CN113493195A - Nitrogen-doped hard carbon material and preparation method and application thereof - Google Patents
Nitrogen-doped hard carbon material and preparation method and application thereof Download PDFInfo
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- 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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- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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Abstract
The invention discloses a nitrogen-doped hard carbon material and a preparation method and application thereof, wherein the preparation method of the hard carbon material comprises the following steps: pretreating, drying and crushing the biomass raw material to obtain primary purified biomass raw material powder; adding biomass raw material powder into dilute nitric acid, heating, cooling to room temperature, filtering, washing and drying to obtain secondary purified biomass powder; calcining the secondarily purified biomass powder in an argon atmosphere, and cooling in the argon atmosphere to obtain a biomass hard carbon material; placing the biomass hard carbon material in plasma equipment for treatment; wherein the power is 400-800 w, and the processing time is 0-75 min. The hard carbon material prepared by the invention has the characteristics of large porosity, large specific surface area and large interlayer spacing, can promote the diffusion of sodium ions, and improves the capacity and dynamics of the carbon cathode of the sodium ion battery, the mass transfer speed, the cycle performance and the first coulomb efficiency.
Description
Technical Field
The invention relates to the field of hard carbon material preparation, in particular to a nitrogen-doped hard carbon material with porous characteristic, a preparation method thereof and application thereof in a sodium ion battery cathode.
Background
The sodium ion battery is a rechargeable battery which can be used as a power supply to provide a power source and is mainly used for a starting battery for starting an automobile engine, a standby power storage power supply, a power grid regulator and power grid-connected equipment. The main constituent materials of the sodium ion battery comprise electrolyte, isolating materials, anode and cathode materials and the like. The negative electrode material occupies a large proportion, because the performance of the negative electrode material directly influences the performance of the lithium ion battery, and the cost directly determines the cost of the battery. There are a wide variety of sodium ion battery negative electrode materials, for example: carbon material and TiO2、SnO2、WO3、NaTi2(PO4)3、Na2CoPO4F、Na2FeSiO4、WS2、Co2P、VP、MoSe2MXene, etc. Among them, biomass carbon materials are receiving attention because of their advantages such as low cost, sustainability, nontoxicity, abundant allotropes, excellent physical/chemical stability, and good electrical conductivity and electrochemical stability. However, commercial carbon-based anodes also expose two non-negligible problems. First, high performance carbon and carbon negative electrodes with fast kinetics during rapid charge/discharge are difficult to obtain. Secondly, the experimental method for synthesizing the high-performance material is complicated and the maintenance cost of the instrument is high. First, in order to obtain a high-performance electrode material, a pseudocapacitance functional group is generally introduced into a carbon material. The pseudocapacitance process is typically a redox reaction at the electrode surface, which can provide a large number of active energy storage sites with fast charge transfer kinetics. Secondly, the conventional methods for synthesizing nitrogen-doped carbon materials mainly include two methods: i) calcining the precursor containing the N element, ii) will be nitrogen-freeAnd mixing the precursor and the precursor containing the N element, and calcining. The disadvantages of these conventional synthetic N-doped carbon materials are evident: the high reaction temperature and expensive equipment are the pressure to bring economic cost, and the synthesis methods are not suitable for popularization to industrialization. This limiting factor in the less strategic synthesis of nitrogen doping has primarily limited the development of high performance N/O doped carbon materials. Therefore, the preparation method has the advantages of low cost, simple operation, short production period and very important industrial value and is easy to be applied to industrial preparation.
Disclosure of Invention
Based on the above technical problems in the prior art, an object of the present invention is to provide a method for preparing a nitrogen-doped hard carbon material, in which the introduced nitrogen element increases the interlayer spacing of the hard carbon material, thereby providing a pseudocapacitance characteristic; the hard carbon material can promote the diffusion of sodium ions by increasing the specific surface area of the hard carbon material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, preparation of carbon source: pretreating, drying and crushing the biomass raw material by high-energy ball milling to obtain primary purified biomass raw material powder;
s2, secondary purification: adding the biomass raw material powder into dilute nitric acid, heating, cooling to room temperature, filtering, washing and drying to obtain secondary purified biomass powder;
s3, calcining: calcining the biomass powder subjected to secondary purification in an argon atmosphere, and cooling in the argon atmosphere after calcining to obtain a biomass carbon material;
s4, plasma treatment: placing the biomass carbon material obtained in the step S3 in plasma equipment, and carrying out ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; wherein the power is 400-800 w, and the processing time is 0-75 min. Wherein the treatment time is more than 0min, and preferably, the plasma treatment time is 5-20 min.
