CN109830670B - Hollow sandwich type SiO for lithium ion battery cathode material2/C/MoS2Hybrid microspheres - Google Patents
Hollow sandwich type SiO for lithium ion battery cathode material2/C/MoS2Hybrid microspheres Download PDFInfo
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Abstract
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a hollow sandwich type SiO for a lithium ion battery cathode material2/C/MoS2Hybrid microspheres. The hybrid microsphere takes monodisperse polystyrene microspheres as a template, and the hollow sandwich type SiO is prepared by hydrolysis of tetraethoxysilane on the surfaces of the microspheres, polymerization of dopamine on the surfaces of the microspheres, hydrothermal treatment in the presence of sodium molybdate dihydrate and high-temperature carbonization processes2/C/MoS2Hybrid microspheres. When the microsphere is used as a negative electrode material of a lithium ion battery, the microsphere presents large reversible capacity, excellent rate performance and excellent cycling stability, and has wide application prospect in the field of lithium ion batteries.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a hollow sandwich type SiO for a lithium ion battery cathode material2/C/MoS2Hybrid microspheres.
Background
Lithium ion batteries have been widely used in various fields such as portable electronic devices and hybrid vehicles because of their advantages of high energy density, no memory effect, environmental friendliness, and long cycle life. Although graphite has been widely used in the negative electrode material of commercial lithium ion batteries, its lower theoretical capacity (372 mAhg)-1) The requirements for developing new high energy density lithium ion batteries have not been met. In order to meet the more severe requirements of lithium ion batteries on energy density and cycle life, the development of high-performance electrode materials becomes an important part of technical innovation in the field of lithium ion batteries.
MoS2Is a typical transition metal sulfide with a graphite-like two-dimensional layered structure, and has higher theoretical specific capacity (669 mAhg)-1) And has attracted great attention. MoS2The molybdenum atoms in the alloy are sandwiched between two layers of closely packed sulfur atoms, forming a sandwich-like structure. MoS2The weak van der waals force between the layers can provide a channel for the rapid diffusion, insertion and extraction of lithium ions. In addition, Mo and Li are accompanied in the discharge process2Generation of S, MoS2The specific capacity of the cathode material is obviously higher than that of graphite, and the rate capability and the cycling stability of the material are further improved. However, in practical applications, the MoS2The low conductivity of the material seriously weakens the rate capability of the material in use, and the problems of volume change in circulation, polysulfide dissolution and the like also reduce the circulation stability of the material, which seriously hinders MoS2The process of commercial use in lithium ion battery negative electrode materials.
Mixing MoS2Compounded with other materials to solve MoS2MaterialInherent defects are an effective means. Such as in the literature [ adv. mater. 2017, 29, 1603020]By designing a three-dimensional MoS2The @ C composite structure is used for improving the performance of the lithium ion battery and effectively solves the problem of MoS2Poor mechanical stability caused by the conductivity and volume expansion of the material. The invention patent with the domestic application number of 201610909639.0 provides graphene-molybdenum disulfide composite conductive slurry for a lithium battery, and the conductivity and the cycling stability of an electrode material of the lithium battery are effectively improved. Although this type of electrode material solves MoS2The specific capacity of the electrode material is still lower, and the specific capacity of the electrode material is required to be further improved. Silicon dioxide (SiO)2) Due to the ultra-high theoretical capacity (1965 mAhg)-1) Low discharge voltage, rich natural reserves, low price and the like, and is a potential cathode material for the lithium ion battery. However, the problems of pulverization of electrode materials and rapid deterioration of capacity caused by large volume change during lithiation and delithiation are troubled, and the electrode materials cannot be well applied so far. If the MoS can be converted into2Carbon and SiO2The three materials are subjected to effective component and structure design, so that the specific capacity of the lithium ion battery anode material can be improved, and the problem of MoS at present can be solved2And SiO2The inherent defects of the material can prepare the cathode material required by the high-performance lithium ion battery. However, so far, no hollow sandwich-type SiO which can be used as lithium ion battery cathode material exists2/C/MoS2Preparation and property testing of hybrid microspheres are reported.
Disclosure of Invention
In order to solve the problems, the invention continuously coats SiO on the surface of the PS microsphere2PDA and MoS2The sheets are carbonized to prepare hollow sandwich type SiO for the cathode material of the ion battery2/C/MoS2Hybrid microspheres.
