CN111362249A - Two-dimensional porous nitrogen-doped carbon, preparation method thereof and application thereof in lithium ion battery - Google Patents
Two-dimensional porous nitrogen-doped carbon, preparation method thereof and application thereof in lithium ion battery Download PDFInfo
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Abstract
The invention discloses two-dimensional porous nitrogen-doped carbon, a preparation method thereof and application thereof in a lithium ion battery, and the molten salt auxiliary preparation method of the two-dimensional porous nitrogen-doped carbon provided by the invention is characterized in that a carbon source, a nitrogen source and molten salt are mixed, high-temperature molten salt is used as a liquid phase reaction medium, and the mixture is calcined in an inert atmosphere to obtain the two-dimensional porous nitrogen-doped carbon; nitrogen doping can provide more active sites, and the wettability of the material is improved; the high-temperature molten salt can perform an etching effect on the carbon product and introduce a pore channel structure, and the template effect of the salt is favorable for controlling the morphology of the two-dimensional porous nitrogen-doped carbon. The two-dimensional porous nitrogen-doped carbon prepared by the method is a micron-sized sheet, the shape is controllable, the ion transmission distance is shortened by the thin two-dimensional structure, a convenient transmission channel is provided for electrolyte ions by rich pore channel structures, and the specific capacity of the material in a lithium ion battery can be improved by nitrogen doping.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, and relates to a two-dimensional porous nitrogen-doped carbon and molten salt auxiliary preparation method and application thereof in a lithium ion battery.
Background
The popularization and application of new energy automobiles become an irreversible trend throughout the world, and many countries have successively released fuel oil automobile sale prohibition countdown, which inevitably brings the vigorous demand on the capacity of power batteries and promotes the rapid development of regional lithium battery industry. The 'scheme for promoting the development of the automobile power battery industry' issued in China provides that the specific energy of a battery cell exceeds 300Wh/kg in 2020, the specific energy of a system reaches 260Wh/kg, the cost is reduced to below 1 yuan/Wh, which is approximately equivalent to 150 dollars/kWh, Japanese is 100 dollars/kWh, the American requirement is 90-125 dollars/kWh, European is 120 dollars/kWh, and the price is very close to the target 100 dollars/Wh of the oil level price, namely, the national policy requires that the electric automobile is required to achieve the cost performance level similar to that of a fuel automobile in about 2020. A series of measures promote the technical upgrading of the industry, the productivity optimization, and the government subsidies the grade fall off, thereby promoting the whole industrial chain and reducing the cost.
At present, the commercial lithium ion battery adopts graphite as a negative electrode, the theoretical specific capacity is only 372mAh/g, and the requirements on a high-power battery and large-scale energy storage are difficult to meet. Based on this, a novel high-performance carbon material has become a research focus of people, and doping modification of the carbon material is a good way to improve the storage capacity of the carbon material. Chinese patent document CN108511200A discloses a nitrogen-doped carbon sheet material with good energy storage performance, in which a certain amount of potassium oxalate and urea are weighed in advance, ball-milled and mixed, then the mixture is heated to 900 ℃ by a program under argon atmosphere, and calcined, and after multiple centrifugal washes with hydrochloric acid solution, a sheet product with wrinkled edges is obtained, but the method has complicated temperature program heating and long required time. Chinese patent document CN107583665A discloses a preparation method and application of two-dimensional porous nitrogen-doped carbon, wherein the material is prepared by using carbon aerogel prepared from biomass strawberry pulp as a carbon source and melamine as a nitrogen source, and sequentially adopting hydrothermal and pyrolysis methods to treat the carbon source and the melamine to obtain nitrogen-doped carbon sheets, the surface of the nitrogen-doped carbon sheets contains a large number of folds and micropores, although an in-situ template method is adopted, the steps of removing a template and the like are avoided, but the whole preparation process is still complex. Compared with other complex nitrogen doping methods, the method adopts a one-step molten salt auxiliary method, the carbon source and the nitrogen source are mixed and pyrolyzed, a small amount of molten salt is used as a template, the morphology and the structure of the two-dimensional porous nitrogen-doped carbon material are regulated and controlled, the molten salt can be recycled, and the process is simple, green and environment-friendly.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of two-dimensional porous nitrogen-doped carbon.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of two-dimensional porous nitrogen-doped carbon comprises the following steps: and uniformly mixing the carbon source, the nitrogen source and the molten salt according to a certain proportion, and calcining at high temperature in an inert atmosphere to obtain the two-dimensional porous nitrogen-doped carbon.
