CN108598443B - Macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material and preparation method thereof - Google Patents

Macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material and preparation method thereof Download PDF

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CN108598443B
CN108598443B CN201810557051.2A CN201810557051A CN108598443B CN 108598443 B CN108598443 B CN 108598443B CN 201810557051 A CN201810557051 A CN 201810557051A CN 108598443 B CN108598443 B CN 108598443B
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sulfide
zinc
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CN108598443A (en
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童汇
姚赢赢
毛高强
龚竹月
郑俊超
张宝
喻万景
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Central South 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
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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    • Y02E60/10—Energy storage using batteries

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Abstract

The macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material is prepared by the following steps: (1) adding an iron source, a zinc source, a sulfur source and a ternary organic carboxylic acid into water, and stirring and dissolving to obtain a uniform solution; (2) sealing, heating for reaction, cooling, filtering, washing and drying to obtain black powder; (3) roasting and cooling the mixture in an inert atmosphere to obtain the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material. The zinc sulfide and the ferrous sulfide in the macroporous spherical zinc sulfide/ferrous sulfide/carbon cathode material are pure phases, the particle size of secondary particles is 5-8 mu m, and the secondary particles contain pore channels with the diameter of 0.1-2.0 mu m; the battery is assembled, and has the advantages of stable structure, small volume expansion, good conductivity, highly reversible charge-discharge reaction and excellent rate performance in the charge-discharge process; the method is simple and convenient, has low raw material cost, and is suitable for industrial production.

