CN114105154A - Nitrogen-doped graphene/modified silicon monoxide-based negative electrode material and preparation method and application thereof - Google Patents

Nitrogen-doped graphene/modified silicon monoxide-based negative electrode material and preparation method and application thereof Download PDF

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CN114105154A
CN114105154A CN202210110876.6A CN202210110876A CN114105154A CN 114105154 A CN114105154 A CN 114105154A CN 202210110876 A CN202210110876 A CN 202210110876A CN 114105154 A CN114105154 A CN 114105154A
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nitrogen
doped graphene
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陈飞
李强
井明召
林盛焕
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Shenzhen Mingshengwei Pilot Technology Co ltd
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Abstract

The invention provides a preparation method of a negative electrode material based on nitrogen-doped graphene/modified silicon monoxide, which comprises the following steps: preparation of SiOxStep of @ C core-shell material, step of preparing modified graphene fiber and preparation baseAnd (3) carrying out a nitrogen-doped graphene/modified silicon oxide negative electrode material step. The mesoporous carbon-coated modified silicon oxide composite material is prepared by the preparation method of the nitrogen-doped graphene/modified silicon oxide-based negative electrode material, the nano mesoporous spheres have good conductivity, so that a large number of surface gaps are formed on the nano mesoporous spheres, the subsequent embedding of the nitrogen-doped graphene and CNTs is facilitated, the function of stabilizing the nitrogen-doped graphene and CNTs is achieved, the construction of a three-dimensional conductive frame is facilitated, the integral conductivity is improved, lithium ions are also facilitated to be embedded or de-embedded into the modified silicon oxide through the three-dimensional conductive frame, and the capacity of an electrode is improved. The invention also provides a negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide and application of the negative electrode material.

Description

Nitrogen-doped graphene/modified silicon monoxide-based negative electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a negative electrode material based on nitrogen-doped graphene/modified silicon monoxide and a preparation method and application thereof.
Background
Lithium ion batteries are widely used as main power sources for mobile phones, tablet computers, notebook computers and other portable electronic products due to their advantages of relatively high energy density, relatively long cycle life, etc., and are gradually expanding as power sources for hybrid vehicles, electric vehicles and electric non-motor vehicles. The lithium ion battery is mainly composed of a positive electrode, a negative electrode, a diaphragm and electrolyte. When the battery is connected through an external circuit, chemical reaction is carried out on the electrodes due to the difference of lithium chemical potentials of the positive electrode and the negative electrode, and electrons form current through the external circuit along with the transfer process of lithium ions in the battery.
The lithium ion battery cathode material realizes the charge-discharge process through the processes of lithium intercalation and deintercalation, and the commonly used cathode material comprises conductive graphite, graphene, carbon black, alloy compound and TiO2Transition metal oxides, and the like. Pure silicon materials are widely studied as electrodes due to the characteristics of high theoretical specific capacity (4200 mAh/g), low cost, abundant reserves, environmental friendliness and the like, and comprise silicon oxides such as silicon oxide, silicon protoxide and the like. The silicon material realizes the charging and discharging of the battery through lithium intercalation and lithium deintercalation, but the lithium intercalation process easily increases the lattice constant of the material, leads to volume expansion to cause active material pulverization, electrode cracking, rapid reduction of lithium intercalation capacity and rapid attenuation of the battery capacity. In addition, the silicon material negative electrode has the defects of poor conductivity, high internal resistance of the battery, incapability of deeply embedding lithium ions and the like, and accordingly, the capacity of the battery is reduced, the stability of the electrode is poor and the like.
Disclosure of Invention
In view of the above, the invention provides a negative electrode material based on nitrogen-doped graphene/modified silicon oxide, and also provides a preparation method and an application of the negative electrode material based on nitrogen-doped graphene/modified silicon oxide, so as to solve the defects of easy pulverization, crack generation, rapid electrode attenuation, poor conductivity, low battery capacity, poor stability and the like of the conventional silicon negative electrode.
