CN114275783A - Mechanical ball milling based chemical activation porous carbon pore depth regulation and control method and compact energy storage application - Google Patents

Mechanical ball milling based chemical activation porous carbon pore depth regulation and control method and compact energy storage application Download PDF

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CN114275783A
CN114275783A CN202210111862.6A CN202210111862A CN114275783A CN 114275783 A CN114275783 A CN 114275783A CN 202210111862 A CN202210111862 A CN 202210111862A CN 114275783 A CN114275783 A CN 114275783A
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porous carbon
ball milling
mechanical ball
energy storage
control method
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孙飞
吴东阳
王桦
张博然
王坤芳
赵广播
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Harbin Institute of Technology
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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Abstract

The invention discloses a mechanical ball milling based depth regulation method for chemically activated porous carbon pores and application of compact energy storage, wherein the method directly obtains high-specific-surface-area porous carbon (namely, porous carbon with high specific surface area) by chemical activation>2000 m2The/g) is used as a raw material, and through simple mechanical ball milling treatment, the deep cutting and recombination of a microscopic carbon microcrystal structure and a pore structure in porous carbon can be realized while the size of macroscopic particles of the porous carbon is reduced, so that the problem of excessive cutting and recombination of the microscopic carbon microcrystal structure and the pore structure in the porous carbon is solvedIneffective pores in the porous carbon pore structure, which are unfavorable for electrolyte and energy-carrying ion storage and transportation, can maintain high ion storage and transportation capacity while improving the density of the porous carbon material, so that the volume energy storage density of the porous carbon electrode is greatly improved. The method can improve the bulk density and the electrode volume energy storage density of the traditional chemically activated porous carbon by more than 5 times, and has important application advantages in the aspect of compact energy storage of super-capacitor electrode materials and secondary ion battery cathode materials.

Description

Mechanical ball milling based chemical activation porous carbon pore depth regulation and control method and compact energy storage application
Technical Field
The invention belongs to the field of porous carbon material preparation and electrochemical energy storage application, relates to a preparation method of a high-energy-storage-density carbon material, and particularly relates to a chemical activated porous carbon pore depth regulation and control method based on mechanical ball milling and compact energy storage application.
Background
The porous carbon material is rich in adjustable pore structure and surface chemical activity, and is widely applied to electrochemical devices such as super capacitors, secondary ion batteries and the like. In the physical and chemical structure of the porous carbon material, the pore structure has a crucial influence on the transport kinetics and the storage capacity of energy-carrying ions in the electrochemical energy storage process. For a super-capacitor carbon electrode material, a developed pore structure and a high specific surface area of porous carbon are important means for improving the mass specific capacitance and mass energy density of the carbon electrode, but the high specific surface area of the porous carbon cannot be fully utilized, and the existence of ineffective pores reduces the density of the electrode material on one hand and causes excessive adsorption of electrolyte on the other hand, so that the volume energy density of the electrode and a device is reduced. For the carbon cathode material of the secondary ion battery, the proper microporous structure in the carbon material can guide reversible adsorption filling of energy-carrying ions, but the excessively high specific surface area can bring about serious irreversible adsorption, thereby reducing the first effect. Therefore, based on the requirement of the portable electronic device and the mobile carrier for dense energy storage of the electrode material, the proper pore size distribution and specific surface area in the porous carbon are the key points for synergistically improving the mass energy density and the volume energy density.