In some embodiments, the pretreatment comprises the steps of removing the endothelium and outer skin, taking a substantial portion thereof, and washing several times with distilled water.
In some embodiments, in step S2, the dilute nitric acid has a concentration of 0.5 to 60 wt% and is heated to 30 to 90 ℃.
In some embodiments, in step S2, the specific purification steps are: adding the biomass raw material powder into dilute nitric acid, refluxing at a constant temperature of 30-90 ℃ under the operation of reflux condensation of condensed water, filtering, washing and drying.
In some embodiments, in step S3, the calcination temperature is 800 to 1400 ℃, and the calcination time is 0.5 to 5 hours.
In some embodiments, in step S1, the biomass raw material is pulverized by a high-energy pulverizer at a rotation speed of 500-9000 r/min for 0.2-15 min.
In some embodiments, the biomass feedstock is at least one of grapefruit peel, durian shell, coconut shell, almonds, corn cobs, shrimp shell, shallots, soybeans, lentinus edodes, orchid leaves.
It is another object of the present invention to provide a nitrogen-doped hard carbon material prepared by the method according to any one of the above embodiments.
In some embodiments, the hard carbon material layer spacing is 0.37-0.46 nm, and the nitrogen content: 2.5 to 6.0 percent.
It is a further object of the present invention to provide a sodium ion battery anode comprising the nitrogen-doped hard carbon material of any of the above embodiments.
The fourth purpose of the invention is to provide a sodium ion battery, which comprises the sodium ion battery negative electrode.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method comprises the steps of carrying out primary purification treatment such as crushing on a biomass raw material through a pretreatment and a high-energy crusher (high-energy ball milling), putting the obtained powder into dilute nitric acid for secondary purification treatment, wherein the secondary purification treatment aims at deeply purifying the biomass raw material powder, and removing natural components which do not contribute to a sodium ion battery negative electrode material in the biomass through the step to purify the biomass raw material; then, washing and drying the biomass raw material powder treated by the dilute nitric acid, then placing the dried biomass raw material powder into a furnace, heating the biomass raw material powder to a target temperature under a protective atmosphere, carrying out heat preservation calcination for a period of time, and finally cooling the biomass raw material powder to normal temperature under the protective atmosphere; and (2) placing the obtained black product (namely the biomass carbon material) in an ammonia gas plasma reactor, introducing functional groups, and carrying out plasma treatment on the obtained biomass carbon material at a certain power at normal temperature by using an ammonia gas plasma strategy to obtain the high-performance nitrogen-doped hard carbon material capable of improving the carbon cathode capacity and dynamics of the sodium ion battery. In the invention, dilute nitric acid is used for purification, aiming at eliminating silicon and other natural impurities in the biomass raw material, so that a high-purity carbon material can be obtained in the subsequent calcining process; ammonia gas is used for processing at a certain power, on one hand, nitrogen elements can be introduced to increase the interlayer spacing, on the other hand, the surface etching is carried out on the biomass carbon material, so that the macroporosity of the carbon material is improved, the interlayer spacing of the carbon material in the carbon material is further increased, and the diffusion of sodium ions can be promoted when the carbon material is applied to a negative electrode of a sodium battery; and the doping of nitrogen element can also obviously reduce the charge transfer resistance and improve the electrode dynamics.
The hard carbon material prepared by the method has larger carbon layer spacing which is 0.37-0.46 nm, and the mass of doped nitrogen element atoms is 2.5-6.0% of that of the hard carbon material. In addition, the material also has pseudo-capacitance characteristics, and can accelerate mass transfer speed, improve cycle performance and improve first coulomb efficiency.