Further, the preparation method of the carbon source, nitrogen source and molten salt mixture comprises the following steps:
weighing a carbon source, a nitrogen source and molten salt in a glove box, and fully grinding in a mortar to uniformly mix the raw materials, wherein the grinding time is preferably 20-50 min.
Further, cleaning and drying the calcined product, and recovering molten salt to obtain two-dimensional porous nitrogen-doped carbon;
preferably, the cleaning is carried out by adopting ultrapure water for washing, the supernatant is evaporated and the fused salt is recovered after the first centrifugation, the bottom precipitate is soaked by dilute hydrochloric acid with the mass fraction of 10-20% and then washed by adopting ultrapure water and absolute ethyl alcohol or directly washed by the ultrapure water and the absolute ethyl alcohol for multiple times;
preferably, the drying temperature is 60-100 ℃, and the drying time is 8-12 h.
Further, the mass ratio of the carbon source, the nitrogen source and the molten salt is 1: 0.5-4: 3-30, preferably 1: 0.5-2: 3-10.
Further, the carbon source is one of glucose, fructose, sucrose, lignin and cellulose;
the nitrogen source is one of melamine, urea and dicyandiamide;
the molten salt is one or more of salts composed of alkali metal cations and halide anions, preferably one or more of lithium bromide, zinc chloride, potassium bromide, cobalt chloride, ferric chloride, sodium chloride and nickel chloride.
Further, the inert atmosphere is nitrogen or argon, preferably argon.
Further, the calcination temperature is 500-1000 ℃, and the calcination time is 0.5-5 h;
preferably, the temperature rise rate during the calcination is 0.5-10 ℃/min.
It is another object of the present invention to provide a two-dimensional porous nitrogen-doped carbon.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a two-dimensional porous nitrogen-doped carbon is prepared by adopting the preparation method of any one of the two-dimensional porous nitrogen-doped carbon.
Further, the thickness of the two-dimensional porous nitrogen-doped carbon is 60-500nm, preferably 100-200 nm;
the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 7-18%, and the nitrogen content is preferably 13%.
The invention also aims to provide application of the two-dimensional porous nitrogen-doped carbon.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: the two-dimensional porous nitrogen-doped carbon is applied to lithium ion batteries.
A lithium ion battery comprises a lithium ion battery electrode prepared by adopting the two-dimensional porous nitrogen-doped carbon;
the lithium ion battery electrode is prepared by uniformly mixing the two-dimensional porous nitrogen-doped carbon with a conductive agent, a binder and a solvent;
preferably, the conductive agent is selected from acetylene black;
preferably, the binder is selected from polyvinylidene fluoride;
preferably, the solvent is selected from N-methylpyrrolidone.
The invention provides a simple one-step molten salt auxiliary method, which is used for preparing a two-dimensional porous nitrogen-doped carbon material with stable physical and chemical properties by high-temperature pyrolysis and can obviously improve the lithium storage performance of the carbon material.
The method adopts a one-step molten salt auxiliary method to prepare the two-dimensional porous nitrogen-doped carbon material, the method uses high-temperature molten salt to provide a liquid-phase uniform environment for a carbon source and a nitrogen source, nitrogen atoms can be successfully doped into the carbon material in situ, and the carbon material can be used as an electrode material of a lithium ion battery and has good lithium storage performance.
As a specific embodiment of the present invention, a method for preparing a two-dimensional porous nitrogen-doped carbon material specifically includes the following steps:
(1) weighing a certain amount of carbon source, nitrogen source and molten salt in a glove box, and fully and uniformly mixing in a mortar;
(2) transferring the mixture into a porcelain boat, calcining according to a certain temperature-rising program under the protection of inert atmosphere, naturally cooling to room temperature, and finely grinding by using a mortar to collect powder;
(3) washing the powder with ultrapure water, centrifuging for the first time, evaporating the supernatant to recover molten salt, soaking the bottom precipitate with dilute hydrochloric acid with the mass fraction of 10-20%, washing with ultrapure water and absolute ethyl alcohol or directly washing with ultrapure water and absolute ethyl alcohol for multiple times, drying the collected product in a drying oven, grinding, sieving and collecting to obtain the final product.
