CN114380285A - One-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material and preparation method and application thereof - Google Patents
One-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/386—Carbon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a one-dimensional and two-dimensional biochar synergistically enhanced carbon aerogel material and a preparation method and application thereof, wherein a one-dimensional and two-dimensional biochar-based precursor is processed for standby; mixing the glucose solution and the molten paraffin, emulsifying to obtain an oil-in-water emulsion, adding the one-dimensional biochar-based precursor, the two-dimensional biochar-based precursor, acrylamide, methylene bisacrylamide and ammonium persulfate, and freeze-drying to obtain a carbon aerogel material precursor at the temperature of 300-600 ℃; and finally, mixing the carbon aerogel material precursor with a potassium hydroxide solution, evaporating to dryness, and carbonizing at a high temperature of 700-900 ℃ to obtain the one-dimensional and two-dimensional biological carbon reinforced carbon aerogel material. According to the invention, the one-dimensional and two-dimensional biological carbon is doped into the carbon aerogel material together in situ, so that the mechanical strength of the carbon aerogel material can be improved, the conductivity of the carbon aerogel material can be improved, and the electrochemical performance, the adsorption performance and the catalytic performance of the carbon aerogel material are further improved.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a one-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material, and a preparation method and application thereof.
Background
The carbon aerogel material is a novel carbon material, and has rich nano-scale pore diameter and high specific surface area (600-1100 m)2And/g), high conductivity, stable physical and chemical properties, controllable structure, easy doping and the like, and can be widely applied to the fields of adsorption, energy storage, conversion, heat insulation, aerospace and aviation and the like.
Since the beginning of the 20 th century 30 years, aerogels have been found to be prepared from a variety of ultra-light porous materials such as silica aerogels, metal foams, CNT aerogels, etc., while carbon aerogels are considered to be ideal energy storage materials, catalysts, catalyst carriers, chemisorption agents, thermal insulators, sound insulation materials, etc., due to their advantages of controllable pore size, low density, good electrical conductivity, low thermal conductivity, etc.
Due to its unique pore structure and its properties, the application and research of carbon aerogel materials in the field of electrochemical energy have become one of the hot fields of research in recent years, especially in the field of lithium secondary batteries, and some applications and advances have been made in recent years. Such as: (1) the carbon aerogel material and the composite material thereof can be used as a carrier of an electrocatalyst in a battery or directly used as a catalyst in an electrochemical process of the electrocatalyst, and due to the special structure of the carbon aerogel material and the composite material thereof, metal particles can be uniformly dispersed, the electrochemical effective surface area, the catalytic activity and the performance of a fuel cell of the catalyst are improved, and meanwhile, the application of the carbon aerogel material and the composite material thereof can reduce the cost and improve the utilization rate and the catalytic activity of the catalyst. (2) The carbon aerogel material can be directly used as an electrode material of the lithium sulfur battery, has high conductivity and large specific surface area due to abundant holes, so that sulfur in the lithium sulfur battery is not easy to dissolve out in the charging and discharging process, and the cycle performance of the battery is improved. (3) The carbon aerogel material can be further doped with carbon materials by utilizing the characteristic of easy compounding of the carbon aerogel material, and the carbon particles can further enrich the internal structure of the carbon aerogel material while improving the conductivity and physical strength of the carbon aerogel material, form a conductive frame and improve the electrochemical performance of the material.
Although carbon aerogel materials have many advantages, their structure and properties can be further improved when used in certain specific applications. When the carbon aerogel material is used as an electrode material, particularly as an electrode material of a lithium-sulfur battery, the problem of large pore size inherent in the carbon aerogel material still influences the adsorption of polysulfide when the carbon aerogel material is used as an electrode material carrier of batteries such as the lithium-sulfur battery, and the performance stability of the lithium-sulfur battery at high cycle cannot be ensured; secondly, the conductivity of the carbon aerogel material itself also plays a decisive role in the cycling performance of the battery. Moreover, the traditional preparation method of the carbon aerogel material is complex and toxic aldehyde substances are used in the preparation process, so that the preparation method of the carbon aerogel material is further improved, the performance of the carbon aerogel material is improved, and the expansion of the carbon aerogel material in the fields of batteries and the like is particularly important.