Description

Macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material and preparation method thereof
Technical Field
The invention relates to a negative electrode material for a lithium ion battery and a preparation method thereof, in particular to a macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material and a preparation method thereof.
Background
With the increase of the demand of people on portable equipment and the development of commercial lithium ion batteries, the current mainstream graphite cathode cannot meet the demand of people on the capacity of the lithium ion batteries. Iron and zinc are cheap metals, and sulfide of the iron and zinc has higher theoretical specific capacity when being used as a negative electrode material of a lithium ion battery, but the structure of the iron and zinc is easy to collapse in the charging and discharging process, so that the specific capacity and the cycle performance are influenced.
CN104882604B discloses ZnS-Al2O3The composite electrode material is prepared from zinc sulfide ZnS nanocrystalline and amorphous alumina Al2O3And N-C, wherein ZnS is an electrochemical active substance, the particle size is 2-3 nm, N-C can improve the conductivity of the composite material, and amorphous Al2O3The composite electrode material has the function of blocking the agglomeration of ZnS in the charge-discharge process, and the composite electrode material has high specific capacity, high rate capability and high cycle stability due to the synergistic effect of the three components. However, at a current density of 0.2A/g, ZnS-Al2O3The charge specific capacity of the first circle of the N-C is 663.7mAh/g, the first circle efficiency is only 58 percent, namely the first efficiency is lower, and the commercialization possibility is lower.
CN 105355890A discloses a preparation method and application of a zinc sulfide-graphene composite material of a lithium ion battery cathode, wherein the ZnS-RGO composite material is obtained by in-situ synthesis, centrifugation and drying and is used as a novel lithium ion battery cathode. Although the discharge specific capacity of the first circle is 1126.6mAh/g when the material is tested under the current density of 40mA/g, the discharge capacity of the material is only 250mAh/g after the material is cycled for 100 circles, and the cycle stability performance is poor.
CN103274474A discloses a rod-like zinc ferrite and a preparation method thereof, wherein the diameter of the rod-like zinc ferrite is 7.0-500 nm, the length-diameter ratio is 3.0-20, the rod-like diameter is composed of 1-20 nano-particles, and the size of each single nano-particle is 7.0-30 nm; the preparation method comprises the steps of selecting ferrous sulfate and zinc chloride as raw materials, taking oxalic acid as a precipitator, carrying out room-temperature precipitation, carrying out mixing reaction, aging, centrifuging, washing, drying and carrying out heat treatment to obtain the rod-shaped zinc ferrite constructed by the nano particles. Although the material has excellent electrochemical performance, in the preparation process, air isolation is required for solution dripping and aging, the requirement on environment is high, and mass production is not facilitated.
CN103413941A discloses a lithium ion battery cathode material and a preparation method thereof, wherein the lithium ion battery cathode material is prepared by a low-temperature hydrothermal method at a certain temperature and for a certain time by using sodium dodecyl sulfate as a surfactant and soluble ferrous salt and urea as raw materials. Although the preparation method of the material is simple, the obtained ferrous carbonate negative electrode material is applied to a lithium ion battery for the first time, the first discharge specific capacity reaches 900-1110 mAh/g under the current density of 0.05-3.0V and 200mA/g, the specific capacity is only 585-640 mAh/g after 100 times of circulating discharge, and the cycle performance of the material is poor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material which has stable cycle performance, higher capacity, simple preparation method and low raw material cost in the charging and discharging process and is suitable for industrial production and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material is prepared by the following method:
(1) adding an iron source, a zinc source, a sulfur source and a ternary organic carboxylic acid into water, and stirring and dissolving to obtain a uniform solution;
(2) sealing the solution obtained in the step (1), carrying out heating reaction, cooling, filtering, washing and drying to obtain black powder;
(3) and (3) roasting the black powder obtained in the step (2) in an inert atmosphere, and cooling to obtain the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material.
Preferably, in the step (1), the molar ratio of the iron element in the iron source to the zinc element in the zinc source is 1: 1-3 (more preferably 1: 1.5-2.5). If the proportion is too large, the material is easy to agglomerate to form larger particles, and if the proportion is too small, the reasonable utilization of resources is not facilitated.
Preferably, in the step (1), the molar ratio of the sulfur source to the sum of the mole numbers of the iron element and the zinc element is 1-5: 1. If the ratio is too small, it is difficult to completely vulcanize the metal, and the upper limit of the ratio is to avoid too much free sulfur from adhering to the surface of the material and affecting the performance of the material.
Preferably, in the step (1), the molar concentration of the sum of the mole numbers of the iron element and the zinc element in the homogeneous solution is 0.08 to 1.0 mol/L (more preferably 0.1 to 0.5 mol/L). If the concentration is too low, a material to be subjected to the next test is difficult to be produced, and if the concentration is too high, precipitation is directly produced, and a uniform solution cannot be formed.
Preferably, in the step (1), the molar concentration of the tri-organic carboxylic acid in the homogeneous solution is 0.08-1.0 mol/L (more preferably 0.1-0.5 mol/L). If the concentration is too high, the carbon content of the reaction product is high, and the material capacity is influenced, and if the concentration is too low, the metal zinc and iron are difficult to complex with a sulfur source, and a plurality of free metal ions are generated.
Preferably, in the step (1), the iron source is an organic iron source.
Preferably, the organic iron source is one or more of ferric acetylacetonate, ferric citrate, ferrocene and the like. Organic iron sources can provide an iron source, while inorganic iron sources are difficult to produce porous structures.
Preferably, in step (1), the zinc source is an inorganic zinc source.
Preferably, the inorganic zinc source is one or more of zinc sulfate, zinc nitrate or zinc chloride, and hydrates thereof.
Preferably, in step (1), the sulfur source is an organic sulfur source.
Preferably, the organic sulfur source is one or more of thioacetamide, thiourea or L-cysteine.