In a first aspect, the invention provides a preparation method of a nitrogen-doped graphene/modified silicon monoxide-based negative electrode material, which comprises the following steps:
preparation of SiOx@ C core-shell material: providing a weak base aqueous solution with the mass fraction of 5-10%, a phenolic resin precursor, nano-silica and a guiding agent, wherein the volume of the phenolic resin precursor is not more than 10% of the volume of the weak base aqueous solution, firstly adding the nano-silica and the guiding agent into the weak base aqueous solution and carrying out primary ultrasonic treatment for 10-60 min, then dropwise adding the phenolic resin precursor into the weak base aqueous solution and carrying out primary ultrasonic treatment for 10-60 min, carrying out reaction at 30-60 ℃, centrifuging and collecting precipitates, drying and carbonizing the precipitates to obtain a modified silica composite material coated with mesoporous carbon, namely a SiO (silicon dioxide) composite material, wherein the modified silica composite material is coated with the mesoporous carbonx@ C core-shell material;
preparing modified graphene fibers: providing N-methylpyrrolidone and SiOxMixing the material with core-shell material of @ C, and mixing the N-methylpyrrolidone and SiOxThe mass ratio of the @ C core-shell material is 100: 5-20, and then nitrogen-doped graphene and CNTs are sequentially added into N-methylpyrrolidone, wherein the SiO isxThe mass ratio of the @ C core-shell material to the nitrogen-doped graphene to the CNTs is 100: 5-20, the CNTs and the nitrogen-doped graphene are added while the N-methylpyrrolidone is subjected to secondary ultrasound, after the ultrasound is finished, the fiber-forming polymer is added into the N-methylpyrrolidone and transferred into an oil bath kettle at the temperature of 120-126 ℃, the mixture is stirred and mixed uniformly to serve as spinning stock solution, and a spinning needle with the inner diameter increasing along the filament outlet direction is used for electrostatic spinning, collecting and shearing to prepare the modified graphene fiber with the length of 0.2-10 mm;
preparing a negative electrode material based on nitrogen-doped graphene/modified silicon oxide: providing modified graphene fibers, conductive graphite, a water-based dispersant, a binder and deionized water, uniformly mixing to obtain primary slurry, transferring the primary slurry to a ball mill for ball milling for 5-20 min, wherein the mass ratio of the modified graphene fibers to the conductive graphite to the binder to the water-based dispersant is 100-500: 2-5: 0.2-2, and obtaining the negative electrode material based on nitrogen-doped graphene/modified silicon oxide after ball milling;
the size of the nano-silica is 50-100 nm.
The preparation method of the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide comprises the following steps: preparation of SiOxThe preparation method comprises the following steps of @ C core-shell material step, modified graphene fiber preparation step and nitrogen-doped graphene/modified silicon oxide-based negative electrode material preparation step. Preparation of SiOxIn the step of the @ C core-shell material, nano-silica and a guiding agent are added into a weak alkali aqueous solution and subjected to primary ultrasound, so that the nano-silica is uniformly dispersed into particles by means of the primary ultrasound and is not agglomerated, and the dispersed nano-silica is used as a template for a subsequent phenolic resin polymerization reaction to assist the generation of subsequent nano-carbon mesoporous spheres. After the first-stage ultrasound is finished, quickly dropwise adding a phenolic resin precursor into a weak alkali aqueous solution, continuously performing the first-stage ultrasound, reacting for 10-60 min at 30-60 ℃, polymerizing the phenolic resin precursor under the catalysis of an alkaline solution to generate a phenolic resin chain, and embedding the generated phenolic resin chain on silicon dioxide nanoparticles by using nano-silica particles as templates under the action of a guiding agent, thereby preparing the rambutan-like silica/phenolic resin core-shell composite structure. After reaction, the precipitate is collected in a centrifugal mode, the precipitate is transferred to a high-temperature carbonization furnace to complete high-temperature carbonization, the carbonization process is that phenolic resin forms nano carbon mesoporous spheres through the high-temperature carbonization process, and nano silicon oxide obtains modified silicon oxide nano particles (namely SiO) through the high-temperature activation processx) Thus obtaining the mesoporous carbon coated modified silicon oxide composite material, namely SiOx@ C core-shell material. The mesoporous resin nanospheres are prepared into mesoporous nanospheres through a high-temperature carbonization process, the mesoporous nanospheres are carbon materials and have good conductivity, and the high-temperature carbonization process enables the mesoporous resin nanospheres to be prepared into mesoporous nanospheresThe nano mesoporous spheres form a large number of surface gaps, so that subsequent embedding of nitrogen-doped graphene and CNTs (carbon nanotubes) is facilitated, the function of stabilizing the nitrogen-doped graphene and the CNTs is achieved, a three-dimensional conductive framework is constructed beneficially, the overall conductivity is improved beneficially, lithium ions are embedded or de-embedded into the modified silicon oxide through the three-dimensional conductive framework, and the capacity of the electrode is improved. In addition, the modified silicon monoxide is used as an electrode active material, the modified silicon monoxide has smaller volume change in the charging and discharging process relative to the silicon monoxide, the volume change is not more than 200%, the modified silicon monoxide nano particles are coated by the nano mesoporous spheres, the modified silicon monoxide nano particles are prevented from agglomerating, the structural stress generated by the volume change of the modified silicon monoxide can be buffered, and electrode pulverization and cracks are prevented.
