CN110233254B - Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid microparticles - Google Patents
Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid microparticles Download PDFInfo
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Abstract
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to bell-shaped Fe for a lithium ion battery cathode material3O4/C/MoS2Hybrid microparticles. The hybrid particles are cubic alpha-Fe with submicron size2O3Preparing the rattle-bell-shaped Fe serving as a template by polymerizing dopamine on the surface of template particles, controllably etching hydrochloric acid, carrying out hydrothermal treatment in the presence of sodium molybdate dihydrate and carrying out high-temperature carbonization3O4/C/MoS2Hybrid microparticles. When the particles are used as the negative electrode material of the lithium ion battery, the particles have the characteristics of large reversible capacity, excellent rate performance, excellent cycle stability and the like, and are innovation in the aspect of the negative electrode material of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to bell-shaped Fe for a lithium ion battery cathode material3O4/C/MoS2Hybrid microparticles.
Background
With the increasing consumption of fossil energy by human beings, the method leads to serious energy crisis and also causes huge environmental pollution. In order to solve this situation, it is important to improve the utilization rate of clean energy such as wind energy, solar energy, and water energy. However, the supply of these energy sources greatly fluctuates due to the influence of seasons, regions, climate and environment, which limits the degree of popularization and utilization. The above problems can be effectively solved if such clean energy can be stored in the rechargeable battery at a stage where the supply thereof is excessive and released when the supply thereof is insufficient. Meanwhile, rapid development of electric vehicles, portable electronic devices, and the like also put higher demands on the performance of rechargeable batteries. Lithium ion batteries have been widely used in various fields such as portable electronic devices and electric vehicles because of their advantages of long cycle life, high energy density, small memory effect, low environmental impact, etc. Although graphite has been widely used in the negative electrode material of commercial lithium ion batteries, it has a low theoretical specific 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. However, in practical applications, the MoS2The problems of low conductivity, volume change in circulation and the like of the material reduce the rate performance and the circulation stability of the material, and seriously hinder MoS2The process of commercial use in lithium ion battery negative electrode materials.
Transition metal oxides have high theoretical specific capacity, and have attracted more and more attention in research on applications of electrode materials. Wherein Fe3O4Due to the theoretical specific capacity of 930 mA h g-1And the iron element has rich reserves, environmental friendliness and low cost in the nature, so that the iron element has potential application prospects in the lithium ion battery cathode material. However, because the lithium storage mechanism is that Fe simple substance and LiO are generated by chemical conversion2The huge volume expansion and contraction (200%) phenomena before and after the reaction can cause the damage of the material structure, and the actual rate capability and the cycling stability of the material are reduced.
The hollow carbon microsphere has larger internal cavity volume, high structural stability and good conductivity, so the hollow carbon microsphere is widely concerned in the field of battery electrode materials. However, the pure hollow carbon microspheres have low graphitization degree and low specific capacity, and cannot meet the design requirements of high-energy density batteries. If it can be combined with MoS2And Fe3O4The materials are effectively combined to solve the problems of low capacity and MoS of the lithium ion battery2And Fe3O4The problems of poor conductivity, weak cycle stability of the composite electrode material and the like have important theoretical and practical significance.
Literature [ adv. mater. 2017, 29, 1702707]By designing the C/Fe shell3O4The nano-box prepares a high-efficiency electrode material of the lithium-sulfur battery. Because the material has a cavity similar to a bell shape, the loading capacity and the conductivity of elemental sulfur are improved, and the problems of poor mechanical stability caused by the elemental sulfur and volume expansion, shuttle effect generated by polysulfide and the like are effectively solved. However, the document neither applies the material to the field of lithium ion batteries, nor realizes effective regulation and control of the bell-shaped structure of the material. Document [ 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 solving the problem of MoS2Poor mechanical stability caused by the conductivity and volume expansion of the material, however, the material has an energy storage mechanism of only insertion-extractionOne way is adopted, and the specific capacity is still low. The invention patents with the domestic application numbers of 201610151315.5 and 201610150933.8 provide a preparation method of a lithium ion battery cathode material and a preparation method of a composite microsphere lithium ion battery cathode material with a yolk structure, and the principles of the invention are that Fe with a yolk-shaped structure is constructed3O4the/C-N composite structure solves the problem of Fe3O4Low conductivity and volume expansion. However, it still fails to efficiently convert Fe3O4Carbon and MoS2The three materials are effectively designed in components and structures, which causes the problems that the lithium storage mechanism is simple, the specific capacity is not high, and the effective regulation between the specific capacity and the cycling stability is difficult to carry out, and the like.