Preferably, in the step (1), the tri-organic carboxylic acid is citric acid and/or trimesic acid and the like. Iron ions and zinc ions can perform a coordination reaction with the ternary organic carboxylic acid to form a metal ion-ternary organic carboxylic acid-metal ion combined complex, so that carbon formed by the ternary organic carboxylic acid can be uniformly compounded with sulfide in the sintering process.
Preferably, in the step (2), the temperature of the heating reaction is 120-250 ℃ (more preferably 160-200 ℃) and the time is 6-24 h (more preferably 10-20 h). The lower limit of the temperature is more favorable for hydrogen in water and a sulfur source to generate hydrogen sulfide, and the upper limit of the temperature is more favorable for the safety of hydrothermal reaction; the lower limit of the time is more favorable for the product to be fully vulcanized when thioacetamide is used as the sulfur source, and the upper limit of the time is more favorable for the product to be fully vulcanized when thiourea is used, and the time is not wasted.
Preferably, in the step (2), the washing mode is that the filtered substances are respectively washed by ethanol and water in a crossed mode for more than or equal to 2 times.
Preferably, in the step (2), the drying temperature is 60-100 ℃ and the drying time is 10-40 h (more preferably 12-30 h).
Preferably, in the step (3), the roasting temperature is 400-600 ℃, and the roasting time is 2-6 h. In the roasting process, the free sulfur is sublimated away from the surface of the material, so that the removal of the free sulfur element is realized, and organic matters in the free sulfur element are converted into a carbon source.
Preferably, in the step (3), the inert atmosphere is argon or nitrogen atmosphere, etc. The argon or the nitrogen is high-purity argon or high-purity nitrogen with the purity of more than or equal to 99.99 percent.
The cooling is naturally cooling to room temperature.
Preferably, the secondary particle size of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material is 5-8 μm, and the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material contains a pore channel with the diameter of 0.1-2.0 μm.
The technical principle of the invention is as follows: the iron-zinc composite sulfide is prepared by a high-temperature solution method, wherein an iron source can easily generate a spherical material with a cavity in the process of compounding with a zinc source, so that the material can still realize good infiltration with an electrolyte and is lithium ion in a micron scaleThe shuttle of (2) provides a larger space, and the microstructure of the shuttle can keep the stable electrochemical performance of the material under a longer cycle; and ternary organic carboxylic acid is used as a carbon source and a complexing agent, so that a zinc sulfide/ferrous sulfide/carbon cathode material with uniformly compounded carbon can be generated after sintering, a stable SEI film is easy to generate, and Li is enabled to effectively prevent solvent molecules from passing through+Can be freely inserted and removed.
The invention has the following beneficial effects:
(1) the macroporous spherical zinc sulfide/ferrous sulfide/carbon cathode material is a composite material formed by mixing zinc sulfide, ferrous sulfide and carbon, wherein the zinc sulfide and the ferrous sulfide are pure phases and have no other impurities, the secondary particle size of the composite material is 5-8 mu m, and the composite material contains pore channels with the diameter of 0.1-2.0 mu m, larger pore channels are more beneficial to the effective contact of electrolyte and the cathode material, the transmission path of lithium ions in the cathode material is shortened, the larger particle size can keep a stable structure in the charge-discharge process, and is beneficial to the stable shuttling of the lithium ions in the charge-discharge process, and the uniform compounding between metal sulfide and carbon ensures that the electrode reaction can be kept in a highly reversible state;
(2) the macroporous spherical zinc sulfide/ferrous sulfide/carbon cathode material is assembled into a battery, and the first discharge specific capacity of the assembled battery can reach 969.3mAh/g and the first efficiency can reach 84.5% under the conditions that the charge-discharge voltage is 3-0.01V and the current density is 50 mA/g; under the current density of 1A/g, after circulating to 1000 circles, the highest specific discharge capacity can still be maintained at 722.3mAh/g, the highest coulombic efficiency is 99.0%, and under the heavy current density of 10A/g, the highest specific discharge capacity of 136.1mAh/g is still maintained, which shows that the material can maintain the stability of the structure, small volume expansion and good conductivity in the charging and discharging process, so that the charging and discharging reaction is highly reversible, and the material has excellent rate capability and can adapt to the heavy current charging and discharging process;
(3) the method is simple and convenient, does not adopt high-cost materials such as graphene, has low raw material cost, and is suitable for industrial production.
Drawings
Fig. 1 is an XRD pattern of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in example 1 of the present invention;
fig. 2 is an SEM image of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in example 1 of the present invention;
fig. 3 is a graph of discharge cycle curve and coulombic efficiency of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in example 1 of the present invention;
fig. 4 is an SEM image of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in example 2 of the present invention;
fig. 5 is a rate capability graph of the zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in example 2 of the present invention;
fig. 6 is a first charge-discharge curve diagram of the zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in example 3 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
The purity of the high-purity argon or the high-purity nitrogen used in the embodiment is 99.99 percent; the starting materials or chemicals used in the examples of the present invention are, unless otherwise specified, commercially available in a conventional manner.
Example 1
(1) Adding 2mmol of ferric acetylacetonate, 3mmol of zinc nitrate hexahydrate, 5 mmol of thioacetamide and 2.5 g (13 mmol) of citric acid into 50 mL of deionized water, and stirring to dissolve the mixture to obtain a uniform solution;
(2) pouring the solution obtained in the step (1) into a 100 mL polytetrafluoroethylene high-temperature reaction kettle, sealing a steel shell, placing the kettle in a forced air oven, heating to 180 ℃, reacting for 16 h, naturally cooling to room temperature, filtering, respectively and alternately washing the filtrate with ethanol and deionized water for 4 times, placing the filtrate in a forced air oven at 60 ℃, and drying for 24 h to obtain black powder;
(3) and (3) roasting the black powder obtained in the step (2) for 3 hours at 600 ℃ in a high-purity argon atmosphere, and naturally cooling to room temperature to obtain the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material.
As shown in fig. 1, zinc sulfide and ferrous sulfide in the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the present invention are pure phases, and no other impurities are present.