In the step of preparing the modified graphene fiber, SiO is addedxThe @ C core-shell material, the nitrogen-doped graphene and the CNTs are added into the N-methyl pyrrolidone, and meanwhile, secondary ultrasound is carried out on the mixed system. The nitrogen-doped graphene is firstly added into N-methyl pyrrolidone, and the nitrogen-doped graphene is preferentially mixed with SiO under the action of ultrasonic dispersionxMixing and embedding of @ C core-shell material into SiOx@ C core-shell material. Compared with graphene, the nitrogen-doped graphene has better hydrophilicity, and the hydrophobic end of the nitrogen-doped graphene tends to be embedded into SiOxIn the @ C core-shell material, the hydrophilic end tends to expose SiOxBesides the @ C core-shell material, the structure can also promote SiOxThe @ C core-shell material has the function of stable dispersion. CNTs are added into the mixed system, the CNTs have smaller volume than nitrogen-doped graphene, and the CNTs can be further embedded into SiO under the action of ultrasonic dispersionx@ C core-shell material and nitrogen-doped graphene for enhancing SiOxThe conducting property of the @ C core-shell material as a charging and discharging unit is nanometer SiOxThe @ C core-shell structure also serves to maintain the dispersed CNTs. Finally, the conductive structure is spun: SiO 2xThe @ C core-shell structure, the nitrogen-doped graphene and the CNTs are fixed on the loose and porous grid fibers together, and the high-efficiency charge-discharge fibers and the conductive fibers are prepared. The charge and discharge components and the conductive components are distributed on the grid fibers, so that the composite material has a good fixing effect,the conductive agent can be effectively prevented from falling off, so that the phenomenon that the newly exposed conductive units (nano mesoporous spheres, nitrogen-doped graphene and CNTs) react with the electrolyte to consume reversible capacity is avoided. On the other hand, after the negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide is coated on a current collector forming electrode, volume change is easily caused in the electrode charging and discharging process, the grid fibers and the nano mesoporous spheres are of a porous structure, so that the negative electrode material has a good buffering effect, stress caused by the volume change can be effectively buffered, a conductive agent (the nano mesoporous spheres, the nitrogen-doped graphene and CNTs) is prevented from falling off or electrode deformation, cracks and the like, lithium ions can conveniently and quickly pass through the negative electrode material, and the multiplying power performance and the cycle stability of the battery are improved.
In the step of preparing the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide, the modified graphene fiber, the conductive graphite, the water-based dispersant, the binder and the deionized water are uniformly mixed to form primary slurry, and then the primary slurry is transferred to a ball mill for ball milling, so that the uniform dispersion and uniform electric conduction of the modified graphene fiber and the conductive graphite are further promoted, and the overall reversible capacity, the electric conductivity, the rate capability and the cycling stability of the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide are improved.
Preferably, in the preparation of SiOxIn the step of the @ C core-shell material, the weak base aqueous solution is ammonia water or sodium carbonate aqueous solution, the phenolic resin precursor comprises phenols and aldehydes, the phenols are phenol or aminophenol, the aldehydes are formaldehyde or acetaldehyde, and the guiding agent is ethylenediamine;
the mass ratio of the phenols, the aldehydes, the nano-sized silica and the ethylenediamine is 500-1000: 10-100: 20-50: 1-5. Therefore, by using the silicon monoxide nanoparticles as a template agent, generating a phenolic resin chain by using a phenolic resin precursor and embedding the silicon monoxide nanoparticles, and coating an electrode active material by adopting the conductive rambutan-shaped mesoporous carbon nanospheres to form stable charge and discharge unit-conductive unit composite nanoparticles, the phenolic resin chain is ensured to be efficiently embedded into the silicon monoxide nanoparticles and the size of a ratchet wheel of the composite nanoparticles is controlled by proper mass ratio, so that the composite nanoparticles, the nitrogen-doped graphene and CNTs can form a stable conductive network.
Preferably, in the preparation of SiOxIn the step of the @ C core-shell material, the carbonization is specifically performed by the following steps: placing the precipitate in a tubular furnace, heating to 1000-1200 ℃ under protective gas, and maintaining for 1-3 h, wherein the protective gas is N2Or Ar. Under the protective environment of high temperature, the nano mesoporous spheres are fully carbonized to form the mesoporous carbon microspheres, the carbonized mesoporous spheres can improve the conductivity, and meanwhile, the carbonization process can promote the surface to form a void structure, thereby being beneficial to buffering the stress generated by the volume change of the active material coated by the mesoporous carbon spheres and being beneficial to doping with nitrogen-doped graphene and CNTs in the later period. Under the high-temperature protective environment, the modified silicon monoxide is generated by modifying the silicon monoxide at high temperature, and the modified silicon monoxide has smaller volume expansion ratio relative to the silicon monoxide, thereby being beneficial to the stability of the whole structure of the electrode.
Preferably, the precipitate is carbonized and then transferred into a microwave digestion instrument for microwave digestion for 5-15 min, the temperature of the microwave digestion is 65-70 ℃, and the power is 280-330W. SiO capable of effectively promoting carbonization in microwave digestion processxThe @ C core-shell material is dispersed into micro powder, so that the microstructure of the mesoporous sphere is effectively maintained, and the collapse of a pore channel is prevented.
