CN109167035B - Carbon-coated ferrous sulfide negative electrode material, preparation method and sodium ion battery prepared from carbon-coated ferrous sulfide negative electrode material - Google Patents

Carbon-coated ferrous sulfide negative electrode material, preparation method and sodium ion battery prepared from carbon-coated ferrous sulfide negative electrode material Download PDF

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CN109167035B
CN109167035B CN201810961175.7A CN201810961175A CN109167035B CN 109167035 B CN109167035 B CN 109167035B CN 201810961175 A CN201810961175 A CN 201810961175A CN 109167035 B CN109167035 B CN 109167035B
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electrode material
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ferrous sulfide
sulfate
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陈卫华
关新新
杨丹
米立伟
张建民
张继雨
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Zhengzhou University
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Abstract

本发明涉及一种碳包覆的硫化亚铁负极材料、制备方法及其制备的钠离子电池，碳包覆的硫化亚铁负极材料是指碳包覆的硫化亚铁及其掺杂修饰材料，其中硫化亚铁颗粒粒径为100~500 nm，碳包覆层的质量为电极材料质量的3%~30%，掺杂修饰元素为M=Co、Ni、Mn、Ti、Cu、Mg、Ba、Pb、Al等中的一种或几种,掺杂修饰元素的质量为负极材料质量的0~30%。制备方法是将金属硫酸盐和碳源添加到去离子水中，室温搅拌溶解混合均匀后冷冻干燥制得前驱体，在惰性气氛下高温煅烧制得碳包覆的硫化亚铁负极材料。本发明作为钠离子电池负极材料，具有原料丰富、制备简单、制备周期短、成本低、无污染、倍率性能好和循环稳定性强的优点，且适合大规模生产。

Figure 201810961175

The invention relates to a carbon-coated ferrous sulfide negative electrode material, a preparation method and a sodium ion battery prepared therefrom. The carbon-coated ferrous sulfide negative electrode material refers to carbon-coated ferrous sulfide and its doped modification material, Among them, the particle size of ferrous sulfide is 100~500 nm, the mass of carbon coating is 3%~30% of the mass of the electrode material, and the doping modification elements are M=Co, Ni, Mn, Ti, Cu, Mg, Ba One or more of , Pb, Al, etc., and the mass of the doping modification element is 0~30% of the mass of the negative electrode material. The preparation method is as follows: adding metal sulfate and carbon source into deionized water, stirring, dissolving, and mixing at room temperature to obtain a precursor, and then calcining at high temperature in an inert atmosphere to obtain a carbon-coated ferrous sulfide negative electrode material. As a negative electrode material for a sodium ion battery, the invention has the advantages of abundant raw materials, simple preparation, short preparation period, low cost, no pollution, good rate performance and strong cycle stability, and is suitable for large-scale production.

Figure 201810961175

Description

Carbon-coated ferrous sulfide negative electrode material, preparation method and sodium ion battery prepared from carbon-coated ferrous sulfide negative electrode material
Technical Field
The invention relates to the technical field of new energy, in particular to a carbon-coated ferrous sulfide negative electrode material, a preparation method and a sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material.
Background
The lithium ion battery has the advantages of small volume, high voltage, high energy density and the like as a chemical energy source. Lithium ion batteries are widely used in human life, and have been used in small devices such as mobile phones and computers, and high-power application devices such as electric vehicles and smart grids. But the characteristics of uneven distribution of lithium resources, high cost and the like limit the large-scale application of the lithium ion battery. The sodium ion battery and the lithium ion battery have similar working principles, and have unique advantages in the fields of next generation transportation, power grids and the like by virtue of the advantages of low price, rich reserves and the like.
Transition metal sulfides are receiving more and more attention in the field of negative electrode materials of sodium ion batteries because of the advantages of high specific capacity, good conductivity and the like. However, such materials expand in volume severely during charge and discharge, and polysulfide dissolves in an electrolyte during a cycle, resulting in loss of an active material, resulting in capacity reduction and deterioration of cycle stability. Particle nanocrystallization and surface carbon coating are effective strategies for solving the problems, but the currently reported synthetic methods are generally complex in process and high in production cost, and organic solvents are mostly adopted, so that the environment is polluted.