As shown in fig. 2, the size of the secondary particle of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the present invention is 6 μm, and the secondary particle contains a pore channel with a diameter of 1.0 μm.
Assembling the battery: weighing 0.40g of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention, adding 0.05g of acetylene black serving as a conductive agent and 0.05g N-methyl pyrrolidone serving as a binder, uniformly mixing, coating the mixture on copper foil to prepare a negative electrode plate, and taking a metal lithium plate as a positive electrode, a lithium battery diaphragm as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
As can be seen from FIG. 3, when the charging and discharging voltage is 3-0.01V and the current density is 50mA/g (the first 3 circles), the first discharging specific capacity of the assembled battery is 923.5mAh/g, the first charging specific capacity is 780.4mAh/g, and the first effect is 84.5%; under the condition that the current density is 1A/g (from the 4 th circle), after the cycle is carried out to 1000 circles, the specific discharge capacity is still maintained at 716.1mAh/g, and the coulombic efficiency is 99.0 percent, which shows that the material can maintain the stability of the structure, has small volume expansion and good conductivity in the charge-discharge process, and ensures that the charge-discharge reaction is highly reversible.
Example 2
(1) Adding 2mmol of ferric acetylacetonate, 3mmol of zinc nitrate hexahydrate, 5 mmol of thioacetamide and 2 g (9.52 mmol) of trimesic acid into 50 mL of deionized water, and stirring to dissolve the mixture to obtain a uniform solution;
(2) pouring the solution obtained in the step (1) into a 100 mL polytetrafluoroethylene high-temperature reaction kettle, sealing a steel shell, placing the kettle in a forced air oven, heating to 200 ℃, reacting for 10 hours, naturally cooling to room temperature, filtering, respectively and alternately washing the filtrate 3 times with ethanol and deionized water, then placing the filtrate in the forced air oven at 100 ℃, and drying for 20 hours to obtain black powder;
(3) and (3) roasting the black powder obtained in the step (2) for 5 hours at 450 ℃ in a high-purity argon atmosphere, and naturally cooling to room temperature to obtain the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material.
Through detection, zinc sulfide and ferrous sulfide in the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention are pure phases, and no other impurities exist.
As shown in FIG. 4, the secondary particle size of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention is 5-8 μm, and the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material contains a pore channel with a diameter of 0.1-1.0 μm.
Assembling the battery: weighing 0.40g of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention, adding 0.05g of acetylene black serving as a conductive agent and 0.05g N-methyl pyrrolidone serving as a binder, uniformly mixing, coating the mixture on copper foil to prepare a negative electrode plate, and taking a metal lithium plate as a positive electrode, a lithium battery diaphragm as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
As shown in fig. 5, under the conditions that the charge-discharge voltage is 3-0.01V and the current density is 50mA/g, the first discharge specific capacity is 955mAh/g, the first charge specific capacity is 759.2 mAh/g, and the first effect is 79.5%, which indicates that the material can keep the stability of the structure in the charge-discharge process, has small volume expansion and good conductivity, and ensures that the charge-discharge reaction is highly reversible; under the heavy current density of 10A/g, the material still keeps the specific discharge capacity of 136.1mAh/g, which shows that the material has excellent rate performance and can adapt to the heavy current charge and discharge process.
Through detection, after the assembled battery is circulated to 1000 circles under the conditions that the charging and discharging voltage is 3-0.01V and the current density is 1A/g, the discharging specific capacity is still maintained at 706.7 mAh/g, and the coulombic efficiency is 98.6%, which shows that the material can maintain the stability of the structure in the charging and discharging process, has small volume expansion and good conductivity, and ensures that the charging and discharging reaction is highly reversible.
Example 3
(1) Adding 2.5 mmol of ferric citrate, 5 mmol of zinc chloride hexahydrate, 22.5 mmol of thiourea and 1.5 g (7.81 mmol) of citric acid into 50 mL of deionized water, and stirring to dissolve to obtain a uniform solution;
(2) pouring the solution obtained in the step (1) into a 100 mL polytetrafluoroethylene high-temperature reaction kettle, sealing a steel shell, placing the kettle in a blast oven, heating to 160 ℃, reacting for 20 hours, naturally cooling to room temperature, filtering, respectively and alternately washing the filtrate with ethanol and deionized water for 4 times, placing the filtrate in the blast oven at 80 ℃, and drying for 12 hours to obtain black powder;
(3) and (3) roasting the black powder obtained in the step (2) for 4 hours at 500 ℃ in a high-purity nitrogen atmosphere, and naturally cooling to room temperature to obtain the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material.
Through detection, zinc sulfide and ferrous sulfide in the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention are pure phases, and no other impurities exist.
Through detection, the size of the secondary particles of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention is 6-8 μm, and the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material contains a pore channel with the diameter of 0.5-1.5 μm.
Assembling the battery: weighing 0.40g of the macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material obtained in the embodiment of the invention, adding 0.05g of acetylene black serving as a conductive agent and 0.05g N-methyl pyrrolidone serving as a binder, uniformly mixing, coating the mixture on copper foil to prepare a negative electrode plate, and taking a metal lithium plate as a positive electrode, a lithium battery diaphragm as a diaphragm and 1mol/L LiPF in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
As can be seen from FIG. 6, the initial discharge specific capacity of the assembled battery is 969.3mAh/g, the initial charge specific capacity is 772.7 mAh/g, and the initial efficiency is 79.7% when the charge-discharge voltage is 3-0.01V and the current density is 50 mA/g.
Through detection, after the assembled battery is circulated to 1000 circles under the conditions that the charging and discharging voltage is 3-0.01V and the current density is 1A/g, the discharging specific capacity is still maintained at 722.3mAh/g, and the coulombic efficiency is 97.7%, which shows that the material can maintain the stability of the structure in the charging and discharging process, has small volume expansion and good conductivity, and ensures that the charging and discharging reaction is highly reversible.

