CN115650207A - Porous carbon material and preparation method and application thereof - Google Patents
Porous carbon material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a porous carbon material and a preparation method and application thereof, wherein tannin, ascorbic acid and a sulfur source are uniformly mixed to obtain a raw material A, acetonitrile or halogenated acetonitrile is dissolved in absolute ethyl alcohol to obtain a raw material B, the raw material A and the raw material B are simultaneously placed into a ball milling tank of a high-energy ball mill for ball milling, a metal source with the mass equivalent to 60-80% of that of the tannin and the ascorbic acid is added, the ball milling is continuously carried out to obtain a semi-solid intermediate, and the obtained intermediate is carbonized in a protective gas atmosphere.
Description
Technical Field
The invention relates to a porous carbon material and a preparation method and application thereof, belonging to the technical field of carbon materials.
Background
The porous carbon material has the advantages of ideal large specific surface area, wide pore size distribution, strong chemical stability, high mechanical stability, wide source, relatively low preparation cost and the like, is widely applied to various industries, and how to obtain the expected specific surface area and pore size distribution becomes a hotspot of research in the field, and the research mainly surrounds doping and modification.
CN115367726A discloses an oxygen-doped titanium nitride hybridized and nitrogen-doped porous carbon material, which realizes a higher specific surface area through oxygen, nitrogen doping and titanium nitride hybridization and is suitable for multiple fields of supercapacitors, fuel cells, lithium ion batteries, lithium sulfur batteries and the like.
CN113493196A discloses a boron-nitrogen co-doped porous carbon material and a preparation method and application thereof, boric acid is used as a boron source, and boric acid is pyrolyzed to become boron oxide which can be used as a template, so that the specific surface area of the carbon material is greatly increased, and the carbon material has a very wide prospect in the fields of battery electrode materials, hydrogen storage materials, adsorption, catalysis and the like.
CN114956040A discloses a nitrogen-oxygen doped graded porous carbon material, and the obtained carbon material can be used for supercapacitor electrode materials, electrolytic water hydrogen evolution and oxygen evolution catalytic electrode materials, electromagnetic shielding and absorption materials, oil-water separation adsorbents and seawater desalination materials.
The present team has been working on the performance studies of porous carbon materials, which are disclosed in the following patents: CN113683074A, CN113233461A, CN110316717A, CN110143582A, this application has made this study in order to further expand the variety of porous carbon materials and improve the uniformity of doping.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provide a porous carbon material with ideal performance and simultaneously provide application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
subject of the technology 1
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing tannic acid, ascorbic acid and a sulfur source to obtain a raw material A, wherein the mass ratio of the tannic acid, the ascorbic acid and the sulfur source is 1: 4~6: 7~8; dissolving acetonitrile or halogenated acetonitrile in absolute ethyl alcohol, and stirring to obtain a raw material B with the mass volume concentration of 4.5-6.5g/100 mL;
s2: putting the raw material A and the raw material B into a ball milling pot of a high-energy ball mill simultaneously, carrying out ball milling for 40-60min, standing for 0.8-1.2h, adding a metal source with the mass equivalent to 60-80% of that of the tannic acid and the ascorbic acid, and continuing ball milling for 0.3-0.8h to obtain a semi-solid intermediate;
s3: and (3) carbonizing the intermediate obtained in the step (S2) for 1-3h at 750-900 ℃ in a protective gas atmosphere, and cooling to room temperature to obtain the porous carbon material.
As a further improvement of the invention, the halogenated acetonitrile in the step S1 is one or a combination of any two or more of trichloroacetonitrile, dichloroacetonitrile or tribromoacetonitrile.
As a further improvement of the invention, the mass ratio of the acetonitrile or halogenated acetonitrile to the tannic acid and the ascorbic acid in the step S1 is 1: 5~7.
As a further improvement of the invention, the sulfur source in step S1 is one or a combination of any two or more of mercaptoethylamine, 3-mercaptoethylamine hydrochloride, tert-butyl 2-methylmercaptoethylamine carbonate and D-pantethine.
And in the step S2, the metal source is selected from one or the combination of any two or more of cobalt chloride hexa-amino, copper glycinate, zinc glycinate and cadmium chloride.
