CN111082013B - Preparation method of carbon-coated nitrogen-magnesium doped porous silicon-based composite material and lithium ion battery - Google Patents
Preparation method of carbon-coated nitrogen-magnesium doped porous silicon-based composite material and lithium ion battery Download PDFInfo
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Abstract
The invention relates to the field of battery material preparation methods, and discloses a preparation method of a carbon-coated nitrogen-magnesium doped porous silicon-based composite material and a lithium ion battery, wherein the method comprises the following steps: dropwise adding a carbon source solution into the nano silicon dioxide powder, and then carrying out high-temperature carbonization operation in a nitrogen atmosphere to obtain a carbon-coated nitrogen-doped silicon dioxide material; carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material in a reducing atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; etching the carbon-coated nitrogen-doped silicon-based composite material to obtain a carbon-coated nitrogen-doped porous silicon-based composite material; carrying out ultrasonic dispersion operation on the carbon-coated nitrogen-doped porous silicon-based composite material to obtain a dispersed mixed turbid solution; and adding the dispersed mixed turbid solution into the magnesium source mixed solution, and then performing separation, washing and drying operations to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material. The method can effectively inhibit the volume expansion of silicon and effectively improve the conductivity and the first effect of the silicon-carbon material.
Description
Technical Field
The invention relates to the field of battery material preparation methods, in particular to a preparation method of a carbon-coated nitrogen-magnesium doped porous silicon-based composite material and a lithium ion battery.
Background
In recent years, lithium ion batteries have been widely used in vehicles, portable electronic devices, hybrid vehicles, electric vehicles, and the like because of their advantages such as high energy, high energy density, good cycle performance, and environmental friendliness. Currently, the negative electrode material of lithium ion batteries used in commercial fields is generally graphite. However, the theoretical specific capacity of the graphite is only 372mAh/g, so that the practical application of the lithium ion battery as a power battery in the fields of traffic, energy storage and the like is restricted. Silicon, silicon-based alloy, silicon oxide and the like have higher theoretical specific capacity and better safety, and are ideal substitute materials of the lithium ion battery cathode material.
According to research, in the repeated lithium intercalation and deintercalation process of silicon carbon, the volume expansion of silicon carbon can be close to 150%, the pulverization of silicon carbon particles is caused, even the contact area with a current collector is reduced, under the condition that a conductive agent is not changed, the electron transmission is seriously hindered, the polarization is obviously increased, a series of side reactions in the battery are caused, the capacity begins to decay rapidly, and the first effect is lower. To conclude, inhibiting the volume expansion of silicon is the most effective way to ameliorate this phenomenon.
At present, most of the mature silicon-carbon cathode materials use liquid phase coating and gas phase coating means. The silicon particles are usually obtained by high-energy ball milling and crushing of large-particle silicon blocks, the silicon particles obtained by the method are large in particle diameter ratio and solid, the volume expansion of silicon cannot be effectively relieved by the structure, and the problems that the conductivity of a silicon-carbon negative electrode material is weak and the first effect is low due to overlarge polarization generally exist. At present, the main method for improving the first effect of enterprises is to supplement lithium, however, lithium powder is a flammable and corrosive substance, the condition for supplementing lithium is harsh, strict protection measures need to be made, and the lithium powder is added into a silicon-carbon negative electrode material in a strict oxygen-free environment, so that combustion and even explosion accidents can be easily caused if oxygen leaks in the process of supplementing lithium, and the cost for supplementing lithium is high, the safety is low, and the method is not suitable for large-scale popularization and use.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides the preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material and the lithium ion battery, which have the advantages of low cost, high safety and strong operability, and can effectively inhibit the volume expansion of silicon and effectively improve the conductivity and the first effect of a silicon-carbon material.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a carbon-coated nitrogen-magnesium doped porous silicon-based composite material comprises the following steps:
dropwise adding a carbon source solution into the nano silicon dioxide powder to obtain a mixed turbid solution; pre-oxidizing the mixed turbid liquid, and then performing high-temperature carbonization in a nitrogen atmosphere to obtain a carbon-coated nitrogen-doped silicon dioxide material;
carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material in a reducing atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; adding an etching solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain a carbon-coated nitrogen-doped porous silicon-based composite material;
adding the carbon-coated nitrogen-doped porous silicon-based composite material into a solvent, and performing ultrasonic dispersion operation to obtain a dispersed mixed turbid solution; mixing the magnesium source solution, alkali liquor and sodium borohydride solution to obtain a magnesium source mixed solution; and adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring for reaction, and then performing separation operation, washing operation and drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
In one embodiment, before the operation of dropwise adding the carbon source solution into the nano-silica powder, a sodium lignosulfonate solution and a polyacrylonitrile solution are further mixed to obtain the carbon source solution.
