CN113140711A - Sulfide mineral-based composite material and preparation and application thereof - Google Patents

Sulfide mineral-based composite material and preparation and application thereof Download PDF

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CN113140711A
CN113140711A CN202010060161.5A CN202010060161A CN113140711A CN 113140711 A CN113140711 A CN 113140711A CN 202010060161 A CN202010060161 A CN 202010060161A CN 113140711 A CN113140711 A CN 113140711A
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graphene
composite material
sulfide
molybdenite
mineral
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CN113140711B (en
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廖立兵
刘昊
海韵
王硕男
梅乐夫
吕国诚
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 sulfide mineral-based composite material and a preparation method thereof, the composite material is obtained by mixing sulfide minerals and graphene suspension liquid, freeze-drying, roasting and microwave treatment, and the composite material is used as an electrode material of a lithium ion battery and has the advantages of high specific capacity, small capacity attenuation, good stability and long cycle performance. The preparation method of the composite material provided by the invention has the advantages of simple process and low production cost, and is suitable for large-scale industrial production.

Description

Sulfide mineral-based composite material and preparation and application thereof
Technical Field
The invention belongs to the field of battery electrodes, and particularly relates to a sulfide mineral-based composite material and a preparation method and application thereof.
Background
Lithium ion batteries have become the main devices of portable mobile power sources due to their high energy density and stable output voltage. Before a new electrochemical energy storage system and a new battery technology appear and are mature, finding a material with higher specific capacity to replace the positive and negative electrodes of the traditional lithium battery is the most critical step for improving the energy density of the lithium ion battery.
Sulfides are one of the potential electrode materials because of their higher theoretical capacity. At present, most sulfide electrode materials are mainly synthesized manually, and have the defects of complex process flow, high cost, long period and the like. Various natural sulfide minerals exist in nature, and have the advantages of various types, rich reserves, low cost and the like. However, the natural minerals have a large particle size (several tens to several hundreds of micrometers) after simple crushing. If the natural mineral is directly used as a secondary battery electrode material, the obtained battery has poor specific capacity and rate capability, so that the application of the natural mineral in the secondary battery electrode is limited.
Therefore, the development of the lithium ion battery electrode material which can be directly prepared from the natural sulfide minerals has important significance.
Disclosure of Invention
In order to solve the problems, the inventor of the present invention has conducted intensive research and designed a sulfide mineral-based composite material, a preparation method and an application thereof, wherein the sulfide mineral-based composite material is obtained by mixing, freeze-drying, roasting and microwave treatment of a natural sulfide mineral and a graphene suspension. The composite material has the advantages of simple preparation process and low production cost, and has the advantages of high specific capacity, small capacity attenuation, good stability and long cycle performance when being used as a battery material, thereby completing the invention.
The invention provides a sulfide mineral-based composite material, which is prepared from sulfide minerals and graphene.
The sulfide minerals are natural sulfide minerals, preferably selected from one or more of molybdenite, stibnite, chalcopyrite, sphalerite or pyrite, further preferably selected from one or more of molybdenite and sphalerite, and more preferably selected from molybdenite.
The graphene is selected from one or more of graphene oxide, hydrogenated graphene and fluorinated graphene, preferably one or more of graphene oxide and hydrogenated graphene, and more preferably graphene oxide.
In a second aspect the present invention provides a method of producing a sulphide mineral-based composite material, the method comprising the steps of:
step 1: preparing a graphene suspension;
step 2: mixing sulfide minerals and the graphene suspension;
step 3, freeze-drying the mixed sample;
step 4, roasting the freeze-dried sample;
and 5, carrying out microwave treatment on the roasted sample.
In the step 1, the ratio of the mass of the graphene in the graphene suspension to the volume of the solvent is 1-10mg:1ml, more preferably 3-8mg:1ml, and still more preferably 5mg:1 ml.
In the step 2, the mass ratio of the sulfide mineral to the graphene is 1-5:1, preferably 1-3: 1.
In the step 3, the freeze drying is firstly pre-frozen for 1 to 10 hours at the temperature of between 80 ℃ below zero and 40 ℃ below zero, then the vacuum pumping is carried out, and the freeze drying is carried out for 12 to 60 hours at the temperature of between 20 ℃ below zero and 0 ℃ below zero; further preferably, the freeze drying is firstly pre-frozen for 2 to 8 hours at the temperature of between 70 ℃ below zero and 50 ℃ below zero, then the vacuum pumping is carried out, and the freeze drying is carried out for 24 to 48 hours at the temperature of between 10 ℃ below zero and 0 ℃.
