CN111384381B - Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof - Google Patents
Silicon @ carbon/MXene ternary composite material for lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the field of lithium ion battery cathode materials, and discloses a silicon @ carbon/MXene ternary composite material for a lithium ion battery and a preparation method thereof. The silicon @ carbon/MXene ternary composite material is prepared by carrying out dopamine hydrochloride autopolymerization on a silicon material to form a polydopamine layer on the surface of the silicon material, then carrying out liquid phase mixing and crosslinking on the polydopamine layer and MXene, and carrying out high-temperature treatment on the polydopamine layer and the MXene. In the method, secondary amine groups of polydopamine on the surface of the silicon material can perform a crosslinking reaction with hydroxyl groups on the surface of MXene to form a covalent bond or a hydrogen bond, so that the agglomeration phenomenon of the silicon material and the MXene is inhibited, and the electrochemical performance of the silicon material is improved. Wherein the size of the silicon material is 20-500nm, the thickness of the carbon coating layer is 3-10nm, and the mass ratio of silicon to MXene is (0.5-4): 1. The pore volume of the obtained silicon @ carbon/MXene ternary composite material is 0.05-0.3cm3Per g, the specific surface area is 60 to 120m2(ii) in terms of/g. The silicon @ carbon/MXene ternary composite material is used as a negative electrode material of a lithium ion battery and has excellent cycle performance and rate capability.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and particularly relates to a silicon @ carbon/MXene ternary composite material for a lithium ion battery and a preparation method thereof
Background
The lithium ion battery is a novel high-energy battery successfully developed in the 20 th century, and Li is used in the process of charging and discharging+In two electricityThe poles are reciprocally inserted and extracted, and are therefore figuratively referred to as "rocking chair batteries". The lithium ion battery has the advantages of high storage energy density, long service life, no memory effect, environmental protection and the like, is more and more widely concerned, and is widely applied to the fields of portable electronic equipment, electric automobiles, aerospace and the like. However, the performance of the lithium ion battery commercialized at present cannot meet the demand of high energy and high power density, so that an electrode material having high capacity becomes a research hotspot.
The theoretical capacity of the silicon-based material is up to 4200mAh g, compared to commercial graphite anodes-1And the material is more than 10 times of graphite material, so that the silicon-based material has great potential as the negative electrode material of the lithium ion battery. However, the silicon-based material shows the defects of large volume expansion and poor conductivity in the reaction process with lithium, so that the cycling stability and rate capability of the silicon-based material still cannot meet the requirements of practical application. The silicon and the carbon material are compounded, so that the problem of poor conductivity of the silicon material can be solved by utilizing the excellent conductivity of the carbon material, and the carbon material can effectively buffer the volume expansion of the silicon in the charge and discharge processes of the battery, so that the electrochemical performance of the silicon material is improved. Among many carbon-based materials, graphene is a popular material compounded with silicon materials due to its advantages of high electrical conductivity, good mechanical flexibility, large specific surface area, and the like. However, the graphene and silicon materials are usually compounded by thermal reduction or chemical reduction of graphene oxide, which greatly increases the cost of the composite material.
Transition metal carbide or nitride, also called MXene, is a novel two-dimensional material discovered for the first time in 2011, has the characteristics of high conductivity of graphene and hydrophilicity of graphene oxide, has the advantages of flexible and adjustable components, rich surface functional groups and the like, and shows great potential in the application aspect of electrode materials of secondary batteries and super capacitors. MXene has high conductivity, can make up the defect of low conductivity of a silicon-based material, and simultaneously, the unique two-dimensional nano structure can also be used for buffering the volume expansion of the silicon-based material in the charging and discharging processes, so that the composite electrode material with better performance is expected to be obtained by compounding the silicon-based material and the MXene.
In recent years, some efforts have been made to compound MXene and silicon-based materials. However, the currently reported method for preparing the Si/MXene composite material is generally a simple ultrasonic mixing or vacuum filtration method, and the like, MXene is seriously agglomerated, a uniformly dispersed composite structure is difficult to form, and the preparation effect is poor. Therefore, how to uniformly compound MXene and a silicon-based material to prepare a high-performance composite electrode material is also a challenging problem.
