CN112447958A - Preparation method of negative electrode material of nitrogen-doped porous carbon-coated porous silicon dioxide - Google Patents
Preparation method of negative electrode material of nitrogen-doped porous carbon-coated porous silicon dioxide Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries and discloses a negative electrode material of nitrogen-doped porous carbon-coated porous silicon dioxide, wherein porous silicon dioxide nanospheres have ultrahigh specific surface area, nitrogen-containing alkali lignin is obtained through Mannich reaction and is subjected to substitution reaction with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to obtain quaternized nitrogen-containing alkali lignin with positive charge, the quaternized nitrogen-containing alkali lignin and the porous silicon dioxide nanospheres are subjected to electrostatic attraction and carbonized to obtain the nitrogen-doped porous carbon-coated porous silicon dioxide which is in a three-dimensional network structure, nitrogen doping is favorable for improving the electrochemical property of the porous carbon, the conductivity of the porous carbon is improved, the silicon dioxide is uniformly dispersed, lithium ion transmission is accelerated, the rate capability and the theoretical specific capacity are improved, the volume change of the silicon dioxide is inhibited by the porous carbon, the cycle performance of the negative electrode material is improved, and the negative electrode material, Rate capability and cycle capability.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a negative electrode material of nitrogen-doped porous carbon-coated porous silicon dioxide.
Background
The lithium ion battery has the advantages of large energy density, long service life and the like, and is widely applied to the fields of mobile power supplies, electronic equipment and the like, so that the development of the lithium ion battery with better performance and related materials thereof has important significance, but the negative electrode material of the current commercial lithium ion battery is graphite, has the defects of low theoretical specific capacity, easy generation of lithium dendrite due to large current and the like, and cannot meet the increasing requirements of people on the negative electrode material with large capacity and good rate capability.
The silicon-based material has higher safety and larger theoretical specific capacity, wherein the silicon dioxide has the advantages of large reserve capacity, low cost, higher theoretical specific capacity and the like, and has a great application prospect on the negative electrode material, but has the defects of serious volume effect, aggregation effect, poor conductivity and the like, so that the cycle performance and the rate capability of the silicon dioxide are poor, the application of the silicon dioxide is limited, and the porous carbon has good conductivity and almost no volume change, is widely applied to the negative electrode material, but has lower theoretical specific capacity, so that the problem is solved by adopting a mode of coating the porous silicon dioxide with the nitrogen-doped porous carbon.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method of a nitrogen-doped porous carbon-coated porous silicon dioxide cathode material, which solves the problems of poor cycle performance and poor rate performance of the silicon dioxide cathode material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the negative electrode material of the nitrogen-doped porous carbon-coated porous silicon dioxide comprises the following steps:
(1) adding deionized water, polyvinylpyrrolidone and nano-silica into a reaction bottle, wherein the mass ratio of the deionized water to the polyvinylpyrrolidone to the nano-silica is 170-200:10, placing the reaction bottle in a water bath ultrasonic device, ultrasonically dispersing the mixture uniformly, refluxing and cooling the mixture for 2 to 4 hours, adding a sodium hydroxide solution, stirring and reacting the mixture for 2 to 3 hours, centrifugally filtering the mixture, washing the mixture with the deionized water, placing the mixture in a muffle furnace, and reacting the mixture for 3 to 5 hours at the temperature of 400-500 ℃ to obtain porous silica nanospheres;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 60-80 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 80-100 ℃, dropwise adding a formaldehyde solution, reacting for 5-7h, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogenous alkali lignin into a reaction bottle, uniformly stirring, reacting at 70-100 ℃ for 3-5h, dialyzing, purifying, rotary-steaming and drying to obtain quaternized nitrogenous alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogenous alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, uniformly stirring, adding dilute sulfuric acid to adjust the pH to be 2-3, reacting at 140-180 ℃ for 1-2h, cooling, centrifuging and drying to obtain quaternized nitrogenous alkali lignin modified porous silicon dioxide nanospheres;
(5) and (3) placing the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, carbonizing and etching, washing with deionized water, and drying to obtain the nitrogen-doped porous carbon coated porous silicon dioxide cathode material.
