CN108232142B - Zinc sulfide/graphene composite material, and preparation method and application thereof - Google Patents
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Abstract
The application discloses zinc sulfide/graphene composite material, cathode material includes zinc sulfide mesoporous sphere and graphite alkene, zinc sulfide mesoporous sphere is by the graphite alkene cladding. The zinc sulfide mesoporous spheres in the material contain rich mesoporous structures and are used as a negative electrode material, so that the contact area between the electrode material and electrolyte can be increased, the reaction rate is improved, and the volume change of the electrode material caused by the intercalation and the deintercalation of sodium ions in the charge-discharge cycle process can be relieved. The characteristic of poor conductivity of the zinc sulfide as a semiconductor can be greatly improved through graphene coating, so that the electrochemical performance of the composite material is improved.
Description
Technical Field
The application relates to a zinc sulfide/graphene composite material, a preparation method thereof and application of the zinc sulfide/graphene composite material as a negative electrode material in a battery, and belongs to the field of electrochemistry.
Background
In recent years, the market of power automobiles is expanding, and the demand of lithium ion batteries, which are the main power batteries of current power automobiles, is increasing sharply, so that the problem of sustainable utilization due to the low content and uneven distribution of lithium resources is becoming more prominent. Sodium is abundant and widely distributed in the world, and has similar physical and chemical properties to lithium, so that sodium ion batteries are receiving wide attention from researchers. Recent research shows that the sodium ion battery has electrochemical performance close to that of the lithium ion battery, and the reserve and price of sodium resources are comprehensively considered, so that the sodium ion battery is considered as an ideal choice for replacing the lithium ion battery as a power source of a next generation of electric automobiles and a power source equipped in a large-scale energy storage power station.
Because metal sodium can be unevenly deposited on the surface of an electrode in the charge-discharge cycle process to generate sodium dendrite, the battery is short-circuited by penetrating a diaphragm to cause explosion, and the melting point of the metal sodium is low, the metal sodium is not suitable for being used as the cathode of the sodium-ion battery. The graphite cathode material widely applied to the lithium ion battery cannot realize the intercalation of sodium ions due to insufficient interlayer spacing and cannot be used as the cathode material of the sodium ion battery. Therefore, exploring and developing a low-cost negative electrode material with high specific capacity and high cycling stability is one of the main challenges facing the development of lithium ion batteries.
Disclosure of Invention
According to one aspect of the application, a zinc sulfide/graphene composite material is provided, which is characterized by comprising zinc sulfide mesoporous spheres and graphene, wherein the zinc sulfide mesoporous spheres are coated by the graphene. The zinc sulfide mesoporous spheres in the material contain rich mesoporous structures and are used as a negative electrode material, so that the contact area between the electrode material and electrolyte can be increased, the reaction rate is improved, and the volume change of the electrode material caused by the intercalation and the deintercalation of sodium ions in the charge-discharge cycle process can be relieved. The characteristic of poor conductivity of the zinc sulfide as a semiconductor can be greatly improved through graphene coating, so that the electrochemical performance of the composite material is improved.
Preferably, the zinc sulfide/graphene composite material consists of zinc sulfide mesoporous spheres and graphene, and the zinc sulfide mesoporous spheres are coated by the graphene.
In one embodiment, the size of the zinc sulfide mesoporous spheres is 80-120 nm; the zinc sulfide mesoporous spheres contain mesopores with the aperture of 3-5 nm.
Preferably, in the zinc sulfide/graphene composite material, the mass percent of zinc sulfide is 70% -90%, and the mass percent of graphene is 10% -30%.
According to another aspect of the application, the preparation method of the zinc sulfide/graphene composite material is simple in process, low in energy consumption, safe and environment-friendly, suitable for industrial production, and capable of stably and efficiently preparing the zinc sulfide/graphene composite material meeting application requirements.
The preparation method of the zinc sulfide/graphene composite material is characterized by comprising the following steps:
1) obtaining zinc sulfide mesoporous spheres;
2) freezing and drying a mixture containing the zinc sulfide mesoporous spheres and graphene oxide to obtain graphene oxide coated zinc sulfide mesoporous spheres;
3) and (3) placing the graphene oxide coated zinc sulfide mesoporous spheres in an atmosphere containing hydrogen, and reducing the material at 350-450 ℃ to obtain the zinc sulfide/graphene composite material.
