CN108199034A - Lithium ion battery zinc sulphide/ferrous sulfide anode material and preparation method - Google Patents

Lithium ion battery zinc sulphide/ferrous sulfide anode material and preparation method Download PDF

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CN108199034A
CN108199034A CN201810134685.7A CN201810134685A CN108199034A CN 108199034 A CN108199034 A CN 108199034A CN 201810134685 A CN201810134685 A CN 201810134685A CN 108199034 A CN108199034 A CN 108199034A
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lithium ion
ion battery
ferrous sulfide
anode material
zinc sulphide
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CN108199034B (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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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

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Abstract

Lithium ion battery zinc sulphide/ferrous sulfide anode material and preparation method, the anode material are made of following methods：（1）Source of iron, zinc source and organic ligand are added in into N, in N dimethyl formamide solutions, stirred evenly, under stirring, heating reaction is cooled down, filtered, washs, dry, obtains brown ceramic powder；（2）In an inert atmosphere, it roasts, cooling obtains black powder；（3）It is soluble in water, add in sulphur source, ultrasonic disperse；（4）It pours into pyroreaction kettle, seals, heating reaction is cooled down, filtered, washs, dry；（5）In an inert atmosphere, it roasts, cooling,.The second particle grain size of anode material of the present invention is 100~200nm, and the battery assembled, charging and discharging capacity is high, and charge-discharge performance is stablized, good cycle；The method of the present invention reaction temperature is low, and the cost of raw material is low, is suitable for industrialized production.

Description

Lithium ion battery zinc sulphide/ferrous sulfide anode material and preparation method
Technical field
The present invention relates to a kind of negative electrode for lithium ion battery composite material and preparation methods, and in particular to a kind of lithium-ion electric Pond zinc sulphide/ferrous sulfide anode material and preparation method.
Background technology
As people are to the graphite cathode of the increase of portable equipment demand and the development, at present mainstream of commercial li-ion battery Can not meet the needs of people are to capacity of lithium ion battery.Iron and zinc are all cheap metals, and sulfide is as lithium ion During cell negative electrode material, there is higher theoretical specific capacity, still, easily reunite in charge and discharge process, influence specific volume Amount and cycle performance.
CN104882604B discloses a kind of ZnS-Al2O3/ N-C combination electrode materials and preparation method, the combination electrode material Material is by zinc sulphide ZnS is nanocrystalline, unformed aluminium oxide Al2O3It is formed with nitrogen-doped carbon N-C three parts, ZnS is electrochemistry Active material, grain size are 2~3nm, and N-C improves conductivity of composite material, and unformed Al2O3Barrier ZnS is then played in charge and discharge The effect reunited in electric process, the synergistic effect of three kinds of components make combination electrode material show height ratio capacity, high rate capability With high circulation stability.But under 0.2A/g current densities, ZnS-Al2O3/ N-C first circle charging quality specific capacities are 663.7mAh/g, first circle efficiency are only 58%, under 0.2A/g current densities, are recycled 200 weeks, the reversible capacity of composite material reaches To 839mAh/g.Although the material circulation performance is stablized, capacity is relatively low.
CN105355890 A disclose the preparation method of negative electrode of lithium ion battery zinc sulphide-graphene composite material and answer With being by fabricated in situ, centrifugation, drying, obtain ZnS-RGO composite materials as new type lithium ion battery cathode.In 40mA/ It is tested under the current density of g, first circle specific discharge capacity is 1126.6mAh/g, and the material after 100 circle of cycle, hold by electric discharge Amount is only 250mAh/g, and cycle performance is relatively low.
CN103274474A discloses a kind of rod-shaped zinc ferrite and preparation method thereof, and the shape zinc ferrite a diameter of 7.0~ 500nm, draw ratio are 3.0~20, and rod-shaped radial direction is made of 1~20 nano particle, the size of single nanoparticle for 7.0~ 30nm；The preparation method, it is raw material to select ferrous sulfate and zinc chloride, using oxalic acid as precipitating reagent, carries out precipitation at room temperature, mixing After reaction, aged, centrifugation, washing, dry and heat treatment obtain the rod-shaped zinc ferrite constructed by nano particle.Although the material Material has excellent chemical property, but during preparation, and solution is added dropwise and ageing is required to isolation air, will to environment It asks higher, is unfavorable for mass production.
