CN107768645B - Porous nitrogen-doped carbon nanosheet composite negative electrode material and preparation method thereof - Google Patents
Porous nitrogen-doped carbon nanosheet composite negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a porous nitrogen-doped carbon nanosheet composite negative electrode material and a preparation method thereof. The Fe prepared by the preparation method provided by the invention4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material has the advantages of good cycling stability and rate capability, simple synthesis method and low cost, and is expected to become a novel negative electrode material for large-scale use.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a porous nitrogen-doped carbon nanosheet composite anode material and a preparation method thereofA preparation method thereof. Wherein the porous nitrogen-doped carbon nanosheet composite negative electrode material is novel Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Background
Lithium ion batteries are currently considered to be the most promising energy storage device in portable electronic devices due to their advantages of higher energy density, less environmental pollution, and long life. As society develops, higher power density and energy density ion batteries are needed, and commercial graphite negative electrodes have not been able to meet the requirements. In order to meet the demand of social development, scientists are striving to explore advanced alternatives to replace graphite negative electrodes. In recent years, transition metal oxides have attracted the attention of scientists as exhibiting higher capacities (approximately 2-3 times as high as graphite). Unfortunately, poor conductivity and large volume changes during charging and discharging remain serious problems that limit their applications.
Transition metal nitrides have high electrical conductivity and electrochemical activity, and appear to scientists as a new and promising lithium ion battery cathode material. Among these transition metal nitrides, iron has the advantages of being non-toxic, abundant, and low in price, and its nitride shows great advantages as a negative electrode material for lithium batteries. However, the iron nitride as a negative electrode material has a rapid capacity fade due to its large volume change during electrochemical reaction, limiting its practical application.
Currently, there are two strategies to solve the above problems. One approach is to reduce the particle size of the electrode active material to nanometers. The smaller particle size of the active material can shorten the lithium ion diffusion path and increase the lithium ion diffusion kinetics, thereby effectively reducing volume changes. In another method, an active material is compounded with a carbon material, and the carbon material can inhibit volume expansion and further improve the conductivity, so that the electrochemical performance is improved. However, because current methods for synthesizing nitrides are limited (J.Mater. chem.A. 3(2015) 1364-1387), iron nitrides with smaller particle sizes are synthesized directlyIt is difficult to composite materials with carbon materials. Recently, scientists reported Fe grown on graphene oxide2N @ C microspheres (chem. Eur. J.21(2015) 3249-3256) and binderless Fe grown on carbon cloth2The N nano-particles (NanoEnergy 11(2015) 348-355) as the lithium battery negative electrode material show better lithium electrical property. However, their synthesis methods are complicated, and the products are obtained by calcination under ammonia conditions. As is well known, ammonia gas is easy to leak and causes danger, and a large amount of unreacted ammonia gas can cause environmental pollution, which are not favorable for large-scale production. Therefore, it becomes important to invent a simple, low-cost, green method for synthesizing iron nitride and carbon composite materials with small particle size as lithium battery negative electrode materials.
In summary, the problems of the prior art are as follows:
the synthesis methods in the prior art are complex, and products can be obtained only by calcining under the condition of ammonia gas; in addition, in the prior art, a large amount of unreacted ammonia gas can cause environmental pollution, and is not beneficial to large-scale production; the product obtained by the prior art has poor stability and rate capability.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a porous nitrogen-doped carbon nanosheet composite anode material and a preparation method thereof.
The invention is realized in such a way that a preparation method of a porous nitrogen-doped carbon nano sheet composite anode material comprises the following steps:
dissolving nonionic polyacrylamide in deionized water, adding ferric nitrate nonahydrate under stirring, and stirring to be viscous under the condition of 90 ℃ water bath;
drying in an oven, and treating the dried sample in an argon atmosphere;
and thirdly, ultrasonically filtering and washing the obtained product by using deionized water, and drying the washed sample in a vacuum oven to obtain the porous nitrogen-doped carbon nanosheet composite negative electrode material.