The novel method for synthesizing the nitrogen-doped hard carbon material at room temperature does not need a high-temperature doping process and high-temperature plasma treatment, can reduce the pressure on economic cost caused by high reaction temperature and expensive instruments and equipment, and is easy to popularize towards the direction of industrialization. In addition, the nitrogen-doped hard carbon material prepared by the invention has high capacity, fast kinetics, large specific surface area and fast mass transfer speed, and can be used as a negative electrode material of a sodium ion battery to obtain the sodium ion battery with high energy density and better cycle performance; and the hard carbon material has low preparation cost, simple operation and short production period, and meets the requirement of industrial production.
Drawings
FIG. 1 is a scanning electron micrograph of a hard carbon material prepared according to example 1;
FIG. 2 is a scanning electron micrograph of a carbon material prepared in comparative example 2;
FIG. 3 is an X-ray diffraction pattern of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2;
fig. 4 is a raman spectrum of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2;
FIG. 5 is a graph showing nitrogen adsorption and desorption curves of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2;
FIG. 6 is a graph of pore size distribution for the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2;
fig. 7 is a constant current charge and discharge graph of the hard carbon material prepared in example 1;
FIG. 8 is a constant current charge and discharge curve diagram of the carbon material prepared in comparative example 2;
FIG. 9 shows carbon materials at 0.5mV s for the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2-1(ii) capacity contribution results;
FIG. 10 is a graph of the cycle performance of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2;
FIG. 11 is a potentiostatic titration plot of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2;
fig. 12 is a graph of charge and discharge rate performance of the carbon material prepared in comparative example 1.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting shaddock peel as a precursor carbon source, removing inner skin and outer skin, taking a woody main part of the shaddock peel, washing the shaddock peel with distilled water for three times, drying the shaddock peel in an oven at 120 ℃ for 24 hours, crushing the shaddock peel for 5 minutes by using a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh shaddock peel powder;
s2, secondary purification: weighing 100g of the shaddock peel powder obtained in the step S1, placing the weighed powder in a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing with distilled water for three times, and then placing the obtained product in an oven to dry for 24h at the temperature of 120 ℃ to obtain the shaddock peel powder after secondary purification;
s3, calcining: weighing 30g of the purified shaddock peel powder obtained in the step S2, placing the powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 5min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 2
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting shaddock peel as a precursor carbon source, removing inner skin and outer skin, taking a woody main part of the shaddock peel, washing the shaddock peel with distilled water for three times, drying the shaddock peel in an oven at 120 ℃ for 24 hours, crushing the shaddock peel for 5 minutes by using a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh shaddock peel powder;
s2, secondary purification: weighing 100g of the shaddock peel powder in the step S1, placing the weighed powder in a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing the mixture in an oil bath kettle for 1h at the temperature of 80 ℃, finally filtering the mixture, washing the mixture three times with distilled water, and drying the mixture in an oven for 24h at the temperature of 120 ℃ to obtain the shaddock peel powder after secondary purification.
S3, calcining: weighing 30g of the shaddock peel powder obtained in the step S2 after secondary purification, placing the powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 20min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 3
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting durian shells as a precursor carbon source, peeling, taking a woody main part of the durian shells, washing the durian shells with distilled water for three times, drying the durian shells in a drying oven at 120 ℃ for 24 hours, then crushing the durian shells for 10min by using a high-energy crusher at the rotating speed of 8000r/min, and sieving to obtain 325-mesh durian shell powder;
s2, secondary purification: weighing 100g of the durian shell powder obtained in the step S1, placing the durian shell powder into a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing with distilled water for three times, and drying for 24h in an oven at the temperature of 120 ℃ to obtain the secondary purified durian shell powder;
s3, calcining: weighing 30g of the twice purified durian shell powder obtained in the step S2, placing the powder in a tube furnace, heating to 1200 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 2h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in an RF plasma device, treating the biomass carbon material for 3 minutes at the power of 500W under the condition of ammonia plasma treatment, washing the biomass carbon material for three times by using diluted hydrochloric acid, then washing the biomass carbon material for three times by using distilled water, and finally drying the biomass carbon material in an oven at the temperature of 120 ℃ for 24 hours.