CN103413941A discloses a kind of lithium ion battery negative material and preparation method thereof, and the lithium ion battery is born Pole material uses hydrothermal reaction at low temperature, and lauryl sodium sulfate is surfactant, and soluble ferrite and urea are raw material, one Micro/nano level ferrous carbonate negative material is prepared under fixed temperature and time.Gained ferrous carbonate negative material for the first time should For lithium ion battery, first discharge specific capacity reaches 900~1110mAh/ under 0.05~3.0V, 200mA/g current densities G maintains 585~640mAh/g by 100 cycle specific discharge capacities.Although the material preparation method is simple, material Cycle performance it is poor, under the current density of 200mA/g, 100 circle after, specific discharge capacity only maintains 585~640mAh/g.
Invention content
The technical problems to be solved by the invention are to overcome drawbacks described above of the existing technology, provide one kind in charge and discharge Stable cycle performance in electric process, capacity is higher, and preparation method reaction temperature is low, and the cost of raw material is low, is suitable for industrializing The lithium ion battery of production zinc sulphide/ferrous sulfide anode material and preparation method.
The technical solution adopted by the present invention to solve the technical problems is as follows：Lithium ion battery zinc sulphide/ferrous sulfide Anode material is made of following methods：
（1）Source of iron, zinc source and organic ligand are added in n,N-Dimethylformamide solution, stirring to formation uniformly mixes molten Liquid, then under agitation, heating reaction is cooled down, is filtered, washs, dry, obtains brown ceramic powder；
（2）By step（1）Gained brown ceramic powder in an inert atmosphere, roasts, and cooling obtains black powder；
（3）By step（2）Gained black powder is soluble in water, adds in sulphur source, and ultrasonic disperse forms uniform suspension；
（4）By step（3）Gained suspension is poured into pyroreaction kettle, sealing, and heating reaction is cooled down, filtered, washs, dry, Obtain zinc sulphide/ferrous sulfide composite material precursor；
（5）By step（4）Gained zinc sulphide/ferrous sulfide composite material precursor in an inert atmosphere, roasts, and cooling obtains lithium Ion battery zinc sulphide/ferrous sulfide anode material.
Preferably, step（1）In, the molar ratio of ferro element and Zn-ef ficiency in zinc source is 7~1 in the source of iron:1.If institute It is excessive to state ratio, then the material is easily reunited, and forms larger particle, if the ratio is too small, is unfavorable for the reasonable profit of resource With.
Preferably, step（1）In, the molar ratio of the sum of the organic ligand and ferro element and Zn-ef ficiency is 1:1~6.If The ratio is excessive, then has more organic ligand to cannot participate in reaction during reaction, can if the ratio is too small Waste excessive metallic element.
Preferably, step（1）In, the dosage of the n,N-Dimethylformamide solution for so that ferro element and Zn-ef ficiency it A concentration of 0.01~0.15mol/L of sum（More preferable 0.05~0.12mol/L）.If the concentration is excessive, the material formed Easily reunite, if the concentration is too small, wasted multi-solvent.N,N-dimethylformamide enables to metal ion and organic matches The complexation reaction of body is easier to occur.
Preferably, step（1）In, the source of iron for ferric sulfate, ferric nitrate, ferric acetyl acetonade or ferric trichloride and it One or more of hydrate etc..
Preferably, step（1）In, the zinc source is in zinc sulfate, zinc nitrate or zinc chloride and their hydrate etc. One or more.
Preferably, step（1）In, the organic ligand is in trimesic acid, terephthalic acid (TPA) or fumaric acid etc. One or more.