Disclosure of Invention
Aiming at the problems of complex manufacturing process, small specific surface area and poor electrical conductivity of the existing carbon aerogel material, the invention aims to provide a one-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a one-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material comprises the following steps:
(1) washing the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor with water, acid washing, washing with water, and drying for later use;
(2) uniformly mixing a glucose aqueous solution and molten paraffin, emulsifying to obtain an oil-in-water emulsion, adding the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor which are prepared in the step (1), adding acrylamide, methylene bisacrylamide and ammonium persulfate to obtain a composite hydrogel, and performing pre-carbonization at 300-600 ℃ after freeze drying to obtain a carbon aerogel material precursor;
(3) and (3) uniformly mixing the carbon aerogel material precursor obtained in the step (2) with a potassium hydroxide solution, evaporating to dryness, and carbonizing at a high temperature of 700-900 ℃ to obtain the one-dimensional and two-dimensional biochar synergistically enhanced carbon aerogel material.
Preferably, in the step (1), the one-dimensional biochar-based precursor is selected from at least one of absorbent cotton, phoenix tree batting and cattail wool; the two-dimensional biochar-based precursor is selected from at least one of peanut shells, hibiscus flower petals and magnolia flower petals.
Preferably, in the step (1), the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor are washed by deionized water, soaked in 30-35 wt% of hydrochloric acid or 10-30 wt% of nitric acid for 8-12 hours, washed to be neutral by ionized water, and dried at 60-100 ℃ for later use.
Preferably, in step (2), the ratio of glucose: and paraffin wax is 3-5: 1, uniformly mixing the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor at 70 ℃, wherein the total addition amount of the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor is 10-50 wt% of glucose; the mass ratio of acrylamide to methylene bisacrylamide to the mass ratio of ammonium persulfate to glucose is 9: 1: 2: 30.
More preferably, in the step (2), the mass ratio of the one-dimensional biochar-based precursor to the two-dimensional biochar-based precursor is 1:1 to 3.
Preferably, in the step (3), the ratio of potassium hydroxide: and (3) preparing a carbon aerogel material precursor, wherein the carbon aerogel material precursor is 2-5: 1 at 100-150 ℃, carbonizing at 700-900 ℃ for 2-4 h, washing with dilute hydrochloric acid, and washing with water to neutrality to obtain the one-dimensional and two-dimensional biochar enhanced carbon aerogel material.
The invention also provides the one-dimensional biological carbon synergistically enhanced carbon aerogel material prepared by the preparation method.
The invention also provides application of the one-dimensional and two-dimensional biochar synergistically enhanced carbon aerogel material in preparation of a lithium-sulfur battery positive electrode material.
The inventor finds that the one-dimensional biochar (such as a carbon micron tube and a carbon fiber material) is small in size, the carbon micron tube or the carbon fiber material is less in mutual contact, and the mutual contact of electrons in the carbon micron tube or the carbon fiber material is not beneficial to effective transmission of electrons in the whole linear network.
The one-dimensional biochar and the two-dimensional biochar formed in the invention can form a large number of hydrophilic groups on the surface after acid treatment in the early stage, so that the hydrophilic groups are tightly combined with the prepared hydrogel, the interface between the one-dimensional biochar material and the carbon aerogel in the carbonization process can be effectively weakened, and the transmission of electrons and ions in the carbon wall is facilitated. In addition, the carbon aerogel prepared by using glucose as a carbon source is hard carbon, and the conductivity is poor. And the first and second-dimensional precursor materials can be effectively graphitized in the carbonization process, so that the conductivity of the carbon aerogel material is improved.