The zinc sulfide mesoporous spheres in the step 1) can be obtained through commercial purchase and preparation according to the method in the prior art, or the zinc sulfide mesoporous spheres are prepared through the method comprising the following steps: and (2) performing hydrothermal crystallization on a mixture containing a zinc source, a sulfur source, gelatin and water at 100-150 ℃ for 36-60 hours to obtain the zinc-containing zinc oxide.
One skilled in the art can select the appropriate types of zinc and sulfur sources as desired.
As an embodiment, the zinc source is selected from at least one of organic zinc salts. Preferably, the zinc source is selected from a carboxylate salt of zinc; further preferably, the zinc source is zinc acetate.
In one embodiment, the sulfur source is at least one selected from the group consisting of sulfur-containing organic compounds. Preferably, the sulfur source is thiourea.
Preferably, in the mixture containing the zinc source, the sulfur source, gelatin and water, the molar ratio of the zinc source to the sulfur source is 1: 3-7;
wherein, the mole number of the zinc source is counted by the mole number of the zinc element contained in the zinc source; the number of moles of the sulfur source is based on the number of moles of elemental sulfur contained therein.
Preferably, the mass ratio of the zinc source to the gelatin is 1: 3-5;
wherein the mass of the zinc source is calculated by the mass of the zinc source; the mass of gelatin is based on the mass of gelatin itself.
The proportion of the zinc sulfide mesoporous spheres to the graphene oxide can be selected by a person skilled in the art according to needs.
In one embodiment, in the step 2), a mass ratio of the graphene oxide to the zinc sulfide mesoporous spheres in the mixture containing the zinc sulfide mesoporous spheres and the graphene oxide is 1: 2 to 6.
Preferably, the mixture containing the zinc sulfide mesoporous spheres and the graphene oxide is subjected to ultrasonic treatment before being subjected to freezing treatment; the ultrasonic treatment time is not less than 10 min. Further preferably, the ultrasonic treatment time is 20min to 40 min.
Preferably, the mass ratio of the graphene oxide to the zinc sulfide mesoporous spheres in the mixture containing the zinc sulfide mesoporous spheres and the graphene oxide is 1:3 to 5. Further preferably, the mass ratio of the graphene oxide to the zinc sulfide mesoporous spheres in the mixture containing the zinc sulfide mesoporous spheres and the graphene oxide is 1: 3.5 to 4.5.
Preferably, the freezing treatment in the step 2) is freezing in liquid nitrogen for 10-20 min.
Preferably, the drying in step 2) is freeze-drying.
In one embodiment, the freezing and drying in step 2) is performed by placing the sample in liquid nitrogen for freezing, and then transferring the sample to a vacuum freeze drying oven for drying for 12-48 h.
In one embodiment, the atmosphere containing hydrogen in step 3) is a mixture of hydrogen and an inert gas. The inert atmosphere is selected from at least one of nitrogen, helium, argon and xenon.
Preferably, the temperature of the reduction treatment in the step 3) is 350-450 ℃.
Preferably, the temperature rise rate of the reduction treatment in the step 3) is 0.8-1.5 ℃/min.
Preferably, the treatment time of the reduction treatment in the step 3) is 1.5-2.5 h.
As a specific embodiment, the preparation method of the zinc sulfide/graphene composite material comprises the following steps:
step one, hydrothermal preparation of zinc sulfide mesoporous spheres
Firstly, weighing (such as 1: 2) zinc acetate dihydrate and thiourea according to a certain mass ratio, adding the zinc acetate dihydrate and the thiourea into deionized water, stirring and mixing the mixture uniformly, weighing gelatin according to a certain mass ratio (gelatin: zinc acetate dihydrate is 4), stirring and dissolving the gelatin at 50 ℃, mixing and stirring the two liquids uniformly, pouring the mixture into a hydrothermal kettle, putting the hydrothermal kettle into an oven for hydrothermal reaction at 120 ℃, centrifuging the reaction product, cleaning and drying to obtain the zinc sulfide mesoporous spheres.
