ml/min, introducing mixed gas of carbon source gas and nitrogen with a mass ratio of 1:2 into the furnace after the furnace temperature is stabilized for 60min, and performing programmed cooling at a cooling rate of 10 ℃/min after the process is required for 120min to obtain a porous carbon material D;
the TEM of the porous carbon material D provided in comparative example 1 is shown in fig. 6, and it can be seen that the pore structure in the prepared porous carbon material D is composed of not only parallel slit pores but also some 1-2nm wedge-shaped pores.
A sodium ion battery was assembled in the same manner as in example 1, and the preparation process was as follows:
uniformly mixing a porous carbon material D serving as a negative electrode active substance, vinylidene fluoride (PVDF) serving as a binder and acetylene black serving as a conductive agent in a mass ratio of 90:5:5 in an NMP (N-methylpyrrolidone) solvent, coating the mixture into an electrode film, drying the electrode film in a vacuum drying oven at 120 ℃ for 12 hours, and rolling and blanking the electrode film to obtain a negative electrode plate; adopts a metal sodium sheet as a counter electrode, and the electrolyte is 1M NaClO 4 in diglyme=1:1 is electrolyte, the negative electrode plate is assembled into a 2032 button battery in a glove box, and the electrochemical performance of the button battery is tested.
The first charge-discharge curve of the sodium-ion battery provided in comparative example 1 is shown in fig. 7, and shows a reversible specific capacity (based on the mass of the anode active material) of 445mAh/g and a first coulombic efficiency of 87% at a current density of 50 mA/g.
The enlarged first-turn charge-discharge curve of the sodium ion cell provided in comparative example 1 is shown in fig. 8, which shows that the average operating potential of the platform segment is lower, at 40mV.
The ratio performance graph of the sodium ion battery provided in comparative example 1 is shown in fig. 9, and it can be seen that the power characteristics of the material are poor, and the capacity retention rate is only 30% at 4C.
Comparative example 2
In step 2, the mass ratio of NaOH to carbon precursor was 2:1.
a method for preparing a porous carbon material, comprising the steps of:
step 1, crushing poplar to 10-20 meshes, putting the crushed poplar into a tube furnace, and carbonizing the poplar in a nitrogen atmosphere at 400 ℃ for 60min to obtain a carbon precursor;
step 2, naOH and the carbon precursor obtained in the step 1 are mixed according to the mass ratio of 2:1, mixing to obtain a mixture A, placing the mixture A in a tube furnace protected by nitrogen atmosphere, introducing nitrogen at a flow rate of 100ml/min, heating to 800 ℃ at a heating rate of 5 ℃/min and maintaining for 3 hours, then performing programmed cooling at a cooling rate of 5 ℃/min to obtain a mixture B, immersing a product cooled to a temperature close to room temperature in an acid solution with a hydrogen ion concentration of 1mol/L for 5 times, washing for 30 minutes each time, drying the obtained product at a temperature of 105 ℃ under normal pressure, and recording as porous carbon;
and 3, placing the porous carbon in a tubular furnace, heating to 900 ℃ at a heating rate of 5 ℃/min under the condition of continuously introducing nitrogen with a flow rate of 100ml/min, introducing mixed gas of carbon source gas and nitrogen with a mass ratio of 1:2 into the furnace after the furnace temperature is stabilized for 60min, and performing program cooling at a cooling rate of 10 ℃/min after introducing the mixed gas for 120min to obtain the porous carbon material D.
The TEM of the porous carbon material D provided in comparative example 2 is shown in fig. 10, and it can be seen that the prepared porous carbon material D has a hierarchical pore structure, and besides parallel slit pores, there are more abundant wedge-shaped pores and cylindrical pores larger than 2 nm.
The porous carbon material D prepared in this comparative example was used as an active material, and a sodium ion battery was assembled in the same manner as in comparative example 1, and the sodium ion battery provided in comparative example 2 exhibited a reversible specific capacity (based on the mass of the negative electrode active material) of 500mAh/g and a first coulombic efficiency of 86% at a current density of 50mA/g, as shown in FIG. 11.
The enlarged first-turn charge-discharge curve of the sodium ion cell provided in comparative example 2 is shown in fig. 12, which shows that the average operating potential of the platform segment is lower, at 30mV.
The ratio performance graph of the sodium ion battery provided in comparative example 2 is shown in fig. 13, and it can be seen that the power characteristics of the material are poor, and the capacity retention rate is only 25% at 4C.
Similarly, the mass ratio of NaOH to carbon precursor is 3:1, the obtained porous carbon material D also has a large number of wedge-shaped holes and cylindrical holes larger than 2 nm.
Comparative example 3
In this comparative example, compared with example 1, the deposition temperature was too low, specifically 600 ℃, the pore was not fully contracted, the pore size was large in the obtained porous carbon material, and the specific surface area obtained by the nitrogen adsorption and desorption test was 560m 2 /g。
A method for preparing a porous carbon material, comprising the steps of:
step 1, crushing poplar to 10-20 meshes, putting the crushed poplar into a tube furnace, and carbonizing the poplar in a nitrogen atmosphere at 400 ℃ for 60min to obtain a carbon precursor;
step 2, the mass ratio of the carbon precursor obtained in the step 1 to NaOH is 1:1, mixing to obtain a mixture A, placing the mixture A in a tube furnace protected by nitrogen atmosphere, introducing nitrogen at a flow rate of 100ml/min, heating to 800 ℃ at a heating rate of 5 ℃/min and maintaining for 3 hours, then performing programmed cooling at a cooling rate of 5 ℃/min to obtain a mixture B, immersing a product cooled to a temperature close to room temperature in an acid solution with a hydrogen ion concentration of 1mol/L for 5 times, washing for 30 minutes each time, drying the obtained product at a temperature of 105 ℃ under normal pressure, and recording as porous carbon;
and 3, placing the porous carbon in a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the condition of continuously introducing nitrogen with a flow rate of 100ml/min, introducing mixed gas of carbon source gas and nitrogen with a mass ratio of 1:2 into the furnace after the furnace temperature is stabilized for 60min, and performing program cooling at a cooling rate of 10 ℃/min after introducing the mixed gas for 120min to obtain the porous carbon material D.
