CN112909244A - Pyrite-based composite material and preparation method and application thereof - Google Patents

Pyrite-based composite material and preparation method and application thereof Download PDF

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CN112909244A
CN112909244A CN201911226923.8A CN201911226923A CN112909244A CN 112909244 A CN112909244 A CN 112909244A CN 201911226923 A CN201911226923 A CN 201911226923A CN 112909244 A CN112909244 A CN 112909244A
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pyrite
xanthate
based composite
powder
composite material
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CN112909244B (en
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孙伟
江锋
常兴华
张丽敏
赵文青
周嘉辉
葛鹏
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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
    • H01M4/58—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 invention discloses a pyrite-based composite material, which has diffraction peaks at the positions of 30.02 degrees, 34.00 degrees, 44.03 degrees and 53.31 degrees of 2 theta in an XRD spectrogram, preferably, the composite material is prepared from pyrite and a carbon source, the pyrite powder is soaked in a xanthate solution, and then the obtained modified pyrite powder is mixed with the carbon source and roasted to prepare the carbon-coated pyrite powder, namely, the pyrite-based composite material The preparation process is reduced, the yield is high, and the method is suitable for large-scale industrial production.

Description

Pyrite-based composite material and preparation method and application thereof
Technical Field
The invention belongs to the field of battery electrodes, and particularly relates to a pyrite-based composite material, and a preparation method and application thereof.
Background
The natural pyrite has the characteristics of high specific capacity, large resource storage capacity and low preparation cost, can be applied to the field of batteries, and pyrite materials are reported in the field of sodium ion batteries, but have poor electrochemical properties, such as poor cycling stability and rate capability and low specific discharge capacity, and probably because the pyrite materials are easy to react with electrolyte to decompose, the batteries have low durability and poor cycling performance.
Therefore, the development of the pyrite-based composite material with high specific capacity, high multiplying power, good stability and long cycle life as a high-performance battery material has important significance.
Disclosure of Invention
In order to overcome the problems, the inventor of the present invention has conducted intensive research to research a pyrite-based composite material, the composite material is prepared from pyrite and a carbon source, the pyrite powder is soaked in a pyrite solution, the obtained modified pyrite powder is mixed with the carbon source and roasted, and then the carbon-coated pyrite powder, namely, the pyrite-based composite material, is prepared.
An object of the present invention is to provide a pyrite-based composite having an XRD spectrum with diffraction peaks at 30.02 °, 34.00 °, 44.03 ° and 53.31 ° 2 θ, preferably made from pyrite and a carbon source.
Wherein the carbon source comprises an organic compound, preferably one or more selected from phenolic resin, polyvinylpyrrolidone, polyacrylamide, polydopamine, polypyridine, chitosan, asphalt and polyaniline.
Another aspect of the present invention provides a method for preparing a pyrite-based composite, the method comprising the steps of:
step 1, preparing pyrite powder;
step 2, adding the pyrite powder into the xanthate solution to obtain modified pyrite powder;
step 3, mixing the modified pyrite powder obtained in the step 2 with a carbon source to obtain a mixture;
and 4, roasting the mixture to obtain the pyrite-based composite material.
Wherein, in the step 1, the particle size of the pyrite powder is 10-100 μm, preferably 10-70 μm.
In step 2, the xanthate solution is prepared from xanthate and a solvent, wherein the xanthate is a hydrocarbyl xanthate, and is preferably selected from one or more of sodium hexyl xanthate, potassium hexyl xanthate, sodium amyl xanthate, potassium amyl xanthate, sodium butyl xanthate and potassium butyl xanthate.
In the step 2, the mass percentage concentration of the xanthate solution is 0.1-5%, and preferably 0.5-2%.
In the step 3, the mass ratio of the modified pyrite powder to the phenolic resin is 1: 3-1: 25, and preferably 1: 5-1: 20.
In the step 3, the mixing comprises heating, wherein the heating temperature is 100-300 ℃, and preferably 150-250 ℃.
In the step 4, the roasting temperature is 400-1000 ℃, and preferably 500-800 ℃;
the roasting time is 1-8 h, preferably 2-5 h.
A further aspect of the invention provides the use of a pyrite-based composite as a high performance battery material.