The exploration for finding a synthetic method of the cathode material with high specific capacity, good circulation stability, rich raw materials, low price, simple synthesis and no pollution is always carried out. According to the Kim topic group, ferrous sulfate is completely dissolved in deionized water at 80 ℃, glycine is added as a ligand, heating and stirring are carried out until complexation is completely carried out, a terminator citric acid is added, the solution is transferred to a drying oven at 110 ℃ to be thermally dried to generate a metal organic complex precursor after the citric acid is completely dissolved, and the metal organic complex precursor is calcined to generate nitrogen and sulfur co-doped honeycomb Carbon-coated ferrous sulfide serving as a lithium ion battery cathode material (Carbon, 2017, 115: 249-364). However, the raw materials are various, the synthesis steps are relatively complex, and the time is long.
Disclosure of Invention
The invention provides a carbon-coated ferrous sulfide negative electrode material, a preparation method and a sodium ion battery prepared from the material. Meanwhile, the material has the electrochemical advantages of high capacity, good rate capability and strong cycle stability. In addition, the sodium ion battery containing the material has wide market application prospect as a new generation battery.
The technical scheme for realizing the invention is as follows: a carbon-coated ferrous sulfide negative electrode material is a carbon-coated ferrous sulfide material, the mass of a carbon coating layer is 3% -30% of the mass of the negative electrode material, and the particle size of ferrous sulfide particles is 100-500 nm.
The cathode material also contains doping modification elements, and the doping modification elements are one or more of Co, Ni, Mn, Ti, Cu, Mg, Ba, Pb and Al; the mass of the carbon coating layer in the negative electrode material is 3% -30% of the mass of the negative electrode material, and the mass of the doped modifying element is 0% -30% of the mass of the negative electrode material.
The preparation method of the carbon-coated ferrous sulfide negative electrode material comprises the following steps:
(1) dissolving a carbon source, ferrous sulfate and doped metal sulfate in deionized water, stirring and mixing uniformly, and then carrying out freeze drying at minus 40 to minus 56 ℃ for 6 to 60 hours to prepare a precursor;
(2) and (2) grinding the precursor obtained in the step (1), and then placing the ground precursor in a tubular furnace in an inert atmosphere to calcine for 1-24 h at 500-850 ℃ to obtain the carbon-coated ferrous sulfide negative electrode material.
In the step (1), the mass ratio of the carbon source, the ferrous sulfate, the doped metal sulfate and the deionized water is (1-10): 1, (0-1): 4-1000.
The carbon source in the step (1) is one or more of citric acid, ascorbic acid and glucose; the doped metal sulfate is one or more of ammonium ferrous sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, titanium sulfate, copper sulfate, magnesium sulfate, barium sulfate, lead sulfate and aluminum sulfate.
The sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material comprises a positive electrode plate, a negative electrode plate, electrolyte, a diaphragm and a shell, wherein the sodium ion battery takes an embeddable sodium active material as the positive electrode material, the carbon-coated ferrous sulfide negative electrode material as the negative electrode material, the diaphragm is one or more of a glass fiber diaphragm, a polypropylene diaphragm, a polyethylene diaphragm and a modified cellulose acetate diaphragm, and a soluble sodium salt organic solution is the electrolyte.
The active material capable of inserting and removing sodium is Na3V2(PO4)3、Na3V2(PO4)2F3、NaFePO4、NaMnO2、NaFeO2、FePO4、Na2.4Fe1.8(SO4)3、Na4Fe(CN)6、Na4Co3(PO4)2P2O7One or more of the electrode materials.
The soluble sodium salt organic solution is obtained by dissolving sodium salt in an organic solvent, wherein the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate and sodium bistrifluoromethylsulfonyl imide, and the organic solvent is one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, diglyme and triglyme.
The positive plate is obtained by filling slurry obtained by uniformly mixing a positive material with a conductive agent, a binder and a dispersing agent into a current collector, the negative plate is obtained by filling slurry obtained by uniformly mixing a negative material with the conductive agent, the binder and the dispersing agent into the current collector, and the current collector is one of a porous, net-shaped or thin-film material of nickel and aluminum, carbon cloth and metal stainless steel; the conductive agent is one or more of acetylene black, graphite or Super P Li; the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, polyacrylic acid, sodium alginate, gelatin or styrene butadiene rubber; the dispersant is one or more of water, ethanol, isopropanol or 1-methyl-2-pyrrolidone.