For porous carbon electrode materials, ineffective pores in pore matching structure of the porous carbon electrode material, which are unfavorable for ion transportation or adsorption, are inhibited or eliminatedThe gap is the key for improving the material and electrode density and the volume energy density of the constructed device and realizing compact energy storage. Reported methods for eliminating ineffective pores, preparing dense porous carbon and improving volume energy storage density mainly focus on solvent evaporation-induced graphene self-assembly. The initial report by Tao Ying et al of the preparation of high-density porous carbon by evaporation-induced drying of graphene hydrogel was that the apparent density of the obtained porous carbon was 70% of that of graphite, and the volumetric capacitance after assembly into a supercapacitor was 376F/cm3However, the graphene oxide suspension as a raw material has problems of production cost and difficulty in mass production (Scientific report, 2013, 10/17/3, volume 3, page 2975). On the basis of the technology, Zhang Jun et al report that the compact graphene electrode is subjected to heat treatment at different temperatures of 300-800 ℃ in an inert atmosphere, and oxygen functional groups and folding textures are quantitatively regulated and controlled; the obtained compact graphene is used as a negative electrode of a sodium ion battery and is 0.05A g-1The initial reversible discharge capacity can reach 141 mA h cm under the current density-3(Advanced Energy Materials, 16.01.2018, Vol.8, No. 11, p. 1702395). In addition, Lin Shuang et al reported a simple multifunctional molten sodium amide treatment process for preparing high density graphene with high capacitive properties in aqueous and lithium battery electrolytes. The obtained high-density graphene electrode can provide 522F cm in potassium hydroxide electrolyte-3The volume capacitance of (a); the mass energy density and the volume energy density of the lithium ion battery electrolyte are respectively 618 Wh kg-1And 740 Wh L-1Even better than commercial LiFePO4(Advanced Energy Materials, 14.07.2017, Vol.7, No. 20, p. 1700766). In conclusion, the existing means for realizing compact energy storage by optimizing the pores of the carbon-based material have the problems of high preparation cost, high operation energy consumption and the like.
Based on chemical activators (KOH, K)2CO3、ZnCl2、H3PO4) The etching reaction with the carbon structure is a convenient and easy means for preparing porous carbon materials with developed pores and high specific surface area, and heavy carbon raw materials such as coal with low cost and high reserveCarbon, biomass and the like are used as raw materials, and are important choices for preparing the porous carbon material with low cost and large quantity. However, when the porous carbon prepared by the chemical activation method is directly used as the cathode of the super-capacitor or secondary ion battery, the negative effect of the ineffective pores on the requirement of compact energy storage exists, the structure stability of the carbon microcrystals and the pore walls in the chemically activated porous carbon is poor, and the structural instability occurs in the electrochemical charging and discharging process, so that the cycle stability is reduced.
Disclosure of Invention
Aiming at key bottlenecks of unreasonable pore structure of porous carbon electrode materials in super capacitors and secondary ion batteries and low volume energy storage density, the invention provides a chemical activation porous carbon pore depth regulation and control method based on mechanical ball milling and compact energy storage application. The method directly obtains the high specific surface area porous carbon by chemical activation (>2000 m2The porous carbon material is prepared from the raw materials,/g) through simple mechanical ball milling treatment, the size of macroscopic particles of the porous carbon is reduced, and meanwhile, deep cutting and recombination of a microscopic carbon microcrystal structure and a pore structure in the porous carbon can be realized, so that invalid pores which are unfavorable for storage and transportation of electrolyte and energy-carrying ions in the porous carbon pore structure are eliminated, the density of the porous carbon material is improved, and meanwhile, high ion storage and transportation capacity is maintained, and the volume energy storage density of the porous carbon electrode is greatly improved. The method can improve the bulk density and the electrode volume energy storage density of the traditional chemically activated porous carbon by more than 5 times, and has important application advantages in the aspect of compact energy storage of super-capacitor electrode materials and secondary ion battery cathode materials.