The invention has the following beneficial effects:
(1) the pyrite-based composite material, namely the carbon-coated pyrite powder, is prepared by mixing and roasting pyrite powder after adsorbing the xanthate with a carbon source, and after the pyrite powder adsorbs the xanthate, a compact carboxyl hydrophobic layer is formed on the surface, so that a carbon-coated structure is easily prepared with the carbon source, and the carbon-coated pyrite powder has excellent electrochemical performance;
(2) the pyrite-based composite material prepared by the method can be used as a high-performance battery material, and the high-performance battery material with high specific capacity, high multiplying power, no volume effect, good stability and long cycle life is developed by controlling the mass ratio of the pyrite powder to the carbon source, so that the method has very important significance for improving the overall performance of the battery;
(3) the pyrite-based composite material provided by the invention is prepared by taking pyrite and a carbon source as raw materials, the natural pyrite powder has high specific capacity, large resource storage capacity and low preparation cost, the production cost of the pyrite-based composite material is greatly reduced, and the obtained pyrite-based composite material integrates the advantages of pyrite and a carbonaceous material;
(4) the pyrite-based composite material provided by the invention is used as a high-performance battery material, and can be applied to lithium ion batteries, lithium ion super capacitors, sodium ion batteries, sodium ion super capacitors and water capacitors as a negative electrode lithium or sodium storage material;
(5) the invention also opens the process route from the ore to the finished battery material, and realizes the breakthrough of preparing the high-performance battery material from the pyrite for the first time. Greatly reduces the production cost, reduces the preparation procedures, has high yield and is suitable for large-scale industrial production.
Drawings
Fig. 1 shows XRD patterns of the pyrite powder obtained in example 1 of the present invention and the pyrite-based composite obtained in examples 1 and 2;
fig. 2 shows SEM, TEM and EDS images of the pyrite powder obtained in example 1 of the present invention, the pyrite-based composite materials obtained in example 1 and example 2;
FIG. 3 shows that the lithium ion battery obtained in Experimental example 1 of the present invention has a current density of 100mA g-1The cycle curve of (d);
FIG. 4 shows that the lithium ion battery obtained in Experimental example 1 of the present invention has a current density of 2000mA g-1The cycle curve of (d);
FIG. 5 shows the current density of 100mA g of the Na-ion battery obtained in Experimental example 1 of the present invention-1The cycle curve of (d);
FIG. 6 shows the current density of the Na-ion battery obtained in Experimental example 1 of the present invention at 2000mA g-1The cycle curve of (2).
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to the present invention, there is provided a pyrite-based composite made from pyrite and a carbon source.
According to the invention, the pyrite is preferably natural pyrite, such as natural pyrite concentrate.
According to the invention, the carbon source comprises an organic compound, preferably one or more selected from phenolic resin, polyvinylpyrrolidone, polyacrylamide, polydopamine, polypyridine, chitosan, asphalt and polyaniline, more preferably phenolic resin, and the phenolic resin and the pyrite prepared pyrite-based composite material can relieve the expansion effect of pyrite during charging and discharging and improve the electrochemical performance of the pyrite-based composite material.
According to the invention, the preparation method of the pyrite-based composite material comprises the following steps:
step 1, preparing pyrite powder.
According to the invention, in step 1, the obtained pyrite powder has a particle size of 1 to 10 μm, preferably 1 to 5 μm, for example 2 μm.
According to the invention, in step 1, pyrite powder can be obtained by the following steps:
step 1.1, grinding the pyrite;
and 1.2, carrying out solid-liquid separation to obtain pyrite powder.
According to the invention, in step 1.1, the pyrite is natural pyrite, which is preferably taken from Guangdong Shaoshaoguan, and is preferably selected from the ore dressing plant flotation pyrite, with a particle size of several hundred micrometers to several millimeters.
According to the invention, in step 1.1, the pyrite is added into a solvent before grinding to prepare a suspension with the pyrite mass percentage concentration of 2% -20%, preferably 5% -15%, and then the suspension is ground.
According to the invention, the solvent is pure water or alcohol (ethanol).
According to the invention, in step 1.1, the grinding treatment is mechanical grinding, preferably by using a planetary ball mill or a nano sand mill, and the ground pyrite is obtained.