The shell is made of organic plastics, an aluminum shell, an aluminum plastic film, stainless steel and a stainless steel composite material and is in a buckled, columnar or square shape.
The invention has the beneficial effects that: according to the invention, the uniform carbon-coated ferrous sulfide can be obtained by uniformly mixing ferrous sulfate and a carbon source in deionized water at room temperature, freezing, drying and calcining, and can be successfully used as a cathode material of a sodium ion battery, and excellent cycle stability and rate capability are shown. Meanwhile, the preparation method is simple, easy for large-scale production and has wide market application prospect. The carbon-coated ferrous sulfide and the doped modified substance thereof are used as the cathode material in a sodium ion battery system, the problems of volume expansion, poor conductivity, polysulfide dissolution and the like of the material can be effectively relieved by the short transmission path of the nano structure and the in-situ carbon coating, and meanwhile, the electrode material has excellent cycle performance and rate capability. The material has the advantages of low price of raw materials, no pollution of a solvent, simple and easy operation of a preparation method, short time consumption, suitability for large-scale production and hopeful realization of commercialization.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction (XRD) pattern of the carbon-coated ferrous sulfide prepared in example 1.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the carbon-coated ferrous sulfide prepared in example 1.
Fig. 3 is a battery first cycle charge and discharge curve of the carbon-coated ferrous sulfide prepared in example 1 as a negative electrode material.
Fig. 4 is a battery rate performance plot of carbon-coated ferrous sulfide prepared in example 2 as a negative electrode material.
Fig. 5 is a first cycle charge and discharge curve of a sodium ion battery assembled with the carbon-coated ferrous sulfide as a negative electrode material prepared in example 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
In the embodiment, the particle size of the ferrous sulfide material coated by carbon is 100-500 nm, wherein the mass of the coating layer is 10% of the mass of the material.
The synthesis steps of the carbon-coated ferrous sulfide material used in the invention are as follows:
(1) 0.96g of ferrous sulfate heptahydrate and 2.18 g of citric acid monohydrate are weighed and dissolved in 7 mL of deionized water, stirred and mixed uniformly, and then the mixture is frozen and dried for 24 hours at the temperature of minus 56 ℃ to prepare a precursor;
(2) and (2) grinding the precursor obtained in the step (1), then placing the ground precursor into a tubular furnace with an inert atmosphere, calcining for 6 hours at 800 ℃, and grinding to obtain a carbon-coated ferrous sulfide substance.
FIG. 1 is an X-ray diffraction (XRD) pattern of a carbon-coated ferrous sulfide material, corresponding to JCPDS 37-0477 standard card of ferrous sulfide, and having good crystallinity. Fig. 2 is a Scanning Electron Microscope (SEM) image of a carbon-coated ferrous sulfide material, in which the diameter range of the ferrous sulfide nanoparticles is 100 to 500nm, and the mass of the carbon coating layer is 10% of the mass of the electrode material.
Taking the prepared carbon-coated ferrous sulfide substance as a negative active material, and mixing the negative active material with conductive carbon (Super P Li) and sodium carboxymethylcellulose in a ratio of 80: 10: mixing at a mass ratio of 10, adopting deionized water as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, drying at 60 ℃, cutting to obtain a negative electrode plate, adopting a metal sodium plate as a counter electrode (the capacity of the negative electrode plate is far greater than that of a cut positive electrode plate), separating the negative electrode plate and the metal sodium plate by adopting a Whatman glass fiber membrane, and adopting 1M NaClO4Dissolution in EC: PC (volume ratio 1: 1) (FEC additive) is chargedAnd (3) assembling the electrolyte and a stainless steel shell as a shell into a CR2025 type button battery, wherein the battery assembled in the process is subjected to charge and discharge tests in a potential range of 0.01-2.5V at room temperature, and the charge and discharge curve of the battery is shown in figure 4. The charge and discharge curves are shown in FIG. 3. The first cycle charging specific capacity is 597.5 Ma h/g, the discharging specific capacity is 649.45mAh/g, and the coulombic efficiency is 92%.
Example 2
This example was prepared as in example 1.