The one-dimensional biological carbon synergistically enhanced carbon aerogel material is realized by emulsifying a water phase taking glucose as a raw material and an oil phase taking paraffin as a raw material, adding a gelling agent and a catalyst to form hydrogel, performing freeze drying to obtain organic aerogel, performing pre-carbonization at 300-600 ℃ to remove the oil phase, finally adding potassium hydroxide, performing heat preservation and pore-forming treatment at 700-900 ℃, forming a large number of micropores on the carbon wall of the carbon aerogel, thinning the carbon wall and facilitating the transmission of conductive particles; on the other hand, for the lithium sulfur battery, the micropores can effectively store sulfur and polysulfide and effectively adsorb the sulfur and the polysulfide, so that the cycling stability of the sulfur positive electrode is improved.
When the carbon aerogel material prepared by the invention is used as a modified material of the lithium-sulfur battery anode:
1. the carbon aerogel material has a large specific surface area, and the doped activated carbon materials (one-dimensional biochar and two-dimensional biochar) can form a conductive framework in the carbon aerogel material and can accommodate the volume expansion of active substances of the lithium-sulfur battery in the reaction process;
2. the carbon aerogel material has a catalytic effect, so that the reaction speed of the lithium-sulfur battery in the shuttling effect in the charging and discharging process can be accelerated, and the loss of active substances is reduced;
3. the doped active carbon material has a large number of oxygen-containing functional groups, and the performance of the lithium-sulfur battery is improved by utilizing the polar adsorption effect of the oxygen-containing functional groups on polysulfide in the lithium-sulfur battery.
Based on the reasons, the lithium-sulfur battery prepared by the invention has excellent cycle performance and specific capacity, and is expected to be widely applied to the field of lithium-sulfur batteries.
The method takes glucose and paraffin as raw materials, uses the carbon aerogel material prepared by a trans-emulsion polymerization method as a carrier, and simultaneously incorporates a one-dimensional biochar-based precursor and a two-dimensional biochar-based precursor to obtain the one-dimensional biochar-enhanced carbon aerogel material and the two-dimensional biochar-enhanced carbon aerogel material. According to the invention, the biochar precursors do not need to be added into the hydrogel after carbonization, so that the influence on a large amount of loss and impurities in the carbonization process of the one-dimensional and two-dimensional biochar precursor materials is reduced, and the interface effect between the formed one-dimensional and two-dimensional biochar materials and the carbon aerogel is weakened. The doped one-dimensional and two-dimensional biological carbon materials can not only improve the conductivity of the carbon aerogel material, but also improve the adsorption performance and the catalytic performance, and also form various structures in the carbon aerogel material, so that the mechanical strength of the material is improved, and meanwhile, a conductive frame is formed, and the service performance of the carbon aerogel material is greatly improved.
Compared with the prior art, the invention has the advantages that:
(1) the one-dimensional biological carbon (such as a carbon micron tube and a carbon fiber material) and the two-dimensional biological carbon (such as a graphene-like material) are jointly doped in situ in the one-dimensional biological carbon and two-dimensional biological carbon synergistically enhanced carbon aerogel material, so that the mechanical strength of the carbon aerogel material can be improved, the conductivity of the carbon aerogel material can be improved, and the electrochemical performance, the adsorption performance and the catalytic performance of the carbon aerogel material can be further improved.
(2) The one-dimensional and two-dimensional biochar synergistically enhanced carbon aerogel material disclosed by the invention is mainly composed of micropores and auxiliary mesopores, and a large number of micron-sized holes are distributed on the surface of particles, so that the material has extremely high porosity and specific surface area, is favorable for polysulfide adsorption, and can play a role in relieving volume expansion inevitably generated by an electrode material, thereby improving the cycle performance of a battery.
Drawings
FIG. 1 is a pore size distribution plot of a one-dimensional biochar co-enhanced carbon aerogel material prepared in example 3;
fig. 2 is a nitrogen adsorption and desorption curve diagram of the carbon aerogel material synergistically enhanced by the one-dimensional biological carbon prepared in example 3.
Detailed Description
The following examples are intended to further illustrate the present invention and are not intended to limit the present invention.