According to the invention, in step 1.1, the grinding speed is 200-600r/min, the grinding time is 2-10 h, preferably the grinding speed is 300-500 r/min, the grinding time is 4-8 h, more preferably the grinding speed is 400r/min, and the grinding time is 6 h.
According to the invention, in step 1.1, the temperature of the suspension is controlled to be 20-40 ℃ during the grinding treatment.
According to the invention, in step 1.2, the pyrite suspension obtained in step 1.2 is subjected to solid-liquid separation to obtain pyrite powder. According to the present invention, in step 1.2, the solid-liquid separation mode is not particularly limited, and is preferably one or more selected from centrifugal drying, freeze drying and evaporation drying.
According to the invention, in step 1.2, solid-liquid separation is carried out by adopting a centrifugal drying mode, the centrifugal rotating speed is 10000rpm-15000rpm, preferably 10000-13000rpm, and the solid obtained after centrifugation is dried at the drying temperature of 50-100 ℃ for 12-24h to obtain the pyrite powder.
In the present invention, the pyrite powder obtained in step 1 contains FeS as a main component2And (3) powder.
According to the invention, the XRD spectrum of the obtained pyrite powder is 28.51Diffraction peaks exist at 33.08 degrees, 37.10 degrees, 40.78 degrees, 47.41 degrees and 56.28 degrees, and are consistent with standard card cubic FeS2(JCPDS No.42-1340) has the (111), (200), (210), (211), (220) and (311) crystal faces corresponding to each other, and no additional peaks appear in the spectrum, indicating that the prepared pyrite powder has high purity.
And 2, adding the pyrite powder into the xanthate solution to obtain modified pyrite powder.
According to the invention, in the step 2, the xanthate solution is obtained by adding xanthate into a solvent, and the mass percentage concentration of the xanthate solution is 0.1-5%, preferably 0.5-2%.
In the invention, the pyrite powder is added into the pyrite solution with a certain concentration range, so that the pyrite can be fully adsorbed on the surface of the pyrite powder, and the loss of redundant pyrite can be avoided.
According to the invention, in step 2, the xanthate is preferably a hydrocarbyl xanthate, preferably selected from one or more of sodium hexyl xanthate, potassium hexyl xanthate, sodium amyl xanthate, potassium amyl xanthate, sodium butyl xanthate, potassium butyl xanthate.
According to the invention, in step 2, the solvent in the xanthate solution is pure water.
According to a preferred embodiment of the present invention, in step 2, the pyrite powder is added to the pyrite solution, soaked, optionally stirred, and then subjected to solid-liquid separation to obtain a modified pyrite powder.
According to the invention, in the step 2, the mass ratio of the pyrite powder to the xanthate is 50:1-10: 1.
According to the invention, in step 2, the pyrite powder is soaked in the xanthate solution, optionally with stirring, for a time of 10-60min, preferably 20-50 min, for example 30 min.
According to the invention, in the step 2, after the soaking, solid-liquid separation is carried out to obtain the modified pyrite powder, the solid-liquid separation mode is not particularly limited, and is preferably carried out by adopting a high-speed centrifugation mode, the rotating speed is 10000-15000rpm, the time is 10-20min, and the rotating speed is 12000-14000 rpm, and the time is 12-18 min.
According to the invention, the pyrite powder is soaked in the xanthate solution, and the pyrite powder absorbs the xanthate and then forms a compact carboxyl hydrophobic layer on the surface of the pyrite powder. The sulfhydryl groups in the pyrite can be adsorbed to iron sites on the surface of the pyrite, so that a compact pyrite layer is formed on the surface of the pyrite. The carboxyl at the other end of the xanthate is hydrophobic, so that the whole surface of the pyrite is hydrophobic, and the full action with an organic compound or an organic polymer in the next step is facilitated.
And 3, mixing the modified pyrite powder obtained in the step 2 with a carbon source to obtain a mixture.
According to the invention, in step 3, the carbon source is an organic compound, preferably one or more selected from phenolic resin, polyvinylpyrrolidone, polyacrylamide, polydopamine, polypyridine, chitosan, asphalt, polyaniline and the like, and the carbon source is carbonized after being calcined at high temperature to form the carbonaceous material.