Further, the first step specifically comprises weighing 1.5g of non-ionic polyacrylamide, dissolving in 100m L deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, and stirring for 2 hours to 8 hours under the water bath condition of 70 ℃ to 90 ℃ to be viscous;
drying in an oven at 100 ℃ for 4-24h, and treating the dried sample at 500-700 ℃ for 1-4h in argon atmosphere;
and in the third step, drying the sample after water washing in a vacuum oven at 60-100 ℃ for 4-24h to obtain the porous nitrogen-doped carbon nano sheet composite negative electrode material.
Further, in the first step, the mass ratio of the nonionic polyacrylamide to the ferric nitrate nonahydrate is 1: and (0.3-3).
Further, in the first step, nickel nitrate hexahydrate is used for replacing ferric nitrate nonahydrate, and other conditions are the same, so that the Ni porous nitrogen-doped carbon nanosheet composite material is prepared.
The invention also aims to provide a porous nitrogen-doped carbon nanosheet composite anode material which is Fe4N/Fe2O3Fe porous nitrogen-doped carbon nanosheet lithium ion battery cathode material.
Another object of the present invention is to provide a method of preparing a lithium battery comprising:
mixing a porous nitrogen-doped carbon nanosheet composite negative electrode material with 20% of a conductive agent, mixing with a N-methylpyrrolidone solution containing 10% of a binder, uniformly stirring, coating on a copper foil, drying at 100 ℃ in a vacuum oven, cutting an electrode plate by using a slicer with the diameter of 14mm, drying for 6-12 h at 80 ℃ in the vacuum oven, transferring into a glove box filled with argon, taking a metal lithium plate as a counter electrode, taking a polypropylene porous membrane as a diaphragm, and taking a mixed solution of 1 mol/L ethylene carbonate and dimethyl carbonate of lithium hexafluorophosphate as an electrolyte to assemble the button cell.
Further, the mass ratio of the porous nitrogen-doped carbon nanosheet composite negative electrode material to the binder is 7: 1, the mass ratio of the porous nitrogen-doped carbon nanosheet composite negative electrode material to the conductive agent is 7: 2.
furthermore, the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the conductive agent is conductive carbon black.
The invention has the advantages and positive effects that:
based on the above discussion, the invention provides a simple, low-price and green method for synthesizing Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite material is used as a lithium battery cathode material and shows good stability and rate capability. Provides a new idea for the synthesis of iron nitride and the application of the iron nitride in lithium batteries.
Compared with the prior art, the invention has the following benefits and effects:
the invention is realized by simple stirring, drying, calcining and washing, the whole process is simple, the controllability is strong, the cost is low, and the method is suitable for industrial production.
Compared with other iron nitride synthesis methods, the nitrogen source used in the method is polyacrylamide, and compared with ammonia gas, the method is pollution-free and high in safety.
The novel cathode material prepared by the invention is applied to the field of lithium ion batteries for the first time, and shows excellent cycle stability and rate capability.
Drawings
Fig. 1 is a flowchart of a preparation method of a porous nitrogen-doped carbon nanosheet composite anode material provided by an embodiment of the present invention.
FIG. 2 shows the novel Fe prepared by the example of the present invention4N/Fe2O3XRD, Raman and N of Fe porous nitrogen-doped carbon nanosheet composite anode material2Adsorption and pore distribution.
In the figure: (a) is an XRD pattern; (b) is a Raman picture; (c) is a nitrogen absorption attached figure; (d) is an aperture distribution diagram.
FIG. 3 shows the novel Fe prepared by the example of the present invention4N/Fe2O3SEM, TEM and HRTEM images of the/Fe porous nitrogen-doped carbon nanosheet composite anode material.
In the figure: (a) and (b) is SEM picture; (c) and (d) are TEM images; (e) HRTEM images are obtained in (f) and (f).
FIG. 4 shows the novel Fe prepared by the example of the present invention4N/Fe2O3Mossbauer spectrum of the/Fe porous nitrogen-doped carbon nanosheet composite anode material.