Step two, preparing the graphene oxide coated zinc sulfide mesoporous sphere composite material
Mixing the zinc sulfide mesoporous spheres with a graphene solution according to a certain mass ratio, ultrasonically stirring, then treating with liquid nitrogen, putting a frozen sample into a freeze dryer, and drying to obtain the graphene oxide coated zinc sulfide mesoporous sphere composite material.
Step three: preparation of graphene-coated zinc sulfide mesoporous sphere composite material
And reducing the graphene oxide into graphene through heat treatment to obtain the graphene-coated zinc sulfide mesoporous sphere composite material.
According to a further aspect of the present application, a battery negative electrode material is provided, wherein the battery negative electrode material contains at least one of any one of the zinc sulfide/graphene composite material and the zinc sulfide/graphene composite material prepared according to any one of the methods. The battery cathode material has good high-current charge and discharge performance and cycle performance.
According to still another aspect of the present application, there is provided a lithium ion battery or a sodium ion battery, characterized by containing the above battery negative electrode material.
The beneficial effects that this application can produce include:
1) the zinc sulfide/graphene composite material provided by the application has the advantages of low raw material price, environmental friendliness and excellent electrochemical performance;
2) according to the zinc sulfide/graphene composite material provided by the application, due to the rich mesoporous structure of mesoporous zinc sulfide, the contact area between an electrode material and electrolyte can be increased, the reaction rate is improved, and the volume change of the electrode material caused by the intercalation and deintercalation of sodium ions in the charge and discharge cycle process can be relieved; the characteristic of poor conductivity of zinc sulfide as a semiconductor can be greatly improved through graphene coating, so that the electrochemical performance of the composite material is improved;
3) the preparation method of the zinc sulfide/graphene composite material is easy to realize, simple and convenient to operate, good in reproducibility and low in requirements on devices and environments;
4) the electrode and the battery both comprise the zinc sulfide/graphene composite material and have good cycle performance and rate performance.
Drawings
Fig. 1 is an X-ray diffraction (XRD) pattern of a zinc sulfide mesoporous sphere sample P1.
Fig. 2 is a pore size distribution diagram of a zinc sulfide mesoporous sphere sample P1.
Fig. 3 is a Transmission Electron Micrograph (TEM) of a zinc sulfide mesoporous sphere sample P1.
Fig. 4 is a Scanning Electron Microscope (SEM) image of the zinc sulfide/graphene composite material S1.
Fig. 5 is a Transmission Electron Micrograph (TEM) of zinc sulfide/graphene composite S1.
FIG. 6 is a graph of the 100 cycle performance of cell C1 at a current density of 100 mA/g.
FIG. 7 is a graph of 140 cycles performance of cell C1 at a current density of 1A/g.
FIG. 8 is a graph of the rate performance of cell C1 at current densities of 0.1A/g, 0.25A/g, 0.5A/g, and 1A/g, respectively.
FIG. 9 is a graph of the 100 cycle performance of cell C4 at a current density of 100 mA/g.
FIG. 10 is a graph of the 100 cycle performance of cell C5 at a current density of 100 mA/g.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and reagents in the examples of the present application were purchased commercially and used without special treatment.
In the examples, transmission electron microscopy of the samples was characterized using a high resolution transmission electron microscope (Tecnai F20).
In the examples, the scanning electron microscope of the sample was characterized by using a Hitachi SU-8020 model field emission scanning electron microscope.
In the examples, X-ray diffraction analysis (XRD) of the samples was characterized using Miniflex 600.
In the examples, the mesoporous data of the samples were characterized using a nitrogen physisorption instrument model Hiden IGA 100B.