In step 4, the freeze-dried sample is calcined at 500 ℃ for 0.5-3h, preferably at 400 ℃ for 200-2 h, and more preferably at 300 ℃ for 1 h.
In step 5, the frequency of the microwave treatment is 915-2450MHz, and more preferably 2450 MHz.
In a third aspect the invention provides the use of a sulphide mineral-based composite material as described in the first aspect of the invention as a high performance battery material.
The invention has the advantages that:
1) the sulfide mineral-based composite material provided by the invention is prepared by simply crushing or grinding micron-sized natural sulfide minerals; graphene oxide with a large number of functional groups on the surface is selected to be compounded with sulfide minerals, so that the compatibility of the graphene oxide and the sulfide minerals can be effectively improved;
2) according to the method for preparing the sulfide mineral-based composite material, the sample is recrystallized on the graphene sheet layer by adopting microwave treatment, the size of the crystal is reduced to a nanometer size, the specific surface area of the obtained product is increased, and the transmission path of a carrier is shortened;
3) according to the method for preparing the sulfide mineral-based composite material, provided by the invention, the mode of alternately performing stirring and microwave operation is adopted, so that the dispersion uniformity of sulfide minerals in the graphene solution can be improved;
4) the sulfide mineral-based composite material provided by the invention has the advantages of high specific capacity, small capacity attenuation, good stability and long cycle performance when being used as a battery material;
5) the method for preparing the sulfide mineral-based composite material provided by the invention greatly reduces the production cost and preparation procedures, has high productivity and is suitable for large-scale industrial production.
Drawings
FIG. 1 shows an SEM picture of molybdenite after grinding in example 1;
fig. 2 shows an SEM image of the molybdenite/graphene composite material prepared in example 1;
fig. 3 shows a rate performance graph of assembled batteries in example 1, comparative example 1, and comparative example 2;
FIG. 4 shows an XRD pattern of molybdenite;
FIG. 5 shows an XRD pattern of stibnite;
figure 6 shows an XRD pattern of chalcopyrite;
figure 7 shows an XRD pattern of zincblende;
fig. 8 shows an XRD pattern of pyrite.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples. The features and advantages of the present invention will become more apparent from the description.
The present invention provides, in a first aspect, a sulfide mineral-based composite material prepared from a sulfide mineral and graphene.
In a preferred embodiment, the sulfide mineral is a natural sulfide mineral, preferably selected from one or more of molybdenite, stibnite, chalcopyrite, sphalerite or pyrite, more preferably selected from one or more of molybdenite or sphalerite, and even more preferably selected from molybdenite.
Wherein, molybdenite is disulfide of molybdenum, belongs to mono-sulfide mineral of hexagonal crystal system, and is preferably taken from Jiangxi Ganxiang. In the present invention, the XRD pattern of molybdenite is shown in FIG. 4, in which the diffraction peak of molybdenite and MoS2The diffraction peaks of the standard card (JCPDS:37-1492) of (1) corresponded, and no additional peaks appeared in the spectrum, indicating that the molybdenite was of high purity and substantially free of impurities.
The chemical composition of stibnite is Sb2S3The crystals belong to the orthorhombic (skew) crystal system of sulphide minerals, preferably taken from the Hunan cold water. In the present invention, the XRD pattern of stibnite is shown in FIG. 5, wherein the diffraction peak of stibnite and Sb2S3The diffraction peaks of the standard card (JCPDS:42-1393) of (1) are corresponding, and no additional peaks appear in the spectrogram, which indicates that the stibnite has high purity and is basically free of impurities.
The main components of chalcopyrite are copper iron sulphide minerals and quartz, preferably taken from dexing, Jiangxi. In the present invention, the XRD pattern of chalcopyrite is shown in FIG. 6, wherein the diffraction peak of chalcopyrite and CuFeS2The diffraction peaks of the standard card (JCPDS:71-0507) and the standard card (JCPDS:85-0798) of quartz correspond to each other, and no additional peak appears in the spectrogram, which indicates that the chalcopyrite except the CuFeS2And quartz, substantially free of impurities.
The zinc blende contains zinc sulfide as chemical component, belongs to sulfide mineral of isometric crystal system, and is preferably taken from Chenzhou, Hunan province. In the present invention, the XRD pattern of zincblende is shown in FIG. 7, in which the diffraction peak of zincblende corresponds to the diffraction peak of standard card of ZnS (JCPDS:05-0566), and no additional peak appears in the spectrum, indicating that zincblende has high purity and is substantially free of impurities.