As a further improvement of the invention, the rotation speed of the ball milling in the step S2 is 450 to 650 revolutions per minute.
As a further improvement of the invention, in the step S3, protective gas N is continuously introduced at the speed of 20 to 30mL/min 2 /Ar，Heating to 200 ℃ at the rate of 2~5 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the rate of 5~7 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the rate of 4~5 ℃/min, and naturally cooling to room temperature.
As a further improvement of the invention, the method comprises the following steps:
s1: uniformly mixing tannic acid, ascorbic acid and mercaptoethylamine to obtain a raw material A, wherein the mass ratio of the tannic acid to the ascorbic acid to the mercaptoethylamine is 1: 4~6: 7~8; dissolving trichloroacetonitrile in absolute ethyl alcohol, and stirring to obtain a raw material B with the mass volume concentration of 4.5-6.5 g/100mL, wherein the mass ratio of the trichloroacetonitrile to the tannic acid and the ascorbic acid is 1: 5~7;
s2: putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill simultaneously, carrying out ball milling for 45min, standing for 1h, adding zinc glycinate which is 60-80% of the total mass of the tannic acid and the ascorbic acid, and continuing ball milling for 0.5h to obtain a semisolid intermediate;
s3: putting the intermediate obtained in the step S2 into a vacuum carbonization furnace, and continuously introducing a protective gas N at the speed of 20-30mL/min 2 and/Ar, heating to 200 ℃ at the rate of 2~5 ℃/min, preserving heat at 200 ℃ for 1 hour, heating to 900 ℃ at the rate of 5~7 ℃/min, preserving heat for 1 hour, cooling to 500 ℃ at the rate of 4~5 ℃/min, and naturally cooling to room temperature.
As a further improvement of the invention, the mass ratio of the tannic acid, the ascorbic acid and the sulfur source is 1: 5: 7.5; the mass ratio of the trichloroacetonitrile to the tannic acid and the ascorbic acid is 1: 6.
Subject matter two
A porous carbon material obtained by the production according to the scheme described in the first technical subject.
Subject three
Use of a porous carbon material prepared according to the protocol described in the first technical subject for double layer capacitors.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
according to the method provided by the invention, the composition of tannic acid and ascorbic acid and acetonitrile or halogenated acetonitrile and a sulfur source are used as raw materials, and are subjected to ball milling and mixing to form hydrogen bond connection among substances, so that metal elements can be more uniformly complexed in a high-speed ball milling process, the stability of a product is better, the uniformity is better, uniform doping of oxygen, nitrogen, sulfur and metal is realized, and the obtained porous carbon material has a large specific surface area and a large pore volume. The electrochemical performance is good, and the method is suitable for double-layer capacitors.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below.
FIG. 1 is an SEM photograph of a porous carbon material of example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail and fully with reference to the following embodiments.
The respective substances used in the present example were commercially available.
Example 1
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The prepared porous carbon material is effectively doped with nitrogen, oxygen, sulfur and zinc elements, and has the following properties:specific surface area 972 m 2 Per g, pore volume 0.70 cm 3 (ii)/g, the capacity retention after 5000 cycles is 98.5% at a current density of 1A/g.
Example 2
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 4g of ascorbic acid and 7g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 3g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 934m 2 Per g, pore volume 0.68 cm 3 (ii)/g, at a current density of 1A/g, the capacity retention after 5000 cycles is 97.2%.
Example 3
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 6g of ascorbic acid and 8g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 5.6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Ar, heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, and keeping the temperature for 1 hourThen the temperature is reduced to 500 ℃ at the speed of 5 ℃/min and then is naturally reduced to the room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 921 m 2 Per g, pore volume 0.66 cm 3 The capacity retention after 5000 cycles was 96.8% at a current density of 1A/g.
Example 4
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of cobalt hexa-amino chloride, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 871 m 2 G, pore volume 0.52cm 3 The capacity retention after 5000 cycles was 96.3% at a current density of 1A/g.
Example 5
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously placing the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of copper glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing to 25mL/miN is continuously introduced into the protective gas N 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 885 m 2 Per g, pore volume 0.54 cm 3 The capacity retention after 5000 cycles was 96.6% at a current density of 1A/g.