Example 1 preparation of mesoporous spheres of zinc sulfide
0.22g of zinc acetate dihydrate (Zn (OAc)2·2H2O) and 0.38g of Thiourea CH4N2S is added into 30ml of deionized water, and the solution is dissolved and mixed evenly; 0.8780g of gelatin is added into 30ml of deionized water, and the gelatin is dissolved by magnetic stirring at 50 ℃; and mixing the two solutions, stirring for 10min at room temperature, transferring to a hydrothermal kettle, sealing, putting into an oven, performing hydrothermal reaction for 48h at 120 ℃, centrifuging the reaction product, washing with deionized water and ethanol, and drying in a vacuum drying oven to obtain the zinc sulfide mesoporous spheres, which are marked as P1.
The concrete steps are the same as the preparation of P1, and the raw material proportion and the preparation conditions are changed according to the data in the table 1 on the basis of P1, so that P2-P6 are obtained.
TABLE 1
Example 2 preparation of zinc sulfide/graphene composite samples
Weighing 80mg of dried zinc sulfide mesoporous spheres P1, dispersing in 20ml of deionized water, adding 10ml of graphene oxide solution with the concentration of 2mg/ml, carrying out ultrasonic treatment (with the power of 200W) for 30min, and stirring to uniformly mix; pouring the mixed solution into a 50ml plastic cup, placing the plastic cup in a liquid nitrogen tank for freezing treatment for 10min, placing the plastic cup into a freeze dryer, and freeze-drying the plastic cup at-45 ℃ for 24 hours to obtain a graphene oxide coated zinc sulfide mesoporous sphere composite material SO 1; coating a zinc sulfide mesoporous sphere composite material SO1 with graphene oxide in hydrogenArgon reducing atmosphere (H)2Ar: 5%/95%) at 400 deg.C for 2h, and the heating rate is 1 deg.C/min. And obtaining the graphene coated zinc sulfide mesoporous sphere composite material S1.
Weighing 80mg of dried zinc sulfide mesoporous spheres P1, dispersing in 20ml of deionized water, adding 10ml of graphene oxide solution with the concentration of 2mg/ml, carrying out ultrasonic treatment (with the power of 200W) for 30min, stirring to uniformly mix, pouring the mixed solution into a 50ml plastic cup, placing the plastic cup into a liquid nitrogen tank for freezing treatment for 10min, placing the plastic cup into a freeze dryer, and carrying out freeze drying at-45 ℃ for 24 hours to obtain a graphene oxide coated zinc sulfide mesoporous sphere composite material SO 2; coating a zinc sulfide mesoporous sphere composite material SO2 with graphene oxide in a hydrogen-argon reduction atmosphere (H)2Ar: 5%/95%) at 450 deg.C for 1.5h, and the heating rate is 1.5 deg.C/min. And obtaining the graphene coated zinc sulfide mesoporous sphere composite material S2.
Weighing 80mg of dried zinc sulfide mesoporous spheres P1, dispersing in 20ml of deionized water, adding 10ml of graphene oxide solution with the concentration of 2mg/ml, carrying out ultrasonic treatment (with the power of 200W) for 30min, stirring to uniformly mix, pouring the mixed solution into a 50ml plastic cup, placing the plastic cup into a liquid nitrogen tank for freezing treatment for 10min, placing the plastic cup into a freeze dryer, and carrying out freeze drying at-45 ℃ for 24 hours to obtain a graphene oxide coated zinc sulfide mesoporous sphere composite material SO 3; coating a zinc sulfide mesoporous sphere composite material SO3 with graphene oxide in a hydrogen-argon reduction atmosphere (H)2Ar: 5%/95%) at 350 deg.C for 2.5h, and the heating rate is 0.8 deg.C/min. And obtaining the graphene coated zinc sulfide mesoporous sphere composite material S3.
Weighing 90mg of dried zinc sulfide mesoporous spheres P1, dispersing in 20ml of deionized water, adding 10ml of graphene oxide solution with the concentration of 2mg/ml, carrying out ultrasonic treatment (with the power of 200W) for 30min, stirring to uniformly mix, pouring the mixed solution into a 50ml plastic cup, placing the plastic cup into a liquid nitrogen tank for freezing treatment for 10min, placing the plastic cup into a freeze dryer, and carrying out freeze drying at-45 ℃ for 24 hours to obtain the graphene oxide coated zinc sulfide mesoporous sphere composite material SO 4. Coating a zinc sulfide mesoporous sphere composite material SO4 with graphene oxide in a hydrogen-argon reduction atmosphere (H)2Ar: 5%/95%) at 350 deg.C for 2.5h, and the heating rate is 0.8 deg.C/min. To obtainTo the graphene coated zinc sulfide mesoporous sphere composite material S4.
