CN111762778A - Preparation method and application of three-dimensional porous carbon material with high specific surface area and adjustable pore size distribution - Google Patents
Preparation method and application of three-dimensional porous carbon material with high specific surface area and adjustable pore size distribution Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a three-dimensional porous carbon material with high specific surface area and adjustable pore size distribution. The preparation method of the three-dimensional porous carbon material comprises the following steps: (1) preparing saturated aqueous solution of sodium chloride, adding saccharides, nitrogen-containing organic matters and nano calcium carbonate, and fully and uniformly dispersing to obtain dispersion liquid; (2) freeze-drying the obtained dispersion; (3) placing the freeze-dried sample in a tubular furnace, and carrying out two-stage carbonization under protective atmosphere to obtain a carbon material 1 containing a template; (4) removing the template in the carbon material 1 to obtain a carbon material 2; (5) mixing and grinding the carbon material 2 and an activating agent, and roasting in a tubular furnace under a protective atmosphere to obtain a carbon material 3; (6) removing the activating agent from the carbon material 3 yields a three-dimensional porous carbon material with a high specific surface area. The prepared three-dimensional porous carbon material provided by the invention is applied as a negative electrode material of a lead-carbon battery, and shows excellent capacitance performance and cycle stability.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a preparation method and application of a three-dimensional porous carbon material with high specific surface area and adjustable pore size distribution.
Background
With the rapid development of society, the traditional petrochemical energy and resources are gradually exhausted, the ecological environment is further deteriorated, and the key for solving the energy problem is to develop new energy technology and search clean energy. At present, renewable energy sources such as wind energy, solar energy and the like gradually become a mainstream new energy production mode in society. Among batteries used in energy storage systems of electric vehicles, wind power, solar power, and the like, lead carbon batteries have taken an important position in the secondary battery industry due to advantages of high safety, low price, reliable performance, and the like.
The lead-carbon battery is developed by combining a super capacitor on the basis of the traditional lead-acid battery, the charging efficiency and the power density of the battery are improved due to the addition of a capacitive carbon material, and particularly the cycle life of the lead-carbon battery is remarkably prolonged under the high-rate partial charge state. The key to the performance of a lead carbon battery is the added carbon material. A great deal of research at home and abroad shows that the carbon material for the cathode of the lead-carbon battery needs to meet the conditions of high specific surface area, hierarchical porous structure, high conductivity, high hydrogen evolution overpotential and the like. The high specific surface area can provide electric double layer capacitance to slow down the damage of heavy current and pulse current to a negative plate, and simultaneously, the reaction surface area of a negative active material is increased, and the charge acceptance is improved; the abundant hierarchical porous structure is favorable for accelerating electrolyte ion transfer and shortening an ion transmission path, and meanwhile, the porous structure is favorable for stabilizing an electrode structure. Due to the diversity of the types of the carbon materials and the difference of physical and chemical parameters, the selection of the carbon materials still has blindness, which restricts the further development of the lead-carbon battery. In order to solve the above problems, the design and improvement of carbon materials on a plurality of physical and chemical parameters are very important. At present, most of optimization research on carbon materials focuses on the influence of single factors such as specific surface area, porous structure, hydrogen evolution and conductivity of the carbon materials on the lead-carbon battery. However, the synergistic effect of multiple parameters of the carbon material and the design thereof are rarely reported, and particularly, the preparation of the three-dimensional porous carbon material with high specific surface area and adjustable pore size distribution by a method with simple operation and low cost still has certain difficulty.
Disclosure of Invention
In view of the above technical situation, the first technical problem to be solved by the present invention is to provide a simple and controllable preparation method of a three-dimensional porous carbon material with adjustable high specific surface area and adjustable pore size distribution, which is low in cost and can be industrially produced.
The second technical problem to be solved by the invention is to provide the application of the prepared three-dimensional porous carbon material as a negative electrode material of a lead-carbon battery.
