CN109755546B - Preparation method of silicon-based composite material for lithium ion power battery - Google Patents
Preparation method of silicon-based composite material for lithium ion power battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicon-based composite material for a lithium ion power battery, which belongs to the field of lithium ion battery cathode materials and comprises the following steps: taking nano-silicon, plastic and montmorillonite as raw materials, adding heavy metal salt as a catalyst, mixing the raw materials, and then extruding and granulating under a melting condition to obtain a nano-silicon/plastic/montmorillonite composite material; adding a nonionic surfactant and a cationic surfactant into a hydrochloric acid solution to obtain a mixed solution, adding the nano-silicon/plastic/montmorillonite composite material into the mixed solution, and carrying out a sol-gel reaction to obtain a nano-silicon/plastic/silicon dioxide composite material; and (3) performing carbothermic reduction on the nano silicon/plastic/silicon dioxide composite material to obtain the nano silicon/plastic/silicon dioxide composite material. The method utilizes the characteristics of inducing and catalyzing plastics and catalyzing graphitization by the heavy metal salt, realizes low-temperature graphitization and uniform coating of the graphitized carbon on the nano silicon particles by using the plastics as a carbon source, and improves the electrochemical performance of the silicon cathode material.
Description
Technical Field
The invention belongs to the field of lithium ion battery cathode materials, and relates to a preparation method of a silicon-based composite material for a lithium ion power battery.
Background
As one of the most promising electrochemical energy storage and transmission systems, lithium ion batteries have been widely used in portable electronic devices, as well as in the fields of electric automobiles and aviation, and the performance of the negative electrode material is one of the main factors affecting the performance of the lithium ion battery, such as lifetime, capacity, safety, etc. Today, the most widely used lithium ion negative electrode is a graphite material, but its theoretical capacity is only 372mA h g-1It is difficult to meet the further development of lithium ion batteries, and therefore, it is essential to the development of high power density of lithium ion batteries to explore alternative anode materials with higher capacity and good cycling stability silicon anodes are due to their ultra-high theoretical capacity (L i at room temperature)15Si43579mA h g-1) Abundant reserve and relatively low de-intercalation potential of lithium: (<0.5 pairs of L i/L i+) And are drawing increasing attention. However, the ultra-low conductivity of the silicon negative electrode, the huge volume expansion upon lithiation and the problem of unstable Solid Electrolyte Interphase (SEI) formation make it difficult to be commercially applied.
In order to reduce the problem of huge volume expansion of a silicon negative electrode material in the lithium desorption and intercalation process and improve the conductivity of the silicon negative electrode material, extensive research is carried out at present, the main direction is the preparation of a nano material and the preparation of a silicon-based composite material, for example, patent CN106935815A discloses a preparation method of a silicon-carbon composite material, which relates to the field of synthesis of the silicon-carbon negative electrode material, the method comprises the steps of uniformly mixing metal silicon and graphite powder according to a certain proportion, placing the mixture into a graphite crucible, then placing the mixture into a closed furnace kiln for heating treatment, and controlling the preparation of the composite material by adjusting the pressure in the furnace kiln in the constant temperature preservation process to obtain the silicon-carbon composite material; patent CN107394122A discloses a preparation method of a composite silicon-carbon negative electrode material, which comprises the steps of dissolving polyacrylonitrile in an organic solution after preparing a silicon-rich material, then adding a silicon-rich material with appropriate mass, fully ball-milling, stirring and mixing, and finally compounding by matching with an electrostatic spinning method and taking a high-molecular organic spinning substance as a carbon source; patent CN107611369A discloses a silicon-carbon negative electrode material for lithium ion batteries and a preparation method thereof, which is to prepare the silicon-carbon negative electrode material by surface treatment, roasting and scattering of silicon or its oxide, then fusing and coating with carbon micropowder and organic carbon source, and finally carbonizing.
The modification method employed in the above patent is to embed silicon into a carbon matrix, thereby effectively relieving the huge volume expansion and improving the electron conductivity of the buffer and conductive matrix. However, compounding with a carbon matrix requires solving the problems of dispersibility and stability of the silicon material in the matrix, and also requires consideration of economic cost for preparing the composite. Therefore, there is a strong need for a simple, efficient and feasible method for preparing silicon-based composites.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a silicon-based composite material for a lithium ion power battery, which has the advantages of stable structure, good dispersibility, excellent electrochemical performance and low cost.