How to solve the above problems is a matter of urgency for those skilled in the art to work.
Disclosure of Invention
To solve the above problems, by making the cubic alpha-Fe at the submicron level2O3Coating Polydopamine (PDA) on the surface of the particle, etching and coating MoS2Lamellar and carbonization treatment, the invention prepares the bell-shaped Fe for the cathode material of the lithium ion battery3O4/C/MoS2Hybrid microparticles.
Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid particles characterized in that the hybrid particles have a bell-shaped structure with submicron-sized cubic Fe at the center3O4The granules, the granules and the inner shell C layer have movable spaces, and the surface of the inner shell C layer is formed by MoS2And (4) coating the nano-sheet layer.
The submicron order cubic Fe3O4The particle size can be adjusted between 0 and 500 nm.
The thickness of the C layer is 18-35 nm.
The MoS2The layer has a thickness of 50-100nm and is composed of nano-MoS in sheet form2And stacking the materials.
Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid fine particles ofThe preparation process comprises the following steps:
1) submicron cubic alpha-Fe2O3The preparation of (1): 27.3 g of iron chloride hexahydrate (FeCl)3·6H2O) is dissolved in 50 ml of deionized water, 10.8 g of sodium hydroxide (NaOH) and 50 ml of deionized water are added dropwise after the mixture is stirred vigorously for 30 min at a constant temperature of 75 ℃, the mixture is transferred to a reaction kettle after being stirred continuously for 10 min, the mixture is cured for 48 h at a constant temperature of 110 ℃, then a sample is taken out and centrifuged for precipitation, and the precipitate is dried for 12 h at a temperature of 60 ℃ and ground to obtain brick red submicron-grade cuboidal alpha-Fe with the side length of 550nm2O3。
2) Core-shell form of alpha-Fe2O3Preparation of/PDA composite particles: weighing 0.32 g of submicron cubic alpha-Fe prepared in step 1)2O3Adding 300 mL of deionized water and 100 mL of absolute ethyl alcohol into a 500 mL flask, carrying out ultrasonic dispersion for 40 min, then weighing a certain amount of Dopamine (DA) and TRIS (hydroxymethyl) aminomethane (TRIS) and adding the Dopamine (DA) and TRIS (hydroxymethyl) aminomethane (TRIS) into the ultrasonic flask, stirring for 12 h, carrying out centrifugal washing for three times by using deionized water, and drying the obtained precipitate at 60 ℃ for 12 h to obtain core-shell alpha-Fe2O3a/PDA composite particle.
3) Bell-shaped alpha-Fe2O3Preparation of/PDA composite particles: subjecting all of the alpha-Fe prepared in step 2)2O3the/PDA composite particles are put into a hydrochloric acid solution with a certain concentration of 4 mol/L and stirred for a certain time at room temperature, and alpha-Fe2O3Partially etching to form bell-shaped alpha-Fe2O3a/PDA composite particle.
4) Bell-shaped alpha-Fe2O3/PDA/MoS2Preparation of hybrid microparticles: weighing 0.1 g of the bell-shaped alpha-Fe prepared in step 3)2O3Adding PDA into 50 mL of deionized water, performing ultrasonic dispersion for 40 min, weighing a certain amount of sodium molybdate dihydrate and thiourea, respectively dissolving in 10 mL of deionized water, adding the sodium molybdate solution and the thiourea solution into the solution, transferring the solution into a reaction kettle, performing hydrothermal reaction at a constant temperature of 200 ℃ for 24 h to obtain the bell-shaped alpha-Fe2O3/PDA/MoS2Hybrid microparticles.