In order to achieve the purpose, the invention adopts the following technical scheme that the method comprises the following steps:
in a first aspect, the invention provides a preparation method of a three-dimensional porous carbon material, which comprises the following steps:
(1) firstly, preparing saturated aqueous solution of sodium chloride, then adding saccharides, nitrogen-containing organic matters and nano calcium carbonate, and fully and uniformly dispersing to obtain dispersion liquid; wherein the mass ratio of the saccharides, the nitrogen-containing organic matters, the nano calcium carbonate and the saturated aqueous solution of sodium chloride is 3-5: 3-5: 2-4: 60, adding a solvent to the mixture;
(2) freeze-drying the dispersion liquid obtained in the step (1);
(3) putting the sample obtained in the step (2) into a tubular furnace, and carrying out two-stage carbonization in a protective atmosphere to obtain a carbon material 1, wherein the carbon material 1 contains a template;
(4) removing the template in the carbon material 1 obtained in the step (3) to obtain a carbon material 2;
(5) mixing and grinding the carbon material 2 obtained in the step (4) and an activating agent, and roasting in a tubular furnace under a protective atmosphere to obtain a carbon material 3;
(6) and removing the activating agent in the carbon material 3 to finally obtain the three-dimensional porous carbon material.
The preparation method has the core that cheap and easily available saccharides are used as a carbon source, the pore structure is accurately designed and regulated by a sodium chloride-nano calcium carbonate double template and freeze drying method, sodium chloride is crystallized in the freeze drying process and plays a role in supporting a pore to stabilize a three-dimensional structure in the subsequent carbonization process, an activating agent is used for etching the carbon material, the specific surface area is increased, and the microporosity is increased, so that the three-dimensional porous carbon material with high specific surface area and adjustable pore size distribution is obtained.
In step (1) of the present invention, the saccharide is used as a carbon source, which is widely available, inexpensive and readily available, and is preferably sucrose or glucose.
In the step (1) of the invention, the nitrogen-containing organic substance is added to effectively improve the conductivity of the carbon material, preferably a high nitrogen-containing organic substance, and more preferably dicyanodiamine.
In the step (1), the nano calcium carbonate is a common hard template, and the particle size of the nano calcium carbonate is preferably 20-500 nm.
In the step (1), the uniformly dispersed dispersion liquid is preferably obtained by stirring and ultrasonic treatment, wherein the stirring time is 4-8 hours, and the ultrasonic treatment time is 1-2 hours.
In step (1) of the present invention, it is particularly preferable that the nitrogen-containing organic substance is dicyanodiamine, the saccharide is sucrose, and the feeding mass ratio of the saccharide, the nitrogen-containing organic substance, the nano calcium carbonate and the saturated aqueous solution of sodium chloride is 4:4:4: 60.
In step (2) of the present invention, the freeze-drying conditions are preferably: and keeping the mixture in a freeze dryer for 36-48 h after the mixture is frozen by liquid nitrogen.
In the step (3), the preferable protective atmosphere is one of argon, nitrogen and helium; the first stage roasting temperature is 450-650 ℃, more preferably 550 ℃, and the heating rate is 3-5 ℃/min; the second-stage roasting temperature is 800-1000 ℃, more preferably 900 ℃, and the heating rate is preferably 3-5 ℃/min.
In the step (4) of the present invention, sodium chloride and nano calcium carbonate in the carbon material 1 need to be removed, and preferably, the following operations can be adopted to remove: and (3) fully washing the carbon material 1 with a dilute hydrochloric acid solution, performing suction filtration and washing to be neutral, and drying to remove the template to obtain the carbon material 2. Further preferably, the concentration of the dilute hydrochloric acid is 5-10 wt%, and the drying temperature is 80-120 ℃.
In the step (5) of the invention, the activating agent is preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and zinc chloride, and in view of avoiding damage to the tube furnace in the calcining process due to too large using amount of the activating agent, the activating agent is more preferably potassium hydroxide, the potassium hydroxide can achieve the same technical effect with the least using amount, and the mass ratio of the carbon material 2 to the activating agent potassium hydroxide is 1 (2-4), more preferably 1 (2-3), and most preferably 1: 3. Preferably, the roasting temperature in the step (5) is 700-900 ℃, and more preferably 750 ℃; the heating rate is 3-5 ℃/min, and the roasting time is 2-3 hours.
In step (6) of the present invention, the removal method of the activating agent is determined by the nature of the activating agent itself, and those skilled in the art can select an appropriate removal method according to the activating agent. When the activator is potassium hydroxide, it is preferably removed by: and (3) fully washing the carbon material 3 with a dilute hydrochloric acid solution, performing suction filtration washing until the carbon material is neutral, and drying to remove the activating agent to obtain the carbon material 2. Further preferably, the concentration of the dilute hydrochloric acid is 5-10 wt%, and the drying temperature is 80-120 ℃.
In a second aspect, the invention provides application of the prepared three-dimensional porous carbon material as a negative electrode material of a lead-carbon battery.