In the above step, the mass ratio of the carbon source, the nitrogen source and the molten salt in step (1) is 1: 0.5-4: 3-30, preferably 1: 0.5-2: 3-10;
preferably, the carbon source is one of glucose, fructose, sucrose, lignin and cellulose;
preferably, the nitrogen source is one of melamine, urea and dicyandiamide;
preferably, the molten salt is one or more of lithium bromide, zinc chloride, potassium bromide, cobalt chloride, ferric chloride, sodium chloride, nickel chloride, and salts of alkali metal cations and halide anions.
In the step (2), preferably, the inert atmosphere is argon or nitrogen, preferably argon;
preferably, the temperature raising procedure is that the calcining temperature is 500-1000 ℃, and the calcining time is 0.5-5 h;
preferably, the temperature rise rate is 0.5-10 ℃/min.
In the step (3), preferably, the centrifugal speed is 10000rpm, and the evaporation temperature is 80-100 ℃;
preferably, the drying temperature is 60-100 ℃, and the drying time is 8-12 h;
preferably, the sieve is a 300 mesh sieve.
Preferably, the thickness of the two-dimensional porous nitrogen-doped carbon is 100-200 nm.
Compared with the prior art, the two-dimensional porous nitrogen-doped carbon and molten salt auxiliary preparation method and the application in the lithium ion battery provided by the invention have the following beneficial effects:
(1) the invention provides a molten salt auxiliary preparation method of two-dimensional porous nitrogen-doped carbon, which comprises the steps of taking biomass carbon such as glucose and the like as a carbon source, nitrogen-containing compounds such as melamine and the like as a nitrogen source, taking high-temperature molten salt as a liquid phase reaction medium, and calcining under an inert atmosphere to obtain the two-dimensional porous nitrogen-doped carbon; in addition, the fused salt can etch the carbon product and introduce a pore channel structure, and the template effect of the salt is favorable for controlling the morphology of the two-dimensional porous nitrogen-doped carbon. In addition, the preparation method is simple in process and environment-friendly, the morphology of the porous nitrogen-doped carbon can be regulated and controlled by using a small amount of molten salt, micron-sized sheets are obtained, and the molten salt can be recycled, so that a basis is provided for industrial production.
(2) The invention provides a two-dimensional porous nitrogen-doped carbon which is prepared by adopting a one-step molten salt auxiliary method, and is a micron-sized sheet, the surface of the two-dimensional porous nitrogen-doped carbon is smooth, obvious pores can be seen at the edge, the appearance size is controllable, the thin two-dimensional structure can shorten the ion transmission distance, the high-nitrogen content doping can improve the wettability of the material and provide active sites, the rich pore structure provides a good application foundation for the material to be used as an electrode material of a lithium ion battery, and the nitrogen doping can improve the specific capacity of the material in the lithium ion battery.
(3) The invention provides a lithium ion battery, which comprises an electrode prepared by adopting two-dimensional porous nitrogen-doped carbon. In view of the advantages of the two-dimensional porous nitrogen-doped carbon, the lithium ion battery has high specific capacity, good cycling stability and rate capability.