5) Bell-shaped Fe3O4/C/MoS2Preparation of hybrid microparticles: alpha-Fe prepared in the step 4)2O3/PDA/MoS2Heating to 600 ℃ in nitrogen environment, keeping the temperature for 2 h, carbonizing PDA to form C shell doped with nitrogen atoms, and Fe of alpha crystal form2O3Reduced by carbon at high temperature to form Fe3O4Finally obtaining bell-shaped Fe3O4/C/MoS2Hybrid microparticles.
Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2The hybrid particle solves some bottlenecks encountered in the application of the current lithium ion battery cathode material through the following structure and component design, and the specific principle of realization is as follows: the particles have a bell-shaped 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 submicron cubic alpha-Fe2O3The size of the ring-shaped particles can be adjusted by etching, so that the size of the cavity inside the ring-shaped particles can be adjusted, the specific capacity of the electrode material can be adjusted, and the later-stage Fe can be adjusted3O4And MoS2The volume expansion in the charging and discharging process provides a controllable buffer space, and the circulation stability of the electrode material is improved; ③ C layer passes through the microsphere and MoS2The interface is tightly connected, so that the conductivity of the electrode material can be effectively improved, the charge transfer efficiency is enhanced, and the insertion and extraction speeds of lithium ions are accelerated; outer layer MoS2The layer has a graphite-like two-dimensional layered structure and high theoretical specific capacity, so that the energy density of the electrode material can be enhanced, and the energy storage mode of the hybrid particles is further enriched by the lithium insertion and extraction mechanism. Thanks to the above improvement, the bell-shaped Fe produced by the present invention3O4/C/MoS2Hybrid particles are at 0.2A g-1Initial capacity at current density of 1130 mA hr g-1After 150 cycles, the specific capacity of the catalyst still reaches 686.5 mA h g-1The performance is far better than that of the bell-shaped Fe of the comparative example3O4a/C electrode.
Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid particles with current MoS2Or Fe3O4Compared with the hybrid material as the lithium ion battery cathode material, the hybrid material has the following advantages:
1) the hybrid particles have cubic Fe with adjustable diameter in the range of 0-500nm3O4The particles can not only realize the regulation and control of the specific capacity of the electrode material, but also can be Fe3O4And MoS2The volume expansion in the charging and discharging process provides a controllable buffer space, and the cycling stability of the electrode material is improved.
2）Fe3O4MoS of particles and outer layer2The lithium ion battery cathode material can not only improve the specific capacity of the whole cathode material and increase the energy density of the battery, but also has two energy storage modes of chemical lithium storage and lithium insertion/extraction storage.
3) Carbon layer with intermediate thickness of 18-35nm and MoS2The layers are tightly connected, which not only can improve the conductivity of the material, but also can stabilize MoS2The function of the layer.
4) The bell-shaped structure not only keeps the excellent performance of each component, but also further enhances the electrochemical performance of the electrode material by the synergistic effect brought by the structure.
Drawings
FIG. 1 is a diagram of submicron cubic α -Fe obtained in example 1 of the present invention2O3Scanning electron micrographs of the particles.
FIG. 2 shows α -Fe obtained in example 1 of the present invention2O3Transmission electron micrograph of/PDA composite particle.
FIG. 3 shows Bell-shaped α -Fe obtained in example 1 of the present invention2O3Scanning electron microscope photograph of/PDA composite particles.
FIG. 4 shows Bell-shaped Fe obtained in example 1 of the present invention3O4/C/MoS2Scanning electron micrographs of the hybrid microparticles.
FIG. 5 shows the use of the present inventionBell-shaped Fe obtained in example 13O4/C/MoS2Transmission electron micrographs of the hybrid microparticles.
FIG. 6 shows Bell-shaped Fe obtained in example 1 of the present invention3O4/C/MoS2X-ray photoelectron spectroscopy of the hybrid microparticles.
FIG. 7 shows Bell-shaped Fe obtained in example 1 of the present invention3O4/C/MoS2Hybrid fine particles and Bell-shaped Fe obtained in comparative example 1 of the present invention3O4the/C hybrid particles are at 0.2A g-1Cycling stability test curve at current density.
