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CN113506866B - Carbon-coated Fe 2 O 3 Hard carbon composite material and preparation method thereof - Google Patents

Carbon-coated Fe 2 O 3 Hard carbon composite material and preparation method thereof Download PDF

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CN113506866B
CN113506866B CN202110720807.2A CN202110720807A CN113506866B CN 113506866 B CN113506866 B CN 113506866B CN 202110720807 A CN202110720807 A CN 202110720807A CN 113506866 B CN113506866 B CN 113506866B
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carbon
hard carbon
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composite material
hard
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CN113506866A (en
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时爽二
陈慧龙
戚昌伟
张立君
王瑛
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Shandong Yuhuang New Energy Technology Co Ltd
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/027—Negative electrodes
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application discloses a carbon-coated Fe 2 O 3 A preparation method of a hard carbon composite material belongs to the technical field of sodium ion batteries. The method comprises the following steps: s1: washing the leaves with water, drying and crushing to obtain leaf particles; s2: soaking the leaf particles in ferric salt solution, filtering the leaf particles, and then drying, calcining and crushing to obtain Fe 2 O 3 Hard carbon material, fe 2 O 3 The particle size of the hard carbon material is 10-15 mu m, the porosity is 30-35%, and the pore diameter is 500nm-1 mu m; s3: the Fe is 2 O 3 Adding hard carbon material into organic carbon source liquid, mixing to obtain slurry, drying, sintering and pulverizing the slurry to obtain carbon-coated Fe 2 O 3 Hard carbon composite material, carbon-coated Fe 2 O 3 The particle size of the hard carbon composite material is 10.5-15.5 mu m, the porosity is 25-30%, and the pore diameter is 30-200 nm.

Description

Carbon-coated Fe 2 O 3 Hard carbon composite material and preparation method thereof
Technical Field
The application relates to carbon-coated Fe 2 O 3 A hard carbon composite material and a preparation method thereof belong to the technical field of sodium ion batteries.
Background
In recent years, the sales of new energy automobiles in China are continuously increased, and the new energy automobiles are stably placed in the first place of the world. However, the traditional lead-acid battery and nickel-cadmium battery have lower energy efficiency and serious pollution, the lithium ion battery has high cost and the safety is to be improved, and the market demand of new energy automobiles is increased rapidly, so that the market demand is difficult to meet. The sodium ion battery has the advantages of high safety, low cost, environmental friendliness and the like, is favored by researchers, and promotes the application of the sodium ion battery in the aspect of power batteries.
The hard carbon material is an amorphous carbon material difficult to graphitize, the structure is short-range ordered and long-range unordered, and the amorphous carbon material can be described as amorphous carbon formed by unordered stacking of countless tiny graphite-like nano-particles, and the amorphous carbon material is full of defects and gaps. The hard carbon material has good physical and chemical stability due to the unique disordered structure, and the carbon-based material has good conductivity, and the hard carbon material can be obtained by pyrolysis of a high polymer material and a biomass material, so that the structural design is easy to carry out, and the hard carbon material is a good composite material matrix. However, when the hard carbon material is used as a negative electrode material of a battery, the battery often has the defects of low reversible capacity, low first efficiency, low discharge voltage and the like, and the use of the hard carbon material is limited.
Disclosure of Invention
In order to solve the above problems, a carbon-coated Fe is provided 2 O 3 Method for preparing hard carbon composite material, and carbon-coated Fe prepared by method 2 O 3 The hard carbon composite material can improve the sodium storage capacity of the material, improve the first charge and discharge efficiency of the hard carbon material, and can improve the conductivity, increase the specific capacity of the battery and absorb stress when being used as a battery cathode material, thereby improving the cycle and the multiplying power performance of the battery.