Disclosure of Invention
Aiming at the problems in the prior art, one of the purposes of the invention is to provide a silicon @ carbon/MXene ternary composite material for a lithium ion battery, namely a ternary composite material formed by a carbon-coated silicon-based material and MXene for the lithium ion battery. The silicon @ carbon/MXene ternary composite material is prepared by carrying out dopamine hydrochloride autopolymerization on a silicon material to form a polydopamine layer on the surface of the silicon material, then carrying out liquid phase mixing and crosslinking on the polydopamine layer and MXene, and then carrying out high-temperature treatment on the polydopamine layer and MXene. The obtained silicon @ carbon/MXene ternary composite material has a layered three-dimensional structure formed by alternately forming MXene layers and silicon @ carbon materials, wherein the silicon @ carbon materials are uniformly dispersed among MXene layers, the silicon @ carbon materials are formed by coating the carbon on the surface of the silicon, the silicon @ carbon materials are uniformly dispersed among the MXene layers, the size of silicon is 20-500nm, the thickness of a carbon coating layer is 3-10nm, and the pore volume of the composite material is 0.05-0.3cm3Per g, the specific surface area is 60 to 120m2(ii) in terms of/g. Wherein the size of the silicon material is 20-500nm, and the thickness of the carbon coating layer is 3-10 nm. In the composite material, the pore volume of the composite material is 0.05-0.3cm3Per g, the specific surface area is 60 to 120m2/g。
The invention also aims to provide a method for preparing the silicon @ carbon/MXene ternary composite material for the lithium ion battery, which comprises the following steps:
(1) mixing tris (hydroxymethyl) aminomethane (C)4H11NO3) Stirring and dispersing in deionized water to prepare a Tris buffer solution with the concentration of 0.01-0.05 mol/L;
(2) adding a silicon material into a Tris buffer solution, carrying out ultrasonic treatment for 10-30min for dispersion, then adding dopamine hydrochloride according to a certain mass ratio, stirring at room temperature for 12-24h, and carrying out self-polymerization reaction of the dopamine hydrochloride on the surface of the silicon material;
(3) centrifugally collecting the reacted silicon material coated with polydopamine, then dispersing the silicon material in deionized water again, adding MXene dispersion liquid according to a certain mass ratio, stirring for 1-2h, and carrying out vacuum filtration to collect a product;
(4) treating the product in a vacuum oven at 50-80 ℃ for 6-12h to perform crosslinking reaction on secondary amine groups of polydopamine and hydroxyl groups of MXene;
(5) and (3) treating the crosslinked product at high temperature for 1-3h under inert atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
Optionally, in the step (2), the mass ratio of silicon to dopamine hydrochloride is (0.5-4):1, preferably (0.5-1): 1.
Optionally, the mass ratio of silicon to MXene in step (3) is (0.25-4):1, preferably (0.5-2): 1.
Optionally, the MXene material in step (3) comprises Ti3C2Tx、Ti2CTx、Ti2NTx、V2CTx、Mo2CTxAnd Nb2CTxOne or more of (a).
Optionally, the inert atmosphere in step (5) is one or more of nitrogen, argon, helium or neon.
Optionally, the high temperature treatment temperature in the step (5) is 400-700 ℃.
The invention provides a preparation method of a silicon @ carbon/MXene ternary composite material for a lithium ion battery; in the invention, dopamine hydrochloride firstly undergoes self-polymerization reaction on the surface of the silicon material to form a poly-dopamine layer, and can undergo cross-linking reaction with hydroxyl on the surface of MXene after being mixed with MXene to form covalent bonds or hydrogen bonds, so that the silicon material and MXene are tightly combined, and the agglomeration and stacking phenomenon of the silicon and MXene is inhibited.
The invention also provides the silicon @ carbon/MXene ternary composite material obtained by the method and application of the silicon @ carbon/MXene ternary composite material as a lithium battery negative electrode material.