Preferably, in the step of preparing the modified graphene fiber, the content of N in the nitrogen-doped graphene is 10% -25%, and the thickness of the nitrogen-doped graphene is not more than 10 nm;
the fiber-forming polymer is PI powder or PAN powder, and the mass fraction of the fiber-forming polymer in the spinning solution is 5-8%. The proper N content and thickness of the nitrogen-doped graphene can improve the hydrophilicity, stability and ion permeability of the nitrogen-doped graphene, and then conductive components (mesoporous spheres, nitrogen-doped graphene and CNTs) are mixed with fiber-forming polymers with low content and spun to form a porous fiber structure.
Preferably, in the step of preparing the modified graphene fiber, the nitrogen-doped graphene is pre-expanded at a high temperature, and the specific high-temperature expansion step is as follows: and transferring the nitrogen-doped graphene to a tubular furnace for high-temperature puffing for 30-90 s, and filling inert gas into the tubular furnace, wherein the temperature of the tubular furnace is 600-800 ℃. The distance between the nitrogen-doped graphene layers can be effectively pulled back through the high-temperature expansion process of the nitrogen-doped graphene, the surface area of the nitrogen-doped graphene is increased, a 'crenellated and castellated' structure of the few-layer nitrogen-doped graphene layer is formed, and the subsequent CNTs are favorably alternated to form a conductive network and lithium ions to pass through.
Preferably, in the step of preparing the aqueous conductive paste, the aqueous dispersant is any one of PVP, SLS or CMC, and the binder is styrene butadiene rubber;
the mass fraction of the modified graphene fiber in the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide is 5-15%. The aqueous dispersant can promote the stable dispersion and electric conduction of the conductive carbon black and the modified graphene fiber. The binder can bind the modified graphene fiber and the conductive graphite to the current collector, so that the charging and discharging unit and the conductive unit are prevented from falling off from the current collector, and the stability of the battery is maintained.
Preferably, the primary ultrasound and the secondary ultrasound are both water bath ultrasound, and the ultrasound power is 200-300W. The first-level ultrasound and the second-level ultrasound both contribute to the dispersion and prevent SiOxThe @ C core-shell material is agglomerated to promote the combination of the CNTs and the nitrogen-doped graphene on the mesoporous nanospheres.
Preferably, the rotating speed of the centrifugation is 8000-12000 rpm, and the time of the centrifugation is 5-10 min.
In a second aspect, the invention also provides a negative electrode material based on nitrogen-doped graphene/modified silicon monoxide, which comprises modified graphene fibers, conductive graphite, a binder and an aqueous dispersant.
The negative electrode material based on the nitrogen-doped graphene/modified silicon oxide comprises modified graphene fibers, conductive graphite, a binder and a water-based dispersant, wherein the modified graphene fibers contain SiOx@ C core-shell material, nitrogen-doped graphene, CNTs (carbon nanotubes), SiOxThe @ C core-shell material comprises a charge and discharge unit-modified silicon monoxide nano particle and a conductive shell-nano carbon mesoporous sphere coating the charge and discharge unit, and the SiO is ensured by a core-shell composite structurexThe @ C core-shell material has high reversible capacity and excellent conductivity. SiO 2xThe @ C core-shell material is connected with the nitrogen-doped graphene and the CNTs, and then the carbon nanotubes are used forThe micron-sized porous fiber net is formed by the electrostatic spinning technology, so that a three-dimensional conductive network is formed, and SiO can be effectively preventedxThe @ C core-shell material, the nitrogen-doped graphene and the CNTs are agglomerated, so that the stress generated by the volume change of the structure can be effectively buffered, and the efficient passing of lithium ions can be guaranteed. Modified graphene fiber can connect in order to realize the electric conduction by oneself, also can further strengthen the electric conduction effect between the modified graphene fiber with the help of electrically conductive graphite, and aqueous dispersant can promote the homodisperse of electrically conductive graphite, strengthens the overall stability of conductive agent, and the binder can ensure to bond to the current collector on the negative electrode material based on nitrogen doping graphite alkene/modified monox, ensures the structural stability of electrode.
In a third aspect, the invention further provides an application of the negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide in a battery, wherein the negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide is coated on a current collector, and is dried to obtain a battery negative electrode and used for assembling the battery.
The negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide is applied to a battery, and specifically can be coated on a metal sheet, an electrode sheet is prepared after drying, and then the electrode sheet, a positive electrode material, an electrode solution, a diaphragm and the like are assembled into the battery. The electrode or battery using the nitrogen-doped graphene/modified silicon oxide-based negative electrode material has excellent reversible capacity, rate capability, cycling stability and the like.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
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In order to more clearly illustrate the contents of the present invention, a detailed description thereof will be given below with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a diagram showing the results of a button cell cycling stability test;
FIG. 2 is a diagram showing the result of the charge-discharge efficiency test of the button cell;
fig. 3 is a diagram showing the result of the rate performance test of the button cell.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
The following describes in detail the preparation method of the negative electrode material based on nitrogen-doped graphene/modified silica and the prepared negative electrode material based on nitrogen-doped graphene/modified silica through specific embodiments.