In one embodiment, before the operation of dropping the carbon source solution into the nano-silica powder, a silicon source, a template agent and an alkali solution are further mixed, and stirred to react to obtain a nano-silica gel, and then subjected to a separation operation, a washing operation and a drying operation to obtain the nano-silica powder.
In one embodiment, the stoichiometric ratio of the magnesium source solution to the sodium borohydride solution is 5-8: 1; the pH value of the magnesium source mixed solution is 9-12.
In one embodiment, the temperature of the pre-oxidation operation is 180-240 ℃, and the time of the pre-oxidation operation is 6-8 h.
In one embodiment, the high-temperature carbonization operation comprises a first stage and a second stage, wherein the temperature of the first stage is 200-400 ℃, and the time of the first stage is 20-40 min; the temperature of the second stage is 800-1200 ℃, and the time of the second stage is 3-6 h.
In one embodiment, the temperature of the high-temperature reduction operation is 1000-1400 ℃, and the time of the high-temperature reduction operation is 2-3 h.
In one embodiment, the nano-silica powder has a particle size of 20nm to 50 nm.
In one embodiment, the carbon source solution is at least one of sodium lignosulfonate, polyacrylonitrile, a phenolic resin, an epoxy resin and an acrylonitrile polymer; or the magnesium source solution is at least one of magnesium chloride, magnesium carbonate and magnesium nitrate.
A lithium ion battery comprises the carbon-coated nitrogen-magnesium doped porous silicon-based composite material prepared by the preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
Compared with the prior art, the invention has at least the following advantages:
the method is low in cost, high in safety and high in operability. The method comprises the steps of coating nano silicon dioxide by a liquid phase, reducing partial silicon dioxide after pre-oxidation and carbonization, and etching to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material. The silicon particle size is 20 nm-50 nm, the volume expansion is reduced greatly, the porous structure is combined, enough space is reserved for the silicon to shrink in the process of repeatedly releasing and embedding lithium, and in addition, the carbon coating on the silicon surface can effectively inhibit the volume expansion, and nitrogen and magnesium are further doped to inhibit the volume expansion of the silicon, so that the electronic conductivity of carbon is improved, and the first effect of the silicon is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flowchart illustrating steps of a method for preparing a carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to an embodiment of the present invention.
Fig. 3 is a first charge-discharge curve diagram of the lithium ion battery of example 2 of the present invention and the lithium ion battery of comparative example 1.
Fig. 4 is a graph of electrochemical impedance curves for the lithium ion battery of example 2 of the present invention and the lithium ion battery of comparative example 1.
Fig. 5 is a graph of the cycle capacity of the lithium ion battery of example 2 of the present invention and the lithium ion battery of comparative example 1.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, referring to fig. 1, a method for preparing a carbon-clad nitrogen-magnesium doped porous silicon-based composite material includes the following steps:
s110, dropwise adding a carbon source solution into the nano silicon dioxide powder to obtain a mixed turbid solution; pre-oxidizing the mixed turbid liquid, and then performing high-temperature carbonization in a nitrogen atmosphere to obtain a carbon-coated nitrogen-doped silicon dioxide material;
s120, carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material in a reducing atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; adding an etching solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain a carbon-coated nitrogen-doped porous silicon-based composite material;
s130, adding the carbon-coated nitrogen-doped porous silicon-based composite material into a solvent, and performing ultrasonic dispersion operation to obtain a dispersed mixed turbid solution; mixing the magnesium source solution, alkali liquor and sodium borohydride solution to obtain a magnesium source mixed solution; and adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring for reaction, and then performing separation operation, washing operation and drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
It should be noted that the method is low in cost, high in safety and strong in operability. To more clearly express the composition of matter, the carbon-coated nitrogen-doped silica material may be expressed as N-SiO2a/C powder material; the carbon-coated nitrogen-doped silicon-based composite material can be expressed as N-SiO2/SiOxa/Si/C powder material; the carbon-coated nitrogen-doped Porous silicon-based composite material can be expressed as Port-N-SiOxa/Si/C powder material, with ports being Porous; the carbon-coated nitrogen-magnesium doped Porous silicon-based composite material can be expressed as ports-N-Mg-SiOx-Si/C powder material.