Drawings
Fig. 1 is an XRD pattern of two-dimensional porous nitrogen-doped carbon provided in comparative example 1, example 2 and example 3 of the present invention;
FIG. 2 is an IR spectrum of a two-dimensional porous nitrogen-doped carbon as provided in examples 1-3 of the present invention;
fig. 3 is an SEM image of two-dimensional porous nitrogen-doped carbon provided in comparative example 1 and examples 1 to 3 of the present invention, wherein (a) is an SEM image of comparative example 1, (b) is an SEM image of example 1, (c) is an SEM image of example 2, and (d) is an SEM image of example 3;
in FIG. 4, (a) (b) are plots of the lithium ion battery rate performance of the lithium ion battery electrodes of example 1 and example 2 of the present invention, respectively, and (c) (d) are plots of the lithium ion battery electrode of example 1 of the present invention at 0.2mV s-1CV plot of the first three cycles at sweep speed and at 500mAg-1The current density of (a);
FIG. 5 is a plot of the lithium ion battery cycle performance for the lithium ion battery electrode of example 3 in which (a) is at 0.2mV s-1The CV curve chart of the first three circles under the sweeping speed, (b) is a multiplying power performance chart under different current densities, (c) is a multiplying power performance chart under 500mA g-1The current density of (a);
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In one aspect of the present invention, a method for doping nitrogen-doped carbon is provided, which comprises the following steps:
(a) weighing a certain amount of carbon source, nitrogen source and molten salt in a glove box, and fully and uniformly mixing in a mortar;
(b) transferring the mixture into a porcelain boat, calcining according to a certain temperature-rising program under the protection of inert atmosphere, naturally cooling to room temperature, and finely grinding by using a mortar to collect powder;
(c) washing the powder with ultrapure water, centrifuging for the first time, evaporating the supernatant to recover molten salt, soaking the bottom precipitate with dilute hydrochloric acid with the mass fraction of 10-20%, washing with ultrapure water and absolute ethyl alcohol or directly washing with ultrapure water and absolute ethyl alcohol for multiple times, drying the collected product in a drying oven, grinding, sieving and collecting to obtain the final product.
In the above step, the mass ratio of the carbon source, the nitrogen source and the molten salt is 1: 0.5-4: 3-30, preferably 1: 0.5-2: 3-10;
the carbon source is one of glucose, fructose, sucrose, lignin and cellulose;
the nitrogen source is one of melamine, urea and dicyandiamide;
the molten salt is one or more of salts composed of alkali metal cations such as lithium bromide, zinc chloride, potassium bromide, cobalt chloride, ferric chloride, sodium chloride, nickel chloride and the like and halide anions.
The inert atmosphere is argon or nitrogen, preferably argon;
the temperature raising procedure is that the calcining temperature is 500-1000 ℃, the calcining time is 0.5-5 h, and the temperature raising speed is 0.5-10 ℃/min.
The centrifugal speed is 10000rpm, and the evaporation temperature is 80-100 ℃;
the drying conditions are as follows: the temperature is 60-100 ℃, and the drying time is 8-12 h;
in the screening process, a 300-mesh screen is selected.
In conclusion, the molten salt auxiliary preparation method of the two-dimensional porous nitrogen-doped carbon provided by the invention mixes the carbon source, the nitrogen source and the molten salt, uses the high-temperature molten salt as a liquid phase reaction medium, and calcines in an inert atmosphere to obtain the two-dimensional porous nitrogen-doped carbon; nitrogen doping can provide more active sites, and the wettability of the material is improved; the high-temperature molten salt can perform an etching effect on the carbon product and introduce a pore channel structure, and the template effect of the salt is favorable for controlling the morphology of the two-dimensional porous nitrogen-doped carbon. The two-dimensional porous nitrogen-doped carbon prepared by the method is a micron-sized sheet, the shape is controllable, the ion transmission distance is shortened by the thin two-dimensional structure, a convenient transmission channel is provided for electrolyte ions by rich pore channel structures, and the specific capacity of the material in a lithium ion battery can be improved by nitrogen doping.
The invention provides a preparation method of a lithium ion battery, which comprises the following steps:
adding a proper amount of solvent into 70 wt% of two-dimensional porous nitrogen-doped carbon negative electrode material, 20 wt% of conductive agent and 10 wt% of binder, fully and uniformly grinding, coating the materials on copper foil, drying the copper foil in a vacuum drying box, cutting an electrode slice by using a slicing machine with the diameter of 12mm, rolling the electrode slice by using the slicing machine, transferring the electrode slice into a glove box filled with argon, wherein the water and oxygen content is lower than 0.1ppm, a metal lithium slice is used as a counter electrode, a polypropylene porous membrane is used as a diaphragm, and 1mol L of the electrode slice is filled with 1mol of the metal lithium slice and the polypropylene-1And (3) assembling the button cell by using a mixed solution of ethylene carbonate and dimethyl carbonate (volume ratio is 1: 1) of lithium hexafluorophosphate as an electrolyte according to a certain sequence.
The conductive agent is acetylene black, the binder is polyvinylidene fluoride (PVDF), and the solvent is N-methyl pyrrolidone.