The main component of pyrite is ferrous disulfide, which is a main mineral raw material for extracting sulfur and producing sulfuric acid, and is preferably taken from Guangdong Shaoshaoguan. In the present invention, the XRD pattern of pyrite is shown in FIG. 8, wherein the diffraction peak of pyrite and FeS2The diffraction peaks of the standard card (JCPDS:42-1340) are corresponding, and no additional peaks appear in the spectrogram, which indicates that the pyrite has high purity and is substantially free of impurities.
In a preferred embodiment, the graphene is selected from one or more of graphene oxide, hydrogenated graphene and fluorinated graphene, more preferably selected from one or more of graphene oxide and hydrogenated graphene, and more preferably is graphene oxide.
The reason is that the surface of the graphene oxide contains a large number of functional groups, such as-OH, -COOH, -O-and the like, which can increase active reaction sites, so that the graphene oxide can be subjected to surface modification more easily, and the compatibility of the graphene oxide and sulfide minerals can be effectively improved.
In the present invention, the mass ratio of the sulfide mineral to the graphene in the sulfide mineral-based composite material is 1 to 5:1, preferably 1 to 3:1, and more preferably 1: 1.
In the invention, the addition of the graphene is crucial to the preparation of sulfide-based composite materials and the improvement of the electrochemical properties of natural mineral-based electrode materials. On one hand, graphene has strong response and absorption to microwaves, pure mineral microwaves have weak response, microwave heating temperature rise is limited, the added graphene can be used as a microwave response medium, electric arcs are generated under the action of an electromagnetic field, the temperature of the added graphene can be rapidly increased to thousands of degrees centigrade within a very short time (millisecond magnitude), sulfide mineral crystals are decomposed and redeposited on the surface of the graphene, and therefore the nano sulfide/graphene composite material is obtained. On the other hand, most natural sulfide minerals are poor in conductivity, the electrochemical properties of the natural sulfide minerals as lithium ion battery electrode materials are poor, the natural sulfide minerals are compounded with graphene to enhance the conductivity, and the electrochemical performance of the composite material is improved.
In a second aspect, the present invention provides a method of preparing a sulphide mineral-based composite material according to the first aspect of the invention, the method comprising the steps of:
step 1: preparing a graphene suspension;
in a preferred embodiment, the graphene is selected from one or more of graphene oxide, hydrogenated graphene and fluorinated graphene, more preferably selected from one or more of graphene oxide and hydrogenated graphene, and more preferably is graphene oxide.
Preferably, the solvent used for preparing the graphene suspension is deionized water or ethanol, and further preferably deionized water. The purpose of preparing the graphene suspension is to improve the effect of mixing graphene and sulfide minerals.
In the invention, the volume ratio of the mass of the graphene to the solvent in the graphene suspension is 1-10mg:1ml, more preferably 3-8mg:1ml, and still more preferably 5mg:1 ml.
Step 2: mixing sulfide minerals and the graphene suspension;
in a preferred embodiment, the sulfide mineral is a natural sulfide mineral, preferably selected from one or more of molybdenite, stibnite, chalcopyrite, sphalerite and pyrite, further preferably selected from one or more of molybdenite and sphalerite, and more preferably molybdenite.
Among them, in order to make the mixture of the sulfide mineral and the graphene more uniform, it is preferable that the sulfide mineral is simply ground before the sulfide mineral is mixed with the graphene suspension. If the sulphide minerals are themselves in the form of large lumps, the process of comminution may be carried out prior to grinding.
In a preferred embodiment, the grinding treatment is mechanical grinding, for example grinding with a ball mill or a nanomiller.
Wherein the grinding is carried out at a rotation speed of 100-700r/min for 1-8 h, preferably at a rotation speed of 300-600 r/min for 2-6 h, and more preferably at a rotation speed of 560r/min for 4 h.
After grinding, the sulfide mineral has a particle size of 1 to 200. mu.m, preferably 1 to 50 μm, and more preferably 1 to 10 μm.
In a preferred embodiment, the mass ratio of the sulfide mineral to the graphene is 1-5:1, preferably 1-3:1, and more preferably 1: 1.
The mass ratio of the sulfide minerals to the graphene has an important influence on the electrical properties of the finally obtained sulfide mineral-based composite material. When the ratio of the two is controlled within the range, the obtained sulfide mineral-based composite material has the advantages of high specific capacity, small capacity attenuation, good stability and long cycle performance when used as a battery material.