The silicon @ carbon/MXene ternary composite material for the lithium ion battery and the preparation method thereof have the following beneficial effects:
(1) in the silicon @ carbon/MXene ternary composite material for the lithium ion battery, the silicon material and the MXene are combined through a covalent bond or a hydrogen bond between the polydopamine derived carbon layer and the MXene, and the excellent conductivity of the MXene greatly improves the conductivity of the silicon @ carbon/MXene ternary composite material and the high-current multiplying power performance when the silicon @ carbon/MXene ternary composite material is used as an electrode;
(2) in the silicon @ carbon/MXene ternary composite material for the lithium ion battery, silicon/carbon particles are combined on the surface of MXene through covalent bonds or hydrogen bonds, so that the agglomeration and stacking phenomenon of silicon and MXene is avoided, the contact reaction area of an active material and an electrolyte is increased, and the specific capacity of the active material serving as an electrode of the lithium ion battery is favorably increased;
(3) in the circulation process, the carbon layer and the MXene can both play a buffering role in the volume expansion of silicon, and the double buffering role is favorable for the silicon @ carbon/MXene ternary composite material to show more stable circulation performance.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a silicon @ carbon material prepared according to example 1 of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the silicon @ carbon/MXene ternary composite material prepared in example 1 of the present invention.
Fig. 3 is a graph showing the cycle performance of the silicon @ carbon/MXene ternary composite material prepared in example 1 of the present invention and the silicon/carbon material prepared in comparative example 1 as a negative electrode material of a lithium ion battery.
FIG. 4 is a Scanning Electron Microscope (SEM) image of the silicon @ carbon/MXene ternary composite prepared in example 2 of the present invention.
Fig. 5 is a graph showing the cycle performance of the silicon @ carbon/MXene ternary composite material prepared in example 2 of the present invention as a lithium ion battery anode material.
Fig. 6 is a graph showing the cycle performance of the silicon @ carbon/MXene ternary composite material prepared in example 4 of the present invention as a lithium ion battery anode material.
Detailed Description
Example 1
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 100mg of dopamine hydrochloride, stirring for 24 hours, and centrifugally collecting to obtain Si @ polydopamine material, namely polydopamine-coated silicon material, as shown in figure 1;
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 25ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material (mass ratio, Si: MXene is 2: 1);
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) and (3) placing the crosslinked Si @ polydopamine/MXene into a tubular furnace, and treating for 2h at 600 ℃ in an argon atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
(5) The morphology and the structure of the silicon @ carbon/MXene ternary composite material are researched. As shown in FIG. 2, the thickness of the silicon surface carbon layer is about 7.8nm, and the silicon/carbon material is uniformly anchored on the surface of the MXene sheet layer, so that the reaction between the MXene sheet layer and the electrolyte is facilitated. The silicon/carbon material of the MXene surface also avoids stacking of its lamellae. The specific surface area of the silicon @ carbon/MXene ternary composite material is 80m through a nitrogen adsorption/desorption test2Per g, pore volume of 0.1cm3/g
(6) Mixing the above materials according to the ratio of active substances: acetylene black: mixing CMC 60:20:20 to prepare an electrode plate, taking Celgard membrane as a diaphragm and 1mol/L LiPF6The EC/DEC system is electrolyte, the lithium foil is a counter electrode, a button half cell is assembled for testing, and the test voltage range is 0.01-2.5V. The cycle performance test result is shown in fig. 3, the silicon @ carbon/MXene ternary composite material shows specific capacity of 1600.8mAh/g under the current density of 420mA/g, after 80 times of cycle, the capacity still keeps 1140.8mAh/g, and the capacity retention rate reaches 1140.8mAh/g71.3 percent, and the specific capacity and the cycling stability are excellent.