The purpose of the invention is realized by the following technical scheme:
a chemical activation porous carbon pore depth regulation and control method based on mechanical ball milling comprises the following steps:
the method comprises the following steps: the method comprises the following steps of taking high-specific-surface-area porous carbon obtained by a chemical activation method as a raw material, and realizing regulation and control of the porous carbon from a macroscopic particle form to a microscopic pore structure through a mechanical ball milling process to obtain the microporous carbon with a pore structure and bulk density which are synergistically optimized, wherein:
the porous carbon with high specific surface area obtained by the chemical activation method comprises one or more mixtures of biomass-based porous carbon, coal-based porous carbon and polymer-based porous carbon;
the biomass material can be plant material (straw, pine wood, sawdust, rice hull, fruit shell, corn husk, shaddock peel, bamboo, wheat flour, etc.) with cellulose, hemicellulose or lignin as main ingredient;
the coal raw material can be specifically one or more of coal with medium-low metamorphic grade, such as lignite, sub-bituminous coal (low-rank eastern Junggar coal) and bituminous coal;
the polymer raw material can be one or more of a conjugated microporous polymer, thermoplastic resin (polystyrene and polyphenyl ether) and thermosetting resin (phenolic resin, urea resin, epoxy resin, polyester resin, polyurethane and rubber);
the chemical activating agent used in the chemical activating method comprises KOH and K2CO3、KCl、K2FeO4、NaOH、NaCl、ZnCl2、H3PO4、Ca(OH)2、(CH3COO)2One or more mixtures of Ca;
the specific surface area of the porous carbon with high specific surface area obtained by the chemical activation method is not less than 2000m2/g；
The mechanical ball milling process adopts a high-energy ball mill, the rotating speed of the ball mill is 100-1000 r/min, the ball milling time is 2-50 h, and the ball milling tank is made of agate, corundum or stainless steel;
the atmosphere in the mechanical ball milling process is inert atmosphere, air atmosphere or carbon dioxide atmosphere;
the mass ratio of the ball milling beads to the porous carbon raw material with the high specific surface area in the mechanical ball milling process is 35-100: 1;
step two: carrying out acid washing treatment for 2-5 times and water washing treatment for 2-5 times on the ball-milled product in sequence to obtain the cleaned ball-milled product, and then carrying out drying treatment, wherein:
the pickling solution adopted in the pickling treatment is a mixture of dilute hydrochloric acid and hydrofluoric acid, and the volume of the mixture is 1: 1;
the concentration of the pickling solution is 0.01-5 mol/L;
the drying treatment temperature is 60-100 ℃, and the drying treatment time is 12-24 hours;
step three: and carrying out heat treatment on the dried product through reducing atmosphere to remove oxygen-containing functional groups introduced to the surface, so as to obtain the target porous carbon material, wherein:
the reducing atmosphere is a mixed gas of hydrogen and inert gas (high-purity argon or high-purity nitrogen), and the volume ratio of the hydrogen in the mixed gas is 1-10%.
In the invention, the acid washing treatment can remove inorganic impurities introduced by chemical activation and mechanical ball milling in the porous carbon material, control the ash content of the discharged product (the ash content is controlled within the range of less than 0.2%), and modify acid groups such as hydroxyl, carboxyl and the like at the edge of unsaturated carbon through weak oxidation to provide precursor functional groups of ion storage and transportation active sites. And (3) screening and modulating oxygen-containing groups in the porous carbon material by reducing atmosphere heat treatment on the basis, removing oxygen-containing functional groups which are adsorbed/unstable on the surface and easily cause irreversible reaction, and converting unstable acidic oxygen-containing groups into more stable ketone and ether groups. The macroscopic properties of the materials such as the pore structure, tap density and the like of the densified porous carbon material are not changed by the acid washing treatment and the reducing atmosphere heat treatment.