The two-dimensional porous nitrogen-doped carbon material (70 wt%) is mixed with 20 wt% of conductive agent and 10 wt% of binding agent, and proper amount of N-methyl pyrrolidone is added, and then the mixture is fully ground uniformly, coated on copper foil, dried in a vacuum drying oven at 120 deg.C for 10h, cut into electrode sheet by using slicing machine with diameter of 12mm, rolled by using tablet machine, and transferred into a glove box filled with argon gas, and its water and oxygen content is less than 0.1ppm, metal lithium sheet is used as counter electrode, polypropylene porous membrane is used as diaphragm, 1mol L of said porous membrane is used as diaphragm-1The method comprises the steps of taking a mixed solution of ethylene carbonate and dimethyl carbonate (volume ratio is 1: 1) of lithium hexafluorophosphate as an electrolyte, assembling into a CR2032 button cell according to a certain sequence, and carrying out constant-current charge-discharge performance test on a Newware cell test system, wherein the charge-discharge cutoff voltage is 0.01-2.5V.
The application of the principles of the present invention will now be described in further detail with reference to specific embodiments.
Example 1
Weighing 2g of glucose, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring to a porcelain boat, calcining in a vacuum tube furnace under the protection of argon atmosphere, and heating at a temperature of 3 ℃ for min-1Raising the temperature to 800 ℃, keeping the temperature for 1h, naturally cooling to room temperature, washing with ultrapure water, centrifuging at the speed of 10000rpm, evaporating the solution to dryness, recovering lithium bromide, continuously washing the precipitate with ultrapure water and absolute ethyl alcohol, drying in a vacuum drying oven at the temperature of 80 ℃ for 10h, fully grinding, and then sieving with a 300-mesh sieve to obtain the obviously layered two-dimensional porous nitrogen-doped carbon material (MCN-LiBr), wherein the XRD (X-ray diffraction) diagram of the material is shown in figure 1, the infrared spectrogram is shown in figure 2, and the SEM (scanning electron microscope) morphology diagram is shown in figure 3 (b). The thickness of the two-dimensional porous nitrogen-doped carbon in the embodiment is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 13%.
The implementation effect is as follows: mixing the two-dimensional porous nitrogen-doped carbon material prepared in the embodiment with acetylene black and PVDF according to the mass percentage of 7:2:1, adding N-methyl pyrrolidone as a solvent, grinding uniformly, assembling into a battery, performing charge and discharge tests, and performing rate performance tests at different current densities to obtain a battery with the capacity of 5000mA g-1The capacity can still be kept at 210mAhg at the current density of-1Return to 200mA g-1The low current density and the capacity of the capacitor can be recovered to 450mAhg-1Showing good rate performance, see fig. 4 (a). FIG. 4(c) is according to 0.2mV s-1The sweep rate of the cyclic voltammetry curve is in a voltage range of 0.01-2.5V, and irreversible reduction peaks of 1.25V and 0.5V in the first circle respectively correspond to a process of decomposing an electrolyte solution to form a Solid Electrolyte Interphase (SEI) film and a process of embedding lithium ions into two-dimensional porous nitrogen-doped carbon, and are important reasons for irreversible capacity loss; the CV curves of the second time and the third time have good coincidence, which shows that the SEI film formed in the first circle is relatively stable, and the electrode material has stable cycle performance. According to 500mA g-1The current density of the lithium ion battery is in a cycle performance graph of 0.01-2.5V voltage interval, and the first discharge specific capacity of the lithium ion battery is 1100mAhg-1The coulombic efficiency of the first circle is 47 percent, and after 300 circles, the stable capacity is 430mAhg-1Exhibit good cycle stabilityAs shown in fig. 4 (d).
Example 2
Weighing 2g of glucose, 2g of melamine and 7.5g of zinc chloride in a glove box, fully grinding, uniformly and quickly transferring to a porcelain boat, calcining in a vacuum tube furnace under the protection of argon atmosphere, and heating at a temperature of 3 ℃ for min-1Raising the temperature to 800 ℃, keeping the temperature for 1h, naturally cooling to room temperature, washing with ultrapure water, centrifuging at the rotation speed of 10000rpm, evaporating the solution to dryness, recovering zinc chloride, continuously washing the precipitate with ultrapure water and absolute ethyl alcohol, drying in a vacuum drying oven at 80 ℃ for 10h, fully grinding, and sieving with a 300-mesh screen to obtain the nitrogen-doped carbon sheet material (MCN-ZnCl)2) The XRD pattern of the material is shown in figure 1, the infrared spectrum is shown in figure 2, and the SEM topography is shown in figure 3 (c). The thickness of the two-dimensional porous nitrogen-doped carbon in the embodiment is 200-400 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 10%.