Claims (8)

1. A macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material is characterized by being prepared by the following method:
(1) adding an iron source, a zinc source, a sulfur source and a ternary organic carboxylic acid into water, stirring and dissolving to obtain a uniform solution, wherein the iron source is
Is an organic iron source; the organic iron source is one or more of ferric acetylacetonate, ferric citrate or ferrocene; the zinc source is an inorganic zinc source; the inorganic zinc source is one or more of zinc sulfate, zinc nitrate or zinc chloride and hydrates thereof; the sulfur source is an organic sulfur source; the organic sulfur source is one or more of thioacetamide, thiourea or L-cysteine; the tri-organic carboxylic acid is citric acid and/or trimesic acid; the molar ratio of the iron element in the iron source to the zinc element in the zinc source is 1: 1-3; the molar ratio of the sulfur source to the sum of the mole numbers of the iron element and the zinc element is 1-5: 1;
(2) sealing the solution obtained in the step (1), heating for reaction, cooling, filtering, washing and drying to obtain black powder
Grinding;
(3) roasting and cooling the black powder obtained in the step (2) in inert atmosphere to obtain macroporous spherical zinc sulfide/sulfide
Ferrous/carbon negative electrode material.
2. The macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material of claim 1, wherein: step (1)
Wherein the molar concentration of the sum of the mole numbers of the iron element and the zinc element in the uniform solution is 0.08-1.0 mol/L; the molar concentration of the tri-organic carboxylic acid in the uniform solution is 0.08-1.0 mol/L.
3. The macroporous spherical zinc sulfide/ferrous sulfide/carbon anode material according to claim 1 or 2, wherein: step (ii) of
(2) The heating reaction is carried out at the temperature of 120-250 ℃ for 6-24 hours.
4. The macroporous spherical zinc sulfide/ferrous sulfide/carbon anode material according to claim 1 or 2, wherein: step (ii) of
(2) In the washing mode, the filtered substances are respectively washed by ethanol and water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 10-40 h.
5. The macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material of claim 3, wherein: step (2)
In the washing mode, the filtered substances are respectively washed by ethanol and water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 10-40 h.
6. The macroporous spherical zinc sulfide/ferrous sulfide/carbon anode material according to claim 1 or 2, wherein: step (ii) of
(3) The roasting temperature is 400-600 ℃, and the roasting time is 2-6 hours; the inert atmosphere is argon or nitrogen.
7. The macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material of claim 3, wherein: step (3)
The roasting temperature is 400-600 ℃, and the roasting time is 2-6 hours; the inert atmosphere is argon or nitrogen.
8. The macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material of claim 4, wherein: in the step (3), the roasting temperature is 400-600 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
CN201810557051.2A 2018-06-01 2018-06-01 Macroporous spherical zinc sulfide/ferrous sulfide/carbon negative electrode material and preparation method thereof Active CN108598443B (en)

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