In the invention, after the chemically activated porous carbon with high specific surface area is subjected to mechanical ball milling and pore depth regulation, the tap density of the obtained target porous carbon can reach 0.66 g/cm3The density is improved by more than 5 times, and the material can be used as a water system super capacitor electrode material and a secondary ion battery cathode material. When used as an electrode material of a water-based super capacitor, the volume specific capacitance of the electrode material is not less than 100F/cm3(ii) a When used as the cathode material of the secondary ion battery, the volume specific capacity of the material is not less than 180 mAh/cm3The secondary ion battery adopts ester electrolyte as electrolyte.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a one-step cooperative regulation and control method for realizing microscopic morphology-microcrystal-pore of porous carbon based on macroscopic mechanical force. The traditional solid phase grinding method can only reduce the particle size of the material, and the depth regulation and control of the microstructure in the material are difficult to realize; in contrast, the chemically activated porous carbon with developed pores is used as a raw material, and based on the formed pore pattern, through the introduction of a high-energy mechanical ball milling process and the regulation and control of mechanical ball milling parameters, the recombination of the porous carbon microcosmic carbon microcrystals and the pore structure can be realized under the action of mechanical forces such as collision, shearing and the like, so that the pore structure which is unfavorable or ineffective for ion storage and transportation in the porous carbon material is greatly reduced, and the density of the porous carbon material is greatly improved. The micro/ultramicropore structure and the compact carbon skeleton after deep optimization can realize compact energy storage.
(2) The porous carbon electrode material obtained by the method shows excellent compact energy storage characteristics in electrode materials of super capacitors and secondary ion batteries. The porous carbon material pore depth optimization method provided by the invention can greatly reduce the ineffective pores in the porous carbon with high specific area, which are ineffective to ion storage and transportation or ineffective to excessive adsorption of electrode solution, and the specific surface area is more than 2000m by using the method provided by the invention2The tap density of the porous carbon/g can be improved by more than 5 times by processing the porous carbon. Compared with untreated porous carbon, the material serving as the electrode material of the super capacitor has the advantages that the mass specific capacitance is not reduced, the volume specific capacitance is improved by 5.6 times and can reach 207F/cm3(ii) a Compared with untreated porous carbon, the porous carbon serving as the negative electrode material of the sodium-ion battery has the advantages that the pores are converted into micropores/micropores promoting reversible adsorption of ions, the first coulombic efficiency is greatly improved, the reversible sodium storage capacity is improved by 17.6 times and can reach 185 mAh/cm3。
(3) The method provided by the invention has the advantages of simplicity, easiness in implementation, low cost and large-scale application. According to the invention, the porous carbon with high specific surface area prepared by chemically activating heavy carbon raw materials (coal, biomass and the like) is directly used as the raw material, and the deep optimization of the porous carbon nano-scale pore structure and the electrode energy storage density can be realized by a simple and large-scale mechanical ball milling process. The porous carbon pore structure optimization method provided by the invention has the advantages of wide raw material source, simplicity in operation, low cost and scale.
Drawings
Fig. 1 is a nitrogen adsorption isotherm diagram of the porous carbon material obtained in comparative example 1.
Fig. 2 is a cyclic voltammetry characteristic curve of the porous carbon material obtained in comparative example 1 for an aqueous three-electrode system supercapacitor.
Fig. 3 shows the rate capability of the porous carbon material obtained in comparative example 1 for the water system three-electrode system supercapacitor.
FIG. 4 is a first turn charge/discharge curve (50 mA/g) of the porous carbon material obtained in comparative example 1 as an anode of a sodium ion battery.
Fig. 5 is a graph showing rate performance at different current densities when the porous carbon material obtained in comparative example 1 was used as a negative electrode of a sodium ion battery.
Fig. 6 is a nitrogen adsorption isotherm diagram of the porous carbon material obtained in example 1.
Fig. 7 is a cyclic voltammetry characteristic curve of the porous carbon material obtained in example 1 for an aqueous three-electrode system supercapacitor.
Fig. 8 shows the rate capability of the porous carbon material obtained in example 1 for an aqueous three-electrode system supercapacitor.
FIG. 9 is a first turn of a charge/discharge curve (50 mA/g) of the porous carbon material obtained in example 1 as a negative electrode of a sodium ion battery.
Fig. 10 is a graph showing rate performance at different current densities when the porous carbon material obtained in example 1 was used as a negative electrode of a sodium ion battery.
Fig. 11 is a nitrogen adsorption isotherm diagram of the porous carbon obtained in example 2.
Fig. 12 is a nitrogen adsorption isotherm diagram of the porous carbon obtained in example 3.