Preparing nitrogen-doped graphene: a growth substrate single crystal copper foil is placed in a growth cavity of a CVD tube furnace, growth raw material aniline is placed at the upwind position of the growth cavity, the growth cavity is connected into a vacuum system, the upwind direction is connected with a protective gas source (argon), and the downwind direction is connected with a vacuum pump. And vacuumizing the growth system, setting the growth temperature to be 400-600 ℃, setting the argon flow to be 200-400 sccm, and growing the nitrogen-doped graphene on the surface of the single crystal copper foil. After the growth is finished, the temperature of the growth cavity is reduced to room temperature, the growth substrate is taken out, the metal material with the large area and few layers of nitrogen-doped graphene paved on the surface is obtained, the growth substrate is etched, and the few layers of nitrogen-doped graphene with the nitrogen content of 10% -25% and the thickness of not more than 10 nm are collected for subsequent procedures. Can further carry out high temperature to few layer nitrogen doping graphite alkene popped based on the experiment demand, the concrete operation is: transferring the few layers of nitrogen-doped graphene to a tube furnace for high-temperature puffing, filling inert gas such as nitrogen or argon after the tube furnace is vacuumized, setting the high-temperature puffing temperature of the tube furnace to be 600-800 ℃, setting the high-temperature puffing time of the tube furnace to be 30-90 s, and cooling the tube furnace to room temperature under the atmosphere of the inert gas to obtain the high-temperature puffed nitrogen-doped graphene.
Preparation of SiOx@ C core-shell material: providing 100 mL of weak base aqueous solution, a phenolic resin precursor, nano-silicon oxide and ethylenediamine, wherein the phenolic resin precursor comprises two reaction monomers of phenols and aldehydes, the particle size distribution range of the nano-silicon oxide is 50-100 nm, and the specific type and concentration of the weak base aqueous solution, the phenols and the aldehydesThe types and the amount of the types, the amount of the nano-silicon oxide and the amount of the ethylenediamine are shown in the table 1. Adding nano-silica and a guiding agent into 100 mL of weak base aqueous solution, and performing water bath ultrasound on the weak base aqueous solution in the adding process, wherein the intensity and the time of the ultrasound are shown in Table 1. After the set ultrasonic time is over, the ultrasonic process of the water bath is stopped, phenols and aldehydes are added into the weak base aqueous solution at the same time, the weak base aqueous solution is heated or cooled to the set temperature for carrying out the phenolic resin polymerization reaction, and the reaction temperature and the reaction time are shown in table 1. And after the reaction is finished, centrifuging the reaction liquid to collect the precipitate to prepare the phenolic resin coated nano-silica composite structure, namely the phenolic resin @ silica composite particles. Wherein, the centrifugal speed and the centrifugal time are shown in the table 1. Transferring the centrifugally collected phenolic resin @ silica composite particles into a tubular furnace, and carbonizing at high temperature in a protective gas atmosphere to obtain a mesoporous carbon coated modified silica composite material, namely SiOx@ C core-shell material. The specific types of protective gas, carbonization temperature, and carbonization time are shown in table 1. In some embodiments, the high-temperature carbonized mesoporous nanospheres are also transferred to a microwave digestion instrument for microwave digestion, and specific microwave digestion time, microwave digestion temperature, microwave digestion power and the like are shown in table 1.
TABLE 1 preparation of SiOxProcess parameters in the step of @ C core-shell materials
Parameters of the preparation Process Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8
Aqueous solution of weak base 5% ammonia water 8% ammonia water 8% ammonia water 10% ammonia water 5% sodium carbonate 10% sodium carbonate 8% sodium carbonate 8% sodium carbonate
Phenols 3-aminophenols Phenol and its preparation 4-aminophenols Phenol and its preparation Ortho-aminophenols Phenol and its preparation 3-aminophenols Phenol and its preparation
Phenol dosage (g) 3 5 2 6 10 8 2 4
Aldehydes Formaldehyde (I) Acetaldehyde Formaldehyde (I) Acetaldehyde Formaldehyde (I) Acetaldehyde Formaldehyde (I) Acetaldehyde
The aldehyde dosage (mg) 150 1000 40 80 100 400 400 80
The amount of the silicon monoxide (g) 60 200 80 300 500 320 200 120
Ethylene diamine dosage (mg) 25 15 10 30 50 12 16 20
Ultrasonic intensity (W) 200 200 300 300 250 250 200 300
Ultrasonic time (min) 20 30 45 60 30 40 10 20
Reaction temperature (. degree.C.) 30 40 30 45 60 45 30 40
Reaction time (min) 20 30 10 40 60 60 20 20
Centrifugal speed (rpm) 10000 12000 8000 10000 12000 8000 10000 8000
Centrifuge time (min) 8 5 10 8 5 10 8 10