In a preferred embodiment, the dispersion treatment is performed after the addition of the sulfide mineral to the graphene suspension, wherein the dispersion treatment comprises stirring and sonication.
In the present invention, the stirring is mechanical stirring, but mechanical stirring has great limitations, and especially in the dispersive mixing of ultrafine agglomerated materials, the microscopic effect of the dispersive mixing of the materials is not satisfactory. The electrical properties of the prepared composite material can be directly influenced by the uniform degree of mixing of the sulfide minerals and the graphene. In order to make up for the deficiency of mechanical stirring, the invention utilizes ultrasonic treatment to improve the material mixing effect, and the agglomerated materials are fully dispersed under the action of high-energy ultrasound.
Further preferably, the stirring and the ultrasonic treatment are performed alternately, more preferably, the stirring and the ultrasonic treatment are performed alternately 3 to 10 times, and preferably, the stirring and the ultrasonic treatment are performed alternately 4 to 8 times, for example, 5 times.
In a preferred embodiment, the stirring speed of the stirring is 100-; the stirring time for stirring is 5-30 min; more preferably 10 to 20min, and still more preferably 15 min.
In a preferred embodiment, the power of the ultrasonic treatment is 200-2000W; more preferably 500 to 1000W, and still more preferably 640 to 700W.
The dispersion effect of the sulfide minerals is better along with the increase of the ultrasonic power; however, when the ultrasonic power reaches a certain value, the dispersion capability of the sulfide minerals reaches the limit, and the dispersion effect tends to be stable and does not change any more.
In a preferred embodiment, the treatment time of the ultrasonic treatment is 1-15 min; more preferably 3-8 min, and even more preferably 5 min.
The inventor finds that the ultrasonic time is too short, and the dispersion effect is not good; the ultrasonic reaction time is more preferably 5min because the ultrasonic reaction time is too long, the dispersion effect is not improved more, and energy is wasted.
Step 3, freeze-drying the mixed sample;
the sulfide minerals are insoluble in the graphene suspension, and can be uniformly dispersed in the graphene suspension under the combined action of stirring and ultrasonic treatment. In order to avoid that the sulphide minerals destabilize the dispersion due to precipitation after the stirring is stopped, the inventors prefer to subject the mixed sample to a freezing treatment.
Meanwhile, the solvent is required to be removed before roasting, and in order to avoid agglomeration caused by drying by adopting a common drying method, the invention preferably directly dries under a freezing condition, so that the solvent is directly sublimated, and the dried powder can be ensured to have good dispersibility.
In a preferred embodiment, the freeze-drying is performed by pre-freezing at-80 ℃ to-40 ℃ for 1 to 10 hours, then evacuating, and performing the pre-freezing at-20 ℃ to 0 ℃ for 12 to 60 hours, further preferably, the freeze-drying is performed by pre-freezing at-70 ℃ to-50 ℃ for 2 to 8 hours, then evacuating, and performing the pre-freezing at-10 ℃ to 0 ℃ for 24 to 48 hours, further preferably, the freeze-drying is performed by pre-freezing at-60 ℃ for 4 hours, then evacuating, and performing the freezing at 0 ℃ for 36 hours.
Step 4, roasting the freeze-dried sample;
in a preferred embodiment, the freeze-dried sample is calcined at 100-500 ℃ for 0.5-3h, more preferably at 200-400 ℃ for 1-2h, and still more preferably at 300 ℃ for 1 h.
The purpose of roasting is to burn off part of functional groups on the surface of graphene oxide to obtain reduced graphene oxide, so that the microwave response capability in microwave treatment is improved.
And 5, carrying out microwave treatment on the roasted sample.
The microwave treatment is a method for heating the whole material to a sintering temperature by using the dielectric loss of the material in an electromagnetic field to realize densification by utilizing the special wave band of microwaves to couple with the basic microstructure of a sample to generate heat. The method has the characteristics of high temperature rise speed, high energy utilization rate, high heating efficiency, safety, sanitation, no pollution and the like, can improve the uniformity and the yield of products, improve the microstructure and the performance of sintered materials, is beneficial to preparing materials with fine and uniform grains at a high temperature rise rate, and increases the specific surface area of the materials.
In the invention, when the roasted sample is subjected to microwave treatment, the highly conductive graphene generates electric arc under the action of an electromagnetic field, and the temperature of the highly conductive graphene can be rapidly increased to thousands of ℃ in a very short time (millisecond magnitude), so that sulfide mineral crystals are decomposed and re-deposited on the surface of the graphene, and the nano sulfide mineral-based composite material, namely the nano sulfide/graphene composite material, is obtained.