The preparation method of the silicon-based composite material for the lithium ion power battery, provided by the invention, comprises the following steps:
taking nano-silicon, plastic and montmorillonite as raw materials, adding heavy metal salt as a catalyst, mixing the raw materials, and then extruding and granulating under a melting condition to obtain a nano-silicon/plastic/montmorillonite composite material;
adding a nonionic surfactant and a cationic surfactant into a hydrochloric acid solution to obtain a mixed solution, adding the nano-silicon/plastic/montmorillonite composite material into the mixed solution, and carrying out a sol-gel reaction to obtain a nano-silicon/plastic/silicon dioxide composite material;
performing carbothermic reduction on the nano-silicon/plastic/silicon dioxide composite material to obtain the nano-silicon/graphitized carbon/silicon monoxide composite material (Si/GC/SiO)x) Namely the silicon-based composite material for the lithium ion power battery.
Preferably, the mass ratio of the nano silicon to the plastic to the montmorillonite is (1-5): (20-40): (2-10).
Preferably, the particle size of the nano silicon is 100-500 nm.
Preferably, the heavy metal salt is one or more of nickel salt, cobalt salt, iron salt and manganese salt, and the addition amount of the heavy metal salt is 1-5 wt% of the raw materials.
Further preferably, the nickel salt is one or more of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride; the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt sulfate and cobalt chloride; the ferric salt is one or more of ferric nitrate, ferric acetate, ferric sulfate and ferric chloride; the manganese salt is one or more of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
Preferably, the nonionic surfactant is one or more of Triton X2100, OP-10, TX-10 and NP-8.6, and the addition amount of the nonionic surfactant is 5-10 wt% of the nano silicon/plastic/montmorillonite composite material.
Preferably, the cationic surfactant is one or more of cetyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride, trialkyl ammonium chloride and trialkyl methyl ammonium chloride, and the addition amount of the cationic surfactant is 15-20 wt% of the nano silicon/plastic/montmorillonite composite material.
Preferably, the concentration of the hydrochloric acid is 1-5 mol/L, and the molar ratio of the hydrochloric acid to the nano silicon/plastic/montmorillonite composite material is (1-10): 1.
Preferably, the plastic is one or more of polypropylene, polyethylene and polystyrene.
Further preferably, the preparation method of the silicon-based composite material for the lithium ion power battery comprises the following steps:
(1) uniformly mixing nano silicon, plastic, heavy metal salt and montmorillonite, placing the mixture in a double-screw extruder, controlling the melting condition, carrying out extrusion granulation at the set screw rotating speed and processing temperature, cooling to room temperature, and taking out to obtain a nano silicon/plastic/montmorillonite composite material;
(2) dissolving a predetermined amount of nonionic surfactant and a predetermined amount of cationic surfactant in a hydrochloric acid solution, adding the nano silicon/plastic/montmorillonite composite material obtained in the step (1) while stirring until the surfactant is completely dissolved and the solution becomes clear, stirring for 0.5-2 h, standing and aging for 10-20 h at room temperature, centrifuging, washing, and drying to obtain a nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material obtained in the step (2) into a tube furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is selected from one or more of helium, argon, neon and nitrogen, the heating system of heat treatment is 1-10 ℃/min, the heat preservation temperature is 500-800 ℃, and the heat preservation time is 2-12 hours, so as to obtain a first-stage sintered product;
and carrying out second-stage reduction atmosphere sintering on the first-stage sintering product, wherein the reduction atmosphere is selected from one or more of hydrogen, helium, argon, neon and nitrogen, the heating system of heat treatment is 5-20 ℃/min, the heat preservation temperature is 900-1500 ℃, the heat preservation time is 2-12 h, the product is naturally cooled to room temperature after sintering is finished, and the product is crushed and classified to obtain the silicon-based composite material for the lithium ion power battery.
Further preferably, in the step (1), the mixing manner is one or more of mechanical stirring, mechanical ball milling and mechanical grinding.
Preferably, in the step (1), the rotating speed of a screw is 30-100 rpm, and the stirring time is 6-10 hours; the processing temperature is 220-270 ℃.
Further preferably, in the step (3), the crushing mode adopts mechanical crushing or air flow crushing, and the classification mode adopts vibration screening or air flow classification.