Detailed Description
The technical solution of the present invention is further described below with reference to the examples, comparative examples and drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
Comparative example 1:
low-order eastern subbituminous coal is used as a raw material, and is subjected to KOH chemical activation at the temperature of 900 ℃ to obtain the porous carbon material with low density and high specific surface area.
Mixing the porous carbon material obtained in the comparative example with conductive carbon black and Polytetrafluoroethylene (PTFE) emulsion according to the weight ratio of 8: 1:1, adding absolute ethyl alcohol, rolling to form a film, cutting to obtain a film with the mass of 1 mg, adding absolute ethyl alcohol again, rolling to obtain a roll with the area of about 1cm2The electrode plate is covered with foam nickel and pressurized, and then is placed in a vacuum drying oven at 110 ℃ for 12 hours to prepare the electrode plate of the super capacitor. The electrode, 6M KOH solution, reference electrode saturated calomel and a counter electrode Pt sheet form a water system three-electrode system for electrochemical performance test.
Mixing the porous carbon material obtained in the comparative example with conductive carbon black and polyvinylidene fluoride (PVDF) according to the weight ratio of 8: 1:1, adding N-methyl pyrrolidone (NMP), grinding into slurry, coating on copper foil, vacuum drying at 70 deg.C for 12 hr, and cutting into 1cm2The electrode material carrying capacity of the left and right electrode plates is 1 mg/cm2. Using a metal sodium sheet as a counter electrode, 1M NaClO4The electrode solution and the glass fiber membrane (Whatman, GF/D) are diaphragms, and are assembled in an inert atmosphere glove box to form a button half cell for electrochemical performance test.
The porous carbon material obtained by the comparative example is tested to have a tap density of 0.13 g/cm3. FIG. 1 is a nitrogen adsorption isotherm of the porous carbon obtained in comparative example 1, and its specific surface area is 3406 m2G, pore volume of 3.55 cm3(ii) in terms of/g. Fig. 2 is a water system three-electrode system supercapacitor cyclic voltammetry characteristic curve of the porous carbon material obtained in the present comparative example. FIG. 3 shows the rate performance of the mass specific capacitance and the volume specific capacitance of the water system three-electrode system supercapacitor of the porous carbon material obtained in the present comparative example with the change of current density, and the mass specific capacitance of the porous carbon material obtained in the present comparative example is 286F/g and the volume specific capacitance is 37.2F/cm at low current density (1A/g)3(ii) a The porous carbon material obtained in this comparative example had a mass specific capacitance of 200F/g and a volume specific capacitance of 26F/cm at a high current density (100A/g)3. FIG. 4 shows the charge and discharge of the porous carbon material obtained in this comparative example as a sodium ion negative electrode in the first cycle at a low current density (50 mA/g)The reversible capacity of the electric curve is only 124 mAh/g, and the first effect is only 11.2%. Fig. 5 is a sodium storage rate performance curve of the porous carbon material obtained in the present comparative example as a sodium ion negative electrode at different current densities, and it can be seen that the porous carbon material has a smaller sodium storage capacity at the tested current densities.
Example 1:
taking the porous carbon material obtained in the comparative example as a raw material, weighing 0.1g of the porous carbon material, and performing mechanical ball milling in a stainless steel ball milling tank, wherein the mass ratio of ball milling beads to porous carbon in the mechanical ball milling process is 40-50: 1, ball milling rotation speed is 500 r/min, and ball milling atmosphere is high-purity nitrogen; controlling the mechanical ball milling time to be 4h, cooling to room temperature at a reduced speed, opening a tank, taking out the ball-milled porous carbon, washing with 2 mol/L hydrochloric acid and 5mol/L hydrofluoric acid, and drying at 80 ℃ for 12 h; for the dried porous carbon sample at 5% H2And carrying out heat treatment for 1h at 900 ℃ under the condition of the/Ar mixed gas to obtain the target porous carbon material.