Preferably, step（1）In, the temperature of the heating reaction is 100~140 DEG C, and the time for heating reaction is 6~24 h.During heating reaction, metal ion is combined with organic ligand, and in the temperature range, reaction is easier to occur, if Temperature is excessively high, then n,N-Dimethylformamide solution can boil, and is unfavorable for the progress of reaction.
Preferably, step（1）In, the mode of the washing is to wash filtrate >=2 time with ethyl alcohol.
Preferably, step（1）In, the temperature of the drying is 60~100 DEG C, and the dry time is 24~40 h.
Preferably, step（2）In, the temperature of the roasting is 500~600 DEG C, and the time of roasting is 4~6h.If roasting Temperature is too low, powder take out when, after contacting with the air can spontaneous combustion immediately, if calcination temperature is excessively high, which can reunite, And metallic element can be reduced into metal simple-substance.During roasting, which can be converted into the nanogold of carbon material cladding Belong to oxide particle, be conducive in sulfidation, metal oxide particle will not reunite.
Preferably, step（2）In, the inert atmosphere is argon gas or nitrogen atmosphere etc..
Preferably, step（3）In, it is 0.05~0.50% that the black powder, which is dissolved in the mass concentration after water,.Water is in high temperature In the case of high pressure, generate hydrogen ion and reacted with sulphur source, generate hydrogen sulfide, hydrogen sulfide and reactive metal oxide, generate metal Sulfide.It, can if the concentration of black powder is too low if the excessive concentration of black powder can cause the material to reunite It causes to waste.
Preferably, step（3）In, the mass ratio of the sulphur source and black powder is 1~5:1.The lower limit of the ratio is Ensureing that metal ion all cures, the upper limit of the ratio is to avoid generating excessive free state sulphur being attached to material surface, Influence material property.
Preferably, step（3）In, the sulphur source is one kind or several in thioacetamide, thiocarbamide or L-cysteine etc. Kind.The sulphur source must be added, if vulcanizing at the beginning, can not obtain nano material, nano material is in the mistake of vulcanization Tend to reunite in journey.
Preferably, step（3）In, the frequency of the ultrasonic disperse is 1.5~2.5kHz, time of ultrasonic disperse for 15~ 25min。
Preferably, step（4）In, the temperature of the heating reaction for 140~180 DEG C, heat time of reaction for 10~ 24 h（More preferable 12~18 h）.The lower limit of the temperature is to ensure that the hydrogen in water generates hydrogen sulfide with sulphur source, the temperature The upper limit is to ensure the safety of hydro-thermal reaction.The lower limit of the time is to ensure when it is sulphur source to use thioacetamide, product Can all it be vulcanized, the upper limit of the time is ensures that when using thiocarbamide, product is fully vulcanized, and is not wasted time.
Preferably, step（4）In, the mode of the washing is to be taken up in order of priority cross washing with ethyl alcohol and deionized water to filter Object >=2 time.
Preferably, step（4）In, the temperature of the drying is 60~100 DEG C, and the dry time is 24~40 h.
Preferably, step（5）In, the temperature of the roasting is 200~700 DEG C（More preferable 400~600 DEG C）, roasting Time is 2~6h（More preferable 3~5h）.Material surface is left in the sulphur distillation of free state in this step roasting process, realizes free The removal of state element sulphur.
Preferably, step（5）In, the inert atmosphere is argon gas or nitrogen atmosphere etc..
It is of the present invention to be cooled to cooled to room temperature.
Argon gas or nitrogen used in the present invention are the high-purity argon gas or high pure nitrogen of purity >=99.99%.
The present invention technical principle be：The metallorganic of zinc and ferrous metal elements compounding is prepared by high-temperature solution method Afterwards, it fixes its pattern by once sintered, forms two metal ion species uniformly compound metal oxide, then by stable metal Oxide is vulcanized by hydro-thermal, becomes the composite material of ferrous sulfide and zinc sulphide, and the wherein crystallization water is removed by double sintering And impurity is to get lithium ion battery zinc sulphide/ferrous sulfide anode material of electrochemical performance.Iron and zinc are all Cheap metal, the invention utilize bimetallic sulfide, more redox/conversion reactions can occur, in head The nanostructured that layering is formed in secondary cycle generates buffering effect, so as to improve specific capacity and cyclical stability, prepares performance Excellent lithium ion battery negative material.