Further preferably, in the step (3), the first-stage inert atmosphere sintering is carried out, the temperature rise system of the heat treatment is 1-5 ℃/min, the heat preservation temperature is 600-700 ℃, and the heat preservation time is 5-10 h.
Preferably, in the step (3), the second-stage reducing atmosphere sintering is performed, the temperature rise system of the heat treatment is 5-10 ℃/min, the heat preservation temperature is 1000-1200 ℃, and the heat preservation time is 5-8 h.
The invention also provides a nano silicon/graphitized carbon/silicon monoxide composite material, wherein the silicon monoxide is a coating layer, the nano silicon and the graphitized carbon are substrates, the nano silicon/graphitized carbon/silicon monoxide composite material forms a core-shell structure, the particle size of the composite material is 10-30 um, and the mass ratio of the nano silicon to the graphitized carbon is 1: (1-10), and the content of the silicon monoxide is 2-5 wt% of the nano silicon/graphitized carbon/silicon monoxide composite material.
The invention also provides an application of the nano silicon/graphitized carbon/silicon monoxide composite material, and the nano silicon/graphitized carbon/silicon monoxide composite material is applied to a lithium ion battery as a negative electrode material.
According to the preparation method of the silicon-based composite material for the lithium ion power battery, the plastic generates a wool ball structure at the melting temperature in the presence of the heavy metal salt and the montmorillonite, the plastic is induced to generate a linear fiber tubular structure by adding the heavy metal salt, and the agglomeration phenomenon in the plastic melting and solidification process is inhibited by utilizing the characteristic that the montmorillonite is poor in wettability in the molten plastic, so that the wool ball particles which are uniformly mixed by nano silicon coated by the montmorillonite and a plastic fiber tube are prepared; silicate contained in the montmorillonite is used as a raw material for preparing silicon dioxide, wool ball particles which are formed by uniformly mixing silicon dioxide-coated nano silicon and a plastic fiber tube are formed after sol-gel treatment, and finally Si/GC/SiO is obtained by carbothermic reductionxA composite material.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the preparation method of the silicon-based composite material for the lithium ion power battery utilizes the characteristics of inducing and catalyzing plastics and catalyzing graphitization in heavy metal salt, realizes low-temperature graphitization and uniform coating of graphitized carbon on the nano silicon particles by using the plastics as a carbon source, can improve the conductivity of silicon, can inhibit volume expansion of a silicon cathode in the charging and discharging process, prevents the problem of pulverization of the silicon cathode material, and improves the electrochemical performance of the silicon cathode material.
(2) The preparation method of the silicon-based composite material for the lithium ion power battery fully utilizes the characteristics of montmorillonite for fixing and separating molten plastics to prepare the wool ball particles through sol-gel and carbon thermal reduction treatment, and the montmorillonite is used as a silicon source to synthesize the silica, so that the uniform coating of the silica is realized, and the Si/GC/SiO is preparedxThe composite material can generate a stable solid electrolyte interphase film (SEI film), thereby further improving the electrochemical performance of the anode material.
(3) The preparation method of the silicon-based composite material for the lithium ion power battery takes cheap and easily-obtained nano silicon and plastic as raw materials, the plastic can be recycled garbage, the carbonization temperature is low, the problems of dispersibility and stability of the silicon material in a matrix can be solved, the cost of the raw materials is low, and the problems of large energy consumption and high economic cost caused by high-temperature graphitization of common silicon-carbon cathode materials can be solved.
(4) The nano silicon/graphitized carbon/silicon monoxide composite material forms a stable core-shell structure, has good dispersibility, high capacity, good rate capability and long cycle life, and is used as a high-performance lithium power battery Si/GC/SiOxThe composite material has wide application prospect.
Drawings
FIG. 1 is a process flow diagram of a preparation method of a silicon-based composite material for a lithium ion power battery according to the invention.
FIG. 2 is a schematic representation of Si/GC/SiO in accordance with the present inventionxSchematic structural diagram of the composite material.
FIG. 3 is the Si/GC/SiO solid prepared in example 4xXRD pattern of the composite.
FIG. 4 is the Si/GC/SiO solid prepared in example 4xTransmission Electron Microscopy (TEM) of the composite.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The experimental procedures described in the following examples are conventional unless otherwise specified, and the reagents and materials described therein are commercially available without further specification.