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) submicron cubic alpha-Fe2O3The preparation of (1): 27.3 g of iron chloride hexahydrate (FeCl)3·6H2O) is dissolved in 50 ml of deionized water to prepare a solution of 2 mol/L, 10.8 g of sodium hydroxide (NaOH) and 50 ml of deionized water are added dropwise after the solution is stirred vigorously for 30 min at a constant temperature of 75 ℃, the solution is stirred continuously for 10 min, the mixed solution is transferred into a reaction kettle, the mixed solution is cured for 48 h at a constant temperature of 110 ℃, then a sample is taken out for centrifugal precipitation, and the precipitate is dried for 12 h at a temperature of 60 ℃ and ground to obtain brick red submicron-scale cubic alpha-Fe with the side length of 550nm2O3。
2) Core-shell form of alpha-Fe2O3Preparation of Polydopamine (PDA) composite particles: weighing 0.32 g of submicron cubic alpha-Fe prepared in step 1)2O3Placing in a 500 mL flask, adding 300 mL deionized water and 100 mL anhydrous ethanol, ultrasonically dispersing for 40 min, adding 0.25 g DA and 0.15 g TRIS, stirring for 12 h, centrifuging and washing with deionized water for three times, and drying the obtained precipitate at 60 deg.C for 12 h to obtain core-shell alpha-Fe2O3a/PDA composite particle.
3) Bell-shaped alpha-Fe2O3Preparation of/PDA composite particles: subjecting all of the alpha-Fe prepared in step 2)2O3the/PDA composite particles are put into 40 mL hydrochloric acid solution with the concentration of 4 mol/L and stirred for 4 h at room temperature, and alpha-Fe2O3Partially etching to form bell-shaped alpha-Fe2O3a/PDA composite particle.
4) Bell-shaped Fe3O4/PDA/MoS2Preparation of hybrid microparticles: weighing 0.1 g of the bell-shaped alpha-Fe prepared in step 3)2O3Adding the/PDA hybrid particles into 50 mL of deionized water, performing ultrasonic dispersion for 40 min, weighing 0.4 g of sodium molybdate dihydrate and 0.6 g of thiourea, respectively dissolving the sodium molybdate dihydrate and the thiourea into 10 mL of deionized water, adding the sodium molybdate solution and the thiourea solution into the solution, transferring the solution into a reaction kettle, performing hydrothermal reaction at a constant temperature of 200 ℃ for 24 h to obtain bell-shaped alpha-Fe2O3/PDA/MoS2Hybrid microparticles.
5) Bell-shaped Fe3O4/C/MoS2Preparation of hybrid microparticles: alpha-Fe prepared in the step 4)2O3/PDA/MoS2Heating to 600 ℃ in nitrogen environment, keeping the temperature for 2 h, carbonizing PDA to form C shell doped with nitrogen atoms, and Fe of alpha crystal form2O3Reduced by carbon at high temperature to form Fe3O4Finally obtaining bell-shaped Fe3O4/C/MoS2Hybrid microparticles.
FIG. 1 is a submicron cubic α -Fe2O3Scanning electron micrographs of the particles showed that most of the particles had a cubic structure with sides of about 550nm and smooth surfaces. FIG. 2 is a view of alpha-Fe2O3Transmission electron micrograph of/PDA composite particle, which shows in cubic form alpha-Fe2O3The particle surface was coated with a layer of PDA, forming a distinct core-shell structure. FIG. 3 shows Bell-shaped α -Fe obtained in example 1 of the present invention2O3Scanning electron microscope photograph of/PDA composite particle. As can be seen from the crushed particles, the composite fine particles have cubic α -Fe inside2O3And after etching, cubic alpha-Fe2O3And an outer layerA gap exists between the PDAs to form a bell-shaped structure. FIG. 4 shows Bell-shaped Fe obtained in example 1 of the present invention3O4/C/MoS2Scanning electron micrographs of the hybrid microparticles. As can be seen, the surface of the microspheres was coated with flaky MoS2The surface roughness of the nano-sheet is obviously increased. FIG. 5 shows Bell-shaped Fe obtained in example 1 of the present invention3O4/C/MoS2Transmission electron micrographs of the hybrid microparticles. As can be seen, the particles form a distinct bell-shaped structure, and the MoS on the surface layer of the microspheres2The sheet layer and the layer C are tightly connected. FIG. 6 shows Bell-shaped Fe obtained in example 1 of the present invention3O4/C/MoS2An X-ray photoelectron spectroscopy spectrum of the hybrid particle. It can be seen that, in the composite particles, Fe, O, Mo, S, C and other elements can be obviously detected, and further, the chemical composition proves that Fe3O4/C/MoS2Formation of hybrid particles.