Preferably, the water bath ultrasonic device in the step (1) comprises a main body, wherein a control module is movably connected to the left side of the main body, a heating module is movably connected to the bottom of the main body, a temperature detector is movably connected to the bottom of the main body, a water outlet is movably connected to the right side of the main body, a valve is movably connected to the top of the water outlet, a magnetic coil is movably connected to the right side of the main body, an ultrasonic probe is movably connected to the right side of the main body, a filter screen is movably connected to the middle of the main body, and.
Preferably, the mass ratio of the alkali lignin, the melamine and the formaldehyde in the step (2) is 100:15-25: 10-16.
Preferably, in the step (3), the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the sodium hydroxide to the nitrogenous alkali lignin is 40-60:5-8: 100.
Preferably, the mass ratio of the sodium dodecyl benzene sulfonate, the quaternized nitrogenous alkali lignin and the porous silica nanospheres in the step (4) is 5-15:100: 5-10.
Preferably, the carbonization and etching processes in the step (5) are carried out for 2-3h after the temperature is raised to 650 ℃ in the nitrogen atmosphere, and then the temperature is raised to 1000 ℃ in 800-.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the negative electrode material of the nitrogen-doped porous carbon-coated porous silicon dioxide is characterized in that a layer of polyvinylpyrrolidone is coated on the surface of the nano silicon dioxide, sodium hydroxide enters pores inside a sphere through surface pores to be etched, and the porous silicon dioxide nanospheres are obtained by calcining, are rich in pore structure and have ultrahigh specific surface area, in a formaldehyde solution, through a Mannich reaction process, hydrogen at the ortho position of phenolic hydroxyl groups of alkali lignin is replaced by formaldehyde, primary amine groups of melamine react with formaldehyde to obtain melamine-modified alkali lignin, rich nitrogen elements are introduced, in an alkaline environment, chlorine atoms of positively charged 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and hydrogen on the phenolic hydroxyl groups of the alkali lignin are subjected to substitution reaction and grafted onto the alkali lignin to obtain positively charged quaternized nitrogen-containing alkali lignin, the porous silicon dioxide nanospheres are electronegative and are subjected to electrostatic attraction with positively charged quaternized nitrogen-containing alkali lignin, the porous silicon dioxide nanospheres are highly dispersed in an alkali lignin matrix, and the porous silicon dioxide nanospheres are carbonized to obtain nitrogen-doped porous carbon uniformly coated with the porous silicon dioxide and uniformly dispersed in the porous carbon matrix.
The negative electrode material of porous silicon dioxide coated with nitrogen-doped porous carbon has the advantages that the nitrogen-doped porous carbon obtained by carbonizing and quaternizing the nitrogen-containing alkali lignin is of a three-dimensional network structure, the pore structure is rich, the specific surface area is ultrahigh, the contact area with electrolyte is increased, meanwhile, the transmission of lithium ions can be accelerated, the nitrogen doping is favorable for improving the electrochemical property of the porous carbon and improving the conductivity of the porous carbon, the silicon dioxide is uniformly dispersed in the three-dimensional network structure based on the electrostatic attraction effect, the agglomeration of the silicon dioxide is reduced, the exposure of more electrochemical active sites is favorable, the contact area with the electrolyte is further improved, the lithium ions are transmitted at a higher speed, the rate capability and the theoretical specific capacity of the negative electrode material are improved, and in the process of embedding and releasing lithium ions, the volume change of the silicon dioxide is inhibited by the three-dimensional network structure of, meanwhile, a buffer space is provided for the volume change of the silicon dioxide, and the cycle performance of the negative electrode material is improved, so that the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon has excellent theoretical specific capacity, rate capability and cycle performance.
Drawings
FIG. 1 is a schematic front view of a water bath ultrasonic device;
fig. 2 is a schematic side view of the ultrasonic device of water bath.