The carbon-coated Fe 2 O 3 The preparation method of the hard carbon composite material comprises the following steps:
s1: washing the leaves with water, drying and crushing to obtain leaf particles;
s2: soaking the leaf particles in ferric salt solution, filtering the leaf particles, and then drying, calcining and crushing to obtain Fe 2 O 3 Hard carbon materialThe Fe is 2 O 3 The particle size of the hard carbon material is 10-15 mu m, the porosity is 30-35%, and the pore diameter is 50-250 nm;
s3: the Fe is 2 O 3 Adding hard carbon material into organic carbon source liquid, mixing to obtain slurry, drying, sintering and pulverizing the slurry to obtain carbon-coated Fe 2 O 3 Hard carbon composite material, said carbon coated Fe 2 O 3 The particle size of the hard carbon composite material is 10.5-15.5 mu m, the porosity is 25-30%, and the pore diameter is 30-200 nm.
Preferably, the carbon-coated Fe 2 O 3 The porosity of the hard carbon composite material is 28-30%, and the pore diameter is 50-150 nm.
More preferably, the carbon-coated Fe 2 O 3 The pore diameter of the hard carbon composite material is more than 50%, preferably more than 60%, more preferably more than 70%, most preferably more than 75% of Kong Zhanbi of 80-100 nm, so that more sodium storage space can be provided, and the specific capacity of the battery can be improved.
Soaking leaves in ferric salt solution and then calcining together to obtain Fe 2 O 3 The hard carbon material has unique dendritic grains, the hard carbon material can be obtained after calcining the tree leaves, more sites can be provided for embedding sodium ions, the iron oxide material has strong physical and chemical stability and strong structural design, has ultrahigh theoretical specific capacity, can increase the specific capacity of the hard carbon material, improves the sodium storage capacity of the hard carbon, and can be used as Fe 2 O 3 The buffer matrix of the material reduces the damage to the electrode structure caused by volume expansion of the composite material in the charge and discharge process.
In the synthesis of Fe 2 O 3 After the hard carbon material is added into the organic carbon source liquid, the mixture is sintered and crushed to obtain the carbon-coated Fe 2 O 3 The coated carbon shell can maintain the stability of the ferric oxide material, fully exert the synergistic effect of the ferric oxide and the carbon, and improve the electronic conductivity of the battery, and can form a carbon layer with short-range order and larger micropores at the sintering temperature, thereby being beneficial to sodium ions with larger ionic radiusAnd the transmission and adhesion are carried out, so that the first charge and discharge efficiency of the hard carbon is improved, and the cycle and rate capability of the battery are further improved.
Synthetic carbon coated Fe 2 O 3 Hard carbon composite material relative to Fe 2 O 3 For hard carbon materials, carbon coated Fe 2 O 3 The particle size of the hard carbon composite material is increased, but the change is not very large, the pore diameter and the porosity are reduced, the specific surface area of the composite material can be increased, the electrolyte can be easily permeated into the composite material, the migration rate of sodium ions in the charge and discharge process is improved, dead sodium is avoided, and the first effect and the circulation rate of the sodium ion battery are improved. The porosity of the composite material is favorable for the adsorption of ferric oxide, the specific capacity of the composite material is improved, and a small part of ferric oxide is embedded into holes, so that the influence on the embedding and the de-embedding of sodium ions is small; the aperture of the composite material is favorable for sodium ion intercalation and deintercalation, the aperture is too small, the intercalation and deintercalation of sodium ions in the charging and discharging process are unfavorable, the aperture is too large, the volume expansion is serious in the sodium intercalation process, the space between pole pieces is reduced, and the capacity of the battery cannot be normally exerted.
Optionally, the calcination temperature in the step S2 is 300-500 ℃ and the time is 1.5-5h;
preferably, the calcination in step S2 is a staged calcination, stage I: calcining at 300-350 ℃ for 20-60min, and stage II: calcining at 350-450 ℃ for 30-90min, and stage III: the calcination time is 450-500 ℃ and 30-200min.
More preferably, stage I: calcining at 320-350 ℃ for 30-50min, and stage II: calcining at 400-450 ℃ for 50-70min, stage III: the calcination time is 470-500 ℃ and 90-120min.
Most preferably, stage I: calcination temperature is 350 ℃, calcination time is 40min, and stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: calcination time was 480℃and 100min.