The carbon material prepared by the invention has a three-dimensional hierarchical porous structure and an ultra-large specific surface area, when the carbon material is used as a negative electrode material of a lead-carbon battery, the ultra-large specific surface area can provide electric double layer capacitance, the impact of large current on a negative plate is relieved, the abundant interconnected porous structures are beneficial to electrolyte and ion transmission, the mass transfer efficiency is improved, and meanwhile, the three-dimensional porous structure is beneficial to stabilizing the electrode structure.
Compared with the prior art, the invention has the following characteristics and advantages:
1) the invention adopts saccharides with wide sources, low price and easy obtainment as the carbon source, obtains the carbon precursor by a double-template and freeze-drying method, and further realizes the accurate and effective design and regulation of the pore structure of the carbon material by controlling the activation temperature and time. The preparation process has no toxic substances, is environment-friendly, has simple process and is suitable for large-scale production.
2) The carbon material prepared by the invention has a three-dimensional porous structure and an ultra-large specific surface area.
3) The carbon material prepared by the invention shows excellent capacitance performance in sulfuric acid electrolyte.
4) When the carbon material prepared by the invention is used as a negative electrode material for a lead-carbon battery, the cycle life and the cycle stability of the battery are obviously improved under the condition of high current.
Drawings
FIG. 1 is a BET plot of the carbon material prepared in example 1;
FIG. 2 is an SEM photograph of the carbon material prepared in example 1;
FIG. 3 is a charge and discharge curve of the carbon material prepared in example 1;
FIG. 4 is a graph showing the cell performance of the carbon material obtained in example 1;
FIG. 5 is an SEM photograph of the carbon material prepared in example 2;
FIG. 6 is a BET plot of the carbon material prepared in example 2;
FIG. 7 is a charge and discharge curve of the carbon material prepared in example 2;
FIG. 8 is a graph showing the cell performance of the carbon material obtained in example 2;
FIG. 9 is a BET plot of the carbon material prepared in example 3;
FIG. 10 is an SEM photograph of the carbon material obtained in example 3;
FIG. 11 is a charge and discharge curve of the carbon material obtained in example 3;
FIG. 12 is a graph showing the cell performance of the carbon material obtained in example 3;
FIG. 13 is a BET plot of the carbon material prepared in example 4;
FIG. 14 is an SEM photograph of the carbon material obtained in example 4;
FIG. 15 is a charge and discharge curve of the carbon material obtained in example 4;
FIG. 16 is a graph showing the cell performance of the carbon material obtained in example 4;
FIG. 17 is an SEM photograph of a carbon material obtained in example 5; FIG. 18 is a charge and discharge curve of the carbon material obtained in example 5;
FIG. 19 is a graph showing the cell performance of the carbon material obtained in example 5;
FIG. 20 is an SEM photograph of a carbon material obtained in example 6;
FIG. 21 is a BET plot of the carbon material prepared in example 6;
FIG. 22 is a charge and discharge curve of the carbon material obtained in example 6;
FIG. 23 is a graph showing the cell performance of the carbon material obtained in example 6;
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
the electrochemical performance in the embodiment of the invention adopts the following test modes: respectively weighing the prepared carbon material, acetylene black and PVDF in a mass ratio of 8:1:1, stirring the carbon material, the acetylene black and the PVDF into slurry by taking 1-methyl-2-pyrrolidone as a solvent, uniformly coating the slurry on a thin carbon sheet, drying the thin carbon sheet in a vacuum drying box to obtain a pole piece, and finally placing the pole piece in a three-electrode system for electrochemical performance test.
Example 1:
44mL of deionized water was added to a 100mL beaker, 16g of sodium chloride was added to form a saturated solution, 4g of sucrose, 4g of dicyanodiamide, and 4g of 200nm calcium carbonate were added in this order, and the mixture was magnetically stirred at room temperature for 4 hours and sonicated at 100Hz for 1 hour.
The mixture was frozen with liquid nitrogen and then quickly transferred to a freeze-dryer for freeze-drying and holding for 48 hours.
Weighing 4g of the freeze-dried sample, placing the sample into a large porcelain boat, paving the sample, and roasting the sample in an argon atmosphere, wherein the roasting temperature of the first stage is 550 ℃, the roasting time is 1h, the heating rate is 5 ℃/min, the roasting temperature of the second stage is 900 ℃, the roasting time is 2h, and the heating rate is 5 ℃/min, so that the three-dimensional porous carbon material is obtained.