Example 2:
1) submicron cubic alpha-Fe2O3The preparation of (1): the procedure is as in example 1.
2) Core-shell form of alpha-Fe2O3Preparation of Polydopamine (PDA) composite particles: weighing 0.32 g of submicron cubic alpha-Fe prepared in step 1)2O3Placing in a 500 mL flask, adding 300 mL deionized water and 100 mL anhydrous ethanol, ultrasonically dispersing for 40 min, adding 0.5 g DA and 0.3 g TRIS, stirring for 12 h, centrifuging and washing with deionized water for three times, and drying the obtained precipitate at 60 deg.C for 12 h to obtain core-shell alpha-Fe2O3a/PDA composite particle.
3) Bell-shaped alpha-Fe2O3Preparation of/PDA composite particle: the procedure is as in example 1.
4) Bell-shaped Fe2O3/PDA/MoS2Preparation of hybrid microparticles: the procedure is as in example 1.
5) Bell-shaped Fe3O4/C/MoS2Preparation of hybrid microparticles: the procedure is as in example 1.
Example 3:
1) submicron cubic alpha-Fe2O3The preparation of (1): the procedure is as in example 1.
2) Core-shell form of alpha-Fe2O3Preparation of/PDA composite particles: the procedure is as in example 1.
3) Bell-shaped alpha-Fe2O3Preparation of/PDA composite particle: all the alpha-Fe prepared in the step 2)2O3the/PDA composite particles are put into 80 mL hydrochloric acid solution with the concentration of 4 mol/L and stirred for 6 h at room temperature, and the alpha-Fe2O3Partially etching to form bell-shaped alpha-Fe2O3a/PDA composite particle.
4) Bell-shaped Fe2O3/PDA/MoS2Preparation of hybrid microparticles: the procedure is as in example 1.
5) Bell-shaped Fe3O4/C/MoS2Preparation of hybrid microparticles: the procedure is as in example 1.
Example 4:
1) submicron cubic alpha-Fe2O3The preparation of (1): the procedure is as in example 1.
2) Core-shell form of alpha-Fe2O3Preparation of/PDA composite particles: the procedure is as in example 1.
3) Bell-shaped alpha-Fe2O3Preparation of/PDA composite particle: the procedure is as in example 1.
4) Bell-shaped Fe2O3/PDA/MoS2Preparation of hybrid microparticles: weighing 0.1 g of the bell-shaped alpha-Fe prepared in step 3)2O3Adding the/PDA hybrid particles into 50 mL of deionized water, performing ultrasonic dispersion for 40 min, weighing 0.3 g of sodium molybdate dihydrate and 0.45 g of thiourea, respectively dissolving the sodium molybdate dihydrate and the thiourea into 10 mL of deionized water, adding the sodium molybdate solution and the thiourea solution into the solution, transferring the solution into a reaction kettle, performing hydrothermal reaction at a constant temperature of 200 ℃ for 24 h to obtain bell-shaped alpha-Fe2O3/PDA/MoS2Hybrid microparticles.
5) Bell-shaped Fe3O4/C/MoS2Preparation of hybrid microparticles: according to implementationExample 1 was carried out.
Comparative example 1:
1) submicron cubic alpha-Fe2O3The preparation of (1): the procedure is as in example 1.
2) Core-shell form of alpha-Fe2O3Preparation of Polydopamine (PDA) composite particles: the procedure is as in example 1.