The invention adopts the following technical scheme:
hollow sandwich type SiO for negative electrode material of ion battery2/C/MoS2The hybrid microsphere is characterized in that the center of the hybrid microsphere is provided with a hollow cavity, and the shell layer is sequentially composed of SiO2Layer, C layer and MoS2And (3) layer composition.
The size of the hollow cavity is between 200 nm and 600 nm.
The SiO2The layer is made of SiO with a diameter of 20-40nm2The particles are piled up.
The thickness of the C layer is 15-40 nm.
The MoS2The thickness of the layer is 20-30 nm.
Hollow sandwich type SiO for negative electrode material of ion battery2/C/MoS2The hybrid microsphere comprises the following specific preparation process steps:
1) preparing PS template microspheres: a certain amount of styrene is measured and dripped into a 250mL round-bottom flask containing 70mL deionized water and equipped with mechanical stirring, high-purity nitrogen is introduced, the mixture is stirred for 30min and then heated to 70 ℃, 15mL deionized water solution containing a certain amount of potassium persulfate is added as an initiator, and the mixture is stirred for 12h at 70 ℃ to obtain the PS microspheres with the diameter of 230-650 nm.
2）PS/SiO2Preparation of hybrid microspheres: ultrasonically dispersing a certain amount of PS microspheres prepared in the step 1) in 160mL of ethanol in a 250mL round-bottom flask, then adding a certain amount of tetraethoxysilane and stirring for 30min, heating the solution to 40 ℃, then adding a certain amount of ammonia water and continuously stirring for 12h by mechanical stirring to hydrolyze TEOS and self-assemble the TEOS on the surfaces of the microspheres, thus obtaining PS/SiO2Hybrid microspheres.
3）PS/SiO2Preparation of/PDA hybrid microspheres: taking a certain amount of PS/SiO prepared in the step 2)2Ultrasonically dispersing the hybrid microspheres in 400mL of mixed solvent with the volume ratio of ethanol to water = 7: 1, adding a certain amount of trihydroxyaminomethane and dopamine, mixing and stirring for 24h at normal temperature, wherein the dopamine is in PS/SiO2Polymerizing the surface of the microsphere to obtain PS/SiO2PDA hybrid microspheres.
4）PS/SiO2/PDA/MoS2Preparation of hybrid microspheres: taking a certain amount of PS/SiO prepared in the step 3)2PDA hybrid microspheres, Na2MoO4·2H2O and CS (NH)2)2Ultrasonically dispersing in a mixed solution consisting of 20mL of deionized water and 10mL of ethanol, stirring for 2h, transferring the solution into a stainless steel high-pressure reaction kettle with the capacity of 100mL and using polytetrafluoroethylene as a lining, heating to 200 ℃, preserving heat for 24h, and finally centrifugally washing with deionized water for three times to obtain PS/SiO2/PDA/MoS2Hybrid microspheres.
5）SiO2/C/MoS2Preparation of hollow hybrid microspheres: the PS/SiO prepared in the step 4) is heated up at a heating rate of 2 ℃/min2/PDA/MoS2Hybrid microspheres at 800 ℃ in N2Roasting for 2h in gas atmosphere to remove the PS template, thus obtaining SiO2/C/MoS2Hollow hybrid microspheres.
Hollow sandwich type SiO for negative electrode material of ion battery2/C/MoS2The hybrid microsphere solves some bottlenecks encountered in the application of the current lithium ion battery cathode material through the following structural and component design, and the specific principle of realization is as follows: the microspheres have a hollow sandwich structure, so that the excellent performances of all components are kept, and the electrochemical performance of the electrode material is further enhanced by a synergistic effect brought by the structure; ② the C layer passes through Si-O-C bond and MoS in the microsphere2The lithium ion battery is tightly connected at the interface, so that the conductivity of an electrode material can be effectively improved, the charge transfer efficiency is enhanced, the insertion and extraction speeds of lithium ions are accelerated, and the volume expansion effect in the charge and discharge processes is reduced; ③ SiO2The layer is made of SiO2The particles are stacked, and gaps among the particles can further reduce the resistance in lithium ion transmission; the hollow structure not only can be used for containing electrolyte, but also can be SiO2And MoS2The volume change in the processes of lithium intercalation and lithium deintercalation provides an effective buffer space, and the cycling stability of the electrode material is improved. Thanks to the above improvements, the SiO produced according to the invention2/C/MoS2Hollow hybrid microspheres at 200mAg-1Can still obtain 757.7 mAhg after circulating for 100 circles under the discharge current-1Reversible capacity of 2 Ag-1Discharge electricityThe flow-down showed 488.9 mAhg-1Excellent rate capability. It is in 1Ag-1After the discharge current is circulated through 300 circles of reversible charge and discharge points, the discharge capacity can be kept at 584.3 mAhg-1The performance of the material is far better than that of the comparative example C/MoS2And an electrode.