Adding 250mL of dilute hydrochloric acid solution with the mass fraction of 10% into a 500mL beaker, then adding 4g of carbon material, ultrasonically dispersing for 1h at room temperature, magnetically stirring for 4h, then performing suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, and transferring the product into a forced air drying oven to keep the temperature at 120 ℃ for 12 h.
Accurately weighing 6g of potassium hydroxide solid, fully grinding the solid in a mortar to form powder, weighing 2g of the three-dimensional porous carbon material, grinding for 5min, uniformly mixing the solid and the powder, putting the mixture into a large porcelain boat, paving the porcelain boat, and then putting the porcelain boat into a tube furnace to roast under the argon atmosphere at the temperature of 750 ℃ for 2h at the heating rate of 5 ℃/min.
Fully grinding the activated carbon material in a mortar, adding the ground carbon material into dilute hydrochloric acid with the mass fraction of 10%, carrying out ultrasonic treatment for 2h at 100Hz, stirring for 2h, carrying out suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, transferring the product into an air-blast drying oven, and keeping the temperature at 120 ℃ for 12h to obtain the three-dimensional porous activated carbon material with high specific surface area.
FIG. 1 is a BET diagram of the three-dimensional porous carbon material with high specific surface area prepared in this example, which is measured by nitrogen desorption method using a Mike ASAP2460 adsorber, and as shown in the diagram, the BET specific surface area of the three-dimensional porous carbon material with high specific surface area prepared is up to 3039m2(g) total pore volume of 1.63cm3Per g, wherein the pore volume of the micropores is 0.96cm3In terms of a/g, the mean pore diameter is 2.15 nm. Fig. 2 is a scanning electron microscope image of the three-dimensional porous carbon material with a high specific surface area prepared in this embodiment, it can be seen that the pores with a size of about 200nm are connected in a staggered manner to form a three-dimensional structure, and the precise control of the pore size is realized by adjusting and controlling the reaction conditions. FIG. 3 is a charge-discharge curve of the obtained carbon material, and the specific capacitance of the carbon material is up to 265F/g under the current density of 0.5A/g, which is superior to that of a commercial activated carbon material. Fig. 4 is a performance diagram of the prepared carbon material battery in a high-rate partial charge state, and it is observed that the service life of the carbon material battery prepared in the embodiment is 4 times of that of a common battery, and the cycle life of the battery is greatly improved.
Example 2:
44mL of deionized water was added to a 100mL beaker, 16g of sodium chloride was added to form a saturated solution, 4g of sucrose, 4g of dicyanodiamide, and 4g of 500nm calcium carbonate were added in this order, and the mixture was magnetically stirred at room temperature for 4 hours and sonicated at 100Hz for 1 hour.
The mixture was frozen with liquid nitrogen and then quickly transferred to a freeze-dryer for freeze-drying and holding for 36 hours.
Weighing 4g of the freeze-dried sample, placing the sample into a large porcelain boat, paving the sample, and roasting the sample in an argon atmosphere, wherein the roasting temperature of the first stage is 550 ℃, the roasting time is 1h, the heating rate is 5 ℃/min, the roasting temperature of the second stage is 800 ℃, the roasting time is 2h, and the heating rate is 5 ℃/min, so that the three-dimensional porous carbon material is obtained.
Adding 250mL of dilute hydrochloric acid solution with the mass fraction of 10% into a 500mL beaker, then adding 4g of carbon material, ultrasonically dispersing for 1h at room temperature, magnetically stirring for 4h, then performing suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, and transferring the product into a forced air drying oven to keep the temperature at 100 ℃ for 12 h.
Accurately weighing 6g of potassium hydroxide solid, fully grinding the solid in a mortar to form powder, weighing 2g of the three-dimensional porous carbon material, grinding for 5min, uniformly mixing the solid and the powder, putting the mixture into a large porcelain boat, paving the porcelain boat, and then putting the porcelain boat into a tube furnace to roast under the argon atmosphere at the temperature of 750 ℃ for 2h at the heating rate of 5 ℃/min.
Fully grinding the activated carbon material in a mortar, adding the ground carbon material into dilute hydrochloric acid with the mass fraction of 10%, carrying out ultrasonic treatment for 2 hours at 100Hz, stirring for 2 hours, carrying out suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, transferring the product into an air-blast drying oven, and keeping the temperature at 100 ℃ for 12 hours to obtain the three-dimensional porous activated carbon material with high specific surface area.
