CN108199034B - Zinc sulfide/ferrous sulfide cathode composite material for lithium ion battery and preparation method thereof - Google Patents

Zinc sulfide/ferrous sulfide cathode composite material for lithium ion battery and preparation method thereof Download PDF

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CN108199034B
CN108199034B CN201810134685.7A CN201810134685A CN108199034B CN 108199034 B CN108199034 B CN 108199034B CN 201810134685 A CN201810134685 A CN 201810134685A CN 108199034 B CN108199034 B CN 108199034B
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composite material
lithium ion
negative electrode
ion battery
sulfide
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CN108199034A (en
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童汇
姚赢赢
毛高强
张宝
郑俊超
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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery and the preparation method thereof are provided, wherein the negative electrode composite material is prepared by the following method: (1) adding an iron source, a zinc source and an organic ligand into an N, N-dimethylformamide solution, uniformly stirring, heating for reaction under stirring, cooling, filtering, washing and drying to obtain brown powder; (2) roasting and cooling the mixture in an inert atmosphere to obtain black powder; (3) dissolving in water, adding a sulfur source, and performing ultrasonic dispersion; (4) pouring into a high-temperature reaction kettle, sealing, heating for reaction, cooling, filtering, washing and drying; (5) roasting in inert atmosphere, and cooling to obtain the final product. The secondary particle size of the cathode composite material is 100-200 nm, and the assembled battery has high specific charge-discharge capacity, stable charge-discharge performance and good cycle performance; the method has low reaction temperature and low raw material cost, and is suitable for industrial production.

Description

Zinc sulfide/ferrous sulfide cathode composite material for lithium ion battery and preparation method thereof
Technical Field
The invention relates to a negative electrode composite material for a lithium ion battery and a preparation method thereof, in particular to a zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery 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 sulfide is easy to agglomerate 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 doped carbon, ZnS is an electrochemical active substance, the particle size is 2-3 nm, N-C improves 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%, the cycle lasts for 200 weeks under the current density of 0.2A/g, and the reversible capacity of the composite material reaches 839 mAh/g. Although the material has stable cycle performance, the capacity 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. 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 performance is low.
CN103274474A discloses rod-shaped zinc ferrite and a preparation method thereof, wherein the diameter of the rod-shaped zinc ferrite is 7.0-500 nm, the length-diameter ratio is 3.0-20, the rod-shaped zinc ferrite is composed of 1-20 nano particles in the radial direction, 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 the environment is high, and the 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, sodium dodecyl sulfate is used as a surfactant, soluble ferrous salt and urea are used as raw materials at a certain temperature and for a certain time to obtain the micro-nano ferrous carbonate cathode material. 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, and the specific capacity is maintained at 585-640 mAh/g after 100 times of cyclic discharge. Although the preparation method of the material is simple, the cycle performance of the material is poor, and the specific discharge capacity is only maintained at 585-640 mAh/g after 100 circles under the current density of 200 mA/g.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a zinc sulfide/ferrous sulfide negative electrode composite material for a lithium ion battery and a preparation method thereof, wherein the zinc sulfide/ferrous sulfide negative electrode composite material has the advantages of stable cycle performance, higher capacity, low reaction temperature of the preparation method and low raw material cost in the charging and discharging process, and is suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery is prepared by the following method:
(1) adding an iron source, a zinc source and an organic ligand into the N, N-dimethylformamide solution, stirring until a uniform mixed solution is formed, heating and reacting under the condition of stirring, cooling, filtering, washing and drying to obtain brown powder;
(2) roasting the brown powder obtained in the step (1) in an inert atmosphere, and cooling to obtain black powder;
(3) dissolving the black powder obtained in the step (2) in water, adding a sulfur source, and performing ultrasonic dispersion to form a uniform suspension;
(4) pouring the suspension obtained in the step (3) into a high-temperature reaction kettle, sealing, heating for reaction, cooling, filtering, washing and drying to obtain a zinc sulfide/ferrous sulfide composite material precursor;
(5) and (4) roasting and cooling the zinc sulfide/ferrous sulfide composite material precursor obtained in the step (4) in an inert atmosphere to obtain the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery.
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 7-1: 1. 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 organic ligand to the sum of the iron element and the zinc element is 1: 1-6. If the ratio is too large, more organic ligands do not participate in the reaction process, and if the ratio is too small, too much metal elements are wasted.