Hollow sandwich type SiO for negative electrode material of ion battery2/C/MoS2Hybrid microspheres with current MoS2Compared with the hybrid material as the battery cathode material, the hybrid material has the following advantages:
1) the hybrid microsphere has a cavity with the diameter of 200-600nm, and can relieve the lithium ions in MoS in the charging and discharging process2And SiO2The damage of volume expansion caused by the insertion and the extraction to the material structure can also contain electrolyte, and the contact between the electrolyte and the electrode material is improved.
2) Inner SiO layer with thickness of 20-40nm2The particle layer improves the specific capacity of the whole negative electrode material and improves the energy density of the battery.
3) A carbon layer with an intermediate thickness of 10-20nm formed by Si-O-C bonding and SiO2Layer connection, and MoS2The layer is tightly packed on the surface of the C layer, which not only can improve the conductivity of the material, but also can stabilize MoS2The function of the layer.
4) MoS with outer layer thickness of 20-30nm2The layer not only has higher theoretical specific capacity, but also has a channel convenient for the insertion and extraction of lithium ions, and can improve the electrochemical performance of the electrode material.
Drawings
FIG. 1 shows SiO obtained in example 1 of the present invention2/C/MoS2Scanning electron microscope photographs of the hollow hybrid microspheres;
FIG. 2 shows SiO obtained in example 1 of the present invention2/C/MoS2Transmission electron microscope photographs of the hollow hybrid microspheres;
FIG. 3 shows SiO obtained in example 1 of the present invention2/C/MoS2Scanning EDX element surface scanning pictures corresponding to the scanning transmission electron microscope photos of the hollow hybrid microspheres;
FIG. 4 is comparative example 1 of the present inventionThe obtained C/MoS2Transmission electron microscope photographs of the hollow hybrid microspheres;
FIG. 5 shows SiO obtained in example 1 of the present invention2/C/MoS2Hollow hybrid microspheres and C/MoS obtained in comparative example 12Comparing the electrochemical properties of the hollow hybrid microspheres with a curve diagram;
FIG. 6 shows SiO obtained in comparative example 1 of the present invention2/C/MoS2A cycle stability test curve of the hollow hybrid microspheres and a digital photo of the lighted LED lamp.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are set forth merely to illustrate the invention and are not intended to limit the scope of the invention.
Example 1:
1) preparing PS template microspheres: adding 11mL St and 70mL deionized water into a 250mL round bottom flask with mechanical stirring, introducing high-purity nitrogen, stirring for 30min, heating to 70 ℃, adding 15mL deionized water solution containing 0.1g KPS as an initiator, and stirring at 70 ℃ for 12h to obtain PS microspheres with the diameter of about 230 nm.
2）PS/SiO2Preparation of hybrid microspheres: ultrasonically dispersing 2g of PS microspheres prepared in the step 1) in 160mL of ethanol in a 250mL round-bottom flask, then adding 1.5mL of TEOS and stirring for 30min, heating the solution to 40 ℃, adding 20mL of ammonia water and continuously stirring for 12h by using mechanical stirring to hydrolyze TEOS and self-assemble the TEOS on the surfaces of the microspheres to obtain PS/SiO2Hybrid microspheres.
3）PS/SiO2Preparation of/PDA hybrid microspheres: taking 0.5g of PS/SiO prepared in the step 2)2Dispersing the hybrid microspheres in 400mL of mixed solvent with the volume ratio of ethanol to water = 7: 1 by ultrasonic, adding 0.25g of Tris and 0.75g of DA, mixing and stirring for 24h at normal temperature, wherein the DA is in PS/SiO2Polymerizing the surface of the microsphere to obtain PS/SiO2PDA hybrid microspheres.