In a preferred embodiment, the microwave treatment is carried out under an inert gas blanket.
The inert gas used in the present invention refers to a gas that does not chemically react with the sulfide mineral and graphene, and is selected from helium, argon, or nitrogen, preferably from argon or nitrogen, such as argon.
In a preferred embodiment, the frequency of the microwave treatment is 915-2450MHz, preferably 2450 MHz.
In a preferred embodiment, the treatment time of the microwave treatment is 0.5 to 20 s; further preferably 0.1 to 5 seconds, and more preferably 1 second.
In a third aspect the invention provides the use of a sulphide mineral-based composite material as described in the first aspect of the invention as a high performance battery material. The sulfide mineral-based composite material (namely the sulfide mineral/graphene composite material) serving as the battery material has the advantages of high specific capacity, small capacity attenuation, good stability and long cycle performance. For example, in a lithium ion half cell obtained by mixing a molybdenite/graphene composite material and a sodium alginate binder in a mass ratio of 9:1, the capacity hardly decays at a high rate of 1C.
Examples
In the examples and comparative examples, molybdenite used was purchased from Haoyu stone handicraft business, and the size of the molybdenite was about 2 × 3cm in a block form. The zinc blende is purchased from the commercial industry of Haoyu stone artware, the grain diameter of the zinc blende ore powder is about 100-.
Example 1
Preparing 5mg/ml graphene oxide suspension, grinding molybdenite at the rotating speed of 560r/min for 4 hours, and dispersing 30mg of ground molybdenite in 6ml graphene oxide suspension;
and (3) carrying out 5 times of alternate stirring and ultrasonic treatment on the mixed sample to uniformly disperse the molybdenite. Wherein the stirring speed is 200r/min, and the stirring time is 15 min; the power of ultrasonic treatment is 640W, and the treatment time of ultrasonic treatment is 5 min;
transferring the mixed sample to a freeze dryer, pre-freezing for 4h at-60 ℃, then vacuumizing, and freeze-drying for 36h at 0 ℃; then roasting the freeze-dried sample at 300 ℃ for 1h, and burning off partial groups of the graphene oxide;
and sealing the roasted sample in a container, placing the sealed container in a microwave oven, placing the microwave oven in a glove box filled with argon, and performing microwave treatment for 1s at 2450MHz to obtain a final sample, wherein the final sample is marked as the molybdenite/graphene composite material.
And mixing the molybdenite/graphene composite material with sodium alginate serving as a binder according to a mass ratio of 9:1, and assembling the lithium ion half-cell.
Example 2
Preparing 5mg/ml graphene oxide suspension, grinding sphalerite for 2 hours at the rotating speed of 300r/min, and dispersing 30mg of grinded sphalerite in 6ml graphene oxide suspension;
and (3) carrying out 5 times of alternate stirring and ultrasonic treatment on the mixed sample to uniformly disperse the sphalerite. Wherein the stirring speed is 200r/min, and the stirring time is 15 min; the power of ultrasonic treatment is 640W, and the treatment time of ultrasonic treatment is 5 min;
transferring the mixed sample to a freeze dryer, pre-freezing for 4h at-60 ℃, then vacuumizing, and freeze-drying for 36h at 0 ℃; then roasting the freeze-dried sample at 300 ℃ for 1h, and burning off partial groups of the graphene oxide;
and sealing the roasted sample in a container, placing the sealed container in a microwave oven, placing the microwave oven in a glove box filled with argon, and performing microwave treatment for 1s at 2450MHz to obtain a final sample, wherein the final sample is marked as the sphalerite/graphene composite material.
And mixing the sphalerite/graphene composite material with sodium alginate serving as a binder according to a mass ratio of 9:1, and assembling the lithium ion half-cell.
Example 3
Preparing 5mg/ml graphene oxide suspension, grinding pyrite for 2 hours at the rotating speed of 300r/min, and dispersing 30mg of ground pyrite in 6ml graphene oxide suspension;
and (3) subjecting the mixed sample to 5 times of alternate stirring and ultrasonic treatment to uniformly disperse the pyrite. Wherein the stirring speed is 200r/min, and the stirring time is 15 min; the power of ultrasonic treatment is 640W, and the treatment time of ultrasonic treatment is 5 min;
transferring the mixed sample to a freeze dryer, freezing for 4h at-60 ℃, then vacuumizing, and freeze-drying for 36h at 0 ℃; then roasting the freeze-dried sample at 300 ℃ for 1h, and burning off partial groups of the graphene oxide;
and sealing the roasted sample in a container, placing the sealed container in a microwave oven, placing the microwave oven in a glove box filled with argon, and performing microwave treatment for 1s at 2450MHz to obtain a final sample, wherein the final sample is marked as the pyrite/graphene composite material.