Example 4
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting coconut shells as a precursor carbon source, peeling, taking a woody main body part, washing the woody main body part with distilled water for three times, drying the woody main body part in an oven for 24 hours at 120 ℃, then crushing the coconut shells for 30 minutes by using a high-energy crusher at the rotating speed of 1000r/min, and sieving to obtain 325-mesh coconut shell powder;
s2, secondary purification: weighing 100g of the coconut shell powder in the step S1, placing the coconut shell powder in a round-bottom flask, adding 1 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, refluxing for 2 hours in an oil bath at the temperature of 60 ℃, finally filtering, washing with distilled water for three times, and drying in an oven at the temperature of 120 ℃ for 24 hours to obtain secondarily purified coconut shell powder;
s3, calcining: weighing 30g of the twice-purified coconut shell powder obtained in the step S2, placing the coconut shell powder in a tube furnace, heating to 1300 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 12 minutes at the power of 700W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; after plasma treatment, the obtained hard carbon material was taken out, washed three times with dilute hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 5
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting badam as a precursor carbon source, peeling, taking a woody main body part, washing the woody main body part with distilled water for three times, drying the woody main body part in an oven for 24 hours at the temperature of 120 ℃, then crushing the woody main body part for 20 minutes by using a crusher at the rotating speed of 4000r/min, and sieving to obtain 325-mesh badam powder;
s2, secondary purification: weighing 100g of the badam powder in the step S1, placing the badam powder in a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing for three times with distilled water, and then drying for 24h in an oven at the temperature of 120 ℃ to obtain secondarily purified badam powder;
s3, calcining: weighing 30g of the secondarily purified badam powder obtained in the step S2, placing the badam powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating for 8min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; after plasma treatment, the obtained hard carbon material was taken out, washed three times with dilute hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 6
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting corn cobs as a precursor carbon source, peeling, taking a woody main body part of the corn cobs, washing the corn cobs with distilled water for three times, drying the corn cobs in an oven at 120 ℃ for 24 hours, crushing the corn cobs for 20 minutes by using a high-energy crusher at the rotating speed of 2000r/min, and screening to obtain 325-mesh corn cob powder;
s2, secondary purification: weighing 100g of the corn cob powder in the step S1, placing the corn cob powder in a round-bottom flask, adding 6 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing with distilled water for three times, and drying for 24h in an oven at the temperature of 120 ℃ to obtain secondarily purified corn cob powder;
s3, calcining: weighing 30g of the corn cob powder obtained in the step S2 after secondary purification, placing the corn cob powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 70min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 7
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting shrimp shells as a precursor carbon source, scraping the shrimp shells, taking a main body part of the shrimp shells, washing the main body part of the shrimp shells with distilled water for three times, drying the shrimp shells in an oven at 120 ℃ for 24 hours, then crushing the shrimp shells for 10 minutes by using a high-energy crusher at the rotating speed of 5500r/min, and sieving to obtain 325-mesh shrimp shell powder;
s2, secondary purification: weighing 100g of the shrimp shell powder in the step S1, placing the shrimp shell powder in a round-bottom flask, adding dilute nitric acid with the concentration of 50 wt% into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing with distilled water for three times, and drying for 24h in an oven at the temperature of 120 ℃ to obtain the shrimp shell powder after secondary purification;
s3, calcining: weighing 30g of the secondarily purified shrimp shell powder obtained in the step S2, placing the shrimp shell powder in a tube furnace, heating to 1100 ℃ at a rate of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 2h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the material in the step (3), placing the material in RF plasma equipment, and treating for 16min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 8
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting scallion as a precursor carbon source, peeling, taking a main body part of the scallion, washing the main body part with distilled water for three times, drying the scallion in an oven at 120 ℃ for 24 hours, then crushing the scallion for 30 minutes by using a high-energy crusher at the rotating speed of 600r/min, and sieving to obtain 325-mesh scallion powder;
s2, secondary purification: weighing 100g of the onion powder obtained in the step S1, placing the onion powder into a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, refluxing for 1h at the temperature of 80 ℃ in an oil bath, finally filtering, washing with distilled water for three times, and drying in an oven at the temperature of 120 ℃ for 24h to obtain the onion powder after secondary purification;
s3, calcining: weighing 30g of the twice-purified onion powder obtained in the step S2, placing the twice-purified onion powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 5min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 9