1. A main body; 2. a control module; 3. a heating module; 4. a temperature detector; 5. a water outlet; 6. a valve; 7. a magnetic coil; 8. an ultrasonic probe; 9. filtering with a screen; 10. and (4) a beaker.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a preparation method of a negative electrode material of porous silicon dioxide coated with nitrogen-doped porous carbon comprises the following steps:
(1) adding deionized water, polyvinylpyrrolidone and nano-silica into a reaction bottle, wherein the mass ratio of the deionized water, the polyvinylpyrrolidone and the nano-silica is 170-, obtaining porous silicon dioxide nanospheres;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 60-80 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 80-100 ℃, dropwise adding a formaldehyde solution, reacting for 5-7h, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin, wherein the mass ratio of the alkali lignin to the melamine to the formaldehyde is 100:15-25: 10-16;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogenous alkali lignin into a reaction bottle in a mass ratio of 40-60:5-8:100, uniformly stirring, reacting at 70-100 ℃ for 3-5h, dialyzing, purifying, rotary-steaming and drying to obtain quaternized nitrogenous alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogen-containing alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the quaternized nitrogen-containing alkali lignin to the porous silicon dioxide nanospheres is 5-15:100:5-10, uniformly stirring, adding dilute sulfuric acid to adjust the pH value to 2-3, reacting for 1-2 hours at the temperature of 140-180 ℃, cooling, centrifuging and drying to obtain the quaternized nitrogen-containing alkali lignin modified porous silicon dioxide nanospheres;
(5) putting the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, and performing carbonization and etching processes, wherein the carbonization and etching processes comprise heating to 550-650 ℃ in a nitrogen atmosphere, carbonizing for 2-3h, heating to 800-1000 ℃, converting nitrogen into carbon dioxide gas, etching for 2-3h, washing with deionized water, and drying to obtain the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon.
Example 1
(1) Adding deionized water, polyvinylpyrrolidone and nano silicon dioxide into a reaction bottle with the mass ratio of 170:10, placing the reaction bottle in a water bath ultrasonic device, the water bath ultrasonic device comprises a main body, wherein the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a heating module, the bottom of the main body is movably connected with a temperature detector, the right side of the main body is movably connected with a water outlet, the top of the water outlet is movably connected with a valve, the right side of the main body is movably connected with a magnetic coil, the right side of the main body is movably connected with an ultrasonic probe, the middle of the main body is movably connected with a filter screen, the top of the filter screen is movably connected with a beaker, the ultrasonic dispersion is uniform, the backflow cooling is carried out for 2 hours, a sodium hydroxide solution is added, the stirring reaction is carried out for 2 hours;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 60 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 80 ℃, dropwise adding a formaldehyde solution, reacting for 5 hours, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin, wherein the mass ratio of the alkali lignin to the melamine to the formaldehyde is 100:15: 10;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogen-containing alkali lignin into a reaction bottle in a mass ratio of 40:5:100, uniformly stirring, reacting at 70 ℃ for 3 hours, dialyzing, purifying, rotary-steaming and drying to obtain quaternized nitrogen-containing alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogen-containing alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the quaternized nitrogen-containing alkali lignin to the porous silicon dioxide nanospheres is 5:100:5, uniformly stirring, adding dilute sulfuric acid to adjust the pH value to 3, reacting for 1h at 140 ℃, cooling, centrifuging and drying to obtain quaternized nitrogen-containing alkali lignin modified porous silicon dioxide nanospheres;
(5) putting the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, and performing carbonization and etching processes, wherein the carbonization and etching processes comprise the steps of heating to 550 ℃ in a nitrogen atmosphere, carbonizing for 2h, heating to 800 ℃, converting nitrogen into carbon dioxide gas, etching for 2h, washing with deionized water, and drying to obtain the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon.