Beneficial effects of the present invention are as follows：
（1）Lithium ion battery of the present invention with zinc sulphide/ferrous sulfide anode material is formed by zinc sulphide and ferrous sulfide Composite material, without other impurity, the second particle grain size of the composite material is 100~200nm, is conducive to electrolyte and cathode Effective contact of material can shorten transmission path of the lithium ion in negative material, and can keep stablizing in charge and discharge process Structure is conducive to shuttle of the lithium ion in charge and discharge process, along with uniform compound between metal sulfide so that electrode Reaction can be maintained at the state of a high reversible；
（2）Lithium ion battery of the present invention is assembled into battery with zinc sulphide/ferrous sulfide anode material, 3.00~ In 0.01V voltage ranges, under the current density of 100mA/g, first discharge specific capacity reaches as high as 1613 mAh/g, initial charge Specific capacity is 1067 mAh/g；In 3.00~0.01V voltage ranges, current density is under 1A/g, after 300 circle of cycle, is discharged Up to 716mAh/g, current density is under 500mA/g specific capacity, after 200 circle of cycle, specific discharge capacity up to 1686 mAh/g, Coulombic efficiency keeps >=98.5% substantially in cyclic process, illustrates that charge-discharge performance is stablized, good cycle；And material is filling During discharge cycles, charging and discharging capacity has the tendency that rising；
（3）The method of the present invention reaction temperature is low, and the cost of raw material is low, is suitable for industrialized production.
Description of the drawings
Fig. 1 is the XRD diagram of 1 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material；
Fig. 2 is the SEM figures of 1 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material；
Fig. 3 is the first charge-discharge of 1 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material Curve graph；
Fig. 4 is that the discharge cycles of 1 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material are bent Line and coulombic efficiency figure；
Fig. 5 is the SEM figures of 2 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material；
Fig. 6 is that the discharge cycles of 2 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material are bent Line and coulombic efficiency figure；
Fig. 7 is the first charge-discharge of 3 gained lithium ion battery zinc sulphide of the embodiment of the present invention/ferrous sulfide anode material Curve graph.
Specific embodiment
With reference to embodiment and attached drawing, the invention will be further described.
The purity of high-purity argon gas used in the embodiment of the present invention or high pure nitrogen is 99.99%；Institute of the embodiment of the present invention The chemical reagent used unless otherwise specified, is obtained by routine business approach.
Embodiment 1
（1）6mmol ferric acetyl acetonades, 5.6mmol zinc nitrate hexahydrates and 2mmol trimesic acids are added in into 100mL N, N- bis- In methylformamide solution, stirring is to uniform mixed solution is formed, then under agitation, and at 100 DEG C, heating is reacted For 24 hours, cooled to room temperature, filtering, washs filtrate 4 times with ethyl alcohol, is placed in convection oven at 60 DEG C, and drying for 24 hours, obtains brown Color powder；
（2）By step（1）Gained brown ceramic powder is in high-purity argon gas atmosphere, at 600 DEG C, roasting 4h, and cooled to room temperature, Obtain black powder；
（3）By 500mg steps（2）Gained black powder is dissolved in 100mL water, 1.5g thioacetamides is added in, in 2kHz frequencies Under, ultrasonic disperse 20min forms uniform suspension；
（4）By step（3）Gained suspension is poured into pyroreaction kettle, sealing, and at 160 DEG C, 12h is reacted in heating, naturally cold But to room temperature, filtering is taken up in order of priority cross washing filtrate 2 times with ethyl alcohol and deionized water, is placed in convection oven at 60 DEG C, Drying for 24 hours, obtains zinc sulphide/ferrous sulfide composite material precursor；
（5）By step（4）Gained zinc sulphide/ferrous sulfide composite material precursor is in high-purity argon gas atmosphere, at 600 DEG C, 3h is roasted, cooling obtains lithium ion battery zinc sulphide/ferrous sulfide anode material.