FIG. 5 shows the novel Fe prepared by the example of the present invention4N/Fe2O3Fe porous nitrogen-doped carbon nanosheet composite negative electrode material and large-particle Fe4Lithium battery performance graph of N (1C ═ 200mA g)-1)。
In the figure: (a) the cycle performance diagram is assembled into a lithium ion battery with the current density of 100mA/g and the voltage range of 3-0.01V; (b) is a multiplying power performance diagram under different current densities; (c) is a graph of the cycling performance at a current density of 1000 mA/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The application of the principles of the present invention will be further described with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, a preparation method of a porous nitrogen-doped carbon nanosheet composite anode material provided by an embodiment of the present invention includes the following steps:
s101, weighing 1.5g of nonionic polyacrylamide, dissolving the nonionic polyacrylamide in 100m L deionized water, adding 0.75g of ferric nitrate nonahydrate under the stirring condition, stirring for 2 hours, and stirring for 4 hours under the water bath condition of 90 ℃ to be viscous;
s102: then drying in an oven at 100 ℃ for 6 hours, and treating the dried sample in an argon atmosphere at 700 ℃ for 1 hour;
s103: and (3) ultrasonically filtering and washing the obtained product by using deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the porous nitrogen-doped carbon nanosheet composite negative electrode material.
The porous nitrogen-doped carbon nanosheet composite cathode material is a lithium ion battery cathode material.
And (3) replacing ferric nitrate nonahydrate with nickel nitrate hexahydrate under the same other conditions to prepare the Ni porous nitrogen-doped carbon nanosheet composite material.
The conditions of the calcination include: the calcination temperature is 500-700 ℃, the calcination time is 1-4h, and the inert atmosphere is provided by at least one of argon, nitrogen and helium;
the water bath conditions include: the water bath temperature is 70-90 ℃, and the water bath time is 2-8 h;
the drying conditions in the 100 ℃ oven comprise: the drying time is 4-24 h;
the mass ratio of the nonionic polyacrylamide to the ferric nitrate nonahydrate is 1: (0.3-3).
The drying conditions of the sample after water washing comprise: the drying temperature is 60-100 deg.C, and the drying time is 4-24 h.
The embodiment of the invention provides Fe4N/Fe2O3Fe porous nitrogen-doped carbon nanosheet lithium ion battery cathode material.
Under all the conditions, nickel nitrate hexahydrate is used for replacing ferric nitrate nonahydrate, and the Ni porous nitrogen-doped carbon nanosheet composite material can be prepared.
The preparation method of the lithium battery provided by the embodiment of the invention comprises the following steps:
another object of the present invention is to provide a method of preparing a lithium battery comprising:
mixing a porous nitrogen-doped carbon nanosheet composite negative electrode material with 20% of a conductive agent, mixing with a N-methylpyrrolidone solution containing 10% of a binder, uniformly stirring, coating on a copper foil, drying at 100 ℃ in a vacuum oven, cutting an electrode plate by using a slicer with the diameter of 14mm, drying for 6-12 h at 80 ℃ in the vacuum oven, transferring into a glove box filled with argon, taking a metal lithium plate as a counter electrode, taking a polypropylene porous membrane as a diaphragm, and taking a mixed solution of 1 mol/L ethylene carbonate and dimethyl carbonate of lithium hexafluorophosphate as an electrolyte to assemble the button cell.
The mass ratio of the porous nitrogen-doped carbon nanosheet composite negative electrode material to the binder is 7: 1, the mass ratio of the porous nitrogen-doped carbon nanosheet composite negative electrode material to the conductive agent is 7: 2.
the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the conductive agent is conductive carbon black.
The material is mixed with 20% of conductive agent, then mixed with N-methyl pyrrolidone solution containing 10% of binder, after being uniformly stirred, coated on copper foil, placed in a vacuum oven for drying at 100 ℃, then cut into electrode slices by a slicer with the diameter of 14mm, placed in the vacuum oven for drying for 6-12 h at 80 ℃, then transferred into a glove box filled with argon, a metal lithium sheet is taken as a counter electrode, a polypropylene porous membrane is taken as a diaphragm, a mixed solution of ethylene carbonate and dimethyl carbonate (volume ratio is 1:1) of 1 mol/L lithium hexafluorophosphate is taken as an electrolyte, a CR2025 button cell is assembled, constant current charging and discharging performance test is carried out on a Neware cell test system, and the charging and discharging cut-off voltage is 0.01-3V.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
Example 1
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L of deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 90 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 700 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, drying the washed sample in a vacuum oven for 10 hours at 70 ℃ to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
The implementation effect is as follows: the novel Fe prepared in this example4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material is assembled into a battery for charge and discharge tests, and a graph (a) in FIG. 5 is a cycle performance graph of the assembled lithium ion battery at a current density of 100mA/g and a voltage range of 3-0.01V. It can be seen that the first discharge capacity is 995, the first reversible capacity is 577mAh/g, the first coulombic efficiency is 58%, and the cycling stability is good. FIG. 5(b) is the rate capability at 2000m for different current densitiesUnder the current density of A/g, the capacity of 330mAh/g still exists, and the multiplying power performance is good. FIG. 5(c) is a graph of cycling performance at a current density of 1000mA/g, and it can be seen that it still exhibits good cycling performance at high current densities.