Taking the prepared carbon-coated ferrous sulfide substance as a negative active material, and mixing the negative active material with conductive carbon (Super P Li) and sodium carboxymethylcellulose in a ratio of 80: 10: mixing at a mass ratio of 10, adopting deionized water as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, drying at 60 ℃, cutting to obtain a negative pole piece, adopting a metal sodium piece as a counter electrode (the capacity of the counter electrode is far greater than that of the cut negative pole piece), separating the negative pole piece and the metal sodium piece by adopting a Whatman glass fiber membrane, and adopting 1M NaCF3SO3Dissolving in diethylene glycol dimethyl ether as electrolyte, using a stainless steel shell as a shell, assembling into a CR2025 type button battery, and performing charge-discharge test on the battery assembled in the process at room temperature within a potential range of 0.3-2.5V. The rate capability is shown in fig. 4. At 10A g-1The specific discharge capacity of the material can reach 315.4mAh/g, 2A g-1The material still keeps 374.7mAh/g capacity after 800 weeks of circulation under the current density, and the capacity retention rate is 92%.
Example 3
This example was prepared as in example 1.
Taking the prepared carbon-coated ferrous sulfide substance as a negative active material, and mixing the negative active material with conductive carbon (Super P Li) and sodium carboxymethylcellulose in a ratio of 80: 10: 10, adopting deionized water as a dispersant, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, and adding Na3V2(PO4)3As the positive electrode active material, the positive electrode active material was mixed with acetylene black and polyvinylidene fluoride in a ratio of 80: 10: 10 mass ratio of 1-2 methylPyrrolidone as a dispersing agent, uniformly mixing the mixture to form slurry, coating the slurry on an aluminum foil, drying and cutting at 60 ℃ to obtain a corresponding negative pole piece and a positive pole piece (the positive pole capacity is far greater than the capacity of the cut negative pole piece), separating the negative pole piece and the positive pole piece by adopting a Whatman glass fiber membrane, and using 1M NaClO4Dissolution in EC: PC (volume ratio 1: 1) (FEC additive) is used as electrolyte, stainless steel shell is used as shell, CR2025 type button cell is assembled, the sodium ion cell assembled in the process is subjected to charge-discharge test in the potential range of 1.0-3.2V at room temperature, and the charge-discharge curve is shown in figure 5. The second cycle specific charge capacity is 528.5 mA h/g, the discharge specific capacity is 482.5 mA h/g, the coulombic efficiency is 91.3 percent, and the specific charge capacity is 0.5A g-1The material still keeps the capacity of 415.6 mA h/g after 100-week circulation under the current density, and the capacity retention rate is 86.8%.
Example 4
In the embodiment, the particle size of the ferrous sulfide material coated by carbon is 300-500 nm, wherein the mass of the coating layer is 15% of the mass of the material.
The preparation method of the carbon-coated ferrous sulfide electrode material comprises the following steps:
(1) weighing 0.96g of ferrous sulfate heptahydrate and 2.44g of ascorbic acid, dissolving in 100mL of deionized water, stirring and mixing uniformly, and then carrying out freeze drying at-40 ℃ for 48h to obtain a precursor;
(2) and (2) grinding the precursor obtained in the step (1), then placing the ground precursor into a tubular furnace with an inert atmosphere, calcining for 8 hours at 800 ℃, and grinding to obtain a carbon-coated ferrous sulfide substance.
The prepared carbon-coated ferrous sulfide substance is used as a negative active material, and the ratio of the negative active material to conductive carbon (acetylene black) and gelatin is 70: 15: mixing at a mass ratio of 15, adopting deionized water as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, drying at 60 ℃, cutting to obtain a negative pole piece, adopting a metal sodium piece as a counter electrode (the capacity of the counter electrode is far greater than that of the cut negative pole piece), separating the negative pole piece and the metal sodium piece by adopting a modified acetate fiber diaphragm, and adopting 1M NaPF6Dissolution in EC: DMC (volume ratio 1: 1) (FEC additive) as electrolyte, stainless steel shell as outer shell, assemblingForming a CR2025 type button cell, and performing charge-discharge test on the cell assembled by the above process at room temperature within a potential range of 0.3-2.5V.
Example 5
This example was prepared as in example 4.