3) Bell-shaped alpha-Fe2O3Preparation of/PDA composite particle: the procedure is as in example 1.
4) Bell-shaped Fe3O4Preparation of/C hybrid particles: the alpha-Fe in the shape of a rattle prepared in the step 3)2O3Heating PDA composite particles to 600 ℃ in nitrogen environment, keeping the temperature for 2 h, carbonizing PDA to form C shell doped with nitrogen atoms, and Fe of alpha crystal form2O3Reduced by carbon at high temperature to form Fe3O4Finally obtaining bell-shaped Fe3O4a/C hybrid particle.
And (3) performance testing:
1) preparing a lithium ion battery negative pole piece: the composite particles prepared in the examples and the comparative examples, conductive carbon black and a binder (PVDF) are sequentially added into an N-methyl-2-pyrrolidone solvent according to a certain mass ratio (8: 1: 1), and after the mixture is uniformly mixed and stirred, the mixture is magnetically stirred for 24 hours at room temperature. And uniformly coating the mixed slurry on a clean copper foil by using a micro coating machine, and drying for 12 hours at 70 ℃ in vacuum. Cutting the dried clean copper foil and the coated copper foil into round electrode plates with the diameter of 14 mm by a slicer, respectively weighing by an analytical balance to obtain the mass of the copper foil and the mixed electrode material, then calculating the mass of the active material according to the proportion, and finally assembling the electrode plates
2) Assembling the battery: a button cell (model CR 2032) was assembled in a glove box, model SMART 1500/750, made by emmite technologies ltd. When the button cell is assembled, a lithium sheet is used as a counter electrode, and the concentration of the lithium sheet is 1 mol L, which is self-made by Zhangjiagang City, Thailand Huarong chemical new material Co., Ltd-1(ethylene carbonate: dimethyl carbonate: methylethyl carbonate, EC: DMC: EMC = 1: 1 vol%) by polymerizationThe porous membrane serves as a separator. And (3) assembling the battery from top to bottom by the coated copper foil, the electrolyte, the diaphragm, the electrolyte, the lithium sheet, the gasket and the elastic sheet in sequence, and finally sealing by using a hydraulic button battery sealing machine. And standing the assembled battery for 24 hours at room temperature, and carrying out electrochemical test after the electrode material is activated.
3) Electrochemical testing: electrochemical performance of the cell was measured at different current densities within a voltage window range of 0.05-3.0V using a blue cell test system model number lan CT2001A (5V,10 mA).
The structural parameters of the bell-shaped composite fine particles obtained in each of the examples and comparative examples are shown in Table 1.
The above examples show that cubic α -Fe in each of the barbell-shaped composite particles in the examples can be achieved by adjusting the amount of acid used in the etching process, the etching time, and the amounts of DA and TRIS used in the coating of PDA, and the amounts of sodium molybdate dihydrate and thiourea used in the hydrothermal treatment3O4Particle size, carbon shell and sheet MoS2The effective adjustment of the layer wall thickness realizes the adjustment of the specific capacity and the cycling stability of the composite particles.
The cycle stability and coulombic efficiency of the negative electrode materials prepared in example 1 and comparative example 1 at different discharge currents are shown in fig. 7, from which it can be seen that the value is 0.2A g-1At current density, Fe3O4/C/MoS2The initial capacity of the electrode material was 1130 mA hr g-1After 150 cycles, the capacity still remains 686.5 mA h g-1The capacity retention rate was 60.8%. In contrast, Fe3O4Initial capacity of/C is only 867.9 mA h g-1And the specific capacity after 150 cycles is 453.2 mA h g-1The capacity was low and the capacity retention was only 52%.