Protective gas species N2 Ar N2 Ar N2 Ar N2 Ar
Carbonization temperature (. degree.C.) 1200 1000 1050 1100 1100 1150 1200 1000
Carbonization time (h) 1 2 2 3 3 1 2
Microwave digestion time (min) / / 5 15 15 15 / /
Microwave digestion temperature (. degree. C.) / / 70 65 70 68 / /
Microwave resolution power (W) / / 280 330 330 300 / /
Preparing modified graphene fibers: providing 100 mL of N-methylpyrrolidone, SiO will be preparedxSiO prepared in the step of @ C core-shell materialxAdding the @ C core-shell material into N-methylpyrrolidone and uniformly mixing, wherein SiOxThe mass of the @ C core-shell material is seen in Table 2. And then, adding nitrogen-doped graphene and CNTs into the N-methylpyrrolidone in sequence, wherein the quality of the nitrogen-doped graphene and the CNTs is shown in a table 2, and the nitrogen-doped graphene in the embodiments 3 and 5 is high-temperature expanded nitrogen-doped graphene. In the process of adding the nitrogen-doped graphene and the CNTs, water bath ultrasound is performed on the N-methylpyrrolidone, and the ultrasonic intensity and the ultrasonic time are shown in Table 2. After the ultrasonic treatment, fiber-forming polymers (PAN, polyacrylonitrile; PI, polyimide) are added into the N-methylpyrrolidone and transferred into an oil bath pot, and the mixture is stirred and heated in an oil bath, wherein the specific types of the fiber-forming polymers, the mass fraction of the fiber-forming polymers in the spinning solution, the oil bath temperature and the oil bath time are shown in Table 2. The mixture is used as spinning solution after being stirred and evenly mixed, electrostatic spinning is carried out by using a spinning needle with the inner diameter increased along the filament outlet direction, and the inner diameter of the thin end of the spinning needle is 0.3 mm, the inner diameter of the thick end of the spinning needle head is 0.36 mm, the electrostatic spinning voltage is 35 KV, and the receiving distance is 30 cm. And cutting the collected spinning fibers into short fibers with different lengths by using a fiber cutting machine, wherein the specific lengths are shown in table 2, so as to obtain the modified graphene fibers.
TABLE 2 Process parameters for the step of preparing modified graphene fibers
Parameters of the preparation Process Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8
Amount (g) of SiOx @ C core-shell material 20 16 12 10 8 5 10 12
Mass (mg) of nitrogen-doped graphene 4 1.6 1.2 0.5 1.6 0.5 1 2
Quality of CNTs (mg) 1 1 1.6 2 0.4 0.5 1 1
Ultrasonic intensity (W) 200 200 300 300 250 250 200 300
Ultrasonic time(s) 5 10 5 10 30 20 5 10
Fiber-forming polymers PAN PI PAN PI PAN PI PAN PI
Mass fraction of fiber-forming polymer (%) 5 6 6 7 7 8 8 5
Oil bath temperature (. degree. C.) 126 125 123 121 120 123 126 125
Oil bath time (min) 40 60 30 40 40 40 60 20
Short fiber length (mm) 0.2 10 2 5 1 0.5 8 0.8
Preparing a negative electrode material based on nitrogen-doped graphene/modified silicon oxide: modified graphene fibers, conductive graphite, a water-based dispersant, styrene butadiene rubber and 1000 mL of deionized water are provided and uniformly mixed to form primary slurry, and the use amounts of the modified graphene fibers and the conductive graphite, the types and the use amounts of the water-based dispersant and the use amount of the styrene butadiene rubber are shown in Table 3. And transferring the primary slurry to a ball mill for ball milling to obtain the negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide, wherein the specific ball milling rotating speed and time are shown in table 3.
TABLE 3 Process parameters for the step of preparing the negative electrode Material
Parameters of the preparation Process Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8
Amount (g) of modified graphene fiber 60 150 120 90 60 150 60 120
Amount of conductive graphite (g) 1.5 6 5 3 2 3 2.4 2
Amount of styrene-butadiene rubber (g) 1.5 1.5 1 0.5 1 3 0.6 4
Kinds of aqueous dispersants CMC SLS PVP SLS CMC PVP SLS CMC
Amount of aqueous dispersant (mg) 1200 150 120 36 60 600 300 600
Ball milling speed (r/min) 3000 2500 2000 2500 3000 2000 2500 3000
Ball milling time (min) 20 5 10 15 5 15 20 10
Effect example 1: testing of cycling stability and Charge/discharge efficiency
The negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide prepared in the examples 3-6 is coated on copper foil, if the thickness of an active layer needs to be increased, the coating process can be repeated to increase the thickness of the negative electrode material, vacuum drying is carried out at 80 ℃ for 12h to obtain a corresponding negative electrode, a lithium sheet is used as a counter electrode, a positive electrode, the negative electrode and the like are assembled into a corresponding button cell, and the cycling stability of the negative electrode is tested. The specific test method comprises the following steps: after a constant current charge-discharge cycle at a current density of 100 mA/g for 10 weeks, the current density was increased to 200 mA/g for 100 weeks.