Example 6
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of acetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 703m 2 G, pore volume 0.46cm 3 The capacity retention after 5000 cycles was 94.3% at a current density of 1A/g.
Example 7
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of dichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 714 m 2 Per g, pore volume 0.49 cm 3 The capacity retention after 5000 cycles was 94.5% at a current density of 1A/g.
Example 8
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of 3-mercaptoethylamine hydrochloride to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 762m 2 Per g, pore volume 0.51cm 3 (iv)/g, at a current density of 1A/g, the capacity retention after 5000 cycles is 95.0%.
Example 9
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of D-pantethine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 788m 2 G, pore volume 0.52cm 3 (ii)/g, at a current density of 1A/g, the capacity retention after 5000 cycles is 95.1%.
Comparative example 1
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 6g of tannic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously placing the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 421m 2 G, pore volume 0.33cm 3 (ii)/g, the capacity retention after 5000 cycles is 70.6% at a current density of 1A/g.
Comparative example 2
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 6g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethanol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously placing the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 367m 2 G, pore volume 0.30cm 3 (ii)/g, the capacity retention after 5000 cycles was 67.4% at a current density of 1A/g.
Comparative example 3
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 2g of tannic acid, 4g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 594m 2 G, pore volume 0.40cm 3 (ii)/g, at a current density of 1A/g, the capacity retention after 5000 cycles is 76.3%.
Comparative example 4
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 9g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 469 m 2 Per g, pore volume 0.36 cm 3 (iv)/g, at a current density of 1A/g, the capacity retention after 5000 cycles is 74.8%.
Comparative example 5
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, and taking 20mL of absolute ethyl alcohol as a solvent;
s2: putting the raw material A and a solvent into a ball milling tank of a high-energy ball mill simultaneously, performing ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and performing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 280 m 2 G, pore volume 0.21cm 3 (iv)/g, at a current density of 1A/g, the capacity retention after 5000 cycles was 51.1%.
Comparative example 6
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 557 m 2 G, pore volume 0.38cm 3 (ii)/g, at a current density of 1A/g, the capacity retention after 5000 cycles is 75.8%.
Comparative example 7
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid and 5g of ascorbic acid to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 438m 2 G, pore volume 0.34cm 3 (ii)/g, the capacity retention after 5000 cycles is 70.4% at a current density of 1A/g.
Comparative example 8
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of glucose in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 and/Ar, heating to 200 ℃ at the speed of 3 ℃/min, keeping the temperature at 200 ℃ for 1 hour, heating to 900 ℃ at the speed of 6 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 322 m 2 G, pore volume 0.23cm 3 The capacity retention after 5000 cycles was 49.8% at a current density of 1A/g.
Comparative example 9
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of thiourea to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 Ar, heating to 200 ℃ at the speed of 3 ℃/min, and keeping the temperature at 200 ℃ for 1 hourThen heating to 900 ℃ at the speed of 6 ℃/min, preserving the heat for 1 hour, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the porous carbon material prepared are as follows: specific surface area 339m 2 G, pore volume 0.29cm 3 The capacity retention after 5000 cycles was 52.3% at a current density of 1A/g.
Comparative example 10
A method for producing a porous carbon material, comprising the steps of:
s1: uniformly mixing 1g of tannic acid, 5g of ascorbic acid and 7.5g of mercaptoethylamine to obtain a raw material A, dissolving 1g of trichloroacetonitrile in 20mL of absolute ethyl alcohol, and stirring at normal temperature to obtain a raw material B;
s2: simultaneously putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill, carrying out ball milling for 45min, standing for 1h, adding 6g of zinc glycinate, and continuing ball milling for 0.5h to obtain a semi-solid intermediate;
s3: putting the semi-solid intermediate obtained in the step S2 into a carbonization furnace, vacuumizing, and continuously introducing protective gas N at the speed of 25mL/min 2 and/Ar, heating to 900 ℃ at the speed of 5 ℃/min, preserving heat for 2 hours, cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to room temperature.