Preferably, in the step (1), the N, N-dimethylformamide solution is used in such an amount that the concentration of the sum of the iron element and the zinc element is 0.01 to 0.15 mol/L (more preferably 0.05 to 0.12 mol/L). if the concentration is too high, the formed material is liable to agglomerate, and if the concentration is too low, an excessive solvent is wasted.
Preferably, in the step (1), the iron source is one or more of ferric sulfate, ferric nitrate, ferric acetylacetonate or ferric trichloride, and hydrates thereof.
Preferably, in the step (1), the zinc source is one or more of zinc sulfate, zinc nitrate or zinc chloride, and hydrates thereof.
Preferably, in the step (1), the organic ligand is one or more of trimesic acid, terephthalic acid or fumaric acid.
Preferably, in the step (1), the heating reaction temperature is 100-140 ℃, and the heating reaction time is 6-24 h. In the heating reaction process, metal ions are combined with organic ligands, the reaction is easier to occur in the temperature range, and if the temperature is too high, the N, N-dimethylformamide solution can boil, so that the reaction is not facilitated.
Preferably, in the step (1), the washing mode is that the filtrate is washed by ethanol for more than or equal to 2 times.
Preferably, in the step (1), the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
Preferably, in the step (2), the roasting temperature is 500-600 ℃, and the roasting time is 4-6 h. If the roasting temperature is too low, the powder can be immediately self-ignited after being contacted with air when being taken out, and if the roasting temperature is too high, the material can be agglomerated, and the metal element can be reduced into a metal simple substance. During the roasting process, the material can be converted into nano metal oxide particles coated by the carbon material, so that the metal oxide particles can not agglomerate in the vulcanization process.
Preferably, in the step (2), the inert atmosphere is argon or nitrogen atmosphere, etc.
Preferably, in the step (3), the mass concentration of the black powder after being dissolved in water is 0.05-0.50%. Under the condition of high temperature and high pressure, hydrogen ions generated by water react with a sulfur source to generate hydrogen sulfide, and the hydrogen sulfide reacts with metal oxide to generate metal sulfide. If the concentration of the black powder is too high, the material may agglomerate, and if the concentration of the black powder is too low, waste may occur.
Preferably, in the step (3), the mass ratio of the sulfur source to the black powder is 1-5: 1. The lower limit of the proportion is to ensure that all metal ions are vulcanized, and the upper limit of the proportion is to avoid generating excessive free sulfur to be attached to the surface of the material to influence the performance of the material.
Preferably, in the step (3), the sulfur source is one or more of thioacetamide, thiourea or L-cysteine, etc., the sulfur source must be added here, and if vulcanization is started, the nano material cannot be obtained, and the nano material tends to agglomerate in the vulcanization process.
Preferably, in the step (3), the frequency of the ultrasonic dispersion is 1.5-2.5 kHz, and the time of the ultrasonic dispersion is 15-25 min.
Preferably, in the step (4), the temperature of the heating reaction is 140 to 180 ℃, and the time of the heating reaction is 10 to 24 hours (more preferably 12 to 18 hours). The lower limit of the temperature is to ensure that hydrogen in the water and a sulfur source generate hydrogen sulfide, and the upper limit of the temperature is to ensure the safety of the hydrothermal reaction. The lower limit of the time is to ensure that the product is fully sulphided when thioacetamide is used as sulphur source and the upper limit of the time is to ensure that the product is fully sulphided when thiourea is used and no time is wasted.
Preferably, in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times.
Preferably, in the step (4), the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
Preferably, in the step (5), the roasting temperature is 200-700 ℃ (more preferably 400-600 ℃), and the roasting time is 2-6 h (more preferably 3-5 h). In the roasting process, the free sulfur is sublimated away from the surface of the material, so that the free sulfur element is removed.
Preferably, in the step (5), the inert atmosphere is argon or nitrogen atmosphere, etc.
The cooling is naturally cooling to room temperature.
The argon or nitrogen used in the invention is high-purity argon or high-purity nitrogen with the purity of more than or equal to 99.99 percent.