As shown in fig. 1-2, the battery prepared in example 3 had a first charge specific capacity of 1392.1 mAh/g, a discharge specific capacity of 1872.5 mAh/g, a first charge-discharge efficiency of 74.3%, and a 100 th cycle charge-discharge efficiency of 98.9%. The battery prepared in example 4 had a first charge specific capacity of 1425.4 mAh/g, a discharge specific capacity of 1856.3 mAh/g, a first charge-discharge efficiency of 76.8%, and a 100 th cycle charge-discharge efficiency of 99.5%. The battery prepared in example 5 had a first charge specific capacity of 1410.5 mAh/g, a discharge specific capacity of 1861.7 mAh/g, a first charge-discharge efficiency of 75.8%, and a 100 th cycle charge-discharge efficiency of 97.8%. The battery prepared in example 6 had a first charge specific capacity of 1405.5 mAh/g, a discharge specific capacity of 1838.7 mAh/g, a first charge-discharge efficiency of 76.4%, and a 100 th cycle charge-discharge efficiency of 99.2%. As can be seen from this, it is,the negative electrode prepared from the negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide can ensure that the battery has higher cycle stability and capacitance retention rate, the charge and discharge efficiency after 100 cycles of charge and discharge is kept above 98%, and the charge and discharge efficiency is obviously higher than that of the battery prepared from the common conductive agent and possibly can be matched with SiOxThe structure of the @ C core-shell material is relatively stable, and the nano-carbon mesoporous sphere coated modified silica nano-particles can stably modify the silica nano-particles on one hand and SiO on the other handxThe @ C core-shell material is in a stable nano state and can also be used for embedding or extracting more lithium ions, so that the reversible capacity of the negative electrode material is improved. Because the modified silicon monoxide nano particles coated by the nano carbon mesoporous spheres can buffer the volume change of the silicon monoxide in the charge and discharge process, the surface structure of the negative plate is relatively more stable, a more stable SEI (solid electrolyte interphase) cured film is formed in the charge and discharge process, and the irreversible consumption of lithium ions is reduced.
Effect example 2: electrode rate capability test
Effect the batteries corresponding to examples 3 and 4 in example 1 were subjected to charge and discharge tests under different current density conditions: testing the charging specific capacity under the current density of 100 mA/g for 1-10 weeks, testing the charging specific capacity under the current density of 200 mA/g for 11-20 weeks, testing the charging specific capacity under the current density of 400 mA/g for 21-30 weeks, testing the charging specific capacity under the current density of 800 mA/g for 31-40 weeks, testing the charging specific capacity under the current density of 1000 mA/g for 41-50 weeks, and testing the charging specific capacity under the current density of 100 mA/g for 51-60 weeks. As shown in FIG. 3, the batteries prepared in example 3 had first-charge specific capacities at current densities of 100 mA/g, 200 mA/g, 400 mA/g, 800 mA/g, 1000 mA/g and 100 mA/g of: 1392.1 mAh/g, 1743.6 mAh/g, 1665.2 mAh/g, 1578.7 mAh/g, 1487.6 mAh/g and 1499.5 mAh/g. The batteries prepared in example 4 had first charge specific capacities at current densities of 100 mA/g, 200 mA/g, 400 mA/g, 800 mA/g, 1000 mA/g and 100 mA/g of: 1425.4 mAh/g, 1725.6 mAh/g, 1658.9 mAh/g, 1594.2 mAh/g, 1521.8 mAh/g and 1537.4 mAh/g. Therefore, the electrodes prepared in examples 3 and 4 have excellent rate performance, which is related to the porous structure of the modified graphene fiber net, and the porous modified graphene fiber net effectively improves the lithium ion circulation effect of the battery.