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting soybeans as a precursor carbon source, peeling, taking a main body part of the soybeans, washing the main body part of the soybeans with distilled water for three times, drying the main body part of the soybeans in an oven at 120 ℃ for 24 hours, then crushing the main body part of the soybeans for 3 minutes by using a crusher at the rotating speed of 8500r/min, and screening out 325-mesh soybean powder;
s2, secondary purification: weighing 100g of the soybean powder obtained in the step S1, placing the soybean powder into a round-bottom flask, adding 10 wt% dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing the mixture for 1h at the temperature of 80 ℃ in an oil bath, finally filtering the mixture, washing the mixture for three times by using distilled water, and drying the mixture for 24h in an oven at the temperature of 120 ℃ to obtain secondarily purified soybean powder;
s3, calcining: weighing 30g of the secondarily purified soybean powder obtained in the step S2, placing the secondarily purified soybean powder in a tube furnace, heating to 1000 ℃ at a speed of 5 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material obtained in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 9min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the hard carbon material was taken out, washed three times with dilute hydrochloric acid, then three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 10
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting shiitake mushrooms as a precursor carbon source, peeling, taking a main body part of the shiitake mushrooms, washing the main body part of the shiitake mushrooms with distilled water for three times, drying the shiitake mushrooms in an oven at 120 ℃ for 24 hours, crushing the shiitake mushrooms for 5 minutes by using a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh shiitake mushroom powder;
s2, secondary purification: weighing 100g of the shiitake powder obtained in the step S1, placing the shiitake powder into a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing with distilled water for three times, and drying in an oven at the temperature of 120 ℃ for 24h to obtain the shiitake powder after secondary purification;
s3, calcining: weighing 30g of the mushroom powder obtained in the step S2 after secondary purification, placing the mushroom powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 20min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Example 11
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting orchid leaves as a precursor carbon source, peeling, taking a main body part of the orchid leaves, washing the main body part with distilled water for three times, drying the main body part in a drying oven at 120 ℃ for 24 hours, crushing the main body part for 5 minutes by using a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh orchid leaf powder;
s2, secondary purification: weighing 100g of the orchid leaf powder in the step S1, placing the weighed orchid leaf powder in a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing for 2 hours in an oil bath pan at the temperature of 50 ℃, finally filtering, washing with distilled water for three times, and drying for 24 hours in an oven at the temperature of 120 ℃ to obtain orchid leaf powder after secondary purification;
s3, calcining: weighing 30g of the orchid leaf powder obtained in the step S2 after secondary purification, placing the orchid leaf powder in a tubular furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating the biomass carbon material for 5min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
Comparative example 1
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting shaddock peel as a precursor carbon source, removing inner skin and outer skin, taking a woody main part of the shaddock peel, washing the shaddock peel with distilled water for three times, drying the shaddock peel in an oven at 120 ℃ for 24 hours, crushing the shaddock peel for 5 minutes by using a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh shaddock peel powder;
s2, calcining: weighing 30g of the shaddock peel powder in the step S1, placing the powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s3, plasma treatment: weighing 1g of the biomass carbon material obtained in the step S2, placing the biomass carbon material in RF plasma equipment, treating the biomass carbon material for 5min at the power of 400W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material, taking out the obtained hard carbon material, washing the hard carbon material with diluted hydrochloric acid for three times, then washing the hard carbon material with distilled water for three times, and finally drying the hard carbon material in an oven at the temperature of 120 ℃ for 24 h;
comparative example 2
A method of preparing a hard carbon material, comprising the steps of:
s1, carbon source preparation (primary purification): selecting shaddock peel as a precursor carbon source, removing inner skin and outer skin, taking a woody main part of the shaddock peel, washing the shaddock peel with distilled water for three times, drying the shaddock peel in an oven at 120 ℃ for 24 hours, crushing the shaddock peel for 5 minutes by a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh shaddock peel powder;
s2, secondary purification: weighing 100g of the shaddock peel powder obtained in the step S1, placing the weighed shaddock peel powder into a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, then refluxing the mixture for 1h at the temperature of 80 ℃ in an oil bath pan, finally filtering, washing the mixture for three times with distilled water, and drying the mixture for 24h in an oven at the temperature of 120 ℃ to obtain the shaddock peel powder after secondary purification;
s3, calcining: and (3) weighing 30g of the purified shaddock peel powder obtained in the step S2, placing the powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain the hard carbon material.