The technical principle of the invention is as follows: after a metal organic compound compounded by zinc and iron metal elements is prepared by a high-temperature solution method, the shape of the metal organic compound is fixed by one-time sintering to form a metal oxide with two metal ions uniformly compounded, then the stable metal oxide is hydrothermally vulcanized to form a composite material of ferrous sulfide and zinc sulfide, and crystal water and impurities in the composite material are removed by secondary sintering to obtain the zinc sulfide/ferrous sulfide cathode composite material for the lithium ion battery with excellent electrochemical performance. Iron and zinc are cheap metals, and the invention creatively utilizes the bimetallic sulfide to generate more redox/conversion reactions, and forms a layered nano structure in the first circulation to generate a buffer effect, thereby improving the specific capacity and the circulation stability and preparing the lithium ion battery cathode material with excellent performance.
The invention has the following beneficial effects:
(1) the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery is a composite material formed by zinc sulfide and ferrous sulfide, has no other impurities, has a secondary particle size of 100-200 nm, is beneficial to effective contact of electrolyte and a negative electrode material, can shorten a transmission path of lithium ions in the negative electrode material, can keep a stable structure in the charging and discharging process, is beneficial to shuttling of the lithium ions in the charging and discharging process, and can keep a highly reversible state due to uniform compounding of metal sulfides;
(2) the zinc sulfide/ferrous sulfide cathode composite material for the lithium ion battery is assembled into the battery, the first discharge specific capacity can reach 1613 mAh/g at the highest voltage range of 3.00-0.01V and the current density of 100mA/g, and the first charge specific capacity is 1067 mAh/g; within the voltage range of 3.00-0.01V, the current density is 1A/g, after circulating for 300 circles, the discharge specific capacity can reach 716mAh/g, the current density is 500mA/g, after circulating for 200 circles, the discharge specific capacity can reach 1686 mAh/g, the coulombic efficiency basically keeps more than or equal to 98.5% in the circulating process, and the stable charging and discharging performance and the good circulating performance are proved; in addition, the charge-discharge specific capacity of the material tends to increase in the charge-discharge cycle process;
(3) the method has low reaction temperature and low raw material cost, and is suitable for industrial production.
Drawings
Fig. 1 is an XRD chart of the zinc sulfide/ferrous sulfide negative electrode composite material for a lithium ion battery obtained in example 1 of the present invention;
fig. 2 is an SEM image of the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in example 1 of the present invention;
fig. 3 is a first charge-discharge curve diagram of the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in example 1 of the present invention;
fig. 4 is a discharge cycle curve and coulombic efficiency chart of the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in example 1 of the present invention;
fig. 5 is an SEM image of the zinc sulfide/ferrous sulfide negative electrode composite material for a lithium ion battery obtained in example 2 of the present invention;
fig. 6 is a discharge cycle curve and coulombic efficiency chart of the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in example 2 of the present invention;
fig. 7 is a first charge-discharge curve diagram of the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery 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 of the invention is 99.99 percent; the chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
(1) Adding 6mmol of ferric acetylacetonate, 5.6mmol of zinc nitrate hexahydrate and 2mmol of trimesic acid into 100m L N, N-dimethylformamide solution, stirring to form a uniform mixed solution, heating to react for 24 hours at 100 ℃ under the stirring condition, naturally cooling to room temperature, filtering, washing the filtrate for 4 times by using ethanol, placing in a forced air oven at 60 ℃, and drying for 24 hours to obtain brown powder;
(2) roasting the brown powder obtained in the step (1) for 4 hours at 600 ℃ in a high-purity argon atmosphere, and naturally cooling to room temperature to obtain black powder;
(3) dissolving 500mg of the black powder obtained in the step (2) in 100m L of water, adding 1.5g of thioacetamide, and performing ultrasonic dispersion for 20min at the frequency of 2kHz to form uniform suspension;
(4) pouring the suspension obtained in the step (3) into a high-temperature reaction kettle, sealing, heating and reacting for 12 hours at 160 ℃, naturally cooling to room temperature, filtering, respectively and alternately washing the filtrate with ethanol and deionized water for 2 times, placing the filtrate in a blast oven at 60 ℃, and drying for 24 hours to obtain a zinc sulfide/ferrous sulfide composite material precursor;
(5) and (4) roasting the zinc sulfide/ferrous sulfide composite material precursor obtained in the step (4) for 3h at 600 ℃ in a high-purity argon atmosphere, and cooling to obtain the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery.
As shown in fig. 1, the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in the embodiment of the present invention is a composite material formed by zinc sulfide and ferrous sulfide, and has no other impurities.