The porous carbon material D prepared in this comparative example is used as an active material, a sodium ion battery is assembled in the same way as in comparative example 1, and the sodium ion battery provided in comparative example 3 shows a reversible specific capacity (based on the mass of the anode active material) of 300mAh/g at a current density of 50mA/g, and the initial coulomb efficiency is 75%, because the chemical vapor deposition temperature is too low, the pore opening is not completely contracted, and serious side decomposition reaction occurs in the electrolyte inlet hole, resulting in an initial efficiency of less than 80%. The average operating potential of the plateau was 50mV, which was lower than that of example 1, and the capacity retention was only 40% at 4C, and the power characteristics were also affected.
Comparative example 4
Compared with the example 1, in the step 2, the activation pore-forming temperature is 700 ℃, the rest is consistent with the example 1, the etching degree is low, the number of parallel slit holes is not rich, the specific capacity of the sodium ion battery 0.1C is 350mAh/g, the initial coulomb efficiency is 87%, the average platform potential is 70mV, and the capacity retention rate is still 60% at 4C.
Comparative example 5
In the comparative example, compared with example 1, in step 2, the activation pore-forming temperature is 1000 ℃, the rest is the same as example 1, a large number of wedge-shaped holes or cylindrical holes with the hole web diameter larger than 1nm are formed in the obtained carbon material, the specific capacity of the sodium ion battery 0.1C is 455mAh/g, the initial coulomb efficiency is 86%, the average platform potential is 45mV, and the capacity retention rate is 42% at 4C.
Comparative example 6
In the comparative example, compared with example 1, in step 2, the mass ratio of NaOH to the precursor is 0.3, the balance is kept consistent with example 1, the number of parallel slit holes in the obtained carbon material is not rich, the specific capacity of the sodium ion battery 0.1C is 300mAh/g, the initial coulomb efficiency is 88%, the average platform potential is 70mV, and the capacity retention rate is 60% at 4C.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a carbon material having parallel slit holes, comprising the steps of:
step 1, carbonizing a biomass precursor with lignin content higher than 30% at a preset temperature to form a carbon precursor;
step 2, dry-mixing the carbon precursor obtained in the step 1 with solid alkali in proportion, wherein the mass ratio of the solid alkali to the carbon precursor is more than 0.4 and less than or equal to 1, then activating and pore-forming under the protection of protective gas at a preset temperature, and pickling and drying after the reaction is finished to obtain porous carbon;
and 3, shrinking the pore openings of the porous carbon obtained in the step 2 by utilizing chemical vapor deposition to obtain the carbon material with parallel slit pores.
2. The method according to claim 1, wherein the predetermined temperature in the step 1 is 400 to 600 ℃, the carbonization time is 60 to 120min, and the carbonization is performed under the protection of a protective gas.
3. The method according to claim 1, wherein the biomass precursor in the step 1 is poplar, pine, chaff, plant straw or walnut shell, the particle size of the biomass precursor is 10-20 mesh, and the solid alkali is NaOH or KOH.
4. The method according to claim 1, wherein the predetermined temperature in the step 2 is 800 to 900 ℃.
5. The method according to claim 1, wherein the time for activating and pore-forming in the step 2 is 120-240min.
6. The preparation method according to claim 1, wherein the washing is performed in the step 2 by using an acid solution having a hydrogen ion concentration of 0.5-2.0mol/L, the drying temperature is 100-120 ℃, and the drying time is 24-48 hours.
7. The method according to claim 1, wherein in the step 3, the specific steps of chemical vapor deposition are as follows: and (3) placing the porous carbon obtained in the step (2) into a tube furnace, introducing 10-100ml/min of protective gas, then heating to 700-1100 ℃, introducing 10-100ml/min of carbon source gas, closing the carbon source gas after the deposition reaction is finished, and cooling to room temperature.
8. The production method according to claim 7, wherein the carbon source gas is methane, ethane, propane, ethylene, acetylene, benzene, toluene or xylene; the shielding gas is nitrogen or argon; the deposition reaction time is 60-1440min; the heating and cooling speeds are 5-10 ℃/min.
9. The carbon material with parallel slit holes prepared by the preparation method according to any one of claims 1 to 8, wherein the diameter of the hole web of the parallel slit holes is less than 1nm, and the diameter of the hole mouth of the parallel slit holes is less than 0.364nm.
10. Use of a carbon material with parallel slit holes as claimed in claim 9 in a battery negative electrode.
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| CN116553547A (en) * | 2023-07-12 | 2023-08-08 | 玖贰伍碳源科技（天津）有限公司 | High-energy high-power carbon material, preparation method and sodium ion battery |
| CN117525426A (en) * | 2023-12-29 | 2024-02-06 | 贝特瑞新材料集团股份有限公司 | Carbon material and preparation method thereof, negative electrode material and preparation method thereof, and lithium ion battery |
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| CN104577120A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium vanadium phosphate and fluorination lithium vanadium phosphate composite positive pole material |
| CN115259136A (en) * | 2022-08-31 | 2022-11-01 | 哈尔滨工业大学 | Method for preparing biomass-based hard carbon material in large batch by using waste biomass |
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