Fig. 5 is a scanning electron microscope image of the three-dimensional porous carbon material with a high specific surface area prepared in this embodiment, as shown in the figure, a large number of pores with a size of about 500nm are connected in a staggered manner to form a three-dimensional structure, and the precise control of the pore size is realized by regulating and controlling the reaction conditions. FIG. 6 is a BET diagram of the three-dimensional porous carbon material with high specific surface area prepared in this example, which is measured by nitrogen desorption method using a Mike ASAP2460 adsorber, and as shown in the diagram, the BET specific surface area of the three-dimensional porous carbon material with high specific surface area is as high as 2886m2(g) total pore volume of 1.54cm3Per g, wherein the pore volume of the micropores is 0.87cm3In terms of a/g, the mean pore diameter is 2.05 nm. FIG. 7 is a charge-discharge curve of the obtained carbon material, and the specific capacitance thereof is as high as 250F/g at a current density of 0.5A/g. Fig. 8 is a performance diagram of the prepared carbon material battery in a high-rate partial charge state, and the cycle life of the battery reaches 30000 weeks, which is benefited by the high specific surface area and the three-dimensional porous structure of the prepared carbon material.
Example 3: without addition of NaCl
44mL of deionized water was added to a 100mL beaker, followed by the addition of 4g of sucrose, 4g of dicyanodiamine, and 4g of 200nm calcium carbonate in that order, magnetically stirred at room temperature for 4h, and sonicated at 100Hz for 1 h.
The mixture was frozen with liquid nitrogen and then quickly transferred to a freeze-dryer for freeze-drying and holding for 48 hours.
Weighing 4g of the freeze-dried sample, placing the sample into a large porcelain boat, paving the sample, and roasting the sample in an argon atmosphere, wherein the roasting temperature of the first stage is 550 ℃, the roasting time is 1h, the heating rate is 5 ℃/min, the roasting temperature of the second stage is 900 ℃, the roasting time is 2h, and the heating rate is 5 ℃/min, so that the three-dimensional porous carbon material is obtained.
Adding 250mL of dilute hydrochloric acid solution with the mass fraction of 10% into a 500mL beaker, then adding 4g of carbon material, ultrasonically dispersing for 1h at room temperature, magnetically stirring for 4h, then performing suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, and transferring the product into a forced air drying oven to keep the temperature at 120 ℃ for 12 h.
Accurately weighing 6g of potassium hydroxide solid, fully grinding the solid in a mortar to form powder, weighing 2g of the three-dimensional porous carbon material, grinding for 5min, uniformly mixing the solid and the powder, putting the mixture into a large porcelain boat, paving the porcelain boat, and then putting the porcelain boat into a tube furnace to roast under the argon atmosphere at the temperature of 800 ℃ for 2h at the heating rate of 5 ℃/min.
Fully grinding the activated carbon material in a mortar, adding the ground carbon material into dilute hydrochloric acid with the mass fraction of 10%, carrying out ultrasonic treatment for 2h at 100Hz, stirring for 2h, carrying out suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, transferring the product into an air-blast drying oven, and keeping the temperature at 120 ℃ for 12h to obtain the three-dimensional porous activated carbon material with high specific surface area.
FIG. 9 is a BET plot of the carbon material prepared in this example, which shows that the BET specific surface area of the prepared high specific surface area three-dimensional porous carbon material is 1799m2Per g, total pore volume 1.12cm3Per g, wherein the pore volume of the micropores is 0.74cm3In terms of/g, the mean pore diameter is 2.5 nm. FIG. 10 is a scanning electron micrograph of the carbon material produced in this example, which is not observedThe three-dimensional porous structure which is cross-linked with each other has disordered sheet shape as a whole, which is caused by the collapse of the three-dimensional structure of the holes due to no addition of sodium chloride. FIG. 11 is a graph showing the charge/discharge curves of the carbon material obtained in this example, wherein the specific capacitance of the carbon material reaches 170F/g at a current density of 0.5A/g. Fig. 12 is a performance diagram of the prepared carbon material battery in a high-rate partial charge state, wherein the cycle life of the prepared carbon material battery is twice that of a common battery, which may cause that the mass transfer rate of the electrolyte in the battery circulation process is reduced compared with that of a three-dimensional porous carbon material battery due to the fact that the prepared carbon material is not of a three-dimensional porous structure.
Example 4: excess activator
44mL of deionized water was added to a 100mL beaker, 16g of sodium chloride was added to form a saturated solution, 4g of sucrose, 4g of dicyanodiamide, and 4g of 200nm calcium carbonate were added in this order, and the mixture was magnetically stirred at room temperature for 4 hours and sonicated at 100Hz for 1 hour.