Calcining at 300-500 deg.C to obtain Fe 2 O 3 Hard carbon material, calcination temperature gradually increases, initial calcination temperatureLower, the obtained ferric oxide and the components in the hard carbon material react incompletely, the amorphous degree and the porosity of the hard carbon are increased, and the calcination temperature is increased later, so that Fe can be obtained 2 O 3 The porosity of the hard carbon material is ensured to be higher, and the reaction of the ferric oxide and the components in the hard carbon material is further promoted, so that the obtained ferric oxide and the hard carbon material still remain amorphous, the porosity can be in a higher range, the intercalation and deintercalation of sodium ions are facilitated, the migration rate of the sodium ions is facilitated, and the first effect of the battery is improved.
Optionally, the concentration of the ferric salt solution is 2.5-3mol/L, preferably 2.5mol/L, the solvent in the ferric salt solution is deionized water, and the weight ratio of the leaf particles to the ferric salt solution is 0.01-0.5:1, preferably 0.2:1.
Optionally, the Fe 2 O 3 Fe in hard carbon material 2 O 3 The content of the iron salt solution is 2-5%, and the iron salt solution also comprises 1% of ethanol, 0.1-0.5% of magnesium carbonate and 0.2-1% of organic silicon resin.
The content of the ferric oxide is controlled to be 2% -5%, so that the high specific capacity of the ferric oxide is exerted, and meanwhile, the excessively high content can be avoided, so that the hard carbon sodium embedding sites are occupied, and the migration of sodium ions is not facilitated. The concentration of the ferric salt solution is favorable for fully infiltrating the leaf particles, and the magnesium carbonate and the organic silicon resin are added into the ferric salt to be adhered to the leaf particles together with the ferric salt in the soaking process of the leaf particles, and when the solution is calcined at the back, the magnesium carbonate can produce carbon dioxide, so that larger holes are generated in the hard carbon material, sites are provided for the adsorption of the ferric oxide material, and meanwhile, the magnesium oxide material is generated, so that Fe can be stabilized 2 O 3 The structure of the hard carbon material can avoid collapse of the hard carbon material caused by overhigh porosity, reduce side reaction of the hard carbon and electrolyte, and further improve the specific capacity of the hard carbon material by cooperation with ferric oxide.
The organic silicon resin can increase the adsorption effect of the ferric oxide, improve the binding force of the ferric oxide and the hard carbon material, and avoid the charging and discharging of the ferric oxideThe falling off occurs in the electric process, thereby affecting the specific capacity of the battery and improving the circulation multiplying power of the battery. At the same time, part of the organic silicon resin can be ablated in the sintering of the step S3, and Fe coated by carbon 2 O 3 The interior of the hard carbon composite material is provided with holes, so that more sites are provided for sodium ion intercalation and deintercalation, and the organic silicon resin is tetraethyl orthosilicate.
Optionally, the sintering temperature in the step S3 is 1000-1500 ℃ and the sintering time is 5-15h;
preferably, the sintering in the step S3 is staged sintering, stage I: sintering temperature is 1000-1100 ℃, sintering time is 1-2h, and stage II: sintering temperature is 1100-1300 ℃, sintering time is 4-12h, and stage III: the sintering time is 1300-1500 ℃ and 1-1.5h.
More preferably, stage I: sintering temperature is 1050-1100 ℃, sintering time is 1-1.5h, and stage II: sintering temperature is 1200-1250 ℃, sintering time is 5-8h, and stage III: the sintering time is 1350-1400 ℃ and 1-1.5h.
Most preferably, stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature is 1200 ℃, sintering time is 6h, and stage III: sintering time is 1350 ℃ and 1.5 hours.
Obtaining the carbon-coated Fe through staged sintering 2 O 3 The hard carbon composite material can enable hard carbon in the composite material to form a short-range ordered structure, the long-range unordered structure is favorable for adsorption of sodium ion surfaces, the long-range unordered structure is favorable for mass embedding of sodium ions, and in the discharging process of a sodium ion battery, the rapid release of the sodium ions can be ensured, and the first discharging efficiency of the battery is improved.
Alternatively, the concentration of the organic carbon source solution is 1.0 to 2.0mol/L, preferably 1.5mol/L, and the Fe 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:5-10, preferably 1:6-8, more preferably 1:7. The proportion can ensure that the carbon layer is uniformly coated with Fe 2 O 3 Hard carbon material, a dense and uniform carbon layer is formed.