Weighing 70mg of dried zinc sulfide mesoporous spheres P1, dispersing in 20ml of deionized water, adding 10ml of graphene oxide solution with the concentration of 2mg/ml, carrying out ultrasonic treatment (with the power of 200W) for 30min, stirring to uniformly mix, pouring the mixed solution into a 50ml plastic cup, placing the plastic cup into a liquid nitrogen tank for freezing treatment for 20min, placing the plastic cup into a freeze dryer, and carrying out freeze drying at-45 ℃ for 24 hours to obtain the graphene oxide coated zinc sulfide mesoporous sphere composite material SO 5. Coating a zinc sulfide mesoporous sphere composite material SO5 with graphene oxide in a hydrogen-argon reduction atmosphere (H)2Ar: 5%/95%) at 350 deg.C for 2.5h, and the heating rate is 0.8 deg.C/min. And obtaining the graphene coated zinc sulfide mesoporous sphere composite material S5.
The specific preparation method and conditions were the same as those of sample S1, except that the zinc sulfide mesoporous spheres P1 were replaced with P2, P3, P4, P5, and P6, and the obtained samples were designated as S6, S7, S8, S9, and S10, respectively.
Example 3 phase analysis of mesoporous sphere samples of Zinc sulfide
Powder X-ray diffraction analysis is carried out on the zinc sulfide mesoporous sphere samples P1-P6 respectively, and the results show that the positions of diffraction peaks on XRD spectrograms of the zinc sulfide mesoporous sphere samples P1-P6 are consistent with data in JCPDS (Joint Committee for powder diffraction standards) cards (72-0162) of zinc sulfide. The XRD spectrum and comparison with the standard spectrum are shown in FIG. 1, which is typical of sample P1. The XRD patterns of P2-P6 are similar to P1, i.e., the peak positions are the same, and the peak intensities vary within + -10% depending on the preparation conditions.
Example 4 nitrogen physical adsorption analysis of mesoporous spheres of zinc sulfide
The mesoporous aperture of the zinc sulfide mesoporous sphere samples P1-P6 is analyzed by nitrogen physical adsorption. The zinc sulfide mesoporous sphere samples P1-P6 all contain abundant mesopores.
As can be seen from the pore size distribution diagram 2 of the mesoporous sphere sample P1 obtained according to the BJH formula, the mesoporous sphere sample P1 contains rich mesopores with the pore size of 3-5 nm.
Example 5 scanning Electron microscopy and Transmission Electron microscopy analysis of samples
Respectively carrying out scanning electron microscope analysis and transmission electron microscope analysis on zinc sulfide mesoporous sphere samples P1-P6 and zinc sulfide/graphene composite material samples S1-S10.
Scanning electron microscope results show that the sizes of zinc sulfide mesoporous sphere samples P1-P6 are distributed between 80-120 nm, and the shapes are regular. The transmission electron microscope result shows that all the zinc sulfide mesoporous sphere samples P1-P6 contain mesopores; in the zinc sulfide/graphene composite material samples S1-S10, graphene is coated outside the zinc sulfide mesoporous spheres.
Typical examples are shown in samples P1 and S1, and the TEM image of sample P1 is shown in FIG. 3. it can be seen from FIG. 3 that P1 contains abundant mesopores, and the average particle size of P1 is about 100 nm. The scanning electron microscope and the transmission electron microscope photographs of the sample S1 are respectively shown in FIG. 4 and FIG. 5, and it can be seen that graphene is coated outside the zinc sulfide mesoporous spheres in the sample S1, and the sample S1 contains rich mesopores with the pore diameter of 3-5 nm.