Example 2
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L deionized water, adding 0.375g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 90 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 700 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, drying the washed sample in a vacuum oven for 10 hours at 70 ℃ to obtain Fe3N/Fe2O3The porous nitrogen-doped carbon nanosheet composite negative electrode material.
The implementation effect is as follows: the novel Fe prepared in this example3N/Fe2O3The porous nitrogen-doped carbon nanosheet composite negative electrode material is assembled into a battery to be subjected to charge-discharge test, the charge-discharge test is performed on the battery at a current density of 100mA/g, the first discharge capacity is 832mAh/g, the charge capacity is 457mAh/g, the first charge-discharge coulombic efficiency is 55%, and the discharge capacity is 439mAh/g after circulation for 100 circles.
Example 3
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L deionized water, adding 1.5g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 90 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 700 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, drying the washed sample in a vacuum oven for 10 hours at 70 ℃ to obtain Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
The implementation effect is as follows: the novel Fe prepared in this example4N/Fe2O3The battery assembled by the Fe porous nitrogen-doped carbon nanosheet composite negative electrode material is subjected to charge and discharge test, the charge and discharge test is carried out on the battery at the current density of 100mA/g, and the battery is discharged for the first timeThe capacity is 886mAh/g, the charge capacity is 557mAh/g, the first charge-discharge coulombic efficiency is 63%, and the discharge capacity is 397mAh/g after circulation for 100 circles.
Example 4
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L of deionized water, adding 0.75g of nickel nitrate hexahydrate under the stirring condition, stirring for 2 hours, stirring for 4 hours under the water bath condition at 90 ℃ to be viscous, drying for 6 hours in a drying oven at 100 ℃, treating the dried sample for 1 hour at 700 ℃ in an argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the Ni porous nitrogen-doped carbon nanosheet composite material.
Example 5
Weighing 1.5g of nonionic polyacrylamide, dissolving in 150m L of deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 90 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 700 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Example 6
Weighing 1.5g of nonionic polyacrylamide, dissolving the nonionic polyacrylamide in 200m L deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 90 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 700 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Example 7
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, and carrying out water bath at 70 DEG CStirring for 4 hours to be viscous under the condition of a workpiece, then drying for 6 hours in a drying oven at 100 ℃, treating the dried sample for 1 hour at 700 ℃ in an argon atmosphere, ultrasonically filtering and washing the obtained product by using deionized water, and drying the washed sample for 10 hours at 70 ℃ in a vacuum drying oven to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Example 8
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L of deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 80 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 700 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, drying the washed sample in a vacuum oven for 10 hours at 70 ℃ to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Example 9
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L of deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 80 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 500 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Example 9
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L of deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 80 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 500 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the Fe4N/Fe2O3/FeThe porous nitrogen-doped carbon nanosheet composite negative electrode material.
Example 10
Weighing 1.5g of nonionic polyacrylamide, dissolving in 100m L of deionized water, adding 0.75g of ferric nitrate nonahydrate under stirring, stirring for 2 hours, stirring for 4 hours under 80 ℃ water bath condition to be viscous, drying for 6 hours in a 100 ℃ oven, treating the dried sample for 1 hour at 600 ℃ in argon atmosphere, ultrasonically filtering and washing the obtained product with deionized water, and drying the washed sample in a vacuum oven at 70 ℃ for 10 hours to obtain the Fe4N/Fe2O3The Fe porous nitrogen-doped carbon nanosheet composite negative electrode material.