Optionally, the carbon coating amount is 2% -8%,the carbon-coated Fe 2 O 3 The thickness of the carbon coating layer in the hard carbon composite material is 20-50nm. The carbon coating amount can promote Fe 2 O 3 And hard carbon, and can enable the composite material to have enough sodium embedding sites, thereby facilitating the embedding of sodium ions and further improving the capacity of the battery. The carbon coating amount is too small, the structure of the composite material is unstable, side reactions are easy to occur, the cycle performance of the battery is reduced, and the carbon coating amount is too large, so that sodium embedding sites can be occupied to a certain extent, and the specific capacity of the battery is reduced.
Optionally, the calcining in the step S2 and the sintering in the step S3 are both performed under a protective gas, and the protective gas is any one or more of nitrogen, argon and helium. The calcination and sintering under the protective gas can reduce the adverse effect of harmful components (water and oxygen) in the atmosphere on the product, is beneficial to the removal of impurities such as silicon, aluminum, magnesium, calcium and the like or oxides thereof, and plays a role in purifying materials.
Optionally, the leaf particles are firstly mixed in the ferric salt solution, then the ferric salt solution is heated to 40-60 ℃, soaked for 2-5 hours and filtered, and the mixing method is any one or more of ball milling, stirring and ultrasonic dispersion. The temperature of the ferric salt is controlled at 40-60 ℃, so that the ferric salt solution is favorable for fully infiltrating the leaf particles, and the ferric oxide and the hard carbon materials are convenient to adsorb and combine.
Optionally, the anion of the iron salt is any one or more of acetate, propionate, oxalate, malonate, succinate, citrate, benzoic acid, phthalic acid, lactic acid, glycinate and salicylate, and is preferably citrate; the negative ions are stable and easy to dissolve in hot water, and the operation is simple.
The organic carbon source is any one or more of citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline, asphalt, phenolic resin, epoxy resin and polyimide, preferably glucose, and the material is easy to obtain, convenient to dissolve, has small influence on the environment and is suitable for mass production.
According to yet another aspect of the present application, there is provided a carbon-coatedFe 2 O 3 A hard carbon composite material prepared using the preparation method of any one of the above.
The beneficial effects of the application include, but are not limited to:
1. according to the preparation method of the composite material, the hard carbon material is obtained after the special dendritic grains in the leaves are utilized and calcined, more sites can be provided for embedding sodium ions, the iron oxide material has strong physical and chemical stability and strong structural design, has ultrahigh theoretical specific capacity, can increase the specific capacity of the hard carbon material, improves the sodium storage capacity of the hard carbon, and can be used as Fe 2 O 3 The buffer matrix of the material reduces the damage to the electrode structure caused by volume expansion of the composite material in the charge and discharge process.
2. According to the preparation method of the composite material, the coated carbon shell can promote Fe 2 O 3 The hard carbon material plays a synergistic effect, improves the specific capacity of the battery, stabilizes various performances of the battery, reduces the heat release of the battery during charge and discharge, improves the cycle performance of the battery, and prolongs the service life of the battery.
3. According to the preparation method of the composite material, the porosity of 25-30% can increase the specific surface area of the composite material, is favorable for sodium ions to migrate in the composite material, improves migration rate, avoids dead sodium, improves the energy density of a sodium ion battery, and is favorable for the adsorption of ferric oxide and improves the specific capacity of the battery.
4. According to the preparation method of the composite material, the pores with the diameter of 30nm-50nm are favorable for embedding and extracting sodium ions, so that the charge and discharge efficiency is improved, the pores with the diameter of more than 50nm are favorable for migration of sodium ions in the hard carbon material, and meanwhile, the volume expansion in sodium embedding is reduced.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
The starting materials and catalysts in the examples of the present application were purchased commercially, including iron salts, organic carbon sources, magnesium carbonate, and silicone resins, unless otherwise specified.
The batteries prepared in the examples and comparative examples of the present application were divided into three batches, five were prepared for each batch, and after defective products were removed, analysis and test were performed on the batteries.