Example 6 sodium ion battery preparation of composite sample as negative electrode material
The performance of samples S1 to S10 as the negative electrode material was measured, specifically:
uniformly mixing the obtained zinc sulfide/graphene composite material sample with conductive carbon black and sodium carboxymethylcellulose (CMC) according to a mass ratio of 8:1:1, adding a small amount of deionized water, grinding and fully mixing to form uniform paste, coating the paste on a copper foil substrate to be used as a test electrode, and performing vacuum drying for 10 hours at 100 ℃ to obtain the negative plate.
Assembling and testing the battery: punching the negative plate into a direct 10mm electrode plate, taking a metal sodium plate as a negative electrode, and taking 1M NaClO as electrolyte4DEC (1:1) +5 wt% FEC, assembled into CR2032 button cells in an argon filled glove box.
The batteries prepared by using the samples S1 to S10 as negative electrode materials are respectively marked as C1 to C10.
Example 7 evaluation of Battery Performance
And (3) carrying out constant-current charge and discharge tests at room temperature at a current density of 100mA/g until the charge and discharge cutoff voltage is 0.01-3.0V.
The result shows that the sodium ion battery prepared by taking the zinc sulfide/graphene composite material as the negative electrode material has good cycle performance and rate performance.
FIG. 6 is a graph of the 100 cycle performance of C1 at a current density of 100 mA/g. As can be seen from FIG. 5, the first discharge capacity was 1049mAh/g at a current density of 100mA/g, and the reversible capacity was 441mAh/g after 100 cycles.
FIG. 7 is a graph of the 140 cycle performance of C1 at a current density of 1A/g. As can be seen from the attached figure 6, under the current density of 1A/g, the reversible capacity after 140 cycles is 319mAh/g, and the coulombic efficiency after 5 cycles is close to 100%, which indicates that the material has better high-current charge and discharge performance.
FIG. 8 is a graph of the cycling performance of cell C1 at current densities of 0.1A/g, 0.25A/g, 0.5A/g, and 1A/g, respectively. As can be seen from the attached figure 8, under the current densities of 0.1A/g, 0.25A/g, 0.5A/g and 1A/g, the reversible specific capacities are 804mAh/g, 698mAh/g, 602mAh/g and 524mAh/g respectively, which indicates that the zinc sulfide/graphene composite material has good rate capability.
The 100-cycle performance test was performed on batteries C4 and C5 at a current density of 100mA/g, in the same manner as in example 7, and the results are shown in fig. 9 and 10.
As can be seen from FIG. 9, the first discharge capacity of cell C4 was 710mAh/g at a current density of 100mA/g, and the reversible capacity after 100 cycles was 267 mAh/g.
As can be seen from FIG. 10, the first discharge capacity of the cell C5 at a current density of 100mA/g was 776mAh/g, and the reversible capacity after 100 cycles was 248 mAh/g.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (15)
1. The zinc sulfide/graphene composite material is characterized by comprising zinc sulfide mesoporous spheres and graphene, wherein the zinc sulfide mesoporous spheres are coated by the graphene;
the zinc sulfide mesoporous spheres comprise mesoporous structures;
the size of the zinc sulfide mesoporous spheres is 80-120 nm;
the zinc sulfide/graphene composite material is used as a negative electrode material;
the zinc sulfide/graphene composite material is obtained by freezing and reducing zinc sulfide mesoporous spheres and graphene oxide.
2. The zinc sulfide/graphene composite material according to claim 1,
the zinc sulfide mesoporous spheres contain mesopores with the aperture of 3-5 nm.
3. The zinc sulfide/graphene composite material according to claim 1, wherein the zinc sulfide/graphene composite material contains 70-90% by mass of zinc sulfide and 10-30% by mass of graphene.
4. The method for preparing the zinc sulfide/graphene composite material according to any one of claims 1 to 3, wherein the method comprises the following steps:
1) obtaining zinc sulfide mesoporous spheres;
2) freezing and drying a mixture containing the zinc sulfide mesoporous spheres and graphene oxide to obtain graphene oxide coated zinc sulfide mesoporous spheres;
3) and (3) placing the graphene oxide coated zinc sulfide mesoporous spheres in an atmosphere containing hydrogen at 350-450 ℃ for reduction treatment to obtain the zinc sulfide/graphene composite material.