The implementation effect is as follows: mixing the two-dimensional porous nitrogen-doped carbon material prepared in the embodiment with acetylene black and PVDF according to the mass percentage of 7:2:1, adding N-methylpyrrolidone as a solvent, grinding uniformly, assembling into a battery, and performing charge and discharge tests according to the proportion of 100mA g-1The current density of the lithium ion battery is in a cycle performance graph of a voltage range of 0.01-2.5V, and the first discharge specific capacity of the lithium ion battery is 1512mAhg-1The coulombic efficiency of the first circle is 52 percent, and after 100 circles, the stable capacity is 100mAhg-1. Passing through 600mA g-1After high current density cycling, the current density is restored to 100mA g-1The specific capacity can still be kept at 550mAhg-1Good rate capability was demonstrated, see fig. 4 (b).
Example 3
Weighing 2g of glucose, 2g of melamine and 7.5g of potassium bromide in a glove box, fully grinding, uniformly and quickly transferring to a porcelain boat, calcining in a vacuum tube furnace under the protection of argon atmosphere, and heating at the temperature rising speed of 3 ℃ for min-1Raising temperature to 800 deg.C, keeping the temperature for 1h, naturally cooling to room temperature, washing with ultrapure water, centrifuging at 10000rpm, evaporating the solution to dryness, recovering potassium bromide, washing the precipitate with ultrapure water and anhydrous ethanol, drying in vacuum drying oven at 80 deg.C for 10h, grinding completely, and passing throughAnd (3) screening with a 300-mesh screen to obtain the two-dimensional porous nitrogen-doped carbon material (MCN-KBr), wherein an XRD (X-ray diffraction) diagram of the material is shown in figure 1, an infrared spectrum diagram of the material is shown in figure 2, and an SEM (scanning electron microscope) morphology diagram of the material is shown in figure 3 (d). The thickness of the two-dimensional porous nitrogen-doped carbon in the embodiment is 60-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 10%.
The implementation effect is as follows: the two-dimensional porous nitrogen-doped carbon material prepared in the embodiment is mixed with acetylene black and PVDF according to the mass percentage of 7:2:1, N-methyl pyrrolidone is added as a solvent, the mixture is uniformly ground and assembled into a battery to carry out charge and discharge tests, and the charge and discharge test is carried out according to 0.2mV s in the graph of fig. 5(a)-1The sweep rate of the cyclic voltammetry curve is in a voltage range of 0.01-2.5V, and irreversible reduction peaks of 1.25V and 0.2V in the first circle respectively correspond to a process of decomposing an electrolyte solution to form a Solid Electrolyte Interphase (SEI) film and a process of embedding lithium ions into two-dimensional porous nitrogen-doped carbon, and are important reasons for irreversible capacity loss; the CV curves of the second time and the third time have good coincidence, which shows that the SEI film formed in the first circle is relatively stable, and the electrode material has stable cycle performance. Graph (b) is the rate capability at different current densities, with the current density returning to 100mA g-1The capacity can still be kept at 350mAhg-1. FIG. (c) shows the amount of g as 500mA-1The first discharge specific capacity of the current density cycle performance diagram is 850mAhg-1The coulombic efficiency of the first circle is 37 percent, and the stable capacity is 290mAhg after 330 circles-1And the good circulation stability is shown.
Example 4
Weighing 2g of glucose, 2g of melamine and 7.5g of cobalt chloride in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, raising the temperature, wherein the temperature procedure refers to example 1, after molten salt is recovered, a precipitate washing process is firstly soaked by hydrochloric acid with the mass fraction of 10-20%, then washing is carried out for multiple times by using ultrapure water and absolute ethyl alcohol, and a two-dimensional porous nitrogen-doped carbon material is obtained after drying and grinding, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-300 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 7%.