Example 2
(1) Adding deionized water, polyvinylpyrrolidone and nano silicon dioxide into a reaction bottle with the mass ratio of 185:10, placing the reaction bottle in a water bath ultrasonic device, the water bath ultrasonic device comprises a main body, wherein the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a heating module, the bottom of the main body is movably connected with a temperature detector, the right side of the main body is movably connected with a water outlet, the top of the water outlet is movably connected with a valve, the right side of the main body is movably connected with a magnetic coil, the right side of the main body is movably connected with an ultrasonic probe, the middle of the main body is movably connected with a filter screen, the top of the filter screen is movably connected with a beaker, the ultrasonic dispersion is uniform, the backflow cooling is carried out for 3 hours, a sodium hydroxide solution is added, the stirring reaction is carried out for 2.5 hours;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 70 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 90 ℃, dropwise adding a formaldehyde solution, reacting for 6 hours, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin, wherein the mass ratio of the alkali lignin to the melamine to the formaldehyde is 100:20: 13;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogen-containing alkali lignin into a reaction bottle in a mass ratio of 50:6.5:100, uniformly stirring, reacting at 85 ℃ for 4 hours, dialyzing, purifying, rotary steaming and drying to obtain quaternized nitrogen-containing alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogen-containing alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the quaternized nitrogen-containing alkali lignin to the porous silicon dioxide nanospheres is 10:100:7.5, uniformly stirring, adding dilute sulfuric acid to adjust the pH value to be 2, reacting at 160 ℃ for 1.5h, cooling, centrifuging and drying to obtain quaternized nitrogen-containing alkali lignin modified porous silicon dioxide nanospheres;
(5) putting the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, and performing carbonization and etching processes, wherein the carbonization and etching processes comprise the steps of carbonizing for 2.5 hours after heating to 600 ℃ in a nitrogen atmosphere, heating to 900 ℃, converting nitrogen into carbon dioxide gas, etching for 2.5 hours, washing with deionized water, and drying to obtain the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon.
Example 3
(1) Adding deionized water, polyvinylpyrrolidone and nano silicon dioxide into a reaction bottle with the mass ratio of 180:10, placing the reaction bottle in a water bath ultrasonic device, the water bath ultrasonic device comprises a main body, wherein the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a heating module, the bottom of the main body is movably connected with a temperature detector, the right side of the main body is movably connected with a water outlet, the top of the water outlet is movably connected with a valve, the right side of the main body is movably connected with a magnetic coil, the right side of the main body is movably connected with an ultrasonic probe, the middle of the main body is movably connected with a filter screen, the top of the filter screen is movably connected with a beaker, the ultrasonic dispersion is uniform, the backflow cooling is carried out for 3 hours, a sodium hydroxide solution is added, the stirring reaction is carried out for 2 hours;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 60 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 100 ℃, dropwise adding a formaldehyde solution, reacting for 6 hours, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin, wherein the mass ratio of the alkali lignin to the melamine to the formaldehyde is 100:18: 12;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogen-containing alkali lignin into a reaction bottle in a mass ratio of 45:6:100, uniformly stirring, reacting at 80 ℃ for 4 hours, dialyzing, purifying, rotary-steaming and drying to obtain quaternized nitrogen-containing alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogen-containing alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the quaternized nitrogen-containing alkali lignin to the porous silicon dioxide nanospheres is 8:100:8, uniformly stirring, adding dilute sulfuric acid to adjust the pH value to 3, reacting for 1h at 150 ℃, cooling, centrifuging and drying to obtain quaternized nitrogen-containing alkali lignin modified porous silicon dioxide nanospheres;
(5) putting the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, and performing carbonization and etching processes, wherein the carbonization and etching processes comprise the steps of heating to 580 ℃ in a nitrogen atmosphere, carbonizing for 2h, heating to 900 ℃, converting nitrogen into carbon dioxide gas, etching for 2h, washing with deionized water, and drying to obtain the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon.