Taking the prepared carbon-coated ferrous sulfide substance as a negative active material, and mixing the negative active material with conductive carbon (Super P Li) and sodium carboxymethylcellulose in a ratio of 80: 10: 10, adopting deionized water as a dispersant, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, and adding Na2.4Fe1.8(SO4)3As a positive electrode active material, the positive electrode active material was mixed with acetylene black and polyvinylidene fluoride in a ratio of 70: 20: mixing at a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on an aluminum foil, drying and cutting at 60 ℃ to obtain a corresponding negative pole piece and a positive pole piece (the capacity of the positive pole is far larger than that of the cut negative pole piece), separating the negative pole piece and the positive pole piece by adopting a Whatman glass fiber membrane, and using 1M NaClO4Dissolution in EC: and PC (the volume ratio is 1: 1) (FEC additive) is used as electrolyte, a stainless steel shell is used as a shell, the CR2025 type button cell is assembled, and the sodium ion cell assembled in the process is subjected to charge-discharge test within a potential range of 1.0-3.2V at room temperature.
Example 6
Carbon coated Fe in this example5Ni4S8The particle size of the material is 300-500 nm, wherein the mass of the coating layer is 3% of the mass of the material, and the mass of the doping element is 30% of the mass of the material.
Carbon coated Fe5Ni4S8The preparation method of the electrode material comprises the following steps:
(1) 0.68g of ammonium ferrous sulfate hexahydrate, 0.46g of nickel sulfate hexahydrate and 3.28g of citric acid monohydrate are weighed and dissolved in 100mL of deionized water, stirred and mixed uniformly, and then freeze-dried for 12 hours at the temperature of minus 40 ℃ to prepare a precursor;
(2) grinding the precursor obtained in the step (1), putting the ground precursor into a tubular furnace with inert atmosphere, calcining for 5 hours at 700 ℃, and grinding to obtain the carbon-coated carbonFe (b) of5Ni4S8An electrode material.
Fe coated with the prepared carbon5Ni4S8The electrode material is used as a negative active material, and the ratio of the negative active material to conductive carbon (Super P Li) and sodium carboxymethyl cellulose is 70: 15: mixing at a mass ratio of 15, adopting deionized water as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, drying at 60 ℃, cutting to obtain a negative pole piece, adopting a metal sodium piece as a negative pole (the capacity of a counter electrode is far greater than that of the cut negative pole piece), separating the negative pole piece and the metal sodium piece by adopting a polypropylene diaphragm, and adopting 1M NaCF3SO3Dissolving in diethylene glycol dimethyl ether as electrolyte, using a stainless steel shell as a shell, assembling into a CR2025 type button battery, and performing charge-discharge test on the battery assembled in the process at room temperature within a potential range of 0.3-2.5V.
Example 7
In the embodiment, the particle size of the carbon-coated copper-doped ferrous sulfide material is 300-500 nm, wherein the mass of the coating layer is 30% of the mass of the material, and the mass of the doping element is 1.3% of the mass of the material.
The synthesis steps of the carbon-coated partially copper-doped ferrous sulfide material used in the present invention are as follows:
(1) weighing 13.6g of ferrous sulfate heptahydrate, 29.1g of citric acid monohydrate and 0.3g of copper sulfate pentahydrate, dissolving in 1000mL of deionized water, stirring and mixing uniformly, and freeze-drying at-40 ℃ for 12h to obtain a precursor;
(2) and (2) grinding the precursor obtained in the step (1), then placing the ground precursor into a tubular furnace with an inert atmosphere, calcining for 2h at 850 ℃, and grinding to obtain a carbon-coated part of copper-doped ferrous sulfide substance.
The prepared carbon-coated part of copper-doped ferrous sulfide substance is used as a negative active material, and the ratio of the negative active material to conductive carbon (acetylene black) and polytetrafluoroethylene is 80: 10: mixing at a mass ratio of 10, adopting isopropanol as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, drying at 60 ℃, cutting to obtain a negative pole piece, wherein a metal sodium piece is a counter electrode (the capacity of the counter electrode is far larger than that of the cut negative pole piece)The negative pole piece and the metal sodium piece are separated by a polyethylene diaphragm, and 1M NaPF is used6Dissolution in EC: and (3) assembling the CR2025 type button cell by using DMC (DMC) (the volume ratio is 1: 1) (FEC additive) as an electrolyte and a stainless steel shell as a shell, and performing charge-discharge test on the cell assembled in the process at room temperature within a potential range of 0.01-2.5V.