Example 5
Weighing 2g of glucose, 2g of melamine and 7.5g of ferric chloride in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, raising the temperature, wherein the temperature procedure refers to example 1, after molten salt is recovered, a precipitate washing process is firstly soaked by hydrochloric acid with the mass fraction of 10-20%, then washing is carried out for multiple times by using ultrapure water and absolute ethyl alcohol, and a two-dimensional porous nitrogen-doped carbon material is obtained after drying and grinding, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 60-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 15%.
Example 6
Weighing 2g of glucose, 2g of melamine and 7.5g of sodium chloride in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, raising the temperature, wherein the temperature procedure refers to example 1, after molten salt is recovered, a precipitate washing process is firstly soaked by hydrochloric acid with the mass fraction of 10-20%, then washing is carried out for multiple times by using ultrapure water and absolute ethyl alcohol, and a two-dimensional porous nitrogen-doped carbon material is obtained after drying and grinding, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-400 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 9%.
Example 7
Weighing 2g of glucose, 2g of melamine and 7.5g of nickel chloride in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, raising the temperature, wherein the temperature procedure refers to example 1, after molten salt is recovered, a precipitate washing process is firstly soaked by hydrochloric acid with the mass fraction of 10-20%, then washing is carried out for multiple times by using ultrapure water and absolute ethyl alcohol, and a two-dimensional porous nitrogen-doped carbon material is obtained after drying and grinding, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-300 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 15%.
Example 8
Weighing 2g of glucose, 2g of melamine, 3.5g of sodium chloride and 3g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 14%.
Example 9
Weighing 2g of glucose, 2g of melamine, 3.5g of sodium chloride and 3g of potassium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 13%.
Example 10
Weighing 2g of glucose, 2g of melamine, 3.5g of sodium chloride and 3g of zinc chloride in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 18%.
Example 11
Weighing 2g of glucose, 2g of melamine, 3.5g of potassium bromide and 3g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-300 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 14%.
Example 12
Weighing 2g of glucose, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, and raising the temperature by the temperature procedure according to example 1, wherein the difference is that the calcination temperature is set to be 500 ℃, and the two-dimensional porous nitrogen-doped carbon material is obtained after drying and grinding, and the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 500 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 18%.
Example 13
Weighing 2g of glucose, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, and raising the temperature by referring to example 1, wherein the difference is that the calcination temperature is set to be 1000 ℃, and the two-dimensional porous nitrogen-doped carbon material is obtained after drying and grinding, and the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 7%.
Example 14
Weighing 2g of glucose, 2g of melamine and 20g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 12%.
Example 15
Weighing 2g of fructose, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing temperature rise and washing and drying processes according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 13%.
Example 16
Weighing 2g of sucrose, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 14%.
Example 17
Weighing 2g of lignin, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the lignin, the melamine and the lithium bromide into a porcelain boat, and obtaining a two-dimensional porous nitrogen-doped carbon material after grinding according to the example 1, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 12%.
Example 18
Weighing 2g of cellulose, 2g of melamine and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing a temperature rise procedure and a washing and drying process according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 60-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 14%.
Example 19
Weighing 2g of glucose, 2g of urea and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, and obtaining a two-dimensional porous nitrogen-doped carbon material after grinding according to the example 1 in the temperature rise procedure and the washing and drying processes, wherein the thickness of the two-dimensional porous nitrogen-doped carbon material in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 10%.
Example 20
Weighing 2g of glucose, 2g of dicyandiamide and 7.5g of lithium bromide in a glove box, fully grinding, uniformly and quickly transferring the mixture into a porcelain boat, performing temperature rise and washing and drying processes according to example 1, and grinding to obtain a two-dimensional porous nitrogen-doped carbon material, wherein the thickness of the two-dimensional porous nitrogen-doped carbon in the example is 100-200 nm; the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 11%.
Comparative example 1
This comparative example provides a preparation method of a porous carbon material, except that melamine was not added, and the remaining raw materials, the amounts, the calcination temperature-raising procedure, and the washing-drying process were the same as in example 1, to obtain a honeycomb-shaped porous carbon material (C-LiBr), whose XRD pattern is shown in fig. 1 and SEM morphology is shown in fig. 3 (a).