The porous carbon material obtained in the embodiment is tested, and the tap density is increased to 0.66 g/cm3It is 5 times or more as large as that of the comparative example. FIG. 6 is a nitrogen adsorption isotherm of the porous carbon obtained in this example, and its specific surface area is 263 m2Per g, pore volume of 0.32 cm3Compared with the high specific surface area porous carbon of the comparative example, the pore structure is deeply regulated, and the specific surface area and the pore volume are greatly reduced. Fig. 7 is a cyclic voltammetry characteristic curve of the water system three-electrode system supercapacitor of the porous carbon material obtained in this example. FIG. 8 shows the rate performance of the mass specific capacitance and the volume specific capacitance of the water system three-electrode system supercapacitor of the porous carbon material obtained in this example as a function of current density, where the mass specific capacitance of the densified porous carbon material obtained in this example is 314F/g and the volume specific capacitance is 207.2F/cm at low current density (1A/g)3(ii) a The densified porous carbon material obtained in this example had a mass specific capacitance of 185F/g and a volume specific capacitance of 122.1F/cm at high current density (100A/g)3(ii) a It can be seen from this that the mass specific capacitance of the densified porous carbon material obtained in this example was not much changed from that of the comparative example, but the volume specific capacitance thereof was improved by 5 times to optimize the pore structureThe above. FIG. 9 is the first-turn charge-discharge curve of the porous carbon material obtained in this example as a sodium ion negative electrode at a low current density (50 mA/g), and the reversible capacity of the porous carbon material reaches 341 mAh/g (225 mAh/cm)3) Compared with the porous carbon obtained by a comparative example, the porous carbon is greatly improved, and in addition, the first effect is also improved to 53%. Fig. 10 is a sodium storage rate performance curve of the porous carbon material obtained in this embodiment as a sodium ion negative electrode at different current densities, and it can be seen that the porous carbon negative electrode obtained in this embodiment still has a sodium storage capacity of 125 mAh/g under the condition of a current density of 10A/g, and compared with the porous carbon obtained in the comparative example, the sodium storage performance is significantly optimized.
Example 2
Taking the porous carbon material obtained in the comparative example as a raw material, weighing 0.1g of the porous carbon material, and performing mechanical ball milling in a stainless steel ball milling tank, wherein the mass ratio of ball milling beads to porous carbon in the mechanical ball milling process is 40-50: 1, ball milling rotation speed is 450 r/min, and ball milling atmosphere is high-purity argon; controlling the mechanical ball milling time to be 30 min, cooling to room temperature at a reduced speed, opening a tank, taking out the ball-milled porous carbon, carrying out combined acid washing on the ball-milled porous carbon by using 2 mol/L dilute hydrochloric acid and 5mol/L hydrofluoric acid, and drying for 12 h at the temperature of 80 ℃; for the dried porous carbon sample at 5% H2And carrying out heat treatment for 1h at 900 ℃ under the condition of the/Ar mixed gas to obtain the target porous carbon material.
Using the densified porous carbon material obtained in this example, it was tested that the tap density was 0.13 g/cm as compared with that of comparative example 13Lifting to 0.27 g/cm3. FIG. 11 is a nitrogen adsorption isotherm of the densified porous carbon obtained in this example, and its specific surface area is 1297 m2Per g, pore volume of 0.89 cm3/g。
Example 3:
taking the porous carbon material obtained in the comparative example as a raw material, weighing 0.1g of the porous carbon material, and performing mechanical ball milling in a stainless steel ball milling tank, wherein the mass ratio of ball milling beads to porous carbon in the mechanical ball milling process is 40-50: 1, ball milling rotation speed is 450 r/min, and ball milling atmosphere is high-purity nitrogen; controlling the mechanical ball milling time to be 2h, cooling to room temperature at a reduced speed, opening a tank, taking out the ball-milled porous carbon, washing with 2 mol/L hydrochloric acid and 5mol/L hydrofluoric acid, and drying at 80 ℃ for 12 h; drying rackThe dried porous carbon sample was at 5% H2And carrying out heat treatment for 1h at 900 ℃ under the condition of the/Ar mixed gas to obtain the target porous carbon material.