4）PS/SiO2/PDA/MoS2Preparation of hybrid microspheres: taking 0.1g of PS/SiO prepared in step 3)2PDA hybrid microspheres, 0.3g Na2MoO4·2H2O and 0.375g CS (NH)2)2Ultrasonically dispersing in a mixed solution of 20mL deionized water and 10mL ethanol, stirring for 2h, transferring the solution into a stainless steel high-pressure reaction kettle with the capacity of 100mL and using polytetrafluoroethylene as a lining, heating to 200 ℃, preserving heat for 24h, and finally centrifugally washing with deionized water for three times to obtain PS/SiO2/PDA/MoS2Hybrid microspheres.
5) Sandwich type SiO2/C/MoS2Preparation of hollow hybrid microspheres: the PS/SiO prepared in the step 4) is heated up at a heating rate of 2 ℃/min2/PDA/MoS2The hybrid microspheres were heated to 800 ℃ and at N2Roasting for 2h in gas atmosphere to remove the PS template, thus obtaining SiO2/C/MoS2Hollow hybrid microspheres.
FIG. 1 is a sandwich type SiO2/C/MoS2Scanning electron micrograph of hollow hybrid microspheres showing that the microsphere surface has flaky MoS2Layer, the microspheres having a hollow structure as seen from the broken microspheres. FIG. 2 is SiO2/C/MoS2Transmission electron microscopy pictures of hollow hybrid microspheres, it can be seen that the microspheres have a typical hollow structure. The inner layer of the hybrid microsphere is a silicon dioxide layer with deeper contrast, and the outer layer is coarse MoS2The sheet, while the intermediate carbon layer, has a low contrast in transmission electron micrographs and is difficult to identify in transmission electron micrographs. However, we can confirm the formation of the sandwich-type microspheres and the distribution of their chemical components by the EDX elemental surface scanning picture corresponding to the scanning transmission electron micrograph of the microspheres in fig. 3.
Example 2:
1) preparing PS template microspheres: the procedure is as in example 1.
2）PS/SiO2Preparation of hybrid microspheres: ultrasonically dispersing 2g of PS microspheres prepared in the step 1) in 160mL of ethanol in a 250mL round-bottom flask, then adding 1.0 mL of TEOS and stirring for 30min, heating the solution to 40 ℃, adding 20mL of ammonia water and continuously stirring for 12h by using mechanical stirring to hydrolyze TEOS and self-assemble the TEOS on the surfaces of the microspheres to obtain PS/SiO2Hybrid microspheres.
3）PS/SiO2Preparation of/PDA hybrid microspheres: the procedure is as in example 1.
4）PS/SiO2/PDA/MoS2Preparation of hybrid microspheres: the procedure is as in example 1.
5）SiO2/C/MoS2Preparation of hybrid microspheres: the procedure is as in example 1.
Example 3:
1) preparing PS template microspheres: the procedure is as in example 1.
2）PS/SiO2Preparation of hybrid microspheres: the procedure is as in example 1.
3）PS/SiO2Preparation of/PDA hybrid microspheres: taking 0.5g of PS/SiO prepared in the step 2)2Dispersing the hybrid microspheres in 400mL of mixed solvent with the volume ratio of ethanol to water = 7: 1 by ultrasonic, adding 0.15g of Tris and 0.45g of DA, mixing and stirring for 24h at normal temperature, wherein the DA is in PS/SiO2Polymerizing the surface of the microsphere to obtain PS/SiO2PDA hybrid microspheres.
4）PS/SiO2/PDA/MoS2Preparation of hybrid microspheres: the procedure is as in example 1.
5）SiO2/C/MoS2Preparation of hybrid microspheres: the procedure is as in example 1.
Comparative example 1:
1) preparing PS template microspheres: the procedure is as in example 1.
2) Preparing PS/PDA hybrid microspheres: taking 0.5g of PS microspheres prepared in the step 1), dispersing the PS microspheres in 400mL of mixed solvent with the volume ratio of ethanol to water = 7: 1 by ultrasonic, adding 0.25g of Tris and 0.75g of DA, mixing and stirring for 24h at normal temperature, and polymerizing the DA on the surfaces of the PS microspheres to obtain the PS/PDA hybrid microspheres.