And mixing the pyrite/graphene composite material with sodium alginate serving as a binder according to a mass ratio of 9:1, and assembling the lithium ion half-cell.
Comparative example
Comparative example 1
And mixing the graphene oxide in the example 1 with sodium alginate serving as a binder according to a mass ratio of 9:1, and assembling the lithium ion half cell.
Comparative example 2
The milled molybdenite of example 1 was mixed with sodium alginate as a binder at a mass ratio of 9:1 to assemble a lithium ion half cell.
Examples of the experiments
Experimental example 1
SEM scans of the milled molybdenite and the molybdenite/graphene composite material of example 1 were performed, and the scanning results after enlarging 18000 times are shown in fig. 1 and 2:
FIG. 1 is an SEM photograph of the milled molybdenite of example 1, wherein the milled molybdenite has a bulk structure and a particle size of about 2-3 μm.
Fig. 2 is an SEM image of the molybdenite/graphene composite material prepared in example 1, and it can be seen from the SEM image that the molybdenite/graphene composite material has molybdenite crystallized on graphene sheets, a significantly reduced crystal size, and a particle size of about 50-100 nm.
Experimental example 2
Rate performance tests were performed on the lithium ion half cells assembled in example 1, comparative example 1, and comparative example 2 under the following test conditions: the test voltage was 0.01-3.00V, and the test was performed at 0.1C, 0.2C, 0.5C, 1C and 2C, respectively, and the test results are shown in FIG. 3.
As can be seen from fig. 3, through the test, the lithium ion half-cell electrode material prepared by using the composite material has higher capacity, the rate performance is significantly improved compared with that of graphene oxide and molybdenite, and the capacity is hardly attenuated under the condition of a large rate of 1C.
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 sulfide mineral-based composite material characterized by: the composite material is prepared from sulfide minerals and graphene.
2. The composite material of claim 1, wherein: the sulfide minerals are natural sulfide minerals, preferably selected from one or more of molybdenite, stibnite, chalcopyrite, sphalerite or pyrite, further preferably selected from one or more of molybdenite or sphalerite, and more preferably selected from molybdenite.
3. The composite material of claim 1, wherein: the graphene is selected from one or more of graphene oxide, hydrogenated graphene and fluorinated graphene, preferably one or more of graphene oxide and hydrogenated graphene, and more preferably graphene oxide.
4. A method of preparing a sulfide mineral-based composite, characterized by: the method comprises the following steps:
step 1: preparing a graphene suspension;
step 2: mixing sulfide minerals and the graphene suspension;
step 3, freeze-drying the mixed sample;
step 4, roasting the freeze-dried sample;
and 5, carrying out microwave treatment on the roasted sample.
5. The method of claim 4, wherein: in step 1, the volume ratio of the mass of the graphene in the graphene suspension to the solvent is 1-10mg:1ml, more preferably 3-8mg:1ml, and still more preferably 5mg:1 ml.
6. The method of claim 4, wherein: in the step 2, the mass ratio of the sulfide mineral to the graphene is 1-5:1, preferably 1-3: 1.
7. The method of claim 4, wherein: in the step 3, the freeze drying is firstly pre-frozen for 1 to 10 hours at the temperature of between 80 ℃ below zero and 40 ℃ below zero, then the vacuum pumping is carried out, and the freeze drying is carried out for 12 to 60 hours at the temperature of between 20 ℃ below zero and 0 ℃ below zero;
further preferably, the freeze drying is firstly pre-frozen for 2 to 8 hours at the temperature of between 70 ℃ below zero and 50 ℃ below zero, then the vacuum pumping is carried out, and the freeze drying is carried out for 24 to 48 hours at the temperature of between 10 ℃ below zero and 0 ℃.
8. The method of claim 4, wherein: in step 4, the frozen sample is calcined at 500 ℃ for 0.5-3h, preferably at 400 ℃ for 1-2h, and more preferably at 300 ℃ for 1 h.
9. The method of claim 4, wherein: in step 5, the frequency of the microwave treatment is 915-2450MHz, and more preferably 2450 MHz.
10. Use of a sulphide mineral-based composite material as a high performance battery material.
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