Bell-shaped Fe3O4/C/MoS2The excellent electrochemical performance of the electrode material is mainly attributed to the bell shapeThe void structure of the hybrid particles can effectively resist Fe in the charge-discharge process3O4And MoS2The volume change of the electrode material enhances the structural stability of the electrode material. At the same time, Fe3O4And MoS2The specific capacity of the electrode material is obviously increased by introducing the C shell, and the Fe can be increased by the existence of the C shell3O4And MoS2Is used for the electrical conductivity of (1). It is due to the synergistic effect of these structures and components that the bell-shaped Fe3O4/C/MoS2The hybrid particulate anode material exhibits 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 (3)
1. Bell-shaped Fe for lithium ion battery cathode material3O4/C/MoS2Hybrid particles characterized in that the hybrid particles have a bell-shaped structure with submicron-sized cubic Fe at the center3O4The granules, the granules and the inner shell C layer have movable spaces, and the surface of the inner shell C layer is formed by MoS2Coating the nano sheet layer; the preparation process of the hybrid particles comprises the following steps: submicron order cubic alpha-Fe2O3The preparation of (1): 27.3 g of ferric chloride hexahydrate (FeCl)3·6H2O) is dissolved in 50 ml of deionized water, the mixture is stirred vigorously for 30 min at a constant temperature of 75 ℃, then a solution prepared by 10.8 g of sodium hydroxide (NaOH) and 50 ml of deionized water is added dropwise, the mixture is stirred continuously for 10 min, then the mixed solution is transferred into a reaction kettle, the mixture is cured for 48 h at a constant temperature of 110 ℃, then a sample is taken out for centrifugal precipitation, and after the precipitate is dried for 12 h at a temperature of 60 ℃, the precipitate is ground to obtain brick red submicron-scale cubic alpha-Fe with the side length of 550nm2O3(ii) a Core-shell form of alpha-Fe2O3Preparation of Polydopamine (PDA) composite particles: weighing 0.32 g of submicron-sized particles prepared in the step ICubic alpha-Fe2O3Placing in a 500 mL flask, adding 300 mL deionized water and 100 mL absolute ethyl alcohol, ultrasonically dispersing for 40 min, adding a certain amount of Dopamine (DA) and TRIS (hydroxymethyl) aminomethane (TRIS), stirring for 12 h, centrifuging and washing with deionized water for three times, and drying the obtained precipitate at 60 deg.C for 12 h to obtain core-shell alpha-Fe2O3PDA composite particles; ③ Bell-shaped alpha-Fe2O3Preparation of/PDA composite particles: all the alpha-Fe prepared in the step II2O3Putting the PDA composite particles into a hydrochloric acid solution with a certain concentration of 4 mol/L, stirring for a certain time at room temperature, and obtaining alpha-Fe2O3Partially etched to form bell-shaped alpha-Fe2O3(iv) PDA composite particles; fourthly, bell-shaped Fe2O3/PDA/MoS2Preparation of hybrid microparticles: weighing 0.1 g of the bell-shaped alpha-Fe prepared in the third step2O3 Adding the/PDA composite particles into 50 mL deionized water, performing ultrasonic dispersion for 40 min, then weighing a certain amount of sodium molybdate dihydrate and thiourea to respectively dissolve in 10 mL deionized water, adding the sodium molybdate solution and the thiourea solution into the solution, then transferring the solution into a reaction kettle, performing hydrothermal reaction at a constant temperature of 200 ℃ for 24 h to obtain the belling-shaped alpha-Fe2O3/PDA/MoS2Hybrid microparticles; wobble bell-shaped Fe3O4/C/MoS2Preparation of hybrid microparticles: alpha-Fe prepared in the step (r)2O3/PDA/MoS2Heating to 600 ℃ in a nitrogen environment, keeping the temperature for 2 h, and carbonizing PDA to form nitrogen atom doped C shell and alpha crystal form Fe2O3Reduced by carbon at high temperatures to form Fe3O4Finally obtaining bell-shaped Fe3O4/C/MoS2Hybrid microparticles.
2. The lithium ion battery negative electrode material of claim 1, wherein the Fe is in the shape of a bell3O4/C/MoS2Hybrid particles, characterized in that the thickness of the inner shell C layer is 18-35 nm.
3. The lithium ion battery of claim 1Bell-shaped Fe for negative electrode material3O4/C/MoS2Hybrid particles, characterized by an outer layer of MoS2The layer has a thickness of 50-100nm and is composed of nano-MoS in sheet form2And stacking the materials.
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