Example 1
The invention relates to a preparation method of a silicon-based composite material for a lithium ion power battery, which has a process flow shown in figure 1 and comprises the following steps:
(1) mixing 1g of nano-silicon, 50g of plastic (polypropylene, PP), 0.56g of nickel chloride and 5g of montmorillonite uniformly in a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 30rpm, stirring for 6 hours, controlling the processing temperature of the extruder to be 220 ℃, extruding and granulating, cooling to room temperature, and taking out to obtain a nano-silicon/plastic/montmorillonite composite material;
(2) dissolving 1.5ml of Triton X2100 and 1.5g of hexadecyl trimethyl quaternary ammonium bromide in 100ml of 1 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, adding 0.1mol of nano silicon/plastic/montmorillonite composite material under stirring, controlling the molar ratio of n (HCl)/n (nano silicon/plastic/montmorillonite composite material) to be 1:1, stirring for 0.5h, standing and aging for 10h at room temperature, centrifuging, washing and drying to obtain the nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is helium, the heating system of heat treatment is 1 ℃/min, the heat preservation temperature is 500 ℃, and the heat preservation time is 12 hours, so as to obtain a first-stage sintered product;
and (2) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and helium, the heating system of heat treatment is 5 ℃/min, the heat preservation temperature is 1000 ℃, the heat preservation time is 8 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and subjected to vibration classification to obtain Si/GC/SiOxA composite material.
The Si/GC/SiO solid obtained in example 1 was mixedxPreparing the composite material, acetylene black and sodium alginate into slurry in a deionized water medium according to the mass ratio of 6:2:2, coating the slurry on a copper foil, performing vacuum drying at 120 ℃, and taking a lithium sheet as a counter electrode, a polypropylene film as a diaphragm and an electrolyte of 1M L L iPF6And (EC: DEC ═ 1:1) + 10% FEC, battery case model 2025, and cycle life test was performed at a voltage range of 0.01 to 1.2V by charging and discharging at a current density of 0.2C (1C ═ 4200 mA/g).
Example 2
The invention relates to a preparation method of a silicon-based composite material for a lithium ion power battery, which comprises the following steps:
(1) mixing 1g of nano silicon, 10g of plastic (polypropylene, PP), 0.13g of nickel sulfate and 2g of montmorillonite uniformly in a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 100rpm, stirring for 10 hours, controlling the processing temperature of the extruder to be 270 ℃, extruding and granulating, cooling to room temperature, and taking out to obtain a nano silicon/plastic/montmorillonite composite material;
(2) dissolving 1ml of OP-10 and 1g of trialkyl ammonium chloride in 200ml of 5 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, adding 0.1mol of nano silicon/plastic/montmorillonite composite material while stirring, controlling the molar ratio of n (HCl)/n (nano silicon/plastic/montmorillonite composite material) to be 10: 1, stirring for 2 hours, standing and aging for 20 hours at room temperature, centrifuging, washing and drying to obtain the nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is nitrogen, the heating system of heat treatment is 5 ℃/min, the heat preservation temperature is 700 ℃, and the heat preservation time is 2 hours, so as to obtain a first-stage sintered product;
and (2) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and nitrogen, the heating system of heat treatment is 10 ℃/min, the heat preservation temperature is 1200 ℃, the heat preservation time is 5 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and subjected to vibration classification to obtain the Si/GC/SiOxA composite material.
The Si/GC/SiO solid obtained in example 2 was usedxComposite materials electrodes, assembled cells and tested for performance were prepared in the same manner as in example 1.
Example 3
The invention relates to a preparation method of a silicon-based composite material for a lithium ion power battery, which comprises the following steps:
(1) mixing 1g of nano silicon, 25g of plastic (polypropylene, PP), 0.29g of nickel acetate and 3g of montmorillonite uniformly in a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out to obtain a nano silicon/plastic/montmorillonite composite material;
(2) dissolving 2ml of NP-8.6 and 2g of trialkyl methyl ammonium chloride in 200ml of 3 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, adding 0.15mol of nano silicon/plastic/montmorillonite composite material while stirring, controlling the molar ratio of n (HCl)/n (nano silicon/plastic/montmorillonite composite material) to be 4: 1, stirring for 1h, standing and aging for 15h at room temperature, centrifuging, washing and drying to obtain the nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is argon, the heating system of heat treatment is 2 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 8 hours, so as to obtain a first-stage sintered product;
and (2) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and argon, the heating system of heat treatment is 6 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and subjected to vibration classification to obtain the Si/GC/SiOxA composite material.