1. The inherent conductivity and electrolyte wettability of silicon are poor, while the conductivity and electrolyte wettability of carbon are far superior to that of silicon, so that the carbon coating can compensate the defect of silicon. In addition, the carbon coating can effectively release the stress caused by the volume expansion of the nano silicon particles in the silicon coating, and can weaken the volume expansion of the siliconAnd the pulverization and the crushing of the silicon are prevented. 2. Carbon has rich pi electrons which are inert, the electronegativity of carbon atoms is 2.55, nitrogen atoms are doped in an electron supply mode, the electronegativity of the nitrogen atoms is 3.04 which is larger than that of the carbon atoms, and the difference of the electronegativity of the nitrogen atoms and the electronegativity of the carbon atoms can change the charge distribution of the carbon material, so that the pi electrons become active, the electron transmission is facilitated, and the conductive capability is enhanced. 3. When the Si-based negative electrode is firstly intercalated with lithium to form an SEI film, Li is intercalated into SiOxIn (B), such as Li is formed2O，Li2Si2O5，Li2SiO3，Li4SiO4And the like, which is the first cause of low coulombic efficiency. However, the doped magnesium element is easy to be mixed with the Porous-N-SiOxActive oxygen in/Si/C forms MgSiO or MgCO which are inert to lithium3Thus, active oxygen is consumed before the film is formed by lithium intercalation, so that the generation amount of irreversible lithium silicate is reduced when the SEI film is formed by lithium intercalation for the first time, and the first coulombic efficiency is improved. 4. Silicon with nano-grade grain diameter is selected, the volume expansion of the silicon is reduced greatly, and the silicon is combined with ports-N-Mg-SiOxThe porous structure of Si/C is sufficient for providing silicon with volume shrinkage in the process of repeatedly releasing and inserting lithium, and the volume expansion of silicon particles in the process of releasing and inserting lithium can be effectively buffered, so that the cycling stability of silicon is improved. Therefore, the method can effectively inhibit the volume expansion of silicon and effectively improve the conductivity and the first effect of the silicon-carbon material.
In one embodiment, referring to fig. 2, the carbon-coated nitrogen-magnesium doped porous silicon-based composite material includes a nitrogen-magnesium doped porous silicon-based core and a carbon coating layer, wherein the carbon coating layer is coated on an outer surface of the nitrogen-magnesium doped porous silicon-based core.
In order to further relieve the volume expansion of silicon, in one embodiment, the nano-silica powder has a particle size of 20nm to 50 nm. For example, the particle size of the nano-silica powder is 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, or 50 nm. This can further alleviate the volume expansion of silicon.
In one embodiment, before the operation of dropping the carbon source solution into the nano-silica powder, a silicon source, a template agent and an alkali solution are mixed, and stirred to react to obtain a nano-silica gel, and then subjected to a separation operation, a washing operation and a drying operation to obtain the nano-silica powder. For example, a common silicon source is tetraethyl orthosilicate, and other silicon sources such as isopropyl silicate, triethylorthosilicate, bis (sec-butanol) orthosilicate aluminum salt, tetrakis (2-methoxyethanol) silicate, tetrakis (2-methoxy-1-methylethyl) silicate, tetrakis (2-ethylhexyl) silicate, tetrakis [2- (2-methoxyethoxy) ethyl ] silicate, tetraisothiocyanatosilicate, dimethiconol, methylsilanol, and the like are also possible. As another example, a common templating agent is cetyltrimethylammonium bromide, as may other prior templating agents. For another example, the common alkali solutions are sodium hydroxide, potassium hydroxide and ammonia water, and other existing alkali solutions are also available. For example, the particle size of the silicon dioxide prepared by using tetraethyl orthosilicate as a silicon source and cetyl trimethyl ammonium bromide as a template agent and adopting the sol-gel and homogeneous precipitation combined method is lower, only 20 nm-50 nm, and the volume expansion of silicon can be effectively relieved.
In one embodiment, the carbon source solution is at least one of sodium lignosulfonate, polyacrylonitrile, a phenolic resin, an epoxy resin and an acrylonitrile polymer. For example, the carbon source solution is a common mixture of sodium lignosulfonate, polyacrylonitrile, a phenol resin, an epoxy resin and an acrylonitrile polymer. For example, the carbon source solution is sodium lignosulfonate, polyacrylonitrile, a phenol resin, an epoxy resin, or an acrylonitrile polymer. For example, the carbon source solution is sodium lignosulfonate and polyacrylonitrile, wherein the mass ratio of the sodium lignosulfonate to the polyacrylonitrile is 1: 1.