Example 1
(1) Cleaning phoenix tree wadding and ground peanut shell with deionized water for 3 times, respectively soaking in 30 wt% hydrochloric acid for 10h, cleaning with ionized water to neutrality, and drying at 80 deg.C;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a water bath kettle at 70 ℃, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 1g of phoenix tree seed and 2g of peanut shell which are treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the carbon aerogel material with the one-dimensional and two-dimensional biological carbon synergistically enhanced.
Example 2
(1) Cleaning absorbent cotton and ground peanut shells for 3 times by using deionized water, respectively soaking in 30 wt% hydrochloric acid for 10h, then cleaning to neutrality by using ionized water, and finally drying at 80 ℃ for later use;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 1g of the absorbent cotton and 2g of the peanut shells treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the carbon aerogel material with the one-dimensional and two-dimensional biological carbon synergistically enhanced.
Example 3
(1) Cleaning phoenix tree wadding, absorbent cotton and ground peanut shell with deionized water for 3 times, respectively soaking in 30 wt% hydrochloric acid for 10h, cleaning with deionized water to neutrality, and drying at 80 deg.C;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 1g of phoenix tree batting, 1g of absorbent cotton and 1g of peanut shell which are treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the carbon aerogel material with the one-dimensional and two-dimensional biological carbon synergistically enhanced.
Example 4
(1) Cleaning phoenix tree wadding, absorbent cotton and ground peanut shell with deionized water for 3 times, respectively soaking in 30 wt% hydrochloric acid for 10h, cleaning with deionized water to neutrality, and drying at 80 deg.C;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 1.25g of phoenix tree wadding, 1.25g of absorbent cotton and 5g of peanut shell which are treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the carbon aerogel material with the one-dimensional and two-dimensional biological carbon synergistically enhanced.
Comparative example 1
(1) Taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting the mixture into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, ultrasonically stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky hydrogel, preserving heat for 30min at 70 ℃, taking out, cooling to room temperature, cutting the milky hydrogel into fine sheets with the thickness of 1-3 mu m, freezing for 12h at-55 ℃, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, and preserving heat for 2h in a nitrogen atmosphere by using a tubular furnace from room temperature to 400 ℃ at the speed of 5 ℃/min to prepare a carbon aerogel material precursor;
(2) putting the carbon aerogel material precursor prepared in the step (1) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the carbon aerogel material.
Comparative example 2
(1) Cleaning phoenix tree wadding with deionized water for 3 times, soaking in 30 wt% hydrochloric acid for 10h, cleaning with deionized water to neutrality, and drying at 80 deg.C;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a water bath kettle at 70 ℃, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 3g of phoenix tree batting treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the one-dimensional biochar reinforced carbon aerogel material.
Comparative example 3
(1) Washing ground peanut shells for 3 times by deionized water, soaking in 30 wt% hydrochloric acid for 10h, washing by using deionized water until the peanut shells are neutral, and finally drying at 80 ℃ for later use;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 3g of peanut shells treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the two-dimensional biochar reinforced carbon aerogel material.
Comparative example 4
(1) Cleaning absorbent cotton for 3 times by using deionized water, soaking the absorbent cotton in 30 wt% hydrochloric acid for 10 hours, then cleaning the absorbent cotton to be neutral by using the deionized water, and finally drying the absorbent cotton at 80 ℃ for later use;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 3g of the absorbent cotton treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the one-dimensional biochar reinforced carbon aerogel material.