3）PS/PDA/MoS2Preparation of hybrid microspheres: 0.1g of the PS/PDA hybrid microspheres prepared in step 2) and 0.3g of Na are taken2MoO4·2H2O and 0.375g CS (NH)2)2Ultrasonically dispersing in a mixed solution of 20mL of water and 10mL of ethanol, stirring for 2h, and transferring the solution to stainless steel with a capacity of 100mL and a polytetrafluoroethylene liningHeating the mixture to 200 ℃ in a high-pressure reaction kettle, preserving heat for 24 hours, and centrifugally washing the mixture for three times by using deionized water to obtain PS// PDA/MoS2Hybrid microspheres.
4）C/MoS2Preparation of hollow hybrid microspheres: heating up all PS/PDA/MoS prepared in the step 3) at a heating rate of 2 ℃/min2Hybrid microspheres at 800 ℃ in N2Roasting for 2h under gas atmosphere to remove the PS template, thus obtaining the C/MoS2The morphology of the hollow hybrid microspheres is shown in FIG. 4.
And (3) performance testing:
1) preparing a lithium ion battery negative pole piece: the battery negative electrode is synthesized by the following formula: 0.025g PVDF (binder) was added to 0.75mL of 1-methyl-2-pyrrolidone solvent and stirred, then 0.025g conductive graphite was added to the solution and stirred uniformly, and finally 0.2g hybrid microspheres (SiO) prepared in each example and comparative example were added2/C/MoS2And C/MoS2) Stirring for 24 h. The prepared sample is uniformly coated on a copper foil by a micro coating machine, and the prepared coated copper foil is dried in a drying oven for 12 hours at the temperature of 60 ℃ to fully volatilize the organic solvent. The coated sample was dried in a vacuum oven at 70 ℃ for 12 h. The active material-coated copper foil was cut into a circular electrode sheet having a diameter of 14 mm using a slicer having a die of 14 mm.
2) Assembling the battery: preparing LiPF with the concentration of 1mol/L by adopting a mixed solvent system with the volume ratio of Ethylene Carbonate (EC) to dimethyl carbonate (DMC) to Diethyl Carbonate (DC) of 1: 16And (3) solution. The solution is used as an electrolyte, a CR2032 type battery case is adopted, the battery is assembled in an Ar gas filled glove box (the humidity and oxygen concentration in the box are required to be lower than 0.5 ppm) from bottom to top in the sequence of an electrode material, the electrolyte, a diaphragm, metal lithium, a gasket and a spring plate, and the battery is tested after standing and activating for 24 hours after the battery is assembled.
3) Electrochemical testing: electrochemical performance of the cell was measured at different current densities within a voltage window range of 1.5-3.0V using a blue cell test system model number lan CT2001A (5V,10 mA). The test cell contained two electrodes with lithium foil as both the reference electrode and the positive electrode.
The relationship between the rate capability and the number of cycles of the negative electrodes prepared in example 1 and comparative example 1 at different discharge currents is shown in fig. 5, and as can be seen from fig. 5, SiO was present in any case2/C/MoS2The rate performance of the hollow hybrid microsphere electrode is superior to that of the comparative example C/MoS2Hollow hybrid microsphere electrodes in 0.1Ag-1Has an initial capacity of up to 1039 mAhg at a current density of-1. After 60 cycles, the discharge current is regulated to 0.1Ag again-1Then, SiO2/C/MoS2The hollow hybrid microsphere electrode still maintains 930mAhg-1The capacity of the microsphere shows that the cathode prepared by the microsphere has excellent rate capability and cycling stability.