The mixture was frozen with liquid nitrogen and then quickly transferred to a freeze-dryer for freeze-drying and holding for 48 hours.
Weighing 8g of a freeze-dried sample, placing the sample into a large porcelain boat, paving the sample, and roasting the sample in an argon atmosphere, wherein the roasting temperature of the first stage is 550 ℃, the roasting time is 1h, the heating rate is 5 ℃/min, the roasting temperature of the second stage is 1000 ℃, the roasting time is 2h, and the heating rate is 5 ℃/min, so that the three-dimensional porous carbon material is obtained.
Adding 250mL of dilute hydrochloric acid solution with the mass fraction of 10% into a 500mL beaker, then adding 4g of carbon material, ultrasonically dispersing for 1h at room temperature, magnetically stirring for 4h, then performing suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, and transferring the product into a forced air drying oven to keep the temperature at 120 ℃ for 12 h.
Accurately weighing 8g of potassium hydroxide solid, fully grinding the solid in a mortar to form powder, weighing 2g of the three-dimensional porous carbon material, grinding for 5min, uniformly mixing the solid and the powder, putting the mixture into a large porcelain boat, paving the porcelain boat, and then putting the porcelain boat into a tube furnace to roast under the argon atmosphere at the temperature of 750 ℃ for 2h at the heating rate of 5 ℃/min.
Fully grinding the activated carbon material in a mortar, adding the ground carbon material into dilute hydrochloric acid with the mass fraction of 10%, carrying out ultrasonic treatment for 2h at 100Hz, stirring for 2h, carrying out suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, transferring the product into an air-blast drying oven, and keeping the temperature at 120 ℃ for 12h to obtain the three-dimensional porous activated carbon material with high specific surface area.
FIG. 13 is a BET plot of the three-dimensional porous carbon material with high specific surface area prepared in this example, which is measured by nitrogen desorption method using a Mike ASAP2460 adsorber, and as shown in the plot, the BET specific surface area of the three-dimensional porous carbon material with high specific surface area is as high as 3307m2(g) total pore volume of 1.81cm3Per g, wherein the pore volume of the micropores is 1.45cm3In terms of/g, the mean pore diameter is 2.16 nm. FIG. 14 is a scanning electron micrograph of the carbon material prepared in this example, showing that most of the three-dimensional pore structure is destroyed, because the pores are severely etched due to the excessive amount of alkali used during the activation process. FIG. 15 is a graph showing the charge/discharge curves of the carbon material prepared in this example, and the specific capacitance of the carbon material reaches 200F/g at a current density of 0.5A/g, which is attributed to the higher specific surface area of the carbon material after activation. Fig. 16 is a performance diagram of the prepared carbon material battery in a high-rate partial charge state, the cycle life of the battery reaches 23000 weeks, which is three times of that of a common battery, and the three-dimensional porous structure of the partially damaged carbon material has certain influence on the cycle performance of the battery.
Example 5:
44mL of deionized water was added to a 100mL beaker, 16g of sodium chloride was added to form a saturated solution, and 4g of glucose, 4g of dicyanodiamine, and 4g of 200nm calcium carbonate were added in this order, magnetically stirred at room temperature for 4 hours, and sonicated at 100Hz for 1 hour.
The mixture was frozen with liquid nitrogen and then quickly transferred to a freeze-dryer for freeze-drying and holding for 48 hours.
Weighing 4g of the freeze-dried sample, placing the sample into a large porcelain boat, paving the sample, and roasting the sample in an argon atmosphere, wherein the roasting temperature of the first stage is 550 ℃, the roasting time is 1h, the heating rate is 5 ℃/min, the roasting temperature of the second stage is 900 ℃, the roasting time is 2h, and the heating rate is 5 ℃/min, so that the three-dimensional porous carbon material is obtained.
Adding 250mL of dilute hydrochloric acid solution with the mass fraction of 5% into a 500mL beaker, then adding 4g of carbon material, ultrasonically dispersing for 1h at room temperature, magnetically stirring for 4h, then performing suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, and transferring the product into a forced air drying oven to keep the temperature at 80 ℃ for 12 h.
Accurately weighing 6g of potassium hydroxide solid, fully grinding the solid in a mortar to form powder, weighing 2g of the three-dimensional porous carbon material, grinding for 5min, uniformly mixing the solid and the powder, putting the mixture into a large porcelain boat, paving the porcelain boat, and then putting the porcelain boat into a tube furnace to roast under the argon atmosphere at the temperature of 750 ℃ for 2h at the heating rate of 5 ℃/min.