The Si/GC/SiO solid obtained in example 3 was usedxComposite materials electrodes, assembled cells and tested for performance were prepared in the same manner as in example 1.
Example 4
The invention relates to a preparation method of a silicon-based composite material for a lithium ion power battery, which comprises the following steps:
(1) mixing 1g of nano-silicon, 25g of plastic (polypropylene, PP), 0.29g of manganese acetate and 3g of montmorillonite uniformly by a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out to obtain a nano-silicon/plastic/montmorillonite composite material;
(2) 2ml of TX-10 and 2g of octadecyl dimethyl benzyl quaternary ammonium chloride are dissolved in 200ml of 3 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, 0.15mol of nano silicon/plastic/montmorillonite composite material is added under stirring, the molar ratio of n (HCl)/n (nano silicon/plastic/montmorillonite composite material) is controlled to be 4: 1, the stirring is carried out for 1h, the standing and aging are carried out for 15h under the condition of room temperature, and then the centrifugation, the washing and the drying are carried out, so as to obtain the nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is neon, the heating system of heat treatment is 2 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 8 hours, so as to obtain a first-stage sintered product;
and (2) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and neon, the heating system of heat treatment is 6 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and subjected to vibration classification to obtain the Si/GC/SiOxA composite material.
The Si/GC/SiO solid obtained in example 4 was usedxComposite materials electrodes, assembled cells and tested for performance were prepared in the same manner as in example 1.
Example 5
The invention relates to a preparation method of a silicon-based composite material for a lithium ion power battery, which comprises the following steps:
(1) mixing 1g of nano silicon, 25g of plastic (polypropylene, PP), 0.29g of cobalt acetate and 3g of montmorillonite uniformly in a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out to obtain a nano silicon/plastic/montmorillonite composite material;
(2) dissolving 2ml of OP-10 and 2g of hexadecyl trimethyl quaternary ammonium bromide in 200ml of 3 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, adding 0.15mol of nano silicon/plastic/montmorillonite composite material under stirring, controlling the molar ratio of n (HCl)/n (nano silicon/plastic/montmorillonite composite material) to be 4: 1, stirring for 1h, standing and aging for 15h at room temperature, centrifuging, washing and drying to obtain the nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is argon, the heating system of heat treatment is 2 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 8 hours, so as to obtain a first-stage sintered product;
and (2) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and argon, the heating system of heat treatment is 6 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and subjected to vibration classification to obtain the Si/GC/SiOxA composite material.
The Si/GC/SiO solid obtained in example 5 was usedxComposite materials electrodes, assembled cells and tested for performance were prepared in the same manner as in example 1.
Example 6
The invention relates to a preparation method of a silicon-based composite material for a lithium ion power battery, which comprises the following steps:
(1) mixing 1g of nano-silicon, 25g of plastic (polyethylene, PE), 0.29g of ferric chloride and 3g of montmorillonite uniformly by a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out to obtain a nano-silicon/plastic/montmorillonite composite material;
(2) dissolving 2ml of TX-10 and 2g of trialkyl methyl ammonium chloride in 200ml of 3 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, adding 0.15mol of nano-silicon/plastic/montmorillonite composite material while stirring, controlling the molar ratio of n (HCl)/n (nano-silicon/plastic/montmorillonite composite material) to be 4: 1, stirring for 1h, standing and aging for 15h at room temperature, centrifuging, washing and drying to obtain the nano-silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is argon, the heating system of heat treatment is 2 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 8 hours, so as to obtain a first-stage sintered product;
and (2) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and argon, the heating system of heat treatment is 6 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and subjected to vibration classification to obtain the Si/GC/SiOxA composite material.
The Si/GC/SiO solid obtained in example 6 was mixedxComposite materials electrodes, assembled cells and tested for performance were prepared in the same manner as in example 1.