Comparative example 3
A preparation method of a nitrogen-doped hard carbon material comprises the following steps:
s1, carbon source preparation (primary purification): selecting shaddock peel as a precursor carbon source, removing inner skin and outer skin, taking a woody main body part of the shaddock peel, washing the shaddock peel with distilled water for three times, drying the shaddock peel in an oven for 24 hours at 120 ℃, then crushing the shaddock peel for 5 minutes by using a high-energy crusher at the rotating speed of 6000r/min, and sieving to obtain 325-mesh shaddock peel powder;
s2, secondary purification: weighing 100g of the shaddock peel powder obtained in the step S1, placing the weighed shaddock peel powder into a round-bottom flask, adding 10 wt% of dilute nitric acid into the round-bottom flask under the operation of reflux condensation of condensed water, refluxing for 1h in an oil bath at the temperature of 80 ℃, finally filtering, washing with distilled water for three times, and drying in an oven at the temperature of 120 ℃ for 24h to obtain secondarily purified shaddock peel powder;
s3, calcining: weighing 30g of the purified shaddock peel powder obtained in the step S2, placing the powder in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min under the argon atmosphere, carrying out high-temperature calcination treatment for 1h under the argon atmosphere of 0.2L/min, and then cooling under the argon atmosphere to obtain a biomass carbon material;
s4, plasma treatment: weighing 1g of the biomass carbon material in the step S3, placing the biomass carbon material in RF plasma equipment, and treating for 5min at the power of 100W under the condition of ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; the obtained hard carbon material was taken out, washed three times with diluted hydrochloric acid, then washed three times with distilled water, and finally dried in an oven at 120 ℃ for 24 hours.
The hard carbon material obtained in example 1 and the hard carbon material obtained in comparative example 2 were subjected to the relevant performance tests, and the test results are shown in fig. 1 to 6 and tables 1 and 2. Wherein fig. 1 and 2 are scanning electron micrographs of the hard carbon material of example 1 and the hard carbon material of comparative example 2, respectively; fig. 3 is an X-ray diffraction pattern of the hard carbon material of example 1 and the hard carbon material of comparative example 2; fig. 4 is a raman spectrum of the hard carbon material of example 1 and the hard carbon material of comparative example 2; fig. 5 is a nitrogen adsorption and desorption graph of the hard carbon material of example 1 and the hard carbon material of comparative example 2; fig. 6 is a pore size distribution diagram of the hard carbon material of example 1 and the hard carbon material of comparative example 2.
TABLE 1 content of nitrogen element in the material
TABLE 2 specific surface area, pore volume and pore diameter of the materials
Example 12
The hard carbon material prepared in example 1, the hard carbon material prepared in example 2, the hard carbon material prepared in comparative example 1 and the hard carbon material prepared in comparative example 2 were applied to a negative electrode of a sodium ion battery, specifically as follows:
(1) the hard carbon material obtained in example 1, sodium carboxymethylcellulose (CMC), and conductive carbon black were uniformly mixed in a mass ratio of 8:1:1, and an appropriate amount of distilled water (H) was added2O) preparing slurry (namely active material), coating the slurry on a copper foil with the diameter of 13mm, drying the copper foil in a vacuum drying oven for 6 hours at the temperature of 80 ℃ after a solvent is volatilized, and assembling the copper foil coated with the active material and an organic electrolyte into a button sodium-ion battery to carry out charge and discharge tests, wherein the voltage range is 0.01-3.0V.