In order to further reduce the cost of the method, in one embodiment, before the operation of adding the carbon source solution dropwise to the nano-silica powder, a sodium lignosulfonate solution and a polyacrylonitrile solution are further mixed to obtain the carbon source solution. Wherein the solid content of the sodium lignin sulfonate solution is 15 percent, and the solid content of the polyacrylonitrile solution is 15 percent. Therefore, by selecting sodium lignosulfonate, a papermaking waste liquid and compounding polyacrylonitrile with the same low price as a carbon source, the cost of the method can be effectively reduced.
In one embodiment, after the operation of dropping the carbon source solution into the nano silica powder, the mixture is further allowed to stand for 2 to 4 hours to be sufficiently mixed. For example, the standing time is 2h, 2.5h, 3h, 3.5h or 4 h. It should be noted that stirring may cause the carbon coating to be broken and irregular, and preferably, the carbon coating is formed on the outer surface of the nano silica particles in a more gentle manner such as standing.
In order to further enhance the oxidation effect on the mixed slurry, in one embodiment, the pre-oxidation operation is performed at a temperature of 180 ℃ to 240 ℃, for example, at 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, or 240 ℃. The pre-oxidation operation time is 6h to 8h, for example, 6h, 6.5h, 7h, 7.5h or 8 h. This can further improve the oxidation effect on the mixed turbid liquid.
In order to further enhance the carbonization effect on the mixed turbid liquid, in one embodiment, the high-temperature carbonization operation includes a first stage and a second stage, the first stage is a preheating stage, and the temperature of the first stage is 200 ℃ to 400 ℃, for example, the temperature of the first stage is 200 ℃, 220 ℃, 250 ℃, 280 ℃, 300 ℃, 330 ℃, 350 ℃, 370 ℃ or 400 ℃; the time of the first stage is 20min to 40min, for example, the time of the first stage is 20min, 23min, 25min, 28min, 30min, 33min, 35min, 38min or 40 min. This enables the second stage to be better performed. The second stage is a high temperature carbonization stage, the temperature of the second stage being 800 ℃ to 1200 ℃, for example, the temperature of the second stage being 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1200 ℃; the time of the second stage is 3h to 6h, for example, the time of the second stage is 3h, 3.5h, 4h, 4.5h, 5h, 5.5h or 6 h. This can further improve the carbonization effect on the mixed turbid liquid.
In order to further improve the reduction effect on the carbon-coated nitrogen-doped silica material, in one embodiment, the temperature of the high-temperature reduction operation is 1000 ℃ to 1400 ℃, for example, 1000 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, or 1400 ℃. The time of the high-temperature reduction operation is 2-3 h. For example, the high temperature reduction operation is performed for 2h, 2.2h, 2.5h, 2.7h or 3 h. Thus, the reduction effect of the carbon-coated nitrogen-doped silicon dioxide material can be further improved.
In order to further improve the reduction effect on the carbon-coated nitrogen-doped silica material, in one embodiment, the reducing atmosphere is at least one of hydrogen, argon and ammonia. Thus, the reduction effect of the carbon-coated nitrogen-doped silicon dioxide material can be further improved.
In order to further improve the etching effect on the carbon-coated nitrogen-doped silicon-based composite material, in one embodiment, the etching solution is hydrofluoric acid or sodium hydroxide. For example, the etching solution is hydrofluoric acid; for example, the etching solution is sodium hydroxide; for example, the etching solution is a saturated hot sodium hydroxide solution. Therefore, the etching effect on the carbon-coated nitrogen-doped silicon-based composite material can be further improved, and the number of holes and the size of the hole diameter of the particles of the carbon-coated nitrogen-doped porous silicon-based composite material are moderate.
In order to further improve the dispersion effect of the carbon-coated nitrogen-doped porous silicon-based composite material, in one embodiment, the time of the ultrasonic dispersion operation is 20min to 40 min. For example, the time of the ultrasonic dispersion operation is 20min, 23min, 25min, 28min, 30min, 33min, 35min, 38min or 40 min. Therefore, the dispersion effect of the carbon-coated nitrogen-doped porous silicon-based composite material can be further improved.
In order to further improve the dispersion effect of the carbon-coated nitrogen-doped porous silicon-based composite material, in one embodiment, the solvent is deionized water, ethanol or ethylene glycol. Therefore, the dispersion effect of the carbon-coated nitrogen-doped porous silicon-based composite material can be further improved.