Analysis of instrument information used for the test:
the model of the testing instrument for particle size and porosity is respectively as follows: mastersizer 3000, NOVA 2000e, pore size testing was performed using a NOVA touch, pore size analyzer, which was purchased from An Dongpa (Shanghai) commercial company, inc., and the prepared composite was subjected to electron microscopy to observe pore size distribution.
The instrument model used for the test was: CT-4008T-5V12A-S1-F, available from Shenzhen New wile electronic Co.
Analysis test conditions:
testing the initial efficiency, the charge-discharge capacity and the energy density of the battery under the voltage range of 1.0-4.2V and the current density of 0.1-5C;
the discharge test was performed for 100 weeks at a voltage ranging from 1.0 to 4.2V and a current density of 1C, to obtain a capacity retention rate after 100 weeks of circulation.
Example 1
(1) Washing the leaves with water, drying and crushing to obtain leaf particles;
(2) The leaf particles in the step (1) are placed in an iron salt solution, the temperature is raised to 50 ℃ for soaking, wherein the negative ions of the iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the solution comprises 1% of ethanol, 0.1% of magnesium carbonate and 1% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, the leaf particles are filtered out after soaking for 4 hours, and then the leaf particles are dried, calcined and crushed, and the calcination is divided into three stages, namely: calcination temperature is 350 ℃, calcination time is 40min, and stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: calcining at 480 ℃ for 100min;
(3) The Fe is mixed with 2 O 3 Adding hard carbon material into organic carbon source solution, mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 1.5mol/L, fe 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:7, and the slurry is preparedDrying, sintering and crushing, wherein the sintering is divided into three stages, namely, stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature is 1200 ℃, sintering time is 6h, and stage III: sintering time is 1350 ℃ and 1.5 hours;
thus obtaining the composite material No. 1.
Example 2
(1) The same as in example 1;
(2) The leaf particles in the step (1) are placed in an iron salt solution, the temperature is raised to 50 ℃ for soaking, wherein the negative ions of the iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, the leaf particles are filtered out after soaking for 4 hours, and then the leaf particles are dried, calcined and crushed, and the calcination is divided into three stages, namely, stage I: calcination temperature is 350 ℃, calcination time is 40min, and stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: calcining at 480 ℃ for 100min;
(3) The same as in example 1;
thus obtaining the composite material No. 2.
Example 3
(1) The same as in example 1;
(2) The leaf particles in the step (1) are placed in an iron salt solution, the temperature is raised to 50 ℃ for soaking, wherein anions of the iron salt are citrate, the concentration of the iron salt solution is 0.5mol/L, the solution comprises 1% of ethanol, 0.1% of magnesium carbonate and 1% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.5:1, the soaked leaf particles are filtered out after 4 hours of filtering, and then the leaf particles are dried, calcined and crushed, and the calcination is divided into three stages, namely, stage I: calcination temperature is 350 ℃, calcination time is 40min, and stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: calcining at 480 ℃ for 100min;
(3) The same as in example 1;
thus obtaining the composite material 3#.
Example 4
(1) (2) the same as in example 1;
(3) The Fe is mixed with 2 O 3 Adding hard carbon material into organic carbon source solution, mixing to obtain slurry, wherein the concentration of the organic carbon source solution is1.5mol/L，Fe 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:10, and the slurry is dried, sintered and crushed, wherein the sintering is divided into three stages, namely, stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature is 1200 ℃, sintering time is 6h, and stage III: sintering time is 1350 ℃ and 1.5 hours;
thus obtaining the composite material No. 4.
Example 5
(1) (2) the same as in example 1;
(3) The Fe is mixed with 2 O 3 Adding hard carbon material into organic carbon source solution, mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 0.5mol/L, fe 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:3, and the slurry is dried, sintered and crushed, wherein the sintering is divided into three stages, namely, stage I: sintering temperature 1050 ℃, sintering time 1.5h, stage II: sintering temperature is 1200 ℃, sintering time is 6h, and stage III: sintering time is 1350 ℃ and 1.5 hours;
thus obtaining the composite material No. 5.