Using the densified porous carbon material obtained in this example, it was tested that the tap density was 0.13 g/cm as compared with that of the comparative example3Lifting to 0.32 g/cm3. FIG. 12 is a nitrogen adsorption isotherm of the densified porous carbon obtained in this example, and its specific surface area is 640 m2Per g, pore volume of 0.57 cm3/g。
Example 4:
the rice hull is used as a carbon source and is mixed and activated with KOH or NaOH according to the mass ratio of 1:3, and the prepared specific surface area is 2300-2500 m2High specific surface area porous carbon per gram; weighing 0.1g of the mixture, and performing mechanical ball milling in a stainless steel ball milling tank, wherein the mass ratio of ball milling beads to porous carbon in the mechanical ball milling process is 40-50: 1, ball milling rotation speed is 500 r/min, and ball milling atmosphere is high-purity nitrogen; controlling the mechanical ball milling time to be 4h, cooling to room temperature at a reduced speed, opening a tank, taking out the ball-milled porous carbon, washing with 2 mol/L hydrochloric acid and 5mol/L hydrofluoric acid, and drying at 80 ℃ for 12 h; for the dried porous carbon sample at 5% H2And carrying out heat treatment for 1h at 900 ℃ under the condition of the/Ar mixed gas to obtain the target porous carbon material.
Example 5:
using bamboo as carbon source, reacting with K2FeO4Mixing and activating according to the mass ratio of 1:10, and preparing the material with the specific surface area of 2000m2High specific surface area porous carbon per gram; weighing 0.1g of the mixture, and performing mechanical ball milling in a stainless steel ball milling tank, wherein the mass ratio of ball milling beads to porous carbon in the mechanical ball milling process is 40-50: 1, ball milling rotation speed is 500 r/min, and ball milling atmosphere is high-purity nitrogen; controlling the mechanical ball milling time to be 6h, cooling to room temperature at a reduced speed, opening a tank, taking out the ball-milled porous carbon, washing with 2 mol/L hydrochloric acid and 5mol/L hydrofluoric acid, and drying at 80 ℃ for 12 h; for the dried porous carbon sample at 5% H2And carrying out heat treatment for 1h at 900 ℃ under the condition of the/Ar mixed gas to obtain the target porous carbon material.
Example 6:
phenolic resin is used as a carbon source and is mixed and activated with NaCl according to the mass ratio of 1:4 to prepare the material with the specific surface area of 1900-2200m2High specific surface area porous carbon per gram; weighing 0.1g of the mixture, and performing mechanical ball milling in a stainless steel ball milling tank, wherein the mass ratio of ball milling beads to porous carbon in the mechanical ball milling process is 40-50: 1, ball milling rotation speed is 500 r/min, and ball milling atmosphere is high-purity nitrogen; controlling the mechanical ball milling time to be 4h, cooling to room temperature at a reduced speed, opening a tank, taking out the ball-milled porous carbon, carrying out acid pickling and water washing on the porous carbon by using a combination of 2 mol/L hydrochloric acid and 5mol/L hydrofluoric acid, and drying for 12 h at the temperature of 80 ℃; for the dried porous carbon sample at 5% H2And carrying out heat treatment for 1h at 900 ℃ under the condition of the/Ar mixed gas to obtain the target porous carbon material.
Aiming at the key problems of low volume energy storage density and poor circulation stability of the porous carbon prepared by a chemical activation method as an electrode material, the invention provides a convenient and feasible mechanical ball milling treatment method for realizing multi-scale depth regulation and control of the chemically activated porous carbon from a macroscopic particle form to a microscopic pore structure; compared with the traditional mechanical grinding process which only realizes the change of the form and the size of macroscopic particles, the method disclosed by the invention realizes the recombination of the porous carbon microscopic carbon microcrystal and the pore structure through the regulation and control of mechanical ball-milling process parameters based on the developed pore pattern in the chemically activated porous carbon, so that the ion storage and transportation capacity of the porous carbon is not reduced while the ineffective pores of the porous carbon are greatly reduced and the material density is improved, and the volume specific capacity/specific energy of the porous carbon is greatly improved.