Comparative example 1
The difference from example 1 is that: taking silicon/carbon powder as an active substance, and mixing the following active substances: acetylene black: the electrode sheets were prepared by mixing CMC 60:20:20, and the button half cells were assembled for testing. Fig. 3 shows the cycling performance of an electrode with silicon/carbon powder as the active material at a current density of 420 mA/g. The silicon/carbon powder electrode is at 420mA g-1The specific capacity of the capacitor reaches 2143mAh/g under the current density, but the capacity is only 788.2mAh/g after the capacitor is cycled for 80 times, and the capacity retention rate is 36.8 percent.
The silicon @ carbon/MXene ternary composite electrode of comparative example 1 and the silicon/carbon powder electrode of comparative example 1 were at 420mA g-1The specific capacity of the silicon @ carbon/MXene ternary composite material electrode in the embodiment 1 is lower than that of a silicon/carbon powder electrode in the previous cycles, but the specific capacity is more stable, and the specific capacity after 80 cycles is higher than 44.7%, which shows that the cyclic specific capacity and the cyclic stability of the silicon/carbon electrode can be remarkably improved by adding MXene in the silicon @ carbon/MXene ternary composite material electrode and bonding the MXene with polydopamine-derived carbon.
Example 2
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 100mg of dopamine hydrochloride, stirring for 24 hours, and centrifugally collecting to obtain Si @ polydopamine material;
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 100ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material (mass ratio, Si: MXene is 0.5: 1);
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) and (3) placing the crosslinked Si @ polydopamine/MXene into a tubular furnace, and treating for 2h at 600 ℃ in an argon atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
(5) The morphology of the silicon @ carbon/MXene ternary composite material is observed, as shown in FIG. 4, the thickness of the carbon layer on the surface of the silicon is about 7.8nm, and the proportion of MXene is increased, so that silicon carbon particles are uniformly dispersed among MXene sheet layers. The specific surface area of the silicon @ carbon/MXene ternary composite material is 100m through a nitrogen adsorption/desorption test2Per g, pore volume of 0.2cm3/g
(6) Mixing the above materials according to the ratio of active substances: acetylene black: the electrode slice is prepared by mixing CMC 60:20:20, the cycle performance test result is shown in figure 5, the second circle of the silicon @ carbon/MXene ternary composite material shows specific capacity of 924.1mAh/g under the current density of 420mA/g, after 80 times of circulation, the capacity still keeps 773.5mAh/g, the capacity retention rate reaches 83.7%, and the electrode slice has excellent specific capacity and cycle stability. Comparing the electrochemical performances of the silicon @ carbon/MXene ternary composite electrode in example 2 and the silicon @ carbon/MXene ternary composite electrode in example 1, the specific capacity of the silicon @ carbon/MXene ternary composite electrode in example 2 is slightly reduced, but the cycling stability is greatly improved.
Example 3
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 100mg of dopamine hydrochloride, stirring for 24 hours, and centrifugally collecting to obtain Si @ polydopamine material;
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 12.5ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material (mass ratio, Si: MXene is 4: 1);
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) and (3) placing the crosslinked Si @ polydopamine/MXene into a tubular furnace, and treating for 2h at 600 ℃ in an argon atmosphere to obtain the silicon @ carbon/MXene ternary composite material. By passingThe specific surface area of the silicon @ carbon/MXene ternary composite material is 60m in a nitrogen adsorption/desorption test2Per g, pore volume of 0.05cm3/g。
(5) Mixing the above materials according to the ratio of active substances: acetylene black: mixing CMC 60:20:20 to prepare an electrode slice, and testing the electrochemical performance of the electrode slice. The second circle of the silicon @ carbon/MXene ternary composite material shows specific capacity of 2287.2mAh/g under the current density of 420mA/g, but due to the fact that the silicon material content is high, after circulation is carried out for 80 times, the capacity still keeps 869.3mAh/g, and the capacity retention rate reaches 38.0%.