Example 8
In the embodiment, the particle size of the ferrous sulfide material particle coated with carbon is 300-500 nm, wherein the mass of the coating layer is 20% of the mass of the material.
The synthesis steps of the carbon-coated ferrous sulfide material used in the invention are as follows:
(1) 0.45g of ferrous sulfate heptahydrate, 1.36g of ferrous ammonium sulfate hexahydrate and 3.82g of citric acid monohydrate are weighed and dissolved in 100mL of deionized water, and are stirred, mixed uniformly and then freeze-dried for 16h at the temperature of minus 50 ℃ to prepare a precursor;
(2) and (2) grinding the precursor obtained in the step (1), then placing the ground precursor into a tubular furnace with an inert atmosphere, calcining for 2 hours at 850 ℃, and grinding to obtain the carbon-coated ferrous sulfide substance.
The prepared carbon-coated ferrous sulfide substance is used as a negative active material, and the ratio of the negative active material to conductive carbon (acetylene black) and polyacrylic acid is 75: 15: mixing at a mass ratio of 10, adopting ethanol as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, drying at 60 ℃, cutting to obtain a negative pole piece, adopting a metal sodium piece as a counter electrode (the capacity of the counter electrode is far greater than that of the cut negative pole piece), separating the negative pole piece and the metal sodium piece by adopting a modified acetate fiber diaphragm, and adopting 1M NaPF6Dissolution in EC: and (3) assembling the CR2025 type button cell by using DMC (DMC) (the volume ratio is 1: 1) (FEC additive) as electrolyte and a stainless steel shell as a shell, and performing charge-discharge test on the cell assembled in the process at room temperature within a potential range of 0.3-2.5V.
Example 9
This example was prepared as in example 8.
The prepared carbon-coated ferrous sulfide substance is used as a negative active material, a negative material and conductive carbon (Super P Li)) Sodium carboxymethylcellulose in an amount of 85: 5: 10, adopting deionized water as a dispersant, uniformly mixing the mixture to prepare slurry, coating the slurry on a copper foil, and adding Na0.44MnO2As the positive electrode active material, the positive electrode active material was mixed with acetylene black and polyvinylidene fluoride in a ratio of 80: 10: mixing at a mass ratio of 10, adopting 1-methyl-2-pyrrolidone as a dispersing agent, uniformly mixing the mixture to prepare slurry, coating the slurry on an aluminum foil, drying at 60 ℃, cutting to obtain a corresponding negative pole piece and a positive pole piece (the capacity of the positive pole is far larger than that of the cut negative pole piece), separating the negative pole piece and the positive pole piece by adopting a Whatman glass fiber membrane, and adopting 1M NaPF6Dissolution in EC: and (3) assembling the CR2025 type button battery by using DMC (DMC) (the volume ratio is 1: 1) (FEC additive) as electrolyte and a stainless steel shell as a shell, and performing charge-discharge test on the sodium ion battery assembled in the process at room temperature within a potential range of 0.8-3.5V.
Example 10
In the embodiment, the particle size of the ferrous sulfide material coated by carbon is 100-200 nm, wherein the mass of the coating layer is 10% of the mass of the material.
The synthesis steps of the carbon-coated ferrous sulfide material used in the invention are as follows:
(1) weighing 0.96g of ferrous sulfate heptahydrate and 0.96g of glucose, dissolving in 3.84 mL of deionized water, stirring and mixing uniformly, and freeze-drying at 50 ℃ for 6h to obtain a precursor;
(2) and (2) grinding the precursor obtained in the step (1), putting the ground precursor into a tubular furnace with inert atmosphere, calcining for 24 hours at 500 ℃, and grinding to obtain the carbon-coated ferrous sulfide substance.
Example 11
In the embodiment, the particle size of the ferrous sulfide material coated by carbon is 300-500 nm, wherein the mass of the coating layer is 15% of the mass of the material.