Example 1 negative electrode made at 1Ag-1The long cycle performance curve at current intensity of (a) is shown in fig. 6. It can be seen that the hollow hybrid microsphere negative electrode prepared in example 1 is 1Ag-1The initial capacity of the battery at the discharge current of (2) is 900mAhg-1After 300 cycles, it still maintained 584 mAh g-1The coulombic efficiency of the electrode is basically maintained at a 100% level in the whole circulation process, and the electrode prepared from the microspheres is proved to have higher specific capacity and excellent circulation stability. The inset in fig. 6 is a digital photograph of a button cell prepared by using the electrode material to light up an LED lamp, which indicates that a lithium ion battery prepared by using the composite microsphere as a lithium ion battery cathode material works normally. SiO 22/C/MoS2The excellent electrochemical performance of the hollow hybrid microsphere electrode is mainly attributed to that the hollow structure of the hybrid microsphere can effectively resist MoS caused by lithium ions in the insertion and extraction processes2And SiO2The damage of volume expansion effect to the electrode structure improves the stability of the electrode structure, and SiO2And MoS2The introduction of the material greatly increases the specific capacity of the battery cathode, and the conductivity of the electrode can be effectively improved by the C layer. Under the synergistic action of the structures and the components, the hollow sandwich type SiO2/C/MoS2The cathode formed by the hybrid microspheres shows excellent electrochemical performance.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to practice the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (2)
1. Hollow sandwich type SiO for lithium ion battery cathode material2/C/MoS2The hybrid microsphere is characterized in that the hybrid microsphere is provided with a hollow cavity, and the shell layer is sequentially composed of SiO from inside to outside2Layer, C layer and MoS2Layer composition; the size of the hollow cavity is between 200 nm and 600 nm; SiO 22The layer is made of SiO with a diameter of 20-40nm2The particles are piled up; the thickness of the C layer is 15-40nm, and the C layer is formed by Si-O-C bond and SiO2Layer connection; MOS device2The thickness of the layer is 20-30 nm.
2. The hollow sandwich type SiO for the anode material of lithium ion battery of claim 12/C/MoS2The hybrid microsphere is prepared by the following steps: preparing Polystyrene (PS) template microspheres: measuring a certain amount of styrene, dropwise adding the styrene into a 250mL round-bottom flask containing 70mL deionized water and equipped with a mechanical stirrer, introducing high-purity nitrogen, stirring for 30min, heating to 70 ℃, adding 15mL deionized water solution containing a certain amount of potassium persulfate as an initiator, and stirring at 70 ℃ for 12h to obtain PS microspheres with the diameter of 230-650 nm; (ii) PS/SiO2Preparation of hybrid microspheres: ultrasonically dispersing a certain amount of PS microspheres prepared in the step I in 160mL of ethanol in a 250mL round-bottom flask, then adding a certain amount of tetraethoxysilane and stirring for 30min, heating the solution to 40 ℃, then adding a certain amount of ammonia water and continuously stirring for 12h by mechanical stirring to hydrolyze TEOS and self-assemble the TEOS on the surfaces of the microspheres, thus obtaining PS/SiO2Hybrid microspheres; (iii) PS/SiO2Preparation of Polydopamine (PDA) hybrid microspheres: taking a certain amount of PS/SiO prepared in the step II2The hybrid microspheres are ultrasonically dispersed in 400mL of ethanol and water in a volume ratio of (7: 1)Adding a certain amount of trihydroxy aminomethane and dopamine into the mixed solvent, mixing and stirring for 24h at normal temperature, wherein the dopamine is in PS/SiO2Polymerizing the surface of the microsphere to obtain PS/SiO2PDA hybrid microspheres; (iv) PS/SiO2/PDA/MoS2Preparation of hybrid microspheres: taking a certain amount of PS/SiO prepared in the step III2PDA hybrid microspheres, Na2MoO4·2H2O and CS (NH)2)2Ultrasonically dispersing in a mixed solution consisting of 20mL of deionized water and 10mL of ethanol, stirring for 2h, transferring the solution into a stainless steel high-pressure reaction kettle with the capacity of 100mL and using polytetrafluoroethylene as a lining, heating to 200 ℃, preserving heat for 24h, and finally centrifugally washing with deionized water for three times to obtain PS/SiO2/PDA/MoS2Hybrid microspheres; hollow sandwich type SiO2/C/MoS2Preparation of hybrid microspheres: heating up the PS/SiO prepared in the step (iv) at a heating rate of 2 ℃/min2/PDA/MoS2Hybrid microspheres at 800 ℃ in N2Roasting for 2h in gas atmosphere to remove the PS template, thus obtaining SiO2/C/MoS2Hollow hybrid microspheres.
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