(6) Comparing the electrochemical performance of the silicon @ carbon/MXene ternary composite electrode in example 3 with that of the silicon @ carbon/MXene ternary composite electrode in example 1, the initial specific capacity of the silicon @ carbon/MXene ternary composite electrode in example 3 is 43% higher than that of the silicon @ carbon/MXene ternary composite electrode in example 1, but the capacity after 80 cycles is 24% lower than that of the silicon @ carbon/MXene ternary composite electrode in example 1, and the cycle stability is poor. However, the silicon @ carbon/MXene ternary composite electrode of example 3 still showed improved specific capacity and cycling stability compared to the silicon @ carbon/MXene ternary composite electrode of comparative example 1.
Example 4
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 100mg of dopamine hydrochloride, stirring for 24 hours, and centrifugally collecting to obtain Si @ polydopamine material;
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 200ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material (mass ratio, Si: MXene is 0.25: 1);
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) placing the crosslinked Si @ polydopamine/MXene in a tube furnace, and treating for 2h at 700 ℃ under the argon atmosphere to obtain silicon @ carbonthe/MXene ternary composite material. The specific surface area of the silicon @ carbon/MXene ternary composite material is 12m through a nitrogen adsorption/desorption test2Per g, pore volume of 0.3cm3/g。
(5) Mixing the above materials according to the ratio of active substances: acetylene black: the electrode sheets were prepared by mixing CMC in a ratio of 60:20:20, and their electrochemical properties were tested as shown in fig. 6. The second circle of the silicon @ carbon/MXene ternary composite material shows 689.5mAh/g specific capacity under the current density of 420mA/g, and due to the fact that the silicon material content is low, the silicon/carbon/MXene electrode has a slight capacity activation phenomenon, after the circulation for 80 times, the specific capacity is low and is only 632.7mAh/g, but the capacity retention rate is high and reaches 88.4%.
Example 5
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 200mg of dopamine hydrochloride, stirring for 24 hours, and centrifugally collecting to obtain Si @ polydopamine material (Si: dopamine hydrochloride is 0.5: 1);
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 25ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material;
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) and (3) placing the crosslinked Si @ polydopamine/MXene into a tubular furnace, and treating for 2h at 600 ℃ in an argon atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
(5) The thickness of the carbon layer on the surface of the silicon is about 10nm according to a transmission electron microscope. The specific surface area of the silicon @ carbon/MXene ternary composite material is 118m through a nitrogen adsorption/desorption test2Per g, pore volume of 0.3cm3/g。
(6) Mixing the above materials according to the ratio of active substances: acetylene black: the electrode sheets were prepared by mixing CMC 60:20:20, and the button half cell was assembled for testing. The silicon @ carbon/MXene ternary composite material shows specific capacity of 1230.8mAh/g under the current density of 420mA/g, after circulation for 80 times, the capacity still keeps 980.8mAh/g, the capacity retention rate reaches 79.6%, and excellent specific capacity and circulation stability are shown.
Example 6
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 50mg of dopamine hydrochloride, stirring for 24 hours, and centrifugally collecting to obtain Si @ polydopamine material (Si: dopamine hydrochloride ═ 2: 1);
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 25ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material;
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) and (3) placing the crosslinked Si @ polydopamine/MXene into a tubular furnace, and treating for 2h at 600 ℃ in an argon atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
(5) The thickness of the carbon layer on the surface of the silicon is about 5.3nm according to a transmission electron microscope. The specific surface area of the silicon @ carbon/MXene ternary composite material is 87m through a nitrogen adsorption/desorption test2Per g, pore volume of 0.21cm3/g。
(6) Mixing the above materials according to the ratio of active substances: acetylene black: mixing CMC 60:20:20 to prepare an electrode slice, and testing the electrochemical performance of the electrode slice. The second circle of the silicon @ carbon/MXene ternary composite material shows specific capacity of 1720.9mAh/g under the current density of 420mA/g, after 80 times of circulation, the specific capacity still keeps 968.1mAh/g, and the capacity retention rate reaches 56.3%.