According to the invention, in the step 3, the mass ratio of the modified pyrite powder to the carbon source is 1: 3-1: 25, preferably 1: 5-1: 20, and more preferably 1: 5-1: 10.
In the invention, the quality ratio of the modified pyrite powder to the carbon source has an important influence on the performance of the finally obtained pyrite-based composite material, and when the ratio is within the range, the obtained pyrite-based composite material as a battery material has the advantages of high specific capacity, high multiplying power, no volume effect, good stability and long cycle performance. The carbon source addition is too small, the coating action force on the modified pyrite powder is not strong, and the volume expansion of the material in the charging and discharging processes is difficult to effectively relieve, so that the circulation stability is poor. And too large addition of the carbon source can reduce the proportion of the active material modified pyrite powder and influence the specific capacity.
According to the invention, in step 3, the modified pyrite powder is mixed with a carbon source in a solvent to obtain a mixture.
According to the invention, in step 3, the solvent is one or more selected from ethanol, methanol, acetone and water, such as ethanol.
According to the invention, in the step 3, the mass concentration of the pyrite in the solvent is 1-10%.
According to the invention, in step 3, the mixture is heated, preferably with stirring, to remove the solvent and to mix homogeneously.
According to the invention, in the step 3, the heating is preferably carried out in a sand bath, the heating temperature is 100-300 ℃, the heating time is 5-24 hours, the heating time is preferably 5-10 hours, and the stirring speed is 100-200 rpm.
In the present invention, the organic compound in the carbon source can be further polymerized by heating, and the solvent is evaporated to dryness to obtain solid particles.
And 4, roasting the mixture obtained in the step 3 to obtain the pyrite-based composite material.
According to the invention, the calcination is carried out in a reducing atmosphere, preferably in an argon atmosphere.
According to the invention, in the step 4, the roasting temperature is 400-1000 ℃, preferably 500-800 ℃, and more preferably 600-700 ℃;
the roasting time is 1-8 h, preferably 2-5 h, and more preferably 2-3 h.
In the invention, the organic matter can be effectively carbonized at the roasting temperature, and amorphous porous carbon can be formed at the same time, which is beneficial to ion transmission in the charging and discharging process.
In the invention, because the ferrous disulfide has a serious volume expansion effect in the charging and discharging processes of the battery and has the problem of loss of the active material, the ferrous disulfide is coated by the carbon source material, so that the volume expansion of the ferrous disulfide can be inhibited, the active material can be fixed, the conductivity of the material can be improved, and the electrochemical performance of the pyrite-based composite material can be improved. According to the invention, after roasting, the carbon source is carbonized, and a uniform carbon coating layer is formed on the surface of the modified pyrite powder, namely the obtained pyrite-based composite material.
The inventor finds that during roasting, the modified pyrite powder is converted into Fe after roasting7S8The pyrite-based composite material is carbon-coated Fe7S8A composite material. With FeS2In contrast, Fe7S8Has better conductivity and relatively betterThe low charge/discharge voltage plateau is favorable for improving the electrochemical reaction kinetics and the power density of the full battery by taking the pyrite-based composite material as a high-performance battery material.
According to the invention, the pyrite-based composite has a carbon shell coating Fe7S8Structure or Fe7S8A structure embedded in a carbon shell, the XRD spectrum of the composite material has diffraction peaks at 30.02 degrees, 34.00 degrees, 44.03 degrees and 53.31 degrees of 2 theta, and hexagonal Fe7S8(JCPDS No.24-0220) the (200), (203), (206) and (220) diffraction planes of the standard card are matched,
the composite material has lattice stripes with distances of 0.30nm, 0.24nm and 0.18nm, which respectively correspond to (200), (115) and (304) hexagonal pyrite Fe7S8Of the plane of (a).
According to the invention, the thickness of the carbon shell in the pyrite-based composite material is about 3-10 nm, and preferably 5 nm.