As shown in Figure 1, the embodiment of the present invention obtained by lithium ion battery with zinc sulphide/ferrous sulfide anode material be by The composite material that zinc sulphide and ferrous sulfide are formed, without other impurity.
As shown in Fig. 2, lithium ion battery is with the two of zinc sulphide/ferrous sulfide anode material obtained by the embodiment of the present invention Secondary particle size distribution is uniform, and grain size is 100~200nm.
The assembling of battery：Lithium ion battery obtained by weighing the 0.40g embodiment of the present invention is answered with zinc sulphide/ferrous sulfide cathode Condensation material, addition 0.05g acetylene blacks make conductive agent and 0.05g N-Methyl pyrrolidones make binding agent, after mixing, are applied to Negative plate is made on copper foil, using metal lithium sheet as anode in vacuum glove box, using lithium electric separator as diaphragm, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
From the figure 3, it may be seen that it is 3~0.01V in charging/discharging voltage, electric current is the electric discharge for the first time of institute's assembled battery under 100mA/g Specific capacity is 1512mAh/g, and initial charge specific capacity is 970mAh/g, and material is capable of the steady of holding structure in charge and discharge process Fixed, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
As shown in Figure 4, it is 3~0.01V in charging/discharging voltage, current density is under 100mA/g, after 35 circle of cycle, is discharged Specific capacity is 841 mAh/g, and first circle coulombic efficiency is 63.98%；Current density is under 1A/g, is recycled to 300 circles, and discharge specific volume It measures as 716mAh/g, coulombic efficiency 99.7%, illustrates that charge-discharge performance is stablized, good cycle.
Embodiment 2
（1）7mmol Fe(NO3)39H2Os, 1mmol zinc chloride and 8mmol terephthalic acid (TPA)s are added in into 160mL N, N- dimethyl methyls In amide solution, stirring is to uniform mixed solution is formed, then under agitation, and at 140 DEG C, 12h is reacted in heating, natural It is cooled to room temperature, filters, wash filtrate 3 times with ethyl alcohol, be placed in convection oven at 100 DEG C, drying for 24 hours, obtains brown ceramic powder；
（2）By step（1）Gained brown ceramic powder is in high-purity argon gas atmosphere, at 550 DEG C, roasting 5h, and cooled to room temperature, Obtain black powder；
（3）By 500mg steps（2）Gained black powder is dissolved in 150mL water, adds in 2g thiocarbamides, under 2kHz frequencies, ultrasound point 20 min are dissipated, form uniform suspension；
（4）By step（3）Gained suspension is poured into pyroreaction kettle, sealing, and at 180 DEG C, 16h is reacted in heating, naturally cold But to room temperature, filtering is taken up in order of priority cross washing filtrate 3 times with ethyl alcohol and deionized water, is placed in convection oven at 60 DEG C, Drying for 24 hours, obtains zinc sulphide/ferrous sulfide composite material precursor；
（5）By step（4）Gained zinc sulphide/ferrous sulfide composite material precursor is in high-purity argon gas atmosphere, at 400 DEG C, 4h is roasted, cooling obtains lithium ion battery zinc sulphide/ferrous sulfide anode material.
After testing, lithium ion battery obtained by the embodiment of the present invention is by sulphur with zinc sulphide/ferrous sulfide anode material Change the composite material that zinc and ferrous sulfide are formed, without other impurity.
As shown in figure 5, lithium ion battery is with the two of zinc sulphide/ferrous sulfide anode material obtained by the embodiment of the present invention Secondary particle size distribution is uniform, and grain size is 100~200nm.