Example 7
(1) Weighing 0.2423g C4H11NO3Dissolving in 200ml deionized water to prepare 0.01mol/L Tris buffer solution. Weighing 100mg of nano silicon material with the size of about 90nm, ultrasonically dispersing the nano silicon material in Tris buffer solution, adding 25mg of dopamine hydrochloride, and stirringAfter 24h, centrifuging and collecting to obtain Si @ polydopamine material (Si: dopamine hydrochloride 4: 1);
(2) re-dispersing the Si @ polydopamine material in 100ml of deionized water, adding 25ml of MXene dispersion liquid (2mg/ml), stirring for 1 hour, and performing vacuum filtration to obtain the Si @ polydopamine/MXene material;
(3) transferring Si @ polydopamine/MXene to a vacuum oven, and carrying out vacuum treatment for 6h at 60 ℃ to enable secondary amine groups of the polydopamine and hydroxyl groups on the surface of MXene to carry out cross-linking reaction to form covalent bonds or hydrogen bonds;
(4) and (3) placing the crosslinked Si @ polydopamine/MXene into a tubular furnace, and treating for 2h at 600 ℃ in an argon atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
(5) The thickness of the carbon layer on the surface of the silicon is about 3nm according to a transmission electron microscope. The specific surface area of the silicon @ carbon/MXene ternary composite material is 63m through a nitrogen adsorption/desorption test2Per g, pore volume of 0.07cm3/g。
(5) Mixing the above materials according to the ratio of active substances: acetylene black: mixing CMC 60:20:20 to prepare an electrode slice, and testing the electrochemical performance of the electrode slice. The second circle of the silicon @ carbon/MXene ternary composite material shows specific capacity of 1765.2mAh/g under the current density of 420mA/g, after 80 times of circulation, the specific capacity is kept at 841mAh/g, and the capacity retention rate reaches 47.6%.
Claims (5)
1. The preparation method of the silicon @ carbon/MXene ternary composite material for the lithium ion battery is characterized in that the silicon @ carbon/MXene ternary composite material has a layered three-dimensional structure formed by alternately forming MXene layers and silicon @ carbon materials, the silicon @ carbon materials are formed by coating carbon on the surface of silicon and are uniformly dispersed among the MXene layers, wherein the size of silicon is 20-500nm, the thickness of a carbon coating layer is 3-10nm, and the pore volume of the composite material is 0.05-0.3cm3Per g, the specific surface area is 60 to 120m2The preparation method comprises the following steps:
(1) stirring and dispersing Tris (hydroxymethyl) aminomethane in deionized water to prepare a Tris buffer solution with the concentration of 0.01-0.05 mol/L;
(2) adding a silicon material into a Tris buffer solution, performing ultrasonic treatment for 10-30min to disperse, then adding dopamine hydrochloride according to a certain mass ratio, stirring at room temperature for 12-24h, and performing dopamine hydrochloride autopolymerization on the surface of the silicon material, wherein the mass ratio of silicon to dopamine hydrochloride is = (0.5-1): 1;
(3) centrifuging and collecting the reacted silicon material coated with polydopamine, then dispersing the silicon material in deionized water again, adding MXene dispersion liquid according to a certain mass ratio, stirring for 1-2h, and performing vacuum filtration to collect a product, wherein the mass ratio of silicon to MXene is = (0.5-2): 1;
(4) treating the product in a vacuum oven at 50-80 ℃ for 6-12h to perform crosslinking reaction on secondary amine groups of polydopamine and hydroxyl groups of MXene;
(5) and (3) treating the crosslinked product at the temperature of 400-700 ℃ for 1-3h under the inert atmosphere to obtain the silicon @ carbon/MXene ternary composite material.
2. The method according to claim 1, wherein the MXene material in the step (3) comprises Ti3C2T x 、Ti2CT x 、Ti2NT x 、V2CT x 、Mo2CT x And Nb2CT x One or more of (a).
3. The method according to claim 1, wherein the inert atmosphere in step (5) is one or more of nitrogen, argon, helium or neon.
4. The silicon @ carbon/MXene ternary composite material prepared by the preparation method of any one of claims 1 to 3.
5. Use of the silicon @ carbon/MXene ternary composite of claim 4 as a lithium ion battery anode material.
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