The properties of the prepared porous carbon material are as follows: specific surface area 512 m 2 G, pore volume 0.34cm 3 (ii)/g, the capacity retention after 5000 cycles is 73.1% at a current density of 1A/g.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for producing a porous carbon material, characterized by comprising the steps of:
s1: uniformly mixing tannin, ascorbic acid and a sulfur source to obtain a raw material A, wherein the mass ratio of the tannin, the ascorbic acid and the sulfur source is 1: 4~6: 7~8; dissolving acetonitrile or halogenated acetonitrile in absolute ethyl alcohol, and stirring to obtain a raw material B with the mass volume concentration of 4.5-6.5 g/100 mL;
s2: putting the raw material A and the raw material B into a ball milling pot of a high-energy ball mill simultaneously, carrying out ball milling for 40-60min, standing for 0.8-1.2h, adding a metal source with the mass equivalent to 60-80% of that of the tannic acid and the ascorbic acid, and continuing ball milling for 0.3-0.8h to obtain a semi-solid intermediate;
s3: and (3) carbonizing the intermediate obtained in the step (S2) for 1-3h at 750-900 ℃ in a protective gas atmosphere, and cooling to room temperature to obtain the porous carbon material.
2. The method for preparing a porous carbon material according to claim 1, wherein the halogenated acetonitrile in step S1 is one or a combination of two or more of trichloroacetonitrile, dichloroacetonitrile and tribromoacetonitrile.
3. The method for preparing a porous carbon material as claimed in claim 1, wherein the mass ratio of acetonitrile or halogenated acetonitrile to the tannin and ascorbic acid in step S1 is 1: 5~7.
4. The method for preparing a porous carbon material according to claim 1, wherein the sulfur source in step S1 is one or a combination of two or more of mercaptoethylamine, 3-mercaptoethylamine hydrochloride, tert-butyl 2-methylmercaptoethylamine carbonate, and D-pantethine; and in the step S2, the metal source is selected from one or the combination of any two or more of cobalt chloride hexa-amino, copper glycinate, zinc glycinate and cadmium chloride.
5. The method for preparing a porous carbon material as claimed in claim 1, wherein the rotation speed of the ball mill in the step S2 is 450 to 650 rpm.
6. The method for preparing a porous carbon material as claimed in claim 1, wherein the step S3 comprises continuously introducing a protective gas N at a rate of 20 to 30mL/min 2 and/Ar, heating to 200 ℃ at the speed of 2~5 ℃/min, keeping the temperature for 1 hour at 200 ℃, heating to 900 ℃ at the speed of 5~7 ℃/min, keeping the temperature for 1 hour, cooling to 500 ℃ at the speed of 4~5 ℃/min, and naturally cooling to room temperature.
7. The method for producing a porous carbon material according to claim 1, comprising the steps of:
s1: uniformly mixing tannic acid, ascorbic acid and mercaptoethylamine to obtain a raw material A, wherein the mass ratio of the tannic acid to the ascorbic acid to the mercaptoethylamine is 1: 4~6: 7~8; dissolving trichloroacetonitrile in absolute ethyl alcohol, and stirring to obtain a raw material B with the mass volume concentration of 4.5-6.5 g/100mL, wherein the mass ratio of the trichloroacetonitrile to the tannic acid and the ascorbic acid is 1: 5~7;
s2: putting the raw material A and the raw material B into a ball milling tank of a high-energy ball mill simultaneously, carrying out ball milling for 45min, standing for 1h, adding zinc glycinate which is 60-80% of the total mass of the tannic acid and the ascorbic acid, and continuing ball milling for 0.5h to obtain a semisolid intermediate;
s3: putting the intermediate obtained in the step S2 into a vacuum carbonization furnace, and continuously introducing a protective gas N at the speed of 20-30mL/min 2 and/Ar, heating to 200 ℃ at the rate of 2~5 ℃/min, preserving heat at 200 ℃ for 1 hour, heating to 900 ℃ at the rate of 5~7 ℃/min, preserving heat for 1 hour, cooling to 500 ℃ at the rate of 4~5 ℃/min, and naturally cooling to room temperature.
8. The preparation method of the porous carbon material according to claim 7, wherein the mass ratio of the tannin, the ascorbic acid and the mercaptoethylamine is 1: 5: 7.5; the mass ratio of the trichloroacetonitrile to the tannic acid and the ascorbic acid is 1: 6.
9. A porous carbon material obtained by the production method according to any one of claims 1 to 8.
10. Use of a porous carbon material as claimed in claim 9 in a double layer capacitor.
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