In one embodiment, the stoichiometric ratio of the magnesium source solution to the sodium borohydride solution is 5-8: 1. For example, the stoichiometric ratio of the magnesium source solution to the sodium borohydride solution is 5:1, 6:1, 7:1, or 8: 1. In one embodiment, the pH of the magnesium source mixed solution is 9 to 12. For example, the pH of the magnesium source mixed solution is 9, 9.5, 10, 10.5, 11. 11.5 or 12. For another example, in one embodiment, the sodium borohydride solution is at least one of sodium borohydride ethanol solution, sodium borohydride aqueous solution, and sodium borohydride ethylene glycol solution. As another example, in one embodiment, the magnesium source solution is at least one of magnesium chloride, magnesium carbonate, and magnesium nitrate. For another example, in one embodiment, the alkali solution is at least one of sodium hydroxide, potassium hydroxide and ammonia. Thus, under the alkaline condition, the magnesium source solution is reduced into magnesium by the sodium borohydride solution, and the magnesium is chemically converted into the magnesium by the Porous-N-SiOxThe synthesis method is relatively green and environment-friendly, has higher safety, lower cost and stronger operability.
In one embodiment, the stirring reaction time is 5 to 10 hours. For example, the stirring reaction time is 5h, 6h, 7h, 8h, 9h or 10 h. It should be noted that the doping content of the magnesium element and the particle size of the magnesium metal are controlled by the stirring reaction time, and when the stirring reaction time is 5 to 10 hours, the doping content of the magnesium element and the particle size of the magnesium metal in the carbon-coated nitrogen-magnesium doped porous silicon-based composite material are more appropriate.
In one embodiment, a lithium ion battery includes the carbon-coated nitrogen-magnesium doped porous silicon-based composite material prepared by the preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to any one of the above embodiments.
Compared with the prior art, the invention has at least the following advantages:
the method is low in cost, high in safety and high in operability. The method comprises the steps of coating nano silicon dioxide by a liquid phase, reducing partial silicon dioxide after pre-oxidation and carbonization, and etching to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material. The silicon particle size is 20 nm-50 nm, the volume expansion is reduced greatly, the porous structure is combined, enough space is reserved for the silicon to shrink in the process of repeatedly releasing and embedding lithium, and in addition, the carbon coating on the silicon surface can effectively inhibit the volume expansion, and nitrogen and magnesium are further doped to inhibit the volume expansion of the silicon, so that the electronic conductivity of carbon is improved, and the first effect of the silicon is improved.
The following are specific examples of the preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material
Example 1
Tetraethyl orthosilicate, hexadecyl trimethyl ammonium bromide and sodium hydroxide are mixed and stirred for reaction to obtain nano-silica gel, and then the nano-silica gel is subjected to separation operation, washing operation and drying operation in sequence to obtain 20-50 nm nano-silica powder.
And mixing the sodium lignosulfonate solution with the solid content of 15% and the polyacrylonitrile solution with the solid content of 15% to obtain the carbon source solution.
Putting the nano silicon dioxide powder into a corundum porcelain boat, then dripping a carbon source solution, and standing for 2 hours to fully mix the nano silicon dioxide powder and the corundum porcelain boat to obtain a mixed turbid liquid; pre-oxidizing the mixed turbid solution at 180 deg.C and 240 deg.C for 3 hr (heating rate of 5 deg.C for min)-1) Placing in a tube furnace under nitrogen atmosphere, and maintaining at 300 deg.C for 30min (heating rate of 5 deg.C for min)-1) And then carbonizing the mixture for 4 hours at the temperature of 800 ℃ to obtain the carbon-coated nitrogen-doped silicon dioxide material.
Carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material for 2h at 1000 ℃ in a hydrogen and argon mixed atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; and adding a hydrofluoric acid solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain the carbon-coated nitrogen-doped porous silicon-based composite material.
Adding the carbon-coated nitrogen-doped porous silicon-based composite material into 200mL of deionized water, and performing ultrasonic dispersion operation for 30min to obtain a dispersed mixed turbid solution; mixing magnesium nitrate and sodium borohydride ethanol solution according to a molar ratio of 5:1, and then adding ammonia water to adjust the pH value to 9 to obtain a magnesium source mixed solution; and slowly adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring and reacting for 10 hours, sequentially carrying out centrifugal separation operation, washing to be neutral, and carrying out vacuum drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
Example 2
Tetraethyl orthosilicate, hexadecyl trimethyl ammonium bromide and sodium hydroxide are mixed and stirred for reaction to obtain nano-silica gel, and then the nano-silica gel is subjected to separation operation, washing operation and drying operation in sequence to obtain 20-50 nm nano-silica powder.