As shown in FIG. 2, the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in the embodiment of the invention has uniform secondary particle size distribution, and the particle size is 100-200 nm.
Weighing 0.40g of zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery 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 sheet, and taking a metal lithium sheet as a positive electrode, a lithium battery diaphragm as a diaphragm and 1 mol/LL iPF mol of the negative electrode sheet 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 is 100mA/g, the first discharging specific capacity of the assembled battery is 1512mAh/g, the first charging specific capacity is 970mAh/g, the material can keep the structural stability in the charging and discharging process, the volume expansion is small, the conductivity is good, and the charging and discharging reaction is highly reversible.
As can be seen from FIG. 4, after 35 cycles with a charge-discharge voltage of 3-0.01V and a current density of 100mA/g, the discharge specific capacity is 841 mAh/g, and the coulombic efficiency of the first cycle is 63.98%; the current density is 1A/g, the current is circulated to 300 circles, the discharge specific capacity is 716mAh/g, the coulombic efficiency is 99.7 percent, and the stable charge and discharge performance and the good circulation performance are proved.
Example 2
(1) Adding 7mmol of ferric nitrate nonahydrate, 1mmol of zinc chloride and 8mmol of terephthalic acid into 160m L N, N-dimethylformamide solution, stirring to form a uniform mixed solution, heating to react for 12h at 140 ℃ under the stirring condition, naturally cooling to room temperature, filtering, washing the filtrate for 3 times with ethanol, placing in a forced air oven at 100 ℃, and drying for 24h to obtain brown powder;
(2) roasting the brown powder obtained in the step (1) for 5 hours at 550 ℃ in a high-purity argon atmosphere, and naturally cooling to room temperature to obtain black powder;
(3) dissolving 500mg of the black powder obtained in the step (2) in 150m L of water, adding 2g of thiourea, and performing ultrasonic dispersion for 20min at the frequency of 2kHz to form uniform suspension;
(4) pouring the suspension obtained in the step (3) into a high-temperature reaction kettle, sealing, heating and reacting for 16h at 180 ℃, naturally cooling to room temperature, filtering, respectively and alternately washing the filtrate 3 times with ethanol and deionized water, placing in a forced air oven at 60 ℃, and drying for 24h to obtain a zinc sulfide/ferrous sulfide composite material precursor;
(5) and (4) roasting the zinc sulfide/ferrous sulfide composite material precursor obtained in the step (4) for 4 hours at 400 ℃ in a high-purity argon atmosphere, and cooling to obtain the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery.
Through detection, the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery, which is obtained in the embodiment of the invention, is a composite material formed by zinc sulfide and ferrous sulfide, and has no other impurities.
As shown in fig. 5, the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery obtained in the embodiment of the present invention has a uniform secondary particle size distribution, and the particle size is 100 to 200 nm.
Weighing 0.40g of zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery 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 sheet, and taking a metal lithium sheet as a positive electrode, a lithium battery diaphragm as a diaphragm and 1 mol/LL iPF mol of the negative electrode sheet in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
Through detection, under the conditions that the charging and discharging voltage is 3-0.01V and the current is 100mA/g, the first discharging specific capacity of the assembled battery is 1613 mAh/g, the first charging specific capacity is 1067 mAh/g, the material can keep the stability of the structure in the charging and discharging process, the volume expansion is small, the conductivity is good, and the charging and discharging reaction is highly reversible.
As can be seen from FIG. 6, after 6 cycles with the charging and discharging voltage of 3-0.01V and the current density of 100mA/g, the discharging specific capacity is 856.3mAh/g, and the first-cycle coulombic efficiency is 66.14%; the current density is 500mA/g, after 200 cycles, the discharge specific capacity is 1686 mAh/g, the coulombic efficiency is 98.7%, which shows that the charge and discharge performance is stable and the cycle performance is good.