The prepared pyrite-based composite material is used as a negative electrode material of a lithium ion battery, and the prepared lithium ion battery has high specific capacity, good cycling stability and long cycle life, for example, for the lithium ion battery and a sodium ion battery, the current density is 100mA g-1Next, after 100 cycles, it can provide high reversible capacity of 1319 and 796mAh g-1, respectively; at 2000mA g-1Still has a considerable capacity of 995mAh g-1 after 1000 cycles and 545mAh g-1 after 400 cycles.
The pyrite-based composite material prepared by the invention integrates the advantages of the carbonaceous material and pyrite, has the advantages of high specific capacity, high multiplying power, no volume effect, good stability and long cycle life, can be used as a high-performance battery cathode material, and has very important significance for improving the overall electrochemical performance of the battery.
The pyrite-based composite material prepared by the invention can be used as a high-performance battery material to be applied to a negative electrode lithium storage material or a sodium storage material in a lithium ion battery, a lithium ion super capacitor, a sodium ion battery, a sodium ion super capacitor and a water-based capacitor.
The invention skillfully utilizes the characteristics of high specific capacity, large resource storage capacity and low preparation cost of natural pyrite, forms a compact carboxyl hydrophobic layer on the surface after the pyrite powder adsorbs the xanthate, and then is mixed with a carbon source and roasted to obtain the carbon-coated pyrite powder, namely the pyrite-based composite material, which can be used as a high-performance battery material.
Examples
Example 1
Grinding the pyrite by adopting a planetary ball mill to obtain a pyrite suspension, centrifuging and drying the pyrite suspension to obtain pyrite powder;
adding 5g of pyrite powder into 100ml of 2% pyrite solution, soaking for 30min while stirring, and then carrying out centrifugal separation at the rotating speed of 12000rpm for 15min to obtain modified pyrite powder;
adding 4g of pyrite powder and 30g of phenolic resin into ethanol, stirring and mixing, adding the mixture into a sand bath kettle for heating and stirring at the heating temperature of 200 ℃ for 10 hours, and obtaining a mixture after the pyrite and the phenolic resin are uniformly mixed after the ethanol volatilizes;
and placing the mixture in a high-temperature furnace, and roasting at the high temperature of 700 ℃ for 2 hours in an argon atmosphere to obtain the pyrite-based composite material after roasting.
Example 2
Adding 10g of pyrite powder into 100ml of 0.2% pyrite solution, soaking for 60min, stirring, and then carrying out centrifugal separation at the rotating speed of 15000rpm for 10min to obtain modified pyrite powder;
adding 2g of pyrite powder and 30g of phenolic resin into ethanol, stirring and mixing, adding the mixture into a sand bath kettle for heating and stirring at the heating temperature of 100 ℃ for 24 hours, and obtaining a mixture after the pyrite and the phenolic resin are uniformly mixed after the ethanol volatilizes;
and placing the mixture in a high-temperature furnace, and roasting at the high temperature of 600 ℃ for 3h in an argon atmosphere to obtain the pyrite-based composite material after roasting.
XRD tests (using Bruker D8X radiation diffractometer) were performed on the pyrite powder prepared in example 1 and the pyrite-based composite materials obtained in examples 1 and 2, and the results are shown in fig. 1, wherein in fig. 1, (a) is the XRD profile of the pyrite powder prepared in example 1, and (b) and (c) are the XRD profiles of the pyrite-based composite materials obtained in examples 1 and 2, respectively.
In FIG. 1, the (a) curve, diffraction peaks at 28.51, 33.08, 37.10, 40.78, 47.41 and 56.28 correspond to standard card cubic FeS2(JCPDS No.42-1340) (111), (200), (210), (211), (220), (311) crystal face, and no additional peak appears in the curve, indicating that the produced pyrite powder has high purity. (b) In (c) four new broad peaks appear, located at 30.02 °, 34.00 °, 44.03 ° and 53.31 °, respectively, corresponding to hexagonal Fe7S8The (200), (203), (206) and (220) diffraction planes of the (JCPDS No.24-0220) standard card match well, indicating that the modified pyrite powder formed hexagonal Fe after calcination7S8。
SEM and TEM tests were performed on the pyrite powder prepared in example 1 and the pyrite-based composite materials obtained in examples 1 and 2, and the results are shown in fig. 2.
(a) For the SEM image of the pyrite powder prepared in example 1, it can be seen that the pyrite powder is in a smooth blocky morphology with a relatively smooth surface, with a particle size of about 2 μm.