And mixing the sodium lignosulfonate solution with the solid content of 15% and the polyacrylonitrile solution with the solid content of 15% to obtain the carbon source solution.
Putting the nano silicon dioxide powder into a corundum porcelain boat, then dripping a carbon source solution, and standing for 2 hours to fully mix the nano silicon dioxide powder and the corundum porcelain boat to obtain a mixed turbid liquid; pre-oxidizing the mixed turbid solution at 180 deg.C and 240 deg.C for 3 hr (heating rate of 5 deg.C for min)-1) Placing in a tube furnace under nitrogen atmosphere, and maintaining at 300 deg.C for 30min (heating rate of 5 deg.C for min)-1) And then carbonizing the mixture for 4 hours at the temperature of 1000 ℃ to obtain the carbon-coated nitrogen-doped silicon dioxide material.
Carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material at 1000 ℃ for 4h under a hydrogen and argon mixed atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; and adding a hydrofluoric acid solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain the carbon-coated nitrogen-doped porous silicon-based composite material.
Adding the carbon-coated nitrogen-doped porous silicon-based composite material into 200mL of deionized water, and performing ultrasonic dispersion operation for 30min to obtain a dispersed mixed turbid solution; mixing magnesium chloride and sodium borohydride ethanol solution according to the molar ratio of 8:1, and then adding sodium hydroxide to adjust the pH value to 10 to obtain magnesium source mixed solution; and slowly adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring and reacting for 5 hours, sequentially carrying out centrifugal separation operation, washing to be neutral, and carrying out vacuum drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
Example 3
Tetraethyl orthosilicate, hexadecyl trimethyl ammonium bromide and sodium hydroxide are mixed and stirred for reaction to obtain nano-silica gel, and then the nano-silica gel is subjected to separation operation, washing operation and drying operation in sequence to obtain 20-50 nm nano-silica powder.
And mixing the sodium lignosulfonate solution with the solid content of 15% and the polyacrylonitrile solution with the solid content of 15% to obtain the carbon source solution.
Putting the nano silicon dioxide powder into a corundum porcelain boat, then dripping a carbon source solution, and standing for 2 hours to fully mix the nano silicon dioxide powder and the corundum porcelain boat to obtain a mixed turbid liquid; pre-oxidizing the mixed turbid solution at 180 deg.C and 240 deg.C for 3 hr (heating rate of 5 deg.C for min)-1) Placing in a tube furnace under nitrogen atmosphere, and maintaining at 300 deg.C for 30min (heating rate of 5 deg.C for min)-1) And then carbonizing the mixture for 4 hours at the temperature of 1200 ℃ to obtain the carbon-coated nitrogen-doped silicon dioxide material.
Carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material for 2h at 1000 ℃ in a hydrogen and argon mixed atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; and adding a saturated sodium hydroxide hot solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain the carbon-coated nitrogen-doped porous silicon-based composite material.
Adding the carbon-coated nitrogen-doped porous silicon-based composite material into 200mL of deionized water, and performing ultrasonic dispersion operation for 30min to obtain a dispersed mixed turbid solution; mixing magnesium chloride and sodium borohydride ethanol solution according to a molar ratio of 6:1, and then adding sodium hydroxide to adjust the pH value to 10 to obtain magnesium source mixed solution; and slowly adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring and reacting for 5 hours, sequentially carrying out centrifugal separation operation, washing to be neutral, and carrying out vacuum drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
Example 4
Mixing isopropyl silicate, cetyl trimethyl ammonium bromide and potassium hydroxide, stirring for reaction to obtain nano silica gel, and sequentially performing separation operation, washing operation and drying operation to obtain 20-50 nm nano silica powder.
Selecting phenolic resin solution as carbon source solution.
Putting the nano silicon dioxide powder into a corundum porcelain boat, then dripping a carbon source solution, and standing for 3 hours to fully mix the nano silicon dioxide powder and the corundum porcelain boat to obtain a mixed turbid liquid; pre-oxidizing the mixed turbid solution at 220 deg.C for 7h (heating rate of 5 deg.C for min)-1) Placing in a tube furnace under nitrogen atmosphere, and maintaining at 200 deg.C for 40min (heating rate of 5 deg.C for min)-1) And then carbonizing the mixture for 6 hours at the temperature of 1000 ℃ to obtain the carbon-coated nitrogen-doped silicon dioxide material.
Carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material at 1200 ℃ for 3h under a hydrogen and argon mixed atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; and adding a saturated sodium hydroxide hot solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain the carbon-coated nitrogen-doped porous silicon-based composite material.
Adding the carbon-coated nitrogen-doped porous silicon-based composite material into 200mL of ethanol, and performing ultrasonic dispersion operation for 20min to obtain a dispersed mixed turbid solution; mixing magnesium chloride and an aqueous solution of sodium borohydride according to a molar ratio of 6:1, and then adding sodium hydroxide to adjust the pH value to 11 to obtain a magnesium source mixed solution; and slowly adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring and reacting for 7 hours, sequentially carrying out centrifugal separation operation, washing to be neutral, and carrying out vacuum drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
Example 5
Mixing tetra (2-ethylhexyl) silicate, hexadecyl trimethyl ammonium bromide and ammonia water, stirring for reaction to obtain nano silicon dioxide gel, and sequentially performing separation operation, washing operation and drying operation to obtain 20-50 nm nano silicon dioxide powder.
And mixing the epoxy resin solution and the acrylonitrile polymer solution to obtain the carbon source solution.
Putting the nano silicon dioxide powder into a corundum porcelain boat, then dripping a carbon source solution, and standing for 4 hours to fully mix the nano silicon dioxide powder and the corundum porcelain boat to obtain a mixed turbid liquid; pre-oxidizing the mixed turbid solution in air at 200 deg.C for 8h (heating rate of 5 deg.C for min)-1) Placing in a tube furnace under nitrogen atmosphere, and maintaining at 400 deg.C for 20min (heating rate of 5 deg.C for min)-1) And then carbonizing the mixture for 3 hours at the temperature of 1000 ℃ to obtain the carbon-coated nitrogen-doped silicon dioxide material.
Carrying out high-temperature reduction operation at 1400 ℃ for 2.5h on the carbon-coated nitrogen-doped silicon dioxide material under the mixed atmosphere of hydrogen and argon to obtain a carbon-coated nitrogen-doped silicon-based composite material; and adding a saturated sodium hydroxide hot solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain the carbon-coated nitrogen-doped porous silicon-based composite material.
Adding the carbon-coated nitrogen-doped porous silicon-based composite material into 200mL of ethylene glycol, and performing ultrasonic dispersion operation for 40min to obtain a dispersed mixed turbid solution; mixing magnesium carbonate and sodium borohydride glycol solution according to a molar ratio of 7:1, and then adding potassium hydroxide to adjust the pH value to 12 to obtain a magnesium source mixed solution; and slowly adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring and reacting for 8 hours, sequentially carrying out centrifugal separation operation, washing to be neutral, and carrying out vacuum drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
Comparative example 1
The silicon carbon material which is relatively common in the market is expressed by Si/C.
Experiment: the carbon-coated nitrogen-magnesium doped Porous silicon-based composite materials obtained in the embodiments 1 to 5 are respectively prepared according to the following mass ratio of Port-N-Mg-SiOx-Si/C: SP: preparing a working electrode by PVDF 70:15:15, matching with a metal lithium sheet and 1M LiPF electrolyte6(EC: EMC: DEC ═ 1:1:1), nickel foam, positive and negative electrode cases assembled CR2032 button cell. Thus, CR2032 button cells of examples 1 to 5 were prepared, respectively. The silicon carbon material of comparative example 1 was prepared in terms of Si/C: SP: preparing a working electrode by PVDF (70: 15: 15), matching with a metal lithium sheet, electrolyte 1M LiPF6 (EC: EMC: DEC: 1:1:1), foamed nickel and positive and negative electrode shells to assemble a CR2032 button cell. The CR2032 button cell of comparative example 1 was prepared in this way. The first charge and discharge current of 0.05C/0.05 was used to perform the charge and discharge experiments on the above listed CR2032 button cell, and the later cycle charge and discharge current of 0.25C/0.25 was used to perform the charge and discharge experiments on the above listed CR2032 button cell, and the experimental results are shown in FIGS. 3-5.
And (3) analyzing an experimental result: as is apparent from FIG. 3, the first lithium intercalation polarization of the Porous-N-Mg-SiOx-Si/C of example 2 as the negative electrode material of the lithium ion battery is 85% and is significantly higher than 76% of the Si/C of comparative example 1, and from the first charge-discharge curves of the two, it can be inferred that the first lithium intercalation polarization of the Porous-N-Mg-SiOx-Si/C of example 2 is significantly lower than that of the Si/C of comparative example 1, which is the most important reason for the difference between the first lithium intercalation polarization and the first lithium intercalation polarization.