The assembling of battery：Lithium ion battery obtained by weighing the 0.40g embodiment of the present invention is answered with zinc sulphide/ferrous sulfide cathode Condensation material, addition 0.05g acetylene blacks make conductive agent and 0.05g N-Methyl pyrrolidones make binding agent, after mixing, are applied to Negative plate is made on copper foil, using metal lithium sheet as anode in vacuum glove box, using lithium electric separator as diaphragm, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
After testing, it is 3~0.01V in charging/discharging voltage, electric current is the ratio of electric discharge for the first time of institute's assembled battery under 100mA/g Capacity is 1613 mAh/g, and initial charge specific capacity is 1067 mAh/g, and material is capable of holding structure in charge and discharge process Stablize, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
It will be appreciated from fig. 6 that it is 3~0.01V in charging/discharging voltage, current density is under 100mA/g, and after 6 circle of cycle, discharge ratio Capacity is 856.3mAh/g, and first circle coulombic efficiency is 66.14%；Current density is under 500mA/g, and after 200 circle of cycle, discharge ratio Capacity is 1686 mAh/g, and coulombic efficiency 98.7% illustrates that charge-discharge performance is stablized, good cycle.
Embodiment 3
（1）Tri- iron chloride hexahydrates of 7.5mmol, 2.5mmol zinc sulfate and 5mmol fumaric acid are added into 100mL N, N- diformazans In base formamide solution, stirring is to uniform mixed solution is formed, then under agitation, and at 120 DEG C, 16h is reacted in heating, Cooled to room temperature, filtering, washs filtrate 4 times with ethyl alcohol, is placed in convection oven at 80 DEG C, and dry 36h obtains brown powder End；
（2）By step（1）Gained brown ceramic powder is in high pure nitrogen atmosphere, at 500 DEG C, roasting 5h, and cooled to room temperature, Obtain black powder；
（3）By 100mg steps（2）Gained black powder is dissolved in 100mL water, 500mg L-cysteines is added in, in 2.5kHz Under frequency, ultrasonic disperse 15min forms uniform suspension；
（4）By step（3）Gained suspension is poured into pyroreaction kettle, sealing, and at 140 DEG C, 18h is reacted in heating, naturally cold But to room temperature, filtering is taken up in order of priority cross washing filtrate 2 times with ethyl alcohol and deionized water, is placed in convection oven at 80 DEG C, Dry 36h, obtains zinc sulphide/ferrous sulfide composite material precursor；
（5）By step（4）Gained zinc sulphide/ferrous sulfide composite material precursor is in high pure nitrogen atmosphere, at 500 DEG C, 4h is roasted, cooling obtains lithium ion battery zinc sulphide/ferrous sulfide anode material.
After testing, lithium ion battery obtained by the embodiment of the present invention is by sulphur with zinc sulphide/ferrous sulfide anode material Change the composite material that zinc and ferrous sulfide are formed, without other impurity.
After testing, lithium ion battery zinc sulphide/ferrous sulfide anode material obtained by the embodiment of the present invention is secondary Particle size distribution is uniform, and grain size is 100~200nm.
The assembling of battery：Lithium ion battery obtained by weighing the 0.40g embodiment of the present invention is answered with zinc sulphide/ferrous sulfide cathode Condensation material, addition 0.05g acetylene blacks make conductive agent and 0.05g N-Methyl pyrrolidones make binding agent, after mixing, are applied to Negative plate is made on copper foil, using metal lithium sheet as anode in vacuum glove box, using lithium electric separator as diaphragm, 1mol/L LiPF6/EC:DMC（Volume ratio 1:1）For electrolyte, it is assembled into the button cell of CR2025.
As shown in Figure 7, it is 3~0.01V in charging/discharging voltage, electric current is the electric discharge for the first time of institute's assembled battery under 100mA/g Specific capacity is 1264 mAh/g, and initial charge specific capacity is 886.5 mAh/g, and material being capable of holding structure in charge and discharge process Stabilization, volume expansion is small, good conductivity, makes discharge and recharge reaction high reversible.