Claims (10)

1. A chemical activation porous carbon pore depth regulation method based on mechanical ball milling is characterized by comprising the following steps:
the method comprises the following steps: the method comprises the following steps of (1) taking porous carbon with high specific surface area obtained by a chemical activation method as a raw material, and carrying out mechanical ball milling to realize regulation and control of the porous carbon from a macroscopic particle form to a microscopic pore structure so as to obtain microporous carbon with a pore structure and stacking density which are cooperatively optimized;
step two: carrying out acid washing treatment and water washing treatment on the ball-milled product in sequence to obtain a washed ball-milled product, and then carrying out drying treatment;
step three: and carrying out heat treatment on the dried product through reducing atmosphere to remove oxygen-containing functional groups introduced to the surface, thereby obtaining the target porous carbon material.
2. The mechanical ball milling-based depth control method for pores of chemically activated porous carbon according to claim 1, wherein the porous carbon with high specific surface area obtained by the chemical activation method comprises one or more mixtures of biomass-based porous carbon, coal-based porous carbon and polymer-based porous carbon, and the specific surface area is not less than 2000m2/g。
3. The mechanical ball milling based depth control method for chemically activated porous carbon pores according to claim 1, wherein the chemical activating agent used in the chemical activating method comprises KOH and K2CO3、KCl、K2FeO4、NaOH、NaCl、ZnCl2、H3PO4、Ca(OH)2、(CH3COO)2One or more of Ca.
4. The mechanical ball milling based chemically activated porous carbon pore depth regulation and control method as claimed in claim 1, characterized in that a high-energy ball mill is adopted in the mechanical ball milling process, the rotating speed of the ball mill is 100-1000 r/min, the ball milling time is 2-50 h, and the ball milling tank is made of agate, corundum or stainless steel; the atmosphere in the mechanical ball milling process is inert atmosphere, air atmosphere or carbon dioxide atmosphere; the mass ratio of the ball milling beads to the porous carbon raw material with the high specific surface area in the mechanical ball milling process is 35-100: 1.
5. the mechanical ball milling based chemical activation porous carbon pore depth regulation and control method is characterized in that the acid washing treatment and the water washing treatment are carried out 2-5 times, acid washing liquid adopted in the acid washing treatment is a mixture of dilute hydrochloric acid and hydrofluoric acid, the volume of the acid washing liquid and the hydrofluoric acid is 1:1, and the concentration of the acid washing liquid is 0.01-5 mol/L.
6. The mechanical ball milling based depth control method for chemically activated porous carbon pores according to claim 1, wherein the drying treatment temperature is 60-100 ℃ and the drying treatment time is 12-24 h.
7. The mechanical ball milling based depth regulation and control method for chemically activated porous carbon pores according to claim 1, characterized in that the reducing atmosphere is a mixed gas of hydrogen and an inert gas, and the volume ratio of hydrogen in the mixed gas is 1-10%.
8. Use of the target porous carbon material obtained by the method of any one of claims 1 to 7 in dense energy storage of supercapacitor electrode materials.
9. Use of the target porous carbon material obtained by the method of any one of claims 1 to 7 for dense energy storage of a secondary ion battery anode material.
10. The application of the target porous carbon material in compact energy storage of a negative electrode material of a secondary ion battery in accordance with claim 9, wherein the secondary ion battery uses an ester electrolyte as an electrolyte.
CN202210111862.6A 2022-01-29 2022-01-29 Mechanical ball milling based chemical activation porous carbon pore depth regulation and control method and compact energy storage application Pending CN114275783A (en)

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