In FIG. 4, it can be determined from the radius of the semi-circle of the electrochemical impedance curve of the two, that the charge transfer impedance of the port-N-Mg-SiOx-Si/C of example 2 is smaller, which also means that the port-N-Mg-SiOx-Si/C of example 2 is more beneficial to the rapid conduction of electrons during the lithium deintercalation process, and the conductivity is better.
In FIG. 5, from the battery capacity curves of the two, the difference between the capacity retention rate of Si/C in comparative example 1 and the capacity retention rate of Port-N-Mg-SiOx-Si/C in example 2 is not large in the first 200 cycles, but the difference gradually expands after 200 cycles, and the circulating capacity retention rate of Si/C in comparative example 1 jumps directly and is vertically and greatly reduced in the 300 cycles. The reason for this difference is probably related to that the Si/C of the comparative example 1 has too large volume expansion in the process of repeatedly releasing and inserting lithium, which causes pulverization of silicon materials, thereby causing complete destruction of conductive network and polarization increase, and on the contrary, the Porous structure of the ports-N-Mg-SiOx-Si/C and the silicon particles with nano-scale particle size of the example 2 can effectively inhibit volume expansion, so that the retention rate of the circulation capacity is more stable, and the occurrence of water jump of the circulation capacity can be avoided.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a carbon-coated nitrogen-magnesium doped porous silicon-based composite material is characterized by comprising the following steps:
dropwise adding a carbon source solution into the nano silicon dioxide powder to obtain a mixed turbid solution; pre-oxidizing the mixed turbid liquid, and then performing high-temperature carbonization in a nitrogen atmosphere to obtain a carbon-coated nitrogen-doped silicon dioxide material;
carrying out high-temperature reduction operation on the carbon-coated nitrogen-doped silicon dioxide material in a reducing atmosphere to obtain a carbon-coated nitrogen-doped silicon-based composite material; adding an etching solution into the carbon-coated nitrogen-doped silicon-based composite material, and performing etching operation to obtain a carbon-coated nitrogen-doped porous silicon-based composite material;
adding the carbon-coated nitrogen-doped porous silicon-based composite material into a solvent, and performing ultrasonic dispersion operation to obtain a dispersed mixed turbid solution; mixing the magnesium source solution, alkali liquor and sodium borohydride solution to obtain a magnesium source mixed solution; and adding the magnesium source mixed solution into the dispersed mixed turbid solution, stirring for reaction, and then performing separation operation, washing operation and drying operation to obtain the carbon-coated nitrogen-magnesium doped porous silicon-based composite material.
2. The method for preparing the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein before the operation of dropwise adding the carbon source solution into the nano-silica powder, a sodium lignosulfonate solution and a polyacrylonitrile solution are further mixed to obtain the carbon source solution.
3. The method for preparing the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein a silicon source, a template agent and an alkali solution are further mixed before the operation of dropwise adding the carbon source solution into the nano-silica powder, stirring reaction is performed to obtain nano-silica gel, and then separation operation, washing operation and drying operation are performed to obtain the nano-silica powder.
4. The preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein the pH of the magnesium source mixed solution is 9-12.
5. The preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein the pre-oxidation operation temperature is 180-240 ℃, and the pre-oxidation operation time is 6-8 h.
6. The method for preparing the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein the high-temperature carbonization operation comprises a first stage and a second stage, the temperature of the first stage is 200-400 ℃, and the time of the first stage is 20-40 min; the temperature of the second stage is 800-1200 ℃, and the time of the second stage is 3-6 h.
7. The method for preparing the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein the temperature of the high-temperature reduction operation is 1000-1400 ℃, and the time of the high-temperature reduction operation is 2-3 h.
8. The method for preparing the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein the particle size of the nano silicon dioxide powder is 20nm to 50 nm.
9. The method for preparing the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to claim 1, wherein the carbon source solution is at least one of sodium lignosulfonate, polyacrylonitrile, phenolic resin, epoxy resin and acrylonitrile polymer; the magnesium source solution is at least one of magnesium chloride, magnesium carbonate and magnesium nitrate.
10. A lithium ion battery comprises a negative electrode, and is characterized in that the negative electrode comprises the carbon-coated nitrogen-magnesium doped porous silicon-based composite material prepared by the preparation method of the carbon-coated nitrogen-magnesium doped porous silicon-based composite material according to any one of claims 1 to 9.
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