Comparative example 5
(1) Cleaning phoenix tree wadding and absorbent cotton with deionized water for 3 times, respectively soaking in 30 wt% hydrochloric acid for 10h, cleaning with ionized water to neutrality, and drying at 80 deg.C;
(2) taking 4g of paraffin and 0.56g of span 80 (span-80), putting into a water bath kettle at 70 ℃, and heating until the paraffin is completely dissolved into colorless and transparent liquid to obtain molten paraffin; taking 15g of glucose, 23.5ml of deionized water and 1.44g of Tween 80 (Tween-80), uniformly stirring, putting into a 70 ℃ water bath kettle, heating to obtain a glucose aqueous solution, slowly adding the glucose aqueous solution into molten paraffin, uniformly stirring, then respectively adding 1.5g of phoenix tree wadding and 1.5g of absorbent cotton which are treated in the step (1), after ultrasonic stirring for 1h at 70 ℃, adding a gelling agent (4.5 g of acrylamide and 0.5g of methylene bisacrylamide) and a catalyst (1 g of ammonium persulfate) to prepare milky-white hydrogel, preserving heat at 70 ℃ for 30min, taking out, cooling to room temperature, cutting into small pieces with the thickness of 1-3 mu m, freezing at-55 ℃ for 12h, vacuum drying for 48h, putting the freeze-dried samples into a porcelain boat, heating to 400 ℃ from room temperature at the speed of 5 ℃/min by using a tube furnace, and preserving heat for 2 hours in a nitrogen atmosphere to prepare a precursor of the carbon aerogel material;
(3) putting the carbon aerogel material precursor prepared in the step (2) into a culture dish, and mixing the carbon aerogel material precursor: the mass ratio of the potassium hydroxide is 1: 3 adding potassium hydroxide and a certain amount of deionized water until the potassium hydroxide is completely dissolved, placing the mixture into a 100 ℃ oven for heat preservation for 12 hours, then scraping the potassium hydroxide and the carbon aerogel material into a porcelain boat together, keeping the temperature in a nitrogen atmosphere from room temperature to 800 ℃ at a heating rate of 5 ℃/min for 3 hours, after the sample is cooled to room temperature, washing the sample with 3mol/L excess dilute hydrochloric acid solution until the sample is weakly acidic, performing suction filtration with deionized water until the sample is neutral, and then placing the sample into a 60 ℃ oven for drying to obtain the one-dimensional biochar reinforced carbon aerogel material.
Preparing a lithium-sulfur battery positive electrode material:
the samples prepared in examples 1-4 and comparative examples 1-5 and nano sulfur were taken, respectively, according to the carbon aerogel material: the mass ratio of the nano sulfur is 3: 7, grinding and uniformly mixing the materials in a mortar, collecting the mixture into a reaction kettle, pumping the reaction kettle to a vacuum state, keeping the temperature of the reaction kettle at 155 ℃ for 12 hours, and then mixing the product with a conductive agent (SuperP) and PVDF according to the ratio of 7: 2: the mixture of the components 1 is mixed and transferred into a mortar to be ground uniformly, N-methyl pyrrolidone (NMP) is used as a dispersing agent, the mixture is transferred to a magnetic stirrer to be stirred for 10 hours after being mixed together, the mixed slurry is coated on a carbon-coated aluminum foil flatly on a coating machine, the coating height of a scraper is set to be 200 mu m, and finally the required lithium-sulfur battery anode material is obtained after constant-temperature drying at 60 ℃ by a vacuum drying oven, wherein the performances of the lithium-sulfur battery anode material are shown in tables 1 to 3.
TABLE 1 TABLE OF PRIOR RELATED PARAMETERS OF SAMPLES PREPARED IN EXAMPLES 1-4 AND COMPARATIVE EXAMPLES 1-5
As shown in Table 1, the samples prepared in examples 1-4 and comparative examples 1-5 have higher specific surface area, but the in-situ co-doping mode of the one-dimensional biochar and the two-dimensional biochar is larger than that of the undoped comparative examples 1-5 or the single one-dimensional or two-dimensional doped comparative examples 1-5.
The samples prepared in the above examples 1 to 4 and comparative examples 1 to 5 were cut into pole pieces of uniform size by a cutting machine for later use.
And assembling the prepared pole piece, battery shell, lithium piece, diaphragm electrolyte, gasket and elastic piece into a battery in a glove box in argon atmosphere. The separator used in assembling the battery was a high-strength thin polyolefin porous membrane, the electrolyte was prepared by dissolving 1MLiTFSI in DOL DME 1:1V at a ratio of 2% lithium nitrate, charging and discharging at 20 ℃ at a rate of 0.5C in a range of 1.7 to 2.8V, and the specific capacity after 100 charging and discharging was recorded, and the results are shown in table 2.
