CN117542997B - Preparation method of carbon-coated basic ferric potassium sulfate ion battery anode material - Google Patents

Preparation method of carbon-coated basic ferric potassium sulfate ion battery anode material Download PDF

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CN117542997B
CN117542997B CN202410011726.9A CN202410011726A CN117542997B CN 117542997 B CN117542997 B CN 117542997B CN 202410011726 A CN202410011726 A CN 202410011726A CN 117542997 B CN117542997 B CN 117542997B
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ferrous sulfate
feohso
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CN117542997A (en
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刘代伙
恽程
李云莉
王澳
宋梦琴
徐春燕
李振江
郑佳琳
张贝诺
陈忠伟
白正宇
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Henan Normal University
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/14—Sulfates
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The invention discloses a preparation method of a carbon-coated basic ferric potassium sulfate battery anode material, which comprises the steps of firstly ball-milling ferrous sulfate heptahydrate crystals and a carbon substrate by a ball milling-redox method to obtain a carbon-coated precursor, ensuring that a coating of an active material is completely covered along with the increase of ball milling time, gradually reducing the particle size of the material, facilitating the remarkable enhancement of capacity and dynamic performance after subsequent calcination, and then calcining in a tube furnace to enable the inside of the material to undergo a redox reaction to obtain FeOHSO 4 @C nanocomposite. The preparation method is simple, green, pollution-free and low in cost, and is easy for mass preparation.

Description

Preparation method of carbon-coated basic ferric potassium sulfate ion battery anode material
Technical Field
The invention belongs to the technical field of positive electrode materials of potassium ion batteries, and particularly relates to a preparation method of a carbon-coated basic ferric sulfate potassium ion battery positive electrode material.
Background
Large-scale energy storage plays a key role in enhancing the stability, safety and reliability of the power grid. Electrochemical energy storage equipment becomes an important solution for intermittent renewable energy power grid energy storage due to the advantages of high energy density, flexibility, expandability and the like. For example, sodium-sulfur batteries and lead-acid batteries have been used for grid energy storage. However, the conventional lead-acid battery is difficult to meet the high-rate energy storage requirement, and the current lithium ion batteries on which electric automobiles and portable electronic devices depend are increasingly demanded. In addition, the scarcity and increasing cost of lithium and cobalt also present challenges to the current further development of lithium ion batteries.
In contrast, potassium ion batteries exhibit great potential due to their rapid ion transport kinetics in the electrolyte and low cost, particularly in the following areas: 1. the potassium resource is abundant and widely distributed, and the content of the potassium resource in the crust is 1.5wt% (the lithium resource content is only 0.17 wt%); 2. potassium ions have a lower standard reduction potential of-2.93V vs. SHE (standard hydrogen electrode abbreviated SHE), lithium and sodium ions are-3.04V vs. SHE and-2.71V vs. SHE, respectively; 3. the standard voltage of the K +/K redox couple in propylene carbonate solvent is lower than Li +/Li and Na +/Na; 4. potassium ions have a smaller stokes radius (potassium ions (3.6 a) < sodium ions (4.6 a) < lithium ions (4.8 a)), and K + has a higher ionic conductivity in propylene carbonate solvent (about 10mS cm -1 in 1M PC); 5. potassium does not alloy with aluminum and therefore cheaper aluminum foil can be used as the positive and negative current collector. The positive electrode material is used as a core material of the potassium ion battery, is a key component for influencing the energy density and the cycle life of the potassium ion battery, and accounts for more than 1/3 of the total cost of the potassium ion battery, so that the improvement of the performance of the positive electrode material of the potassium ion battery has become one of the most active research fields at present.
The positive electrode material of the potassium ion battery can be classified into prussian blue and analogues thereof, layered transition metal oxides, polyanion compounds and organic materials according to kinds. The polyanion compound has strong covalent skeleton, low diffusion energy to alkali metal ion, low oxygen loss, high heat stability, high work voltage, long circulation stability and other advantages, and its anion is tetrahedral or octahedral coordination in crystal structure, and its inducing effect can raise the oxidation-reduction potential of electrode material. The iron-based sulfate is used as one of the emerging polyanion systems of the potassium ion battery, has high working voltage and higher capacity, and is low in price and high in safety as the positive electrode material of the potassium ion battery. However, iron-based sulfates are sensitive to water/oxygen, have poor electrical conductivity, and readily decompose and release SO 2 at high temperatures, which limits their synthesis, storage, and use, thereby affecting their commercialization pace. Some reports claim to solve the problems by carbon coating, nano-processing and the like, but no report is made to date on basic ferric sulfate as a positive electrode material of a rechargeable potassium ion battery.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of the carbon-coated basic ferric sulfate potassium ion battery anode material which has the advantages of simple process, mild reaction condition, low cost and higher cost performance.