Example 4
(1) Adding deionized water, polyvinylpyrrolidone and nano silicon dioxide into a reaction bottle with the mass ratio of 200:10, placing the reaction bottle in a water bath ultrasonic device, the water bath ultrasonic device comprises a main body, wherein the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a heating module, the bottom of the main body is movably connected with a temperature detector, the right side of the main body is movably connected with a water outlet, the top of the water outlet is movably connected with a valve, the right side of the main body is movably connected with a magnetic coil, the right side of the main body is movably connected with an ultrasonic probe, the middle of the main body is movably connected with a filter screen, the top of the filter screen is movably connected with a beaker, the ultrasonic dispersion is uniform, the backflow cooling is carried out for 4 hours, a sodium hydroxide solution is added, the stirring reaction is carried out for 3 hours;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 80 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 100 ℃, dropwise adding a formaldehyde solution, reacting for 7 hours, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin, wherein the mass ratio of the alkali lignin to the melamine to the formaldehyde is 100:25: 16;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogen-containing alkali lignin into a reaction bottle in a mass ratio of 60:8:100, uniformly stirring, reacting at 100 ℃ for 5 hours, dialyzing, purifying, rotary-steaming and drying to obtain quaternized nitrogen-containing alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogen-containing alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the quaternized nitrogen-containing alkali lignin to the porous silicon dioxide nanospheres is 15:100:10, uniformly stirring, adding dilute sulfuric acid to adjust the pH value to 2, reacting for 2 hours at 180 ℃, cooling, centrifuging and drying to obtain quaternized nitrogen-containing alkali lignin modified porous silicon dioxide nanospheres;
(5) putting the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, and performing carbonization and etching processes, wherein the carbonization and etching processes comprise the steps of carbonizing for 3 hours after heating to 650 ℃ in a nitrogen atmosphere, heating to 1000 ℃, converting nitrogen into carbon dioxide gas, etching for 3 hours, washing with deionized water, and drying to obtain the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon.
Comparative example 1
(1) Adding deionized water, polyvinylpyrrolidone and nano silicon dioxide into a reaction bottle with the mass ratio of 150:10, placing the reaction bottle in a water bath ultrasonic device, the water bath ultrasonic device comprises a main body, wherein the left side of the main body is movably connected with a control module, the bottom of the main body is movably connected with a heating module, the bottom of the main body is movably connected with a temperature detector, the right side of the main body is movably connected with a water outlet, the top of the water outlet is movably connected with a valve, the right side of the main body is movably connected with a magnetic coil, the right side of the main body is movably connected with an ultrasonic probe, the middle of the main body is movably connected with a filter screen, the top of the filter screen is movably connected with a beaker, the ultrasonic dispersion is uniform, the backflow cooling is carried out for 3 hours, a sodium hydroxide solution is added, the stirring reaction is carried out for 2 hours;
(2) adding deionized water and alkali lignin into a reaction bottle, performing ultrasonic dispersion uniformly, heating to 70 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 90 ℃, dropwise adding a formaldehyde solution, reacting for 6 hours, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin, wherein the mass ratio of the alkali lignin to the melamine to the formaldehyde is 100:10: 6;
(3) adding deionized water, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogen-containing alkali lignin into a reaction bottle at a mass ratio of 30:3:100, uniformly stirring, reacting at 80 ℃ for 4 hours, dialyzing, purifying, rotary-steaming and drying to obtain quaternized nitrogen-containing alkali lignin;
(4) adding absolute ethyl alcohol, cosolvent sodium dodecyl benzene sulfonate and quaternized nitrogen-containing alkali lignin into a reaction bottle, uniformly stirring, adding porous silicon dioxide nanospheres, wherein the mass ratio of the sodium dodecyl benzene sulfonate to the quaternized nitrogen-containing alkali lignin to the porous silicon dioxide nanospheres is 3:100:3, uniformly stirring, adding dilute sulfuric acid to adjust the pH value to 2, reacting for 2 hours at 160 ℃, cooling, centrifuging and drying to obtain quaternized nitrogen-containing alkali lignin modified porous silicon dioxide nanospheres;
(5) putting the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, and performing carbonization and etching processes, wherein the carbonization and etching processes comprise the steps of heating to 550 ℃ in a nitrogen atmosphere, carbonizing for 2h, heating to 800 ℃, converting nitrogen into carbon dioxide gas, etching for 3h, washing with deionized water, and drying to obtain the negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon.
Respectively adding polyvinylidene fluoride, conductive carbon black, the negative electrode materials of the nitrogen-doped porous carbon-coated porous silica obtained in the examples and the comparative examples into N-methylpyrrolidone, uniformly stirring, uniformly coating the negative electrode materials on copper foil by using a coating machine, drying, using a working electrode, using a lithium sheet as a counter electrode, using a polyethylene film as a diaphragm and using 1mol/L electrolyte of LiPF6The solution is assembled into a lithium ion half battery in an argon glove box, constant-current charging and discharging tests are carried out on a 3568 type battery comprehensive tester, and the discharging specific capacity of the lithium ion half battery is tested, wherein the test standard is GB/T36276 plus 2018.