Comparative example 1
(1) Mixing 1g of nano silicon, 25g of plastic (PP) and 3g of montmorillonite uniformly in a mechanical grinding mode, placing the mixture in a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out;
(2) dissolving 2ml of NP-8.6 and 2g of trialkyl methyl ammonium chloride in 200ml of hydrochloric acid solution of 3 mol/L until the surfactant is completely dissolved and the solution becomes clear, adding 0.15mol of the material obtained in the step (1) while stirring, controlling the molar ratio of n (HCl)/n (material) to be 4: 1, stirring for 1h, standing and aging for 15h at room temperature, centrifuging, washing and drying;
(3) placing the material obtained in the step (2) in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is argon, the heating system of heat treatment is 2 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 8 hours, so as to obtain a first-stage sintered product;
and (3) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and argon, the heating system of heat treatment is 6 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and classified by vibration to obtain the silicon-based composite material.
The silicon-based composite material obtained in comparative example 1 was used to prepare an electrode, assemble a battery and test the performance in the same manner as in example 1.
Comparative example 2
(1) Mixing 1g of nano silicon, 25g of plastic (PP) and 0.26g of nickel acetate in a mechanical grinding mode, putting the mixture into a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out;
(2) dissolving 2ml of NP-8.6 and 2g of trialkyl methyl ammonium chloride in 200ml of hydrochloric acid solution of 3 mol/L until the surfactant is completely dissolved and the solution becomes clear, adding 0.15mol of the material obtained in the step (1) while stirring, controlling the molar ratio of n (HCl)/n (material) to be 4: 1, stirring for 1h, standing and aging for 15h at room temperature, centrifuging, washing and drying;
(3) placing the material obtained in the step (2) in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is argon, the heating system of heat treatment is 2 ℃/min, the heat preservation temperature is 650 ℃, and the heat preservation time is 8 hours, so as to obtain a first-stage sintered product;
and (3) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and argon, the heating system of heat treatment is 6 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and classified by vibration to obtain the silicon-based composite material.
The silicon-based composite material obtained in comparative example 2 was used to prepare an electrode, assemble a battery and test the performance in the same manner as in example 1.
Comparative example 3
(1) Mixing 1g of nano silicon, 25g of plastic (PP), 0.29g of nickel acetate and 3g of montmorillonite uniformly in a mechanical grinding mode, putting the mixture into a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 50rpm, stirring for 8 hours, controlling the processing temperature of the extruder to be 250 ℃, extruding and granulating, cooling to room temperature, and taking out;
(2) dissolving 2ml of NP-8.6 and 2g of trialkyl methyl ammonium chloride in 200ml of hydrochloric acid solution of 3 mol/L until the surfactant is completely dissolved and the solution becomes clear, adding 0.15mol of the material obtained in the step (1) while stirring, controlling the molar ratio of n (HCl)/n (material) to be 4: 1, stirring for 1h, standing and aging for 15h at room temperature, centrifuging, washing and drying;
(3) and (3) placing the material obtained in the step (2) into a tubular furnace for sintering treatment, wherein the sintering atmosphere is a mixed gas of hydrogen and argon, the heating system of the heat treatment is 5 ℃/min, the heat preservation temperature is 1100 ℃, the heat preservation time is 6h, after sintering is finished, naturally cooling to room temperature, and mechanically crushing and vibrating and grading the product to obtain the silicon-based composite material.
The silicon-based composite material obtained in comparative example 3 was used to prepare an electrode, assemble a battery and test the performance in the same manner as in example 1.
Comparative example 4
(1) Mixing 1g of nano silicon, 10g of plastic (PP), 0.1g of nickel acetate and 10g of montmorillonite in a mechanical grinding mode, putting the mixture into a double-screw extruder, controlling the melting condition, controlling the screw rotating speed of the extruder to be 20rpm, stirring for 2 hours, controlling the processing temperature of the extruder to be 200 ℃, extruding and granulating, cooling to room temperature, and taking out;
(2) dissolving 5ml of NP-8.6 and 5g of trialkyl methyl ammonium chloride in 100ml of 0.5 mol/L hydrochloric acid solution until the surfactant is completely dissolved and the solution becomes clear, adding 0.5mol of the material obtained in the step (1) while stirring, controlling the molar ratio of n (HCl)/n (material) to be 1: 10, stirring for 5 hours, standing and aging for 5 hours at room temperature, then centrifuging, washing and drying;
(3) placing the material obtained in the step (2) in a tubular furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is argon, the heating system of heat treatment is 10 ℃/min, the heat preservation temperature is 400 ℃, and the heat preservation time is 20 hours, so as to obtain a first-stage sintered product;
and (3) performing second-stage reduction atmosphere sintering on the first-stage sintered product, wherein the reduction atmosphere is a mixed gas of hydrogen and argon, the heating system of heat treatment is 20 ℃/min, the heat preservation temperature is 700 ℃, the heat preservation time is 10 hours, the product is naturally cooled to room temperature after sintering is finished, and the product is mechanically crushed and classified by vibration to obtain the silicon-based composite material.