Comparative example 1
(1) The same as in example 1;
(2) The leaf particles in the step (1) are placed in an iron salt solution, the temperature is raised to 50 ℃ for soaking, wherein the negative ions of the iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the solution comprises 1% of ethanol, 0.1% of magnesium carbonate and 1% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, the leaf particles are filtered out after soaking for 4 hours, and then the leaf particles are dried, calcined and crushed, the calcining temperature is 500 ℃, and the calcining time is 3 hours;
(3) The same as in example 1.
Thus obtaining the comparative composite material No. 1.
Comparative example 2
(1) The same as in example 1;
(2) The leaf particles in the step (1) are placed in an iron salt solution, the temperature is raised to 50 ℃ for soaking, wherein anions of the iron salt are citrate, the concentration of the iron salt solution is 2.5mol/L, the solution comprises 1% of ethanol, 1% of magnesium carbonate and 5% of organic silicon resin, the weight ratio of the leaf particles to the iron salt solution is 0.2:1, the soaked leaf particles are filtered out after 4 hours of soaking, and then the leaf particles are dried, calcined and crushed, and the calcination is divided into three stages, namely: calcination temperature is 350 ℃, calcination time is 40min, and stage II: calcination temperature 420 ℃, calcination time 60min, stage iii: calcining at 480 ℃ for 100min;
(3) The same as in example 1;
thus obtaining the comparative composite material No. 2.
Comparative example 3
(1) (2) the same as in example 1
(3) The Fe is mixed with 2 O 3 Adding hard carbon material into organic carbon source solution, mixing to obtain slurry, wherein the concentration of the organic carbon source solution is 1.5mol/L, fe 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:7, and the slurry is dried, sintered and crushed, wherein the sintering temperature is 1200 ℃ and the sintering time is 9 hours;
thus obtaining the comparative composite material No. 3.
The particle size, pore diameter and porosity of the prepared composite material 1# -5# and comparative composite material 1# -3# are tested, and the results are shown in table 1:
TABLE 1
Experimental example
The composite material 1# -5# prepared in the example and the comparative composite material 1# -3# prepared in the comparative example are respectively prepared by mixing conductive carbon black and sodium carboxymethyl cellulose according to a mass ratio of 80:10:10 are mixed in deionized water, ground into paste, coated on a copper foil current collector, then dried for 12 hours at 80 ℃, a plurality of pole pieces with the diameter of 12mm are cut out by a cutting machine, weighed, the mass of hard carbon materials (active substances) is calculated, then in an argon protection glove box, a metal sodium sheet is taken as a positive electrode, glass fibers are taken as a diaphragm, and 1mol/L NaClO is taken as a diaphragm 4 And (3) taking the PC solution as electrolyte, assembling 2032 button type half-cell, and carrying out charge and discharge test on the sodium ion half-cell in a constant current charge and discharge mode, wherein the voltage range is 1.0-4.2V. The test results are shown in Table 2The illustration is:
TABLE 2
The experimental data show that when the composite material prepared by the application is used as the negative electrode material of the sodium ion battery, the side reaction of the negative electrode material and electrolyte can be reduced, the cycle performance of the battery is improved, meanwhile, the pore diameter of the composite material is beneficial to the infiltration of the electrolyte, the migration rate of sodium ions in the electrolyte is improved, the sodium death phenomenon is reduced, the first effect and the energy density of the sodium ion battery are improved, the adsorption of ferric oxide is facilitated, the specific capacity of the composite material is improved, the service time of the sodium ion battery is prolonged, and the large-scale production is facilitated.
The above description is only an example of the present application, and the scope of the present application is not limited to the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.