The invention adopts the following technical scheme to solve the technical problems, and is characterized by comprising the following specific steps:
Step S1: preparation of carbon-coated ferrous sulfate heptahydrate powder
Adding blue ferrous sulfate heptahydrate crystals, a carbon-based material and agate ball-milling beads into an agate ball-milling tank for ball-milling treatment to obtain carbon-coated ferrous sulfate heptahydrate powder;
step S2: preparation of carbon-coated ferrous sulfate precursor
Placing the carbon-coated ferrous sulfate heptahydrate powder obtained in the step S1 into a tubular furnace for low-temperature dehydration heat treatment, so that the carbon-coated ferrous sulfate heptahydrate powder is dehydrated and crystallized to become loose precursor with slightly expanded volume, wherein the low-temperature dehydration heat treatment temperature is 60-120 , the low-temperature dehydration heat treatment time is 2-48 hours, and grinding the carbon-coated ferrous sulfate heptahydrate powder in a mortar uniformly after the low-temperature dehydration heat treatment is completed to obtain carbon-coated ferrous sulfate precursor;
Step S3: preparation of carbon-coated basic ferric sulfate material
And (3) heating the carbon-coated ferrous sulfate precursor obtained in the step (S2) to 140-260 at a heating rate of -1 in a temperature of 1-2 under an air atmosphere condition for 12-30 hours to obtain a carbon-coated basic ferric sulfate material, wherein the carbon-coated basic ferric sulfate material is used as a positive electrode material of a potassium ion battery.
Further defined, the carbon-based material in step S1 is one or more of conductive carbon black, acetylene black, ketjen black, carbon nanotubes, carbon quantum dots, or reduced graphene oxide.
Further defined, the specific preparation process of the carbon-coated ferrous sulfate heptahydrate powder in step S1 is as follows: 0.7900~0.8100g FeSO 47H2 O and 0.1900-0.2100 g of conductive carbon black are weighed and placed in an agate ball milling tank, 10g of agate ball milling beads are added for ball milling, the ball milling speed is 500r/min, and the ball milling time is 8h.
Further defined, in step S3, the carbon-coated basic ferric sulfate material is specifically FeOHSO 4 @c nanocomposite, and the carbon content in the FeOHSO 4 @c nanocomposite is 3% -20% by mass of the FeOHSO 4 @c nanocomposite.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. Compared to the heating instruments commonly used in laboratories such as: the invention adopts a tube furnace to heat the precursor material coated by carbon, and has the advantages that: (1) The heating speed of the tube furnace is high, so that the heating time is greatly shortened, and the production efficiency and the energy utilization efficiency are improved; (2) The temperature control is accurate, the heating temperature and the constant temperature time of the materials can be accurately controlled, the temperature fluctuation in the experimental process is ensured to be small, and the result is stable and reliable; (3) The heating device can uniformly heat, ensure that the materials are uniformly heated in the heating process, and avoid the phenomenon of uneven local heating.
2. Compared with the traditional synthesis method of basic ferric sulfate, the carbon-coated basic ferric sulfate material prepared by the ball milling-oxidation reduction method has excellent performance, and the preparation method is simple, low in cost, green, pollution-free, high in reaction yield and easy to produce and collect in batches. The iron source (ferrous sulfate heptahydrate crystal) and the carbon-based material used in the synthesis process are low in price, convenient and easy to obtain, and the greenhouse gas CO 2 can not be generated in the reaction process, so that the environment is protected.
3. The FeOHSO 4 @C nanocomposite prepared by the method has the structural advantages that: the existence of hydroxyl (OH ) enables the hydroxyl sulfate anode to have the structure and chemical stability of resisting the erosion of moisture, and the synthesized crystal form has the space group of P21/c symmetrical monoclinic crystal form, has reversible exchange capacity on K + and has excellent electrochemical performance in energy storage application. The crystal is a three-dimensional potassium ion diffusion channel formed by co-point connection of SO 4 tetrahedron and FeO 6 octahedron through sharing O atoms, and has the capacity of one K +/formula unit.