Then respectivelyWorking electrodes were prepared in the same manner using the hard carbon materials prepared in example 2, comparative example 1, and comparative example 2, and were used to form button sodium ion batteries for charge and discharge tests with the voltage test range unchanged. The test results are shown in fig. 7 to 12 and table 3. Wherein, fig. 7 is a constant current charge and discharge curve diagram of the hard carbon material prepared in example 1; FIG. 8 is a constant current charge and discharge curve diagram of the carbon material prepared in comparative example 2; FIG. 9 shows carbon materials at 0.5mV s for the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2-1(ii) capacity contribution results; FIG. 10 is a graph of the cycle performance of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2; FIG. 11 is a potentiostatic titration plot of the hard carbon material prepared in example 1 and the carbon material prepared in comparative example 2; FIG. 12 is a graph of charge and discharge rate performance for the carbon material prepared in comparative example 1; table 3 shows the resistance values and the electrical conductivities of the hard carbon material prepared in example 1 and the hard carbon material prepared in comparative example 2.
TABLE 3 impedance and conductivity of the materials
As shown in fig. 7 and 8, at 0.1A g-1The negative electrode capacity of the sodium ion battery assembled in example 1 was 360.4mA hr g at the current density of (1)-1(ii) a While the negative electrode capacity of the sodium ion battery of comparative example 2 was 242.4mA hr g-1；
As shown in FIG. 9, at 0.5mV s-1At sweep rate, the capacity contribution of the sodium ion battery negative electrode of example 1 was 77.4%, while the capacity contribution of the sodium ion battery negative electrode assembled in comparative example 2 was in the 63.5% range;
as shown in fig. 10 and 11, the cycle performance and the ion diffusion coefficient of the hard carbon material prepared in example 1 were significantly superior to those of the hard carbon material prepared in comparative example 2.
As shown in fig. 7, 8 and 12, the capacity and rate performance of the hard carbon material prepared in example 1 is significantly superior to those of the hard carbon material prepared in comparative example 1.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a nitrogen-doped hard carbon material is characterized by comprising the following steps:
s1, preparation of carbon source: pretreating, drying and crushing the biomass raw material by high-energy ball milling to obtain primary purified biomass raw material powder;
s2, secondary purification: adding the biomass raw material powder into dilute nitric acid, heating, cooling to room temperature, filtering, washing and drying to obtain secondary purified biomass powder;
s3, calcining: calcining the biomass powder subjected to secondary purification in an argon atmosphere, and cooling in the argon atmosphere after calcining to obtain a biomass carbon material;
s4, plasma treatment: placing the biomass carbon material obtained in the step S3 in plasma equipment, and carrying out ammonia plasma treatment to obtain a nitrogen-doped hard carbon material; wherein the power is 400-800 w, and the processing time is 0-75 min.
2. The method for preparing a nitrogen-doped hard carbon material according to claim 1, wherein in the step S2, the dilute nitric acid is heated to 30 to 90 ℃ with a concentration of 0.5 to 60 wt%.
3. The method for preparing nitrogen-doped hard carbon material according to claim 2, wherein in step S2, the specific purification steps are: adding the biomass raw material powder into dilute nitric acid, refluxing at a constant temperature of 30-90 ℃ under the operation of reflux condensation of condensed water, filtering, washing and drying.
4. The method for preparing nitrogen-doped hard carbon material according to claim 1, wherein in step S3, the calcination temperature is 800-1400 ℃ and the calcination time is 0.5-5 h.
5. The method for preparing nitrogen-doped hard carbon material according to claim 1, wherein in step S1, the biomass raw material is pulverized by a high-energy pulverizer at a rotation speed of 500-9000 r/min for 0.2-15 min.
6. The method of claim 1, wherein the biomass feedstock is at least one of grapefruit peel, durian shell, coconut shell, badam, corn cob, shrimp shell, shallot, soybean, shiitake, orchid.
7. A nitrogen-doped hard carbon material produced by the production method according to any one of claims 1 to 6.
8. The nitrogen-doped hard carbon material according to claim 7, wherein the hard carbon material layer pitch is 0.37-0.46 nm, and the nitrogen content: 2.5 to 6.0 percent.
9. A sodium ion battery negative electrode comprising the nitrogen-doped hard carbon material according to claim 7 or 8.
10. A sodium ion battery comprising the negative electrode of claim 9.
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