Claims (6)
1. The negative electrode material of the porous silicon dioxide coated with the nitrogen-doped porous carbon is characterized in that: the preparation method of the negative electrode material of the nitrogen-doped porous carbon-coated porous silicon dioxide comprises the following steps:
(1) adding polyvinylpyrrolidone and nano-silica into deionized water at a mass ratio of 170-200:10, placing the mixture in a water bath ultrasonic device, ultrasonically dispersing the mixture uniformly, refluxing and cooling the mixture for 2 to 4 hours, adding a sodium hydroxide solution, stirring and reacting the mixture for 2 to 3 hours, centrifugally filtering the mixture, washing the mixture, placing the mixture in a muffle furnace, and reacting the mixture for 3 to 5 hours at a temperature of 400-500 ℃ to obtain porous silica nanospheres;
(2) adding alkali lignin into deionized water, performing ultrasonic dispersion uniformly, heating to 60-80 ℃, adding melamine, performing ultrasonic dispersion uniformly, heating to 80-100 ℃, dropwise adding a formaldehyde solution, reacting for 5-7h, performing centrifugal filtration and drying to obtain nitrogen-containing alkali lignin;
(3) adding 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, sodium hydroxide and nitrogenous alkali lignin into deionized water, stirring uniformly, reacting at 70-100 ℃ for 3-5h, dialyzing, purifying, rotary steaming and drying to obtain quaternized nitrogenous alkali lignin;
(4) adding cosolvents sodium dodecyl benzene sulfonate and quaternized nitrogenous alkali lignin into absolute ethyl alcohol, uniformly stirring, adding porous silicon dioxide nanospheres, uniformly stirring, adding dilute sulfuric acid to adjust the pH to 2-3, reacting at the temperature of 140-180 ℃ for 1-2h, cooling, centrifuging and drying to obtain quaternized nitrogenous alkali lignin modified porous silicon dioxide nanospheres;
(5) and (3) placing the porous silicon dioxide nanospheres modified by the quaternized nitrogenous alkali lignin in an atmosphere tube furnace, carbonizing and etching, washing with deionized water, and drying to obtain the nitrogen-doped porous carbon coated porous silicon dioxide cathode material.
2. The negative electrode material of nitrogen-doped porous carbon-coated porous silica according to claim 1, wherein: the water bath ultrasonic device in the step (1) comprises a main body, wherein a control module is movably connected to the left side of the main body, a heating module is movably connected to the bottom of the main body, a temperature detector is movably connected to the bottom of the main body, a water outlet is movably connected to the right side of the main body, a valve is movably connected to the top of the water outlet, a magnetic coil is movably connected to the right side of the main body, an ultrasonic probe is movably connected to the right side of the main body, a filter screen is movably connected to the middle of the main body.
3. The negative electrode material of nitrogen-doped porous carbon-coated porous silica according to claim 1, wherein: the mass ratio of the alkali lignin, the melamine and the formaldehyde in the step (2) is 100:15-25: 10-16.
4. The negative electrode material of nitrogen-doped porous carbon-coated porous silica according to claim 1, wherein: in the step (3), the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the sodium hydroxide to the nitrogenous alkali lignin is 40-60:5-8: 100.
5. The negative electrode material of nitrogen-doped porous carbon-coated porous silica according to claim 1, wherein: in the step (4), the mass ratio of the sodium dodecyl benzene sulfonate, the quaternized nitrogenous alkali lignin and the porous silicon dioxide nanospheres is 5-15:100: 5-10.
6. The negative electrode material of nitrogen-doped porous carbon-coated porous silica according to claim 1, wherein: the carbonization and etching process in the step (5) comprises the steps of heating to 550-650 ℃ in the nitrogen atmosphere, carbonizing for 2-3h, heating to 800-1000 ℃, converting nitrogen into carbon dioxide gas, and etching for 2-3 h.
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