Fully grinding the activated carbon material in a mortar, adding the ground carbon material into dilute hydrochloric acid with the mass fraction of 10%, carrying out ultrasonic treatment for 2 hours at 100Hz, stirring for 2 hours, carrying out suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, transferring the product into an air-blast drying oven, and keeping the temperature at 80 ℃ for 12 hours to obtain the three-dimensional porous activated carbon material with high specific surface area.
Fig. 17 is a scanning electron microscope image of the carbon material prepared in this example, as shown in the figure, it can be seen that the holes with the size of about 200nm are connected in a staggered manner to form a three-dimensional structure, and the precise control of the hole size is realized by adjusting and controlling the reaction conditions. FIG. 18 is a graph showing the charge/discharge curves of the carbon material obtained in this example, wherein the specific capacitance of the carbon material reaches 235F/g at a current density of 0.5A/g. Fig. 19 is a performance diagram of the prepared carbon material battery in a high-rate partial charge state, and the cycle life of the battery is more than three times that of a common battery.
Example 6:
44mL of deionized water was added to a 100mL beaker, 16g of sodium chloride was added to form a saturated solution, 4g of sucrose, 4g of dicyanodiamide, and 4g of 200nm calcium carbonate were added in this order, and the mixture was magnetically stirred at room temperature for 4 hours and sonicated at 100Hz for 1 hour.
The mixture was frozen with liquid nitrogen and then quickly transferred to a freeze-dryer for freeze-drying and holding for 48 hours.
Weighing 8g of the freeze-dried sample, placing the sample into a large porcelain boat, paving the sample, and roasting the sample in an argon atmosphere, wherein the roasting temperature of the first stage is 550 ℃, the roasting time is 1h, the heating rate is 5 ℃/min, the roasting temperature of the second stage is 900 ℃, the roasting time is 2h, and the heating rate is 5 ℃/min, so that the three-dimensional porous carbon material is obtained.
Adding 250mL of dilute hydrochloric acid solution with the mass fraction of 10% into a 500mL beaker, then adding 4g of carbon material, ultrasonically dispersing for 1h at room temperature, magnetically stirring for 4h, then performing suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, and transferring the product into a forced air drying oven to keep the temperature at 120 ℃ for 12 h.
Accurately weighing 2g of potassium hydroxide solid, fully grinding the potassium hydroxide solid in a mortar to form powder, weighing 2g of the three-dimensional porous carbon material, grinding for 5min, uniformly mixing the two materials, putting the mixture into a large porcelain boat, paving the mixture, and then putting the mixture into a tube furnace to roast under the argon atmosphere at the temperature of 750 ℃ for 2h at the heating rate of 5 ℃/min.
Fully grinding the activated carbon material in a mortar, adding the ground carbon material into dilute hydrochloric acid with the mass fraction of 10%, carrying out ultrasonic treatment for 2h at 100Hz, stirring for 2h, carrying out suction filtration, repeatedly washing with deionized water until the pH value of filtrate is 7, transferring the product into a forced air drying oven, and keeping the temperature at 120 ℃ for 12h to obtain the activated carbon material.
FIG. 20 is a scanning electron microscope image of the carbon material prepared in this example, as shown in the figure, it can be seen that the pores with a size of about 200nm are connected in a staggered manner to form a three-dimensional structure, and the morphology is not changed significantly after activation with the activator in a ratio of 1: 1. FIG. 21 is a BET diagram of the three-dimensional porous carbon material prepared in this example, which is measured by nitrogen desorption method using a Mike ASAP2460 adsorber, and shows that the BET specific surface area of the three-dimensional porous carbon material prepared reaches 566.58m2Per g, total pore volume of 0.36cm3Per g, wherein the pore volume of the micropores is 0.20cm3In terms of/g, the mean pore diameter is 2.48 nm. FIG. 22 is a graph showing the charge/discharge curves of the carbon material obtained in this example, wherein the specific capacitance of the carbon material reaches 150F/g at a current density of 0.5A/g. Fig. 23 is a performance graph of the prepared carbon material battery in a high-rate partial charge state, and the battery cycle life reaches 15000 weeks, which may be caused by that the carbon material with a lower specific surface area fails to fully exert the electric double layer capacitance characteristic in the high-rate partial charge state.