After testing, it is 3~0.01V in charging/discharging voltage, current density is under 100mA/g, and after 10 circle of cycle, discharge specific volume It measures as 766.1mAh/g, first circle coulombic efficiency is 70.1%；Current density is under 5A/g, and after 700 circle of cycle, specific discharge capacity is 736.1mAh/g, coulombic efficiency 99.4% illustrate that charge-discharge performance is stablized, good cycle.

Claims (10)

1. a kind of lithium ion battery zinc sulphide/ferrous sulfide anode material, which is characterized in that be made of following methods：
（1）Source of iron, zinc source and organic ligand are added in n,N-Dimethylformamide solution, stirring to formation uniformly mixes molten Liquid, then under agitation, heating reaction is cooled down, is filtered, washs, dry, obtains brown ceramic powder；
（2）By step（1）Gained brown ceramic powder in an inert atmosphere, roasts, and cooling obtains black powder；
（3）By step（2）Gained black powder is soluble in water, adds in sulphur source, and ultrasonic disperse forms uniform suspension；
（4）By step（3）Gained suspension is poured into pyroreaction kettle, sealing, and heating reaction is cooled down, filtered, washs, dry, Obtain zinc sulphide/ferrous sulfide composite material precursor；
（5）By step（4）Gained zinc sulphide/ferrous sulfide composite material precursor in an inert atmosphere, roasts, and cooling obtains lithium Ion battery zinc sulphide/ferrous sulfide anode material.
2. lithium ion battery according to claim 1 or claim 2 zinc sulphide/ferrous sulfide anode material, it is characterised in that： Step（1）In, the molar ratio of ferro element and Zn-ef ficiency in zinc source is 7~1 in the source of iron:1；The organic ligand and ferro element Molar ratio with the sum of Zn-ef ficiency is 1:1~6；The dosage of the N,N-dimethylformamide solution is so that ferro element and zinc member A concentration of 0.01~0.15mol/L of the sum of element.
3. lithium ion battery according to claim 1 or claim 2 zinc sulphide/ferrous sulfide anode material, it is characterised in that： Step（1）In, the source of iron is one in ferric sulfate, ferric nitrate, ferric acetyl acetonade or ferric trichloride and their hydrate Kind is several；The zinc source is one or more of zinc sulfate, zinc nitrate or zinc chloride and their hydrate；It is described Organic ligand is one or more of trimesic acid, terephthalic acid (TPA) or fumaric acid.
4. according to one of claims 1 to 3 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（1）In, the temperature of the heating reaction is 100~140 DEG C, and the time for heating reaction is 6~24 h.
5. according to one of Claims 1 to 4 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（1）In, the mode of the washing is to wash filtrate >=2 time with ethyl alcohol；The temperature of the drying is 60~100 DEG C, the dry time is 24~40 h.
6. according to one of Claims 1 to 5 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（2）In, the temperature of the roasting is 500~600 DEG C, and the time of roasting is 4~6h；The inert atmosphere is argon Gas or nitrogen atmosphere.
7. according to one of claim 1~6 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（3）In, it is 0.05~0.50% that the black powder, which is dissolved in the mass concentration after water,；The sulphur source and black powder Mass ratio be 1~5:1；The sulphur source is one or more of thioacetamide, thiocarbamide or L-cysteine；The ultrasound The frequency of dispersion is 1.5~2.5kHz, and the time of ultrasonic disperse is 15~25min.
8. according to one of claim 1~7 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（4）In, the temperature of the heating reaction is 140~180 DEG C, and the time for heating reaction is 10~24 h.
9. according to one of claim 1~8 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（4）In, the mode of the washing is to be taken up in order of priority cross washing filtrate >=2 time with ethyl alcohol and deionized water；Institute It is 60~100 DEG C to state dry temperature, and the dry time is 24~40 h.
10. according to one of claim 1~9 lithium ion battery zinc sulphide/ferrous sulfide anode material, feature It is：Step（5）In, the temperature of the roasting is 200~700 DEG C, and the time of roasting is 2~6h；The inert atmosphere is argon Gas or nitrogen atmosphere.
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