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 present 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 negative electrode material based on nitrogen-doped graphene/modified silicon oxide is characterized by comprising the following steps:
preparation of SiOx@ C core-shell material: providing a weak base aqueous solution with the mass fraction of 5-10%, a phenolic resin precursor, nano-silica and a guiding agent, wherein the volume of the phenolic resin precursor is not more than 10% of the volume of the weak base aqueous solution, firstly adding the nano-silica and the guiding agent into the weak base aqueous solution and carrying out primary ultrasonic treatment for 10-60 min, then dropwise adding the phenolic resin precursor into the weak base aqueous solution and carrying out primary ultrasonic treatment for 10-60 min, carrying out reaction at 30-60 ℃, centrifuging and collecting precipitates, drying and carbonizing the precipitates to obtain a modified silica composite material coated with mesoporous carbon, namely a SiO (silicon dioxide) composite material, wherein the modified silica composite material is coated with the mesoporous carbonx@ C core-shell material;
preparing modified graphene fibers: providing N-methylpyrrolidone and SiOxMixing the material with core-shell material of @ C, and mixing the N-methylpyrrolidone and SiOxThe mass ratio of the @ C core-shell material is 100: 5-20, and then nitrogen-doped graphene and CNTs are sequentially added into N-methylpyrrolidone, wherein the SiO isxThe mass ratio of the @ C core-shell material to the nitrogen-doped graphene to the CNTs is 100: 5-20, the CNTs and the nitrogen-doped graphene are added while the N-methylpyrrolidone is subjected to secondary ultrasound, after the ultrasound is finished, the fiber-forming polymer is added into the N-methylpyrrolidone and transferred into an oil bath kettle at the temperature of 120-126 ℃, the obtained mixture is stirred and mixed uniformly to serve as spinning stock solution, and a spinning needle with the inner diameter increasing along the filament discharging direction is used for static mixingCarrying out electrospinning, collecting and shearing to prepare a modified graphene fiber with the length of 0.2-10 mm;
preparing a negative electrode material based on nitrogen-doped graphene/modified silicon oxide: providing modified graphene fibers, conductive graphite, a water-based dispersant, a binder and deionized water, uniformly mixing to obtain primary slurry, transferring the primary slurry to a ball mill for ball milling for 5-20 min, wherein the mass ratio of the modified graphene fibers to the conductive graphite to the binder to the water-based dispersant is 100-500: 2-5: 0.2-2, and obtaining the negative electrode material based on nitrogen-doped graphene/modified silicon oxide after ball milling;
the size of the nano-silica is 50-100 nm.
2. The method for preparing the nitrogen-doped graphene/modified silicon monoxide-based anode material as claimed in claim 1, wherein the SiO is preparedxIn the step of the @ C core-shell material, the weak base aqueous solution is ammonia water or sodium carbonate aqueous solution, the phenolic resin precursor comprises phenols and aldehydes, the phenols are phenol or aminophenol, the aldehydes are formaldehyde or acetaldehyde, and the guiding agent is ethylenediamine;
the mass ratio of the phenols, the aldehydes, the nano-sized silica and the ethylenediamine is 500-1000: 10-100: 20-50: 1-5.
3. The method for preparing the nitrogen-doped graphene/modified silicon monoxide-based anode material as claimed in claim 1, wherein the SiO is preparedxIn the step of the @ C core-shell material, the carbonization is specifically performed by the following steps: placing the precipitate in a tubular furnace, heating to 1000-1200 ℃ under protective gas, and maintaining for 1-3 h, wherein the protective gas is N2Or Ar.
4. The preparation method of the negative electrode material based on the nitrogen-doped graphene/modified silicon monoxide as claimed in claim 3, wherein the precipitate is carbonized and then transferred into a microwave digestion instrument for microwave digestion for 5-15 min, wherein the microwave digestion temperature is 65-70 ℃, and the power is 280-330W.
5. The method for preparing the nitrogen-doped graphene/modified silicon oxide-based negative electrode material according to claim 1, wherein in the step of preparing the modified graphene fiber, the content of N in the nitrogen-doped graphene is 10-25%, and the thickness of the nitrogen-doped graphene is not more than 10 nm;
the fiber-forming polymer is PI powder or PAN powder, and the mass fraction of the fiber-forming polymer in the spinning solution is 5-8%.
6. The method for preparing the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide according to claim 1, wherein in the step of preparing the modified graphene fiber, the nitrogen-doped graphene is subjected to high-temperature puffing in advance, and the specific high-temperature puffing step is as follows: and transferring the nitrogen-doped graphene to a tubular furnace for high-temperature puffing for 30-90 s, and filling inert gas into the tubular furnace, wherein the temperature of the tubular furnace is 600-800 ℃.
7. The method for preparing the nitrogen-doped graphene/modified silica-based negative electrode material according to claim 1, wherein in the step of preparing the aqueous conductive paste, the aqueous dispersant is any one of PVP, SLS or CMC, and the binder is styrene-butadiene rubber;
the mass fraction of the modified graphene fiber in the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide is 5-15%.
8. The preparation method of the nitrogen-doped graphene/modified silicon monoxide-based negative electrode material as claimed in claim 1, wherein the primary ultrasound and the secondary ultrasound are both water bath ultrasound, and the ultrasound power is 200-300W.
9. The nitrogen-doped graphene/modified silica-based negative electrode material prepared by the preparation method of the nitrogen-doped graphene/modified silica-based negative electrode material as claimed in any one of claims 1 to 8, which is characterized by comprising modified graphene fibers, conductive graphite, a binder and an aqueous dispersant.
10. The application of the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide on the battery as claimed in claim 9, wherein the negative electrode material based on the nitrogen-doped graphene/modified silicon oxide is coated on a current collector, and after drying, a battery negative electrode is obtained and is used for assembling the battery.
CN202210110876.6A 2022-01-29 2022-01-29 Nitrogen-doped graphene/modified silicon monoxide-based negative electrode material and preparation method and application thereof Pending CN114105154A (en)

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