Claims (13)

1. Carbon-coated Fe 2 O 3 The preparation method of the hard carbon composite material is characterized by comprising the following steps:
s1: washing the leaves with water, drying and crushing to obtain leaf particles;
s2: soaking the leaf particles in ferric salt solution, filtering the leaf particles, and then drying, calcining and crushing to obtain Fe 2 O 3 Hard carbon material, fe 2 O 3 The particle size of the hard carbon material is 10-15 mu m, the porosity is 30-35%, and the pore diameter is 50-250 nm;
s3: the Fe is 2 O 3 Adding hard carbon material into organic carbon source liquid, mixing to obtain slurry, drying, sintering and pulverizing the slurry to obtain carbon-coated Fe 2 O 3 Hard carbonComposite material, carbon-coated Fe 2 O 3 The particle size of the hard carbon composite material is 10.5-15.5 mu m, the porosity is 25-30%, and the pore diameter is 30-200 nm;
the calcination temperature in the step S2 is 300-500 ℃ and the time is 1.5-5h, and the calcination in the step S2 is staged calcination; stage I in the staged calcination: calcining at 300-350 ℃ for 20-60min, and stage II: calcining at 350-450 ℃ for 30-90min, and stage III: calcining for 30-200min at 450-500 ℃;
the sintering temperature in the step S3 is 1000-1500 ℃ and the time is 5-15h, and the sintering in the step S3 is staged sintering; stage I in the staged sintering: sintering temperature is 1000-1100 ℃, sintering time is 1-2h, and stage II: sintering temperature is 1100-1300 ℃, sintering time is 4-12h, and stage III: sintering time is 1300-1500 ℃ and 1-1.5h;
the Fe is 2 O 3 Fe in hard carbon material 2 O 3 The content of the iron salt solution is 2-5%, and the iron salt solution also comprises 1% of ethanol, 0.1-0.5% of magnesium carbonate and 0.2-1% of organic silicon resin.
2. The carbon-coated Fe of claim 1 2 O 3 The preparation method of the hard carbon composite material is characterized in that the concentration of the ferric salt solution is 2.5-3mol/L, and the solvent in the ferric salt solution is deionized water;
the weight ratio of the leaf particles to the ferric salt solution is 0.01-0.5:1.
3. The carbon-coated Fe of claim 2 2 O 3 The preparation method of the hard carbon composite material is characterized in that the concentration of the ferric salt solution is 2.5mol/L.
4. The carbon-coated Fe of claim 2 2 O 3 The preparation method of the hard carbon composite material is characterized in that the weight ratio of the leaf particles to the ferric salt solution is 0.2:1.
5. The carbon-coated Fe of claim 1 2 O 3 The preparation method of the hard carbon composite material is characterized in that the concentration of the organic carbon source solution is 1.0-2.0mol/L;
the Fe is 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:5-10.
6. The carbon-coated Fe of claim 5 2 O 3 A method for producing a hard carbon composite material, characterized in that the concentration of the organic carbon source solution is 1.5mol/L.
7. The carbon-coated Fe of claim 5 2 O 3 A process for producing a hard carbon composite material, characterized in that the Fe 2 O 3 The weight ratio of the hard carbon material to the organic carbon source solution is 1:7.
8. The carbon-coated Fe of claim 5 2 O 3 A method for producing a hard carbon composite material, characterized in that the carbon-coated amount is 2% -8%, and the carbon-coated Fe 2 O 3 The thickness of the carbon coating layer in the hard carbon composite material is 20-50nm.
9. The carbon-coated Fe of claim 1 2 O 3 The preparation method of the hard carbon composite material is characterized in that the calcination in the step S2 and the sintering in the step S3 are carried out under the protection gas, and the protection gas is one or more of nitrogen, argon and helium; and/or
The leaf particles are firstly mixed in the ferric salt solution, then the ferric salt solution is heated to 40-60 ℃, soaked for 2-5 hours and filtered, and the mixing method is any one or more of ball milling, stirring and ultrasonic dispersion.
10. The carbon-coated Fe of claim 1 2 O 3 A method for preparing a hard carbon composite material, characterized in that,the negative ions of the ferric salt are any one or more of acetate, propionate, oxalate, malonate, succinate, citrate, benzoic acid, phthalic acid, lactic acid, glycinate and salicylate;
the organic carbon source is any one or more of citric acid, sucrose, glucose, polyvinylpyrrolidone, starch, dextrin, polyaniline, asphalt, phenolic resin, epoxy resin and polyimide.
11. The carbon-coated Fe of claim 10 2 O 3 The preparation method of the hard carbon composite material is characterized in that the anion of the ferric salt is citrate.
12. The carbon-coated Fe of claim 10 2 O 3 The preparation method of the hard carbon composite material is characterized in that the organic carbon source is glucose.
13. Carbon-coated Fe 2 O 3 Hard carbon composite material, characterized in that it is produced by the production method according to any one of claims 1 to 12.
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