(b) And (c) SEM images of the pyrite-based composite obtained in examples 1 and 2, respectively, from which it can be seen that the pyrite-based composite is also in the form of a block, having a rougher surface and a relatively large particle size.
(d) In order to obtain a TEM image of the pyrite-based composite obtained in example 1, (e) and (f) are both high-resolution TEM images (HRTEM) of the pyrite-based composite obtained in example 1. From the figure canTo see, bulk Fe7S8Closely covered by a carbon shell, smaller particles of Fe7S8Uniform embedding into the carbon shell, a thickness of about 5nm of the carbon shell being obtainable from (e). From (f), clear lattice images were observed, and lattice fringes at distances of 0.30nm, 0.24nm and 0.18nm were resolved, corresponding to (200), (115) and (304) hexagonal pyrite Fe, respectively7S8Consistent with XRD results.
(g) The SEM images of the pyrite-based composite obtained in example 2, (1), (2), (3) are EDS images of C, S, Fe of the surface of the pyrite-based composite, respectively, (h) and (i) are the results of elemental analyses of the composites obtained in examples 1 and 2, respectively. This results in a homogeneous distribution of Fe and S elements in the pyrite-based composite, with Fe of examples 1 and 2: the molar ratio of S is 1: 1.51 and 1: 1.47.
example 3
Adding 5g of pyrite powder into 100ml of 0.1% pyrite solution, soaking for 20min, stirring, and then carrying out centrifugal separation at the rotation speed of 10000rpm for 20min to obtain modified pyrite powder;
adding 2g of pyrite powder and 50g of phenolic resin into ethanol, stirring and mixing, adding the mixture into a sand bath kettle for heating and stirring at the heating temperature of 300 ℃ for 5h, and obtaining a mixture after the pyrite and the phenolic resin are uniformly mixed after the ethanol volatilizes;
and placing the mixture in a high-temperature furnace, performing high temperature treatment in an argon atmosphere at 500 ℃ for 5 hours to obtain the pyrite-based composite material after roasting.
Examples of the experiments
Experimental example 1
The pyrite-based composite material obtained in example 1 was used as a negative electrode material of a lithium ion battery to prepare the lithium ion battery.
The prepared lithium ion battery was subjected to constant current cycle performance test in a voltage range of 0.01-3V using Arbin Battery test System (BT2000), and the obtained test results are shown in FIGS. 3 and 4, in which FIG. 3 is a graph showing that the current density is 100mA g-1Cycle performance ofThe curve, FIG. 4, is a plot of current density 2000mA g-1Cycle performance curve of (a).
As can be seen from FIG. 3, the current density was 100mA g-1Then, 1319mAh g can be obtained after 100 cycles of circulation-1The specific capacity of (A) is shown in FIG. 4, at a current density of 2000mA g-1995mAh g can be obtained after 1000 cycles-1The specific capacity of (A).
The pyrite-based composite material obtained in example 1 was used as a negative electrode material of a sodium ion battery to prepare a sodium ion battery.
The prepared sodium ion battery was subjected to a constant current cycle performance test in a voltage range of 0.01 to 3V using an Arbin cell test System (BT2000), and the obtained test results are shown in FIGS. 5 and 6, which are obtained from FIGS. 3 and 4, at a current density of 100mA g-1Then, the 796mAh g can be obtained after 100 cycles of circulation-1Specific capacity of (2) at a current density of 2000mA g-1Then, 545mAh g can be obtained after circulating for 400 circles-1The specific capacity of (A).
Experimental example 2
The pyrite-based composite material obtained in example 2 was used as a negative electrode material of a lithium ion battery to prepare the lithium ion battery.
The prepared lithium ion battery is subjected to constant current circulation performance test in a voltage range of 0.01-3V by adopting an Arbin battery test system (BT2000), and the current density is 100mA g-1Then, 932mAh g can be obtained after 100 cycles of circulation-1Specific capacity of (2) at a current density of 2000mA g-1Circulating for 1000 circles to obtain 761mAh g-1The specific capacity of (A).
The pyrite-based composite material obtained in example 2 was used as a negative electrode material of a sodium ion battery to prepare a sodium ion battery.