TABLE 2 tables of cycle performance of samples prepared in examples 1 to 4 and comparative examples 1 to 5
As shown in table 2, the one-dimensional and two-dimensional bio-carbon synergistically enhanced carbon aerogel material inhibits the shuttle effect and the volume expansion defect inherent in the lithium sulfur battery to a certain extent, and improves the cycle performance of the battery, and the cycle performance improvement range of the one-dimensional and two-dimensional co-doping modes of examples 1 to 4 is more obvious than that of the undoped or single one-dimensional or two-dimensional doping modes of comparative examples 1 to 5.
Four-probe resistance tests were performed for examples 1 to 4 and comparative examples 1 to 5, and the results are shown in table 3 below.
TABLE 3 TABLE of four-Probe resistance test results for samples prepared in examples 1 to 4 and comparative examples 1 to 5
As shown in table 3, the one-dimensional and two-dimensional biochar synergistically enhanced carbon aerogel materials of the present invention have very excellent conductivity, wherein the resistance of the one-dimensional and two-dimensional in-situ co-doped examples 1 to 4 is lower than that of the undoped or single one-dimensional or two-dimensional in-situ doped comparative examples 1 to 5, and the conductivity is significantly improved.
Claims (8)
1. A preparation method of a one-dimensional and two-dimensional biological carbon synergistically enhanced carbon aerogel material is characterized by comprising the following steps:
(1) washing the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor with water, acid washing, washing with water, and drying for later use;
(2) uniformly mixing a glucose aqueous solution and molten paraffin, emulsifying to obtain an oil-in-water emulsion, adding the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor which are prepared in the step (1), adding acrylamide, methylene bisacrylamide and ammonium persulfate to obtain a composite hydrogel, and performing pre-carbonization at 300-600 ℃ after freeze drying to obtain a carbon aerogel material precursor;
(3) and (3) uniformly mixing the carbon aerogel material precursor obtained in the step (2) with a potassium hydroxide solution, evaporating to dryness, and carbonizing at a high temperature of 700-900 ℃ to obtain the one-dimensional and two-dimensional biochar synergistically enhanced carbon aerogel material.
2. The method of claim 1, wherein: in the step (1), the one-dimensional biochar-based precursor is selected from at least one of absorbent cotton, phoenix tree wadding and cattail wool; the two-dimensional biochar-based precursor is selected from at least one of peanut shells, hibiscus flower petals and magnolia flower petals.
3. The method of claim 1, wherein: in the step (1), the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor are washed by deionized water, soaked in 30-35 wt% of hydrochloric acid or 10-30 wt% of nitric acid for 8-12 hours, washed to be neutral by ionized water, and dried at 60-100 ℃ for later use.
4. The method of claim 1, wherein: in the step (2), according to the glucose: and paraffin wax is 3-5: 1, uniformly mixing the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor at 70 ℃, wherein the total addition amount of the one-dimensional biochar-based precursor and the two-dimensional biochar-based precursor is 10-50 wt% of glucose; the mass ratio of acrylamide to methylene bisacrylamide to the mass ratio of ammonium persulfate to glucose is 9: 1: 2: 30.
5. the method of claim 4, wherein: in the step (2), the mass ratio of the one-dimensional biochar-based precursor to the two-dimensional biochar-based precursor is 1:1 to 3.
6. The method of claim 1, wherein: in the step (3), adding potassium hydroxide: and (3) preparing a carbon aerogel material precursor, wherein the carbon aerogel material precursor is 2-5: 1 at 100-150 ℃, carbonizing at 700-900 ℃ for 2-4 h, washing with dilute hydrochloric acid, and washing with water to neutrality to obtain the one-dimensional and two-dimensional biochar enhanced carbon aerogel material.
7. A carbon aerogel material having synergistically enhanced mono-dimensional biochar prepared by the production process as claimed in any one of claims 1 to 6.
8. The use of a one-dimensional biochar co-enhanced carbon aerogel material according to claim 7, wherein: the method is used for preparing the lithium-sulfur battery cathode material.
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