The silicon-based composite material obtained in comparative example 4 was used to prepare an electrode, assemble a battery and test the performance in the same manner as in example 1.
FIG. 2 shows the present inventionWhile the Si/GC/SiOxThe structural schematic diagram of the composite material is a wool ball structure of the silica-coated nano-silicon and graphitized carbon fiber tube. FIG. 3 is the Si/GC/SiO solid prepared in example 4xThe XRD pattern of the composite material shows that the obtained sample has a distinct broad peak in the range of 10 to 40 ° 2 θ, and shows characteristic peaks of crystal planes of Si (111), (220), and (311) near 28.6 °, 47.6 °, and 56.2 ° 2 θ, corresponding to the amorphous characteristic of SiOx. FIG. 4 is the Si/GC/SiO solid prepared in example 4xTransmission Electron Microscopy (TEM) of the composite material, and as can be seen from the TEM, nano silicon, graphitized carbon fiber tube and silicon monoxide are compounded to form the Si/GC/SiOxA composite material.
The results of testing the silicon-based composite materials obtained in examples 1 to 6 and comparative examples 1 to 4 on a lithium half cell are shown in table 1, and it can be seen from the results of the electrochemical performance test that examples 1 to 6 all have good comprehensive electrochemical performance in the lithium ion half cell.
TABLE 1 electrochemical Performance test results of silicon-based composites obtained in examples 1-6 and comparative examples 1-4
In comparative example 1, no heavy metal salt was added, so that the added high molecular polymer PP plastic could not form a linear fiber tubular structure, and in the heat treatment process, carbon prepared by carbonizing the PP plastic did not have graphitization property, and was poor in conductivity, and further poor in electrochemical performance.
In comparative example 2, because no montmorillonite is added, the agglomeration phenomenon in the melting and solidifying process of PP plastic cannot be inhibited in the material preparation process, and the montmorillonite can not be used as a silicon source to realize the uniform coating of the silica, the electrochemical performance is poor.
In comparative example 3, since two-stage sintering is not performed, carbonization and carbothermic reduction effects are poor, and the PP plastic can not be carbonized well, and the silica can not be reduced, so that the electrochemical performance is poor.
In comparative example 4, the prepared parameters are not matched ideally, and the selected parameters are not in the preferred range, so that the structure and the morphology of the material cannot be well controlled in the preparation process of the material, and the electrochemical performance is poor.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (9)
1. A preparation method of a silicon-based composite material for a lithium ion power battery is characterized by comprising the following steps:
taking nano-silicon, plastic and montmorillonite as raw materials, adding heavy metal salt as a catalyst, mixing the raw materials and the catalyst, and then extruding and granulating under a melting condition to obtain a nano-silicon/plastic/montmorillonite composite material;
adding a nonionic surfactant and a cationic surfactant into a hydrochloric acid solution to obtain a mixed solution, adding the nano-silicon/plastic/montmorillonite composite material into the mixed solution, and standing for aging reaction to obtain a nano-silicon/plastic/silicon dioxide composite material;
carrying out carbothermic reduction on the nano silicon/plastic/silicon dioxide composite material to obtain a nano silicon/graphitized carbon/silicon monoxide composite material, namely the silicon-based composite material for the lithium ion power battery;
the plastic is one or more of polypropylene, polyethylene and polystyrene;
the heavy metal salt is one or more of nickel salt, cobalt salt, ferric salt and manganese salt;
the carbothermic reduction is two-stage sintering, and comprises the following specific steps: and (3) placing the nano silicon/plastic/silicon dioxide composite material in a tubular furnace to perform first-stage inert atmosphere sintering, and performing second-stage reducing atmosphere sintering on the first-stage sintered product.