The Arbin battery test system (BT2000) is adopted to carry out constant current circulation performance test on the prepared sodium ion battery within the voltage range of 0.01-3V, and the current density is 100mA g-1Then, 618mAh g can be obtained after 100 cycles of circulation-1Specific capacity of (2) at a current density of 2000mA g-1Then, after circulating for 400 circles, 375mAh g can be obtained-1The specific capacity of (A).
Experimental example 3
The pyrite-based composite material obtained in example 3 was used as a negative electrode material of a lithium ion battery to prepare the lithium ion battery.
The prepared lithium ion battery is subjected to constant current circulation performance test in a voltage range of 0.01-3V by adopting an Arbin battery test system (BT2000), and the current density is 100mA g-1Then, the circulation is performed for 100 circles to obtain 715mAh g-1Specific capacity of (2) at a current density of 2000mA g-1After 1000 cycles, 583mAh g can be obtained-1The specific capacity of (A).
The pyrite-based composite material obtained in example 3 was used as a negative electrode material of a sodium ion battery to prepare a lithium ion battery.
The Arbin battery test system (BT2000) is adopted to carry out constant current circulation performance test on the prepared sodium ion battery within the voltage range of 0.01-3V, and the current density is 100mA g-1Then, 446mAh g can be obtained after 100 cycles of circulation-1Specific capacity of (2) at a current density of 2000mA g-1Then, 292mAh g can be obtained after 400 cycles of circulation-1The specific capacity of (A).
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (10)

1. A pyrite-based composite characterized by an XRD pattern that exhibits diffraction peaks at 30.02 °, 34.00 °, 44.03 ° and 53.31 ° 2 Θ, preferably said composite is made from pyrite and a carbon source.
2. The composite material according to claim 1, wherein the carbon source comprises an organic compound, preferably one or more selected from the group consisting of phenolic resin, polyvinylpyrrolidone, polyacrylamide, polydopamine, polypyridine, chitosan, pitch, and polyaniline.
3. A method for preparing a pyrite-based composite, comprising the steps of:
step 1, preparing pyrite powder;
step 2, adding the pyrite powder into the xanthate solution to obtain modified pyrite powder;
step 3, mixing the modified pyrite powder obtained in the step 2 with a carbon source to obtain a mixture;
and 4, roasting the mixture to obtain the pyrite-based composite material.
4. A method according to claim 3, characterized in that in step 1 the pyrite powder has a particle size of 10-100 μ ι η, preferably 10-70 μ ι η.
5. The method according to claim 3, wherein in step 2, the xanthate solution is prepared from xanthate and solvent, wherein the xanthate is alkyl xanthate, preferably selected from one or more of sodium hexyl xanthate, potassium hexyl xanthate, sodium amyl xanthate, potassium amyl xanthate, sodium butyl xanthate and potassium butyl xanthate.
6. The method according to claim 3, wherein in the step 2, the xanthate solution has a mass percentage concentration of 0.1-5%, preferably 0.5-2%.
7. The method according to claim 3, wherein in the step 3, the mass ratio of the modified pyrite powder to the phenolic resin is 1: 3-1: 25, preferably 1: 5-1: 20.
8. The method according to claim 3, wherein in step 3, the mixing comprises heating at a temperature of 100-300 ℃, preferably 150-250 ℃.
9. The method according to claim 3, wherein in the step 4, the roasting temperature is 400-1000 ℃, preferably 500-800 ℃;
the roasting time is 1-8 h, preferably 2-5 h.
10. The application of the pyrite-based composite material as a high-performance battery material.
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CN114361425A (en) * 2022-01-17 2022-04-15 中南大学 Method for directly preparing pyrophosphate sodium iron phosphate composite material from pyrite, pyrophosphate sodium iron phosphate composite material and application thereof
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CN117865227A (en) * 2024-03-12 2024-04-12 钛科(大连)新能源有限公司 Method for synthesizing ferrous sulfide material by using pyrite raw material and application thereof
CN117865227B (en) * 2024-03-12 2024-05-07 钛科(大连)新能源有限公司 Method for synthesizing ferrous sulfide material by using pyrite raw material and application thereof

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