4. According to the FeOHSO 4 @C nanocomposite prepared by the method, through carrying out mechanical ball milling on ferrous sulfate heptahydrate crystals and carbon-based materials, carrying out in-situ coating on multiple contacts of conductive carbon black, transferring electrons into an active material, along with the increase of ball milling time, ensuring complete coverage of the coating of the active material, gradually reducing the particle size of the material, facilitating remarkable enhancement of the capacity and dynamic performance of the material after subsequent calcination, greatly shortening the movement path of electrons by a one-dimensional conductive structure, and forming a crosslinked conductive network.
5. The FeOHSO 4 @C cathode material prepared by the method is optimally finished on the basis of the previously reported preparation of FeOHSO 4 cathode material. By adding the grinding procedure in the precursor process, the iron source and the carbon-based material can be mixed more uniformly, the relative surface area of the solid substance is increased, and the crystal structure can be better stabilized during calcination. According to the invention, the ball milling method is used for simple carbon coating, so that the reaction time is saved, the material is well coated with carbon, the conductivity of the material is improved, and the electrochemical performance of the material is improved.
6. According to the invention, firstly, ferrous sulfate heptahydrate crystals and a carbon substrate are subjected to ball milling by a ball milling-oxidation reduction method to obtain a carbon coated precursor, the coating of an active material can be ensured to be completely covered along with the increase of ball milling time, the particle size of the material is gradually reduced, the capacity and the dynamic performance of the material are obviously enhanced after subsequent calcination, and then the material is calcined in a tubular furnace to generate oxidation-reduction reaction (Fe 2+ is oxidized into Fe 3+) to obtain the FeOHSO 4 @C nanocomposite, and the material has excellent potassium storage performance, high conductivity and structural stability, and a one-dimensional conductive internal structure established after carbon coating can greatly reduce the migration path of electrons, so that a crosslinked conductive network can be used as a positive electrode material of a high-performance potassium ion battery.
7. The process of preparing the FeOHSO 4 @C positive electrode material adopts a two-step heat treatment process, as the calcining temperature can have bad influence on the crystallinity of the crystal material, generally, the crystallinity of the crystal material can be increased along with the increase of the temperature, and too high calcining temperature can also have negative influence on the crystallinity of the crystal material.
8. The electrochemical test result of the assembled potassium ion battery shows that the specific capacity retention rate of FeOHSO 4 @C positive electrode material after being activated at 5mA g -1 and circulated for 150 circles under the condition of 10mA g -1 is 90.2%, and the specific capacity retention rate of FeOHSO 4 positive electrode material after being activated at 5mA g -1 and circulated for 100 circles under the condition of 10mA g -1 is only 16.87%, so that compared with FeOHSO 4 positive electrode material, the FeOHSO 4 @C positive electrode material prepared by the method has excellent electrochemical performance when being used for the positive electrode material of the potassium ion battery. In addition, compared with Prussian blue potassium electric positive electrode materials, feOHSO 4 @C rate performance prepared by the method is far superior to that of the reported Prussian blue and analogues thereof.
Drawings
Fig. 1 is an X-ray diffraction pattern of FeOHSO 4 @ C positive electrode material prepared in example 1 and FeOHSO 4 positive electrode material prepared in comparative example 1.
Fig. 2 is a scanning electron microscope image of FeOHSO 4 positive electrode material prepared in comparative example 1.
FIG. 3 is a scanning electron microscope image of FeOHSO 4 @C cathode material prepared in example 1.
Fig. 4 is a schematic view of the crystal structure of FeOHSO 4 @ C cathode material prepared in example 1.
Fig. 5 is a graph showing the rate performance of FeOHSO 4 @ C positive electrode material prepared in example 1 and FeOHSO 4 positive electrode material prepared in comparative example 1 as positive electrode materials for potassium ion batteries.
Fig. 6 is a graph showing the cycle performance of FeOHSO 4 @ C positive electrode material prepared in example 1 and FeOHSO 4 positive electrode material prepared in comparative example 1 as positive electrode materials for potassium ion batteries.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Example 1
Preparation of FeOHSO 4 @ C cathode Material
Weighing 0.8000g of FeSO 47H2 O and 0.2000g of conductive carbon black material in an agate ball milling tank, adding 10g of agate ball milling beads for ball milling at the speed of 500r/min for 8h to obtain carbon-coated ferrous sulfate heptahydrate powder, placing the obtained carbon-coated ferrous sulfate heptahydrate powder in a tubular furnace for low-temperature dehydration heat treatment to remove crystal water to become a loose body with slightly expanded volume, wherein the low-temperature dehydration heat treatment temperature is 80 , the low-temperature dehydration heat treatment time is 40h, grinding the loose body in a mortar uniformly to obtain precursor powder, heating the obtained precursor powder to 180 at the heating rate of -1 for 24h under the air atmosphere condition to obtain a carbon-coated basic ferric sulfate material, namely FeOHSO 4 @C positive electrode material, and grinding the carbon-coated basic ferric sulfate material uniformly in the mortar for standby.