Example 3
(1) Adding 7.5mmol ferric trichloride trihydrate, 2.5mmol zinc sulfate and 5mmol fumaric acid into 100m L N, N-dimethylformamide solution, stirring to form a uniform mixed solution, heating to react for 16h at 120 ℃ under the stirring condition, naturally cooling to room temperature, filtering, washing the filtrate with ethanol for 4 times, placing in a forced air oven at 80 ℃, and drying for 36h to obtain brown powder;
(2) roasting the brown powder obtained in the step (1) for 5 hours at 500 ℃ in a high-purity nitrogen atmosphere, and naturally cooling to room temperature to obtain black powder;
(3) dissolving 100mg of the black powder obtained in the step (2) in 100m L of water, adding 500mg of L-cysteine, and performing ultrasonic dispersion for 15min at the frequency of 2.5kHz to form uniform suspension;
(4) pouring the suspension obtained in the step (3) into a high-temperature reaction kettle, sealing, heating and reacting for 18h at 140 ℃, naturally cooling to room temperature, filtering, respectively and alternately washing the filtrate with ethanol and deionized water for 2 times, placing in a forced air oven at 80 ℃, and drying for 36h to obtain a zinc sulfide/ferrous sulfide composite material precursor;
(5) and (4) roasting the zinc sulfide/ferrous sulfide composite material precursor obtained in the step (4) for 4 hours at 500 ℃ in a high-purity nitrogen atmosphere, and cooling to obtain the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery.
Through detection, the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery, which is obtained in the embodiment of the invention, is a composite material formed by zinc sulfide and ferrous sulfide, and has no other impurities.
Through detection, the secondary particles of the zinc sulfide/ferrous sulfide cathode composite material for the lithium ion battery are uniformly distributed, and the particle size is 100-200 nm.
Weighing 0.40g of zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery 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 sheet, and taking a metal lithium sheet as a positive electrode, a lithium battery diaphragm as a diaphragm and 1 mol/LL iPF mol of the negative electrode sheet in a vacuum glove box6DMC (volume ratio 1: 1) as electrolyte, and assembling into a CR2025 button cell.
As can be seen from FIG. 7, when the charging and discharging voltage is 3-0.01V and the current is 100mA/g, the initial discharging specific capacity of the assembled battery is 1264 mAh/g, the initial charging specific capacity is 886.5 mAh/g, the material can keep the stability of the structure in the charging and discharging process, the volume expansion is small, the conductivity is good, and the charging and discharging reaction is highly reversible.
Through detection, after 10 cycles under the conditions that the charging and discharging voltage is 3-0.01V and the current density is 100mA/g, the discharging specific capacity is 766.1mAh/g, and the first-cycle coulombic efficiency is 70.1%; the current density is 5A/g, after 700 cycles, the discharge specific capacity is 736.1mAh/g, the coulombic efficiency is 99.4 percent, and the stable charge and discharge performance and the good cycle performance are proved.

Claims (30)

1. A zinc sulfide/ferrous sulfide negative electrode composite material for a lithium ion battery is characterized by being prepared by the following method:
(1) adding an iron source, a zinc source and an organic ligand into the N, N-dimethylformamide solution, stirring until a uniform mixed solution is formed, heating and reacting under the condition of stirring, cooling, filtering, washing and drying to obtain brown powder;
(2) roasting the brown powder obtained in the step (1) in an inert atmosphere, and cooling to obtain black powder; the roasting temperature is 500-600 ℃, and the roasting time is 4-6 h; the inert atmosphere is argon or nitrogen atmosphere;
(3) dissolving the black powder obtained in the step (2) in water, adding a sulfur source, and performing ultrasonic dispersion to form a uniform suspension;
(4) pouring the suspension obtained in the step (3) into a high-temperature reaction kettle, sealing, heating for reaction, cooling, filtering, washing and drying to obtain a zinc sulfide/ferrous sulfide composite material precursor;
(5) and (4) roasting and cooling the zinc sulfide/ferrous sulfide composite material precursor obtained in the step (4) in an inert atmosphere to obtain the zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery.
2. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1, wherein in the step (1), the molar ratio of an iron element in the iron source to a zinc element in the zinc source is 7-1: 1, the molar ratio of the organic ligand to the sum of the iron element and the zinc element is 1: 1-6, and the N, N-dimethylformamide solution is used in such an amount that the concentration of the sum of the iron element and the zinc element is 0.01-0.15 mol/L.
3. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2, characterized in that: in the step (1), the iron source is one or more of ferric sulfate, ferric nitrate, ferric acetylacetonate or ferric trichloride and hydrates thereof; the zinc source is one or more of zinc sulfate, zinc nitrate or zinc chloride and hydrates thereof; the organic ligand is one or more of trimesic acid, terephthalic acid or fumaric acid.
4. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2, characterized in that: in the step (1), the heating reaction temperature is 100-140 ℃, and the heating reaction time is 6-24 h.
5. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 3, characterized in that: in the step (1), the heating reaction temperature is 100-140 ℃, and the heating reaction time is 6-24 h.
6. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2, characterized in that: in the step (1), the washing mode is that the filtered substances are washed for more than or equal to 2 times by using ethanol; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
7. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 3, characterized in that: in the step (1), the washing mode is that the filtered substances are washed for more than or equal to 2 times by using ethanol; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
8. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 4, characterized in that: in the step (1), the washing mode is that the filtered substances are washed for more than or equal to 2 times by using ethanol; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
9. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2 is characterized in that in the step (3), the mass concentration of the black powder after being dissolved in water is 0.05-0.50%, the mass ratio of the sulfur source to the black powder is 1-5: 1, the sulfur source is one or more of thioacetamide, thiourea or L-cysteine, the ultrasonic dispersion frequency is 1.5-2.5 kHz, and the ultrasonic dispersion time is 15-25 min.
10. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 3 is characterized in that in the step (3), the mass concentration of the black powder after the black powder is dissolved in water is 0.05-0.50%, the mass ratio of the sulfur source to the black powder is 1-5: 1, the sulfur source is one or more of thioacetamide, thiourea or L-cysteine, the ultrasonic dispersion frequency is 1.5-2.5 kHz, and the ultrasonic dispersion time is 15-25 min.
11. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 4 is characterized in that in the step (3), the mass concentration of the black powder after the black powder is dissolved in water is 0.05-0.50%, the mass ratio of the sulfur source to the black powder is 1-5: 1, the sulfur source is one or more of thioacetamide, thiourea or L-cysteine, the ultrasonic dispersion frequency is 1.5-2.5 kHz, and the ultrasonic dispersion time is 15-25 min.
12. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 6 is characterized in that in the step (3), the mass concentration of the black powder after the black powder is dissolved in water is 0.05-0.50%, the mass ratio of the sulfur source to the black powder is 1-5: 1, the sulfur source is one or more of thioacetamide, thiourea or L-cysteine, the ultrasonic dispersion frequency is 1.5-2.5 kHz, and the ultrasonic dispersion time is 15-25 min.
13. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2, characterized in that: in the step (4), the heating reaction temperature is 140-180 ℃, and the heating reaction time is 10-24 hours.
14. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 3, characterized in that: in the step (4), the heating reaction temperature is 140-180 ℃, and the heating reaction time is 10-24 hours.
15. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 4, characterized in that: in the step (4), the heating reaction temperature is 140-180 ℃, and the heating reaction time is 10-24 hours.
16. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 6, characterized in that: in the step (4), the heating reaction temperature is 140-180 ℃, and the heating reaction time is 10-24 hours.
17. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 9, characterized in that: in the step (4), the heating reaction temperature is 140-180 ℃, and the heating reaction time is 10-24 hours.
18. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2, characterized in that: in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
19. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 3, characterized in that: in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
20. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 4, characterized in that: in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
21. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 6, characterized in that: in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
22. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 9, characterized in that: in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
23. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 13, wherein: in the step (4), the washing mode is that the filtered substances are respectively washed by ethanol and deionized water in a crossed manner for more than or equal to 2 times; the drying temperature is 60-100 ℃, and the drying time is 24-40 h.
24. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 1 or 2, characterized in that: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
25. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 3, characterized in that: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
26. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 4, characterized in that: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
27. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 6, characterized in that: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
28. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 9, characterized in that: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
29. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 13, wherein: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
30. The zinc sulfide/ferrous sulfide negative electrode composite material for the lithium ion battery according to claim 18, wherein: in the step (5), the roasting temperature is 200-700 ℃, and the roasting time is 2-6 h; the inert atmosphere is argon or nitrogen.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868102A (en) * 2015-06-10 2015-08-26 中南大学 Sodium ion battery zinc sulfide based negative electrode material and preparation method thereof
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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868102A (en) * 2015-06-10 2015-08-26 中南大学 Sodium ion battery zinc sulfide based negative electrode material and preparation method thereof
CN107611409A (en) * 2017-09-27 2018-01-19 中南大学 A kind of preparation method of flake nano FeS2/C negative materials

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FeS–ZnS Composite Nanosheets for Enhanced Lithium Storage Properties;Chen Xu et.al;《CHEMNANOMAT》;20170630;第3卷(第6期);第420-427页 *

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