The synthesis steps of the carbon-coated ferrous sulfide material used in the invention are as follows:
(1) 0.96g of ferrous sulfate heptahydrate and 9.6 g of citric acid monohydrate are weighed and dissolved in 960 mL of deionized water, and are stirred and mixed uniformly, and then are frozen and dried for 60 hours at the temperature of minus 40 ℃ to prepare a precursor;
(2) and (2) grinding the precursor obtained in the step (1), then placing the ground precursor into a tubular furnace with an inert atmosphere, calcining for 12 hours at 600 ℃, and grinding to obtain a carbon-coated ferrous sulfide substance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a carbon-coated ferrous sulfide negative electrode material is characterized by comprising the following steps:
(1) dissolving a carbon source, ferrous sulfate and doped metal sulfate in deionized water, stirring and mixing uniformly, and then carrying out freeze drying at minus 40 to minus 56 ℃ for 6 to 60 hours to prepare a precursor;
(2) grinding the precursor obtained in the step (1), and then placing the ground precursor in a tubular furnace in an inert atmosphere to calcine for 1-24 hours at 500-850 ℃ to obtain a carbon-coated ferrous sulfide negative electrode material;
the cathode material is a carbon-coated ferrous sulfide material, the mass of the carbon coating layer is 3% -30% of the mass of the cathode material, and the particle size of ferrous sulfide particles is 100-500 nm.
2. The method of preparing a carbon-coated ferrous sulfide negative electrode material of claim 1, wherein: the cathode material also contains doping modification elements, and the doping modification elements are one or more of Co, Ni, Mn, Ti, Cu, Mg, Ba, Pb and Al; the mass of the carbon coating layer in the negative electrode material is 3% -30% of the mass of the negative electrode material, and the mass of the doped modifying element is 0% -30% of the mass of the negative electrode material.
3. The method of preparing a carbon-coated ferrous sulfide negative electrode material of claim 1, wherein: in the step (1), the mass ratio of the carbon source, the ferrous sulfate, the doped metal sulfate and the deionized water is (1-10): 1, (0-1): 4-1000.
4. The method of preparing a carbon-coated ferrous sulfide negative electrode material of claim 1, wherein: in the step (1), the carbon source is one or more of citric acid, ascorbic acid and glucose; the doped metal sulfate is one or more of ammonium ferrous sulfate, cobalt sulfate, nickel sulfate, manganese sulfate, titanium sulfate, copper sulfate, magnesium sulfate, barium sulfate, lead sulfate and aluminum sulfate.
5. The sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material prepared by the preparation method of claim 1 comprises a positive plate, a negative plate, electrolyte, a diaphragm and a shell, and is characterized in that: the sodium ion battery takes an active material capable of inserting and removing sodium as a positive electrode material, carbon-coated ferrous sulfide as a negative electrode material, the diaphragm is one or more of a glass fiber diaphragm, a polypropylene diaphragm, a polyethylene diaphragm and a modified cellulose acetate diaphragm, and a soluble sodium salt organic solution is an electrolyte.
6. The sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material as claimed in claim 5, wherein: the active material capable of inserting and removing sodium is Na3V2(PO4)3、Na3V2(PO4)2F3、NaFePO4、NaMnO2、NaFeO2、FePO4、Na2.4Fe1.8(SO4)3、Na4Fe(CN)6、Na4Co3(PO4)2P2O7One or more of the electrode materials.
7. The sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material as claimed in claim 5, wherein: the soluble sodium salt organic solution is obtained by dissolving sodium salt in an organic solvent, wherein the sodium salt is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium trifluoromethanesulfonate and sodium bistrifluoromethylsulfonyl imide, and the organic solvent is one or more of ethylene carbonate, propylene carbonate, diethyl carbonate, diglyme and triglyme.
8. The sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material as claimed in claim 5, wherein: the positive plate is obtained by filling slurry obtained by uniformly mixing a positive material with a conductive agent, a binder and a dispersing agent into a current collector, the negative plate is obtained by filling slurry obtained by uniformly mixing a negative material with the conductive agent, the binder and the dispersing agent into the current collector, and the current collector is one of a porous, net-shaped or thin-film material of nickel and aluminum, carbon cloth and metal stainless steel; the conductive agent is one or more of acetylene black, graphite or Super P Li; the binder is one or more of polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethylcellulose, polyacrylic acid, sodium alginate, gelatin or styrene butadiene rubber; the dispersant is one or more of water, ethanol, isopropanol or 1-methyl-2-pyrrolidone.
9. The sodium ion battery prepared from the carbon-coated ferrous sulfide negative electrode material as claimed in claim 5, wherein: the shell is made of organic plastics, an aluminum shell, an aluminum plastic film, stainless steel and a stainless steel composite material and is in a buckled, columnar or square shape.
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