Comparative example 1
Preparation FeOHSO 4 of cathode Material
Weighing 1.0000g of FeSO 47H2 O in an agate ball milling tank, adding 10g of agate ball milling beads for ball milling at the speed of 500r/min for 8h to obtain ferrous sulfate heptahydrate powder, placing the obtained ferrous sulfate heptahydrate powder in a tube furnace for low-temperature dehydration heat treatment to remove crystal water into slightly expanded bulk, wherein the low-temperature dehydration heat treatment temperature is 80 , the low-temperature dehydration heat treatment time is 40h, grinding the bulk into precursor powder uniformly in a mortar, heating the obtained precursor powder to 180 for 24h at the heating rate of -1 min at the temperature of 1 under the air atmosphere condition to obtain a pale yellow basic ferric sulfate material, namely FeOHSO 4 anode material, and grinding the pale yellow basic ferric sulfate material uniformly in the mortar for standby.
Example 2
Preparation of FeOHSO 4 @ C cathode Material
Weighing 0.8000g of FeSO 47H2 O and 0.2000g of carbon nanotube material in an agate ball milling tank, adding 10g of agate ball milling beads for ball milling at the speed of 500r/min for 8h, ball milling to obtain carbon-coated ferrous sulfate heptahydrate powder, placing the obtained carbon-coated ferrous sulfate heptahydrate powder in a tube furnace for low-temperature dehydration heat treatment to remove crystal water to form a loose body with slightly expanded volume, wherein the low-temperature dehydration heat treatment temperature is 80 , the low-temperature dehydration heat treatment time is 40h, grinding the loose body in a mortar uniformly to obtain precursor powder, heating the obtained precursor powder to 180 for 24h at the heating rate of 1 min -1 under the air atmosphere condition to obtain a carbon-coated basic ferric sulfate material, namely FeOHSO 4 @C positive electrode material, and grinding the carbon-coated basic ferric sulfate material in the mortar uniformly for standby.
Example 3
Preparation of FeOHSO 4 @ C cathode Material
Weighing 0.8000g of FeSO 47H2 O and 0.2000g of carbon quantum dot material in an agate ball milling tank, adding 10g of agate ball milling beads for ball milling at the speed of 500r/min for 8h, ball milling to obtain carbon-coated ferrous sulfate heptahydrate powder, placing the obtained carbon-coated ferrous sulfate heptahydrate powder in a tube furnace for low-temperature dehydration heat treatment to remove crystal water to form a loose body with slightly expanded volume, wherein the low-temperature dehydration heat treatment temperature is 80 , the low-temperature dehydration heat treatment time is 40h, grinding the loose body in a mortar uniformly to obtain precursor powder, heating the obtained precursor powder to 180 for 24h at the heating rate of 1 min -1 under the air atmosphere condition to obtain a carbon-coated basic ferric sulfate material, namely FeOHSO 4 @C positive electrode material, and grinding the carbon-coated basic ferric sulfate material in the mortar uniformly for standby.
Fig. 1 is an XRD pattern of FeOHSO 4 @ C positive electrode material prepared in example 1 and FeOHSO 4 positive electrode material prepared in comparative example 1. As can be seen from fig. 1, the XRD peaks of FeOHSO 4 @ C and FeOHSO 4 cathode materials are consistent, and the peak height of FeOHSO 4 @ C cathode material is reduced compared with FeOHSO 4 cathode material, the crystallinity is reduced, and it is proved that the carbon-based material is well coated on the surface of FeOHSO 4, and the synthesized FeOHSO 4 @ C cathode material and FeOHSO 4 cathode material are well matched with the standard card (PDF # 73-1580) of FeOHSO 4 phase.
The FeOHSO 4 @C cathode material prepared in example 1 (figure 3) and the FeOHSO 4 cathode material prepared in comparative example 1 (figure 2) are characterized by SEM, and according to comparison, feOHSO 4 cathode material (figure 2) is changed into FeOHSO 4 @C cathode material (figure 3) nano-sheets from a smooth micron sphere through carbon coating, and the particle size of the particles is reduced after the carbon coating, so that a uniform conductive layer is formed on the surface through the good coating of the carbon-based material, and the following electrochemical performance improvement is well paved.