2. The preparation method of the silicon-based composite material for the lithium ion power battery according to claim 1, wherein the mass ratio of the nano silicon to the plastic to the montmorillonite is (1-5): (20-40): (2-10).
3. The preparation method of the silicon-based composite material for the lithium ion power battery as claimed in claim 1 or 2, wherein the particle size of the nano silicon is 100-500 nm.
4. The preparation method of the silicon-based composite material for the lithium ion power battery as claimed in claim 1 or 2, wherein the addition amount of the heavy metal salt is 1-5 wt% of the raw material.
5. The preparation method of the silicon-based composite material for the lithium ion power battery according to claim 4, wherein the nickel salt is one or more of nickel nitrate, nickel acetate, nickel sulfate and nickel chloride; the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt sulfate and cobalt chloride; the ferric salt is one or more of ferric nitrate, ferric acetate, ferric sulfate and ferric chloride; the manganese salt is one or more of manganese nitrate, manganese acetate, manganese sulfate and manganese chloride.
6. The preparation method of the silicon-based composite material for the lithium ion power battery according to claim 1 or 2, wherein the nonionic surfactant is one or more of Triton X2100, OP-10, TX-10 and NP-8.6, and the addition amount of the nonionic surfactant is 5-10 wt% of the nano silicon/plastic/montmorillonite composite material; the cationic surfactant is one or more of cetyl trimethyl quaternary ammonium bromide, octadecyl dimethyl benzyl quaternary ammonium chloride, trialkyl ammonium chloride and trialkyl methyl ammonium chloride, and the addition amount of the cationic surfactant is 15-20 wt% of the nano silicon/plastic/montmorillonite composite material.
7. The preparation method of the silicon-based composite material for the lithium ion power battery as claimed in claim 1 or 2, wherein the concentration of the hydrochloric acid solution is 1-5 mol/L, and the molar ratio of the hydrochloric acid to the nano silicon/plastic/montmorillonite composite material is (1-10): 1.
8. The preparation method of the silicon-based composite material for the lithium ion power battery according to claim 1, which is characterized by comprising the following steps:
(1) uniformly mixing nano silicon, plastic, heavy metal salt and montmorillonite, placing the mixture in a double-screw extruder, controlling the melting condition, carrying out extrusion granulation at the set screw rotating speed and processing temperature, cooling to room temperature, and taking out to obtain a nano silicon/plastic/montmorillonite composite material;
(2) dissolving a predetermined amount of nonionic surfactant and a predetermined amount of cationic surfactant in a hydrochloric acid solution, adding the nano silicon/plastic/montmorillonite composite material obtained in the step (1) while stirring until the surfactant is completely dissolved and the solution becomes clear, stirring for 0.5-2 h, standing and aging for 10-20 h at room temperature, centrifuging, washing, and drying to obtain a nano silicon/plastic/silicon dioxide composite material;
(3) placing the nano silicon/plastic/silicon dioxide composite material obtained in the step (2) into a tube furnace to perform first-stage inert atmosphere sintering, wherein the inert atmosphere is selected from one or more of helium, argon, neon and nitrogen, the heating system of heat treatment is 1-10 ℃/min, the heat preservation temperature is 500-800 ℃, and the heat preservation time is 2-12 hours, so as to obtain a first-stage sintered product;
and carrying out second-stage reduction atmosphere sintering on the first-stage sintering product, wherein the reduction atmosphere is selected from one or more of hydrogen, helium, argon, neon and nitrogen, the heating system of heat treatment is 5-20 ℃/min, the heat preservation temperature is 900-1500 ℃, the heat preservation time is 2-12 h, the product is naturally cooled to room temperature after sintering is finished, and the product is crushed and classified to obtain the silicon-based composite material for the lithium ion power battery.
9. The nano silicon/graphitized carbon/silicon monoxide composite material prepared by the preparation method according to any one of claims 1 to 8, wherein the silicon monoxide is a coating layer, the graphitized carbon and the nano silicon are used as a matrix, the nano silicon/graphitized carbon/silicon monoxide composite material forms a core-shell structure, the particle size of the nano silicon/graphitized carbon/silicon monoxide composite material is 10 to 30um, and the mass ratio of the nano silicon to the graphitized carbon is 1: (1-10), and the content of the silicon monoxide is 2-5 wt% of the nano silicon/graphitized carbon/silicon monoxide composite material.
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