FIG. 2 shows the novel Fe prepared by the example of the present invention4N/Fe2O3XRD, Raman and N of Fe porous nitrogen-doped carbon nanosheet composite anode material2Adsorption and pore distribution.
In the figure: (a) is an XRD pattern; (b) is a Raman picture; (c) is a nitrogen absorption attached figure; (d) is an aperture distribution diagram.
FIG. 3 shows the novel Fe prepared by the example of the present invention4N/Fe2O3SEM, TEM and HRTEM images of the/Fe porous nitrogen-doped carbon nanosheet composite anode material.
In the figure: (a) and (b) is SEM picture; (c) and (d) are TEM images; (e) HRTEM images are obtained in (f) and (f).
FIG. 4 shows the novel Fe prepared by the example of the present invention4N/Fe2O3Mossbauer spectrum of the/Fe porous nitrogen-doped carbon nanosheet composite anode material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. A preparation method of a porous nitrogen-doped carbon nanosheet composite anode material is characterized by comprising the following steps of:
dissolving nonionic polyacrylamide in deionized water, adding ferric nitrate nonahydrate under stirring, and stirring to be viscous under the condition of 90 ℃ water bath;
drying in an oven, and treating the dried sample in an argon atmosphere;
thirdly, ultrasonically filtering and washing the obtained product by using deionized water, and drying the washed sample in a vacuum oven to obtain the porous nitrogen-doped carbon nanosheet composite negative electrode material;
in the third step, the porous nitrogen-doped carbon nanosheet composite anode material obtained is Fe4N/Fe2O3A Fe porous nitrogen-doped carbon nanosheet lithium ion battery cathode material;
the method for preparing the lithium battery by using the porous nitrogen-doped carbon nanosheet composite anode material comprises the following steps of:
mixing a porous nitrogen-doped carbon nanosheet composite negative electrode material with 20% of a conductive agent, mixing with a N-methylpyrrolidone solution containing 10% of a binder, uniformly stirring, coating on a copper foil, drying at 100 ℃ in a vacuum oven, cutting an electrode plate by using a slicer with the diameter of 14mm, drying for 6-12 h at 80 ℃ in the vacuum oven, transferring into a glove box filled with argon, taking a metal lithium plate as a counter electrode, taking a polypropylene porous membrane as a diaphragm, and taking a mixed solution of 1 mol/L ethylene carbonate and dimethyl carbonate of lithium hexafluorophosphate as an electrolyte to assemble the button cell.
2. The preparation method of the porous nitrogen-doped carbon nanosheet composite anode material of claim 1, wherein in the first step, 1.5g of nonionic polyacrylamide is weighed and dissolved in 100m L deionized water, 0.75g of ferric nitrate nonahydrate is added under stirring for 2 hours, and the mixture is stirred for 2 hours to 8 hours under the water bath condition of 70 ℃ to 90 ℃ to be viscous;
drying in an oven at 100 ℃ for 4-24h, and treating the dried sample at 500-700 ℃ for 1-4h in argon atmosphere;
and in the third step, drying the sample after water washing in a vacuum oven at 60-100 ℃ for 4-24h to obtain the porous nitrogen-doped carbon nano sheet composite negative electrode material.
3. The preparation method of the porous nitrogen-doped carbon nanosheet composite anode material of claim 1, wherein in the first step, the mass ratio of the nonionic polyacrylamide to the ferric nitrate nonahydrate is 1: (0.3-3).
4. The preparation method of the porous nitrogen-doped carbon nanosheet composite anode material as claimed in claim 1,
in the first step, nickel nitrate hexahydrate is used for replacing ferric nitrate nonahydrate, and other conditions are the same, so that the Ni porous nitrogen-doped carbon nanosheet composite material is prepared.
5. The method of preparing the porous nitrogen-doped carbon nanosheet composite anode material of claim 1, wherein the mass ratio of the porous nitrogen-doped carbon nanosheet composite anode material to the binder is 7: 1, the mass ratio of the porous nitrogen-doped carbon nanosheet composite negative electrode material to the conductive agent is 7: 2.
6. the method for preparing the porous nitrogen-doped carbon nanosheet composite anode material of claim 5, wherein the binder is polyvinylidene fluoride, the solvent is N-methylpyrrolidone, and the conductive agent is conductive carbon black.
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