Fig. 4 is a schematic crystal structure of FeOHSO 4 @ C cathode material prepared in example 1, from which it can be seen that the basic ferric sulfate material structure is composed of co-angular FeO 4.(OH)2 tetrahedra and SO 4 tetrahedra, each SO 4 tetrahedra sharing four vertices with four octahedra, forming a three-dimensional open channel.
The FeOHSO 4 @ C cathode material prepared in example 1, conductive carbon (Super P) and binder (PVDF) were ground and mixed in a mass ratio of 7:2:1, and then a certain amount of N-methylpyrrolidone (NMP) was added dropwise to the mixture, ground into a slurry, and the slurry was uniformly coated on an aluminum foil current collector to obtain a working electrode, using metallic potassium as a counter electrode, using a glass fiber microporous filter GF/a as a separator, and using 0.8mol L - 1KPF6 as an electrolyte, and assembling a battery in a glove box. And placing the assembled battery in air, standing for 10 hours, and then performing charge and discharge test on a new Wei charge and discharge tester, wherein the charge and discharge interval of the test is 1.6-4.1V. The rate capability of the assembled battery was tested at a current density of 0.005A g-10.01A g-10.02A g-10.03A g-10.05A g-10.08A g-10.1A g-1. The cycling performance of the assembled cells was then tested at a current density of 0.01A g -1.
As can be seen from fig. 5, the FeOHSO 4 @ C cathode material prepared in example 1 has a first reversible specific capacity of 102mah g -1 at a current density of 0.005A g -1, while the FeOHSO 4 cathode material prepared in comparative example 1 has a first reversible specific capacity of only 75mah g -1 at a current density of 0.005A g -1. It can be seen from fig. 6 that the FeOHSO 4 @ C cathode material prepared in example 1 had a specific capacity retention of 90% after 150 cycles of activation at 0.005A g -1 at 0.01A g -1, while the FeOHSO 4 cathode material prepared in comparative example 1 had a specific capacity retention of only 16% after 100 cycles of activation at 0.005A g -1 at 0.01A g -1. It was revealed that FeOHSO 4 @ C cathode material prepared in example 1 exhibited good rate performance and cycle stability performance when used as a cathode material for a potassium ion battery, as compared to FeOHSO 4 cathode material prepared in comparative example 1.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.

Claims (2)

1. The preparation method of the carbon-coated basic ferric potassium sulfate battery anode material is characterized by comprising the following specific steps:
Step S1: preparation of carbon-coated ferrous sulfate heptahydrate powder
Adding blue ferrous sulfate heptahydrate crystals, a carbon-based material and agate ball-milling beads into an agate ball-milling tank for ball-milling treatment to obtain carbon-coated ferrous sulfate heptahydrate powder, wherein the carbon-based material is one or more of conductive carbon black, acetylene black, ketjen black, carbon nanotubes, carbon quantum dots or reduced graphene oxide;
step S2: preparation of carbon-coated ferrous sulfate precursor
Placing the carbon-coated ferrous sulfate heptahydrate powder obtained in the step S1 into a tubular furnace for low-temperature dehydration heat treatment, so that the carbon-coated ferrous sulfate heptahydrate powder is dehydrated and crystallized to become loose precursor with slightly expanded volume, wherein the low-temperature dehydration heat treatment temperature is 60-120 , the low-temperature dehydration heat treatment time is 2-48 hours, and grinding the carbon-coated ferrous sulfate heptahydrate powder in a mortar uniformly after the low-temperature dehydration heat treatment is completed to obtain carbon-coated ferrous sulfate precursor;
Step S3: preparation of carbon-coated basic ferric sulfate material
And (2) heating the carbon-coated ferrous sulfate precursor obtained in the step (S2) to 140-260 at a heating rate of -1 in an air atmosphere condition for 12-30 hours to obtain the carbon-coated basic ferric sulfate material, wherein the carbon-coated basic ferric sulfate material is a FeOHSO 4 @C nanocomposite, the carbon content in the FeOHSO 4 @C nanocomposite is 3-20% of the mass percentage of the FeOHSO 4 @C nanocomposite, and the carbon-coated basic ferric sulfate material is used as a positive electrode material of a potassium ion battery.
2. The method for preparing a carbon-coated basic ferric sulfate potassium ion battery positive electrode material according to claim 1, wherein the specific preparation process of the carbon-coated ferrous sulfate heptahydrate powder in step S1 is as follows: 0.7900~0.8100g FeSO 47H2 O and 0.1900-0.2100 g of conductive carbon black are weighed and placed in an agate ball milling tank, 10g of agate ball milling beads are added for ball milling, the ball milling speed is 500r/min, and the ball milling time is 8h.
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