The foregoing is a detailed description of the present invention with reference to preferred embodiments, but it should not be construed that the present invention is limited to the embodiments. Numerous modifications and alterations can be made without departing from the spirit of the invention, which is defined by the claims appended hereto.
Claims (10)
1. A preparation method of a three-dimensional porous carbon material comprises the following steps:
(1) firstly, preparing saturated aqueous solution of sodium chloride, then adding saccharides, nitrogen-containing organic matters and nano calcium carbonate, and fully and uniformly dispersing to obtain dispersion liquid; wherein the mass ratio of the saccharides, the nitrogen-containing organic matters, the nano calcium carbonate and the saturated aqueous solution of sodium chloride is 3-5: 3-5: 2-4: 60, adding a solvent to the mixture;
(2) freeze-drying the dispersion liquid obtained in the step (1);
(3) putting the sample obtained in the step (2) into a tubular furnace, and carrying out two-stage carbonization in a protective atmosphere to obtain a carbon material 1, wherein the carbon material 1 contains a template;
(4) removing the template in the carbon material 1 obtained in the step (3) to obtain a carbon material 2;
(5) mixing and grinding the carbon material 2 obtained in the step (4) and an activating agent, and roasting in a tubular furnace under a protective atmosphere to obtain a carbon material 3;
(6) and removing the activating agent in the carbon material 3 to finally obtain the three-dimensional porous carbon material.
2. The method of preparing three-dimensional porous carbon according to claim 1, wherein: in the step (1), the saccharide is sucrose or glucose.
3. The method of preparing three-dimensional porous carbon according to claim 1, wherein: in the step (1), the nitrogen-containing organic substance is dicyanodiamine.
4. The method of preparing three-dimensional porous carbon according to claim 1, wherein: in the step (1), the particle size of the nano calcium carbonate is 20-500 nm.
5. The method of preparing three-dimensional porous carbon according to claim 1, wherein: in the step (1), the nitrogen-containing organic matter is dicyanodiamine, the saccharide is sucrose, and the feeding mass ratio of the saccharide, the nitrogen-containing organic matter and the saturated aqueous solution of nano calcium carbonate and sodium chloride is 4:4:4: 60.
6. The method of producing three-dimensional porous carbon according to any one of claims 1 to 5, characterized in that: in the step (2), the freeze drying conditions are as follows: and keeping the mixture in a freeze dryer for 36-48 h after the mixture is frozen by liquid nitrogen.
7. The method of producing three-dimensional porous carbon according to any one of claims 1 to 5, characterized in that: in the step (3), the protective atmosphere is one of argon, nitrogen and helium; the first stage roasting temperature is 450-650 ℃, and the heating rate is 3-5 ℃/min; the second stage roasting temperature is 800-1000 ℃, and the heating rate is 3-5 ℃/min.
8. The method of producing three-dimensional porous carbon according to any one of claims 1 to 5, characterized in that: in the step (5), the activating agent is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and zinc chloride; the activating agent is preferably potassium hydroxide, and the mass ratio of the carbon material 2 to the activating agent potassium hydroxide is 1 (2-4), more preferably 1 (2-3), and most preferably 1: 3.
9. The method of producing three-dimensional porous carbon according to any one of claims 1 to 5, characterized in that: the roasting temperature in the step (5) is 700-900 ℃, the heating rate is 3-5 ℃/min, and the roasting time is 2-3 hours.
10. The application of the three-dimensional porous carbon material prepared by the preparation method according to claim 1 as a negative electrode material of a lead-carbon battery.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113562728A (en) * | 2021-03-12 | 2021-10-29 | 南京林业大学 | Method for preparing activated carbon by sucrose one-pot method |
| CN115367750A (en) * | 2022-09-23 | 2022-11-22 | 山东理工大学 | Biomass porous carbon material, preparation method thereof and application thereof in lead-acid battery |
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| CN115367750B (en) * | 2022-09-23 | 2023-10-27 | 山东理工大学 | Biomass porous carbon material, preparation method thereof and application thereof in lead-acid battery |
| CN117613250A (en) * | 2024-01-24 | 2024-02-27 | 帕瓦(长沙)新能源科技有限公司 | Three-dimensional conductive lead-carbon composite material, preparation method thereof, negative electrode and lead-acid battery |
| CN117613250B (en) * | 2024-01-24 | 2024-04-19 | 帕瓦(长沙)新能源科技有限公司 | Three-dimensional conductive lead-carbon composite material, preparation method thereof, negative electrode and lead-acid battery |
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