5. The preparation method according to claim 4, wherein the zinc sulfide mesoporous spheres are prepared by a method comprising the following steps:
and (2) performing hydrothermal crystallization on a mixture containing a zinc source, a sulfur source, gelatin and water at 120-180 ℃ for 12-48 hours to obtain the zinc-containing zinc oxide.
6. The method according to claim 5, wherein the zinc source is at least one organic zinc salt.
7. The method of claim 5, wherein the zinc source is selected from the group consisting of zinc carboxylates.
8. The method of claim 5, wherein the zinc source is zinc acetate;
the sulfur source is at least one selected from organic compounds containing sulfur.
9. The method according to claim 5, wherein the sulfur source is thiourea.
10. The preparation method according to claim 5, wherein in the mixture containing the zinc source, the sulfur source, the gelatin and the water, the molar ratio of the zinc source to the sulfur source is 1: 3-7;
wherein, the mole number of the zinc source is counted by the mole number of the zinc element contained in the zinc source; the moles of the sulfur source are calculated by the moles of sulfur element contained in the sulfur source;
the mass ratio of the zinc source to the gelatin is 1: 3-5;
wherein the mass of the zinc source is calculated by the mass of the zinc source; the mass of gelatin is based on the mass of gelatin itself.
11. The preparation method according to claim 4, wherein in the step 2), the mass ratio of the graphene oxide to the zinc sulfide mesoporous spheres in the mixture containing the zinc sulfide mesoporous spheres and the graphene oxide is 1: 2 to 6.
12. The preparation method according to claim 11, wherein the mass ratio of the graphene oxide to the zinc sulfide mesoporous spheres in the mixture containing the zinc sulfide mesoporous spheres and the graphene oxide is 1:3 to 5.
13. The preparation method according to claim 4, wherein the freezing treatment in the step 2) is freezing in liquid nitrogen for 10-20 min.
14. A negative electrode material comprising at least one of the zinc sulfide/graphene composite material according to any one of claims 1 to 3 and the zinc sulfide/graphene composite material produced by the method according to any one of claims 4 to 13.
15. A lithium ion battery or a sodium ion battery, comprising the negative electrode material according to claim 14.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711402881.XA CN108232142B (en) | 2017-12-22 | 2017-12-22 | Zinc sulfide/graphene composite material, and preparation method and application thereof |
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| CN201711402881.XA CN108232142B (en) | 2017-12-22 | 2017-12-22 | Zinc sulfide/graphene composite material, and preparation method and application thereof |
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| CN108232142A CN108232142A (en) | 2018-06-29 |
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| CN109326786A (en) * | 2018-10-25 | 2019-02-12 | 济南大学 | A kind of zinc sulphide containing sulphur vacancy/rGO composite material and preparation method and application |
| CN109647584A (en) * | 2018-12-10 | 2019-04-19 | 桂林理工大学 | A kind of sand milling method of modifying of lithium ion battery mineral negative electrode material |
| CN109728283A (en) * | 2018-12-29 | 2019-05-07 | 桑德集团有限公司 | The preparation method and negative electrode material of composite material with graphene coated layer |
| CN109768265B (en) * | 2019-03-07 | 2020-12-11 | 肇庆市华师大光电产业研究院 | Lithium ion battery cathode material and preparation method thereof |
| CN111293295B (en) * | 2020-01-13 | 2021-08-03 | 博尔特新材料(银川)有限公司 | Electrode material for waste rubber material-based secondary battery and preparation method thereof |
| CN112142096A (en) * | 2020-08-11 | 2020-12-29 | 中国科学院福建物质结构研究所 | Zinc sulfide composite electrode material prepared by zinc-containing ionic liquid |
| CN112768656A (en) * | 2021-01-11 | 2021-05-07 | 昆明理工大学 | Carbon-coated mesoporous transition metal sulfide negative electrode material and preparation method and application thereof |
| CN116443956A (en) * | 2023-04-28 | 2023-07-18 | 天能电池集团股份有限公司 | Preparation method of nano nickel oxide/graphene composite electrode material |
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