Comparative example 2
The comparative example provides a preparation method of a carbon material, which is different in that glucose is not added, other raw materials, the using amount, the calcining temperature-raising program and the washing and drying processes are the same as those in example 1, most of products volatilize, a small amount of carbon nitride material is obtained on the tube wall, the important function of a basic carbon source is shown, and the high-yield two-dimensional porous nitrogen-doped carbon cannot be obtained by mixing and calcining a single nitrogen source and molten salt.
Comparative example 3
The comparison example provides a preparation method of a carbon material, which is different in that no molten salt is added, and the rest raw materials, the using amount, the calcining temperature-raising program and the washing and drying process are the same as those in example 1, so that the amorphous caking carbon-nitrogen material is obtained, and the molten salt has certain influence on the morphology of the material and has a template effect.
Taking examples 1-3 as an example and comparative example 1 as an illustration, XRD, infrared and SEM data characterization was performed on the provided two-dimensional porous nitrogen-doped carbon, as shown in fig. 1-3.
As can be seen from fig. 1, the XRD spectrum of comparative example 1 shows two slightly sharp diffraction peaks near 22 ° and 44 °, and the diffraction peaks of examples 1 to 3 after nitrogen doping have been shifted significantly, which indicates that nitrogen has been successfully doped into the carbon material, and two broad diffraction peaks near 26 ° and 44 °, indicating that the nitrogen-doped nanosheet is amorphous, has a low graphitization degree, and the broadening of the diffraction peaks indicates that the interplanar spacing is large, which is beneficial to the intercalation and deintercalation of lithium ions.
The surface functional groups of the porous nitrogen-doped carbon treated by different molten salts in examples 1-3 were further analyzed by infrared spectroscopy, specifically 2970cm as shown in FIG. 2-1Corresponding to the stretching vibration of saturated C-H, 2208cm-1Corresponding to C ≡ C or C ≡ N, 1540, 1442cm-1Denotes C ═ C, 1250cm-1The vicinity below may be C-N or C-O, 1380cm-1Corresponding to C-N telescopic vibration, the porous aza-carbon obtained by different molten salt treatments has different surface functional groups, and the surface groups of the embodiment 1 are rich and have better wettability with electrolyte, thereby being beneficial to the diffusion of lithium ions on the surface of the material.
In order to investigate the influence of the morphology of the two-dimensional porous nitrogen-doped carbon on the lithium storage performance, the materials provided in comparative example 1 and examples 1-3 were subjected to electron microscope scanning, and fig. 3(a) shows that the honeycomb-shaped porous carbon material of comparative example 1 shows obvious macropores; (b) for the scanned picture of example 1, the two-dimensional porous nitrogen-doped carbon exhibits a stacked layered structure, with an edge profile exhibiting a rich microporous structure; (c) the scanned picture of example 2 shows a dense lamellar structure, and the pore structure is not sufficiently prominent. (d) The scan of example 3 shows a scattered arrangement of lamellae, about 60-200nm thick, rich pore structure seen in cross section. The comparison shows that different molten salts have good regulating effect on the shape and surface groups of the material.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of two-dimensional porous nitrogen-doped carbon is characterized by comprising the following steps: and uniformly mixing the carbon source, the nitrogen source and the molten salt according to a certain proportion, and calcining at high temperature in an inert atmosphere to obtain the two-dimensional porous nitrogen-doped carbon.
2. The method for preparing two-dimensional porous nitrogen-doped carbon according to claim 1, wherein the method for preparing the mixture of the carbon source, the nitrogen source and the molten salt comprises the following steps:
weighing the carbon source, the nitrogen source and the molten salt in a glove box, and fully grinding in a mortar to uniformly mix the raw materials.
3. The method for preparing two-dimensional porous nitrogen-doped carbon according to claim 1, wherein the calcined product is cleaned and dried, and the molten salt is recovered to obtain two-dimensional porous nitrogen-doped carbon;
preferably, the cleaning is carried out by adopting ultrapure water for washing, the supernatant is evaporated and the fused salt is recovered after the first centrifugation, the bottom precipitate is soaked by dilute hydrochloric acid with the mass fraction of 10-20% and then washed by adopting ultrapure water and absolute ethyl alcohol or directly washed by the ultrapure water and the absolute ethyl alcohol for multiple times;
preferably, the drying temperature is 60-100 ℃, and the drying time is 8-12 h.
4. The method for preparing two-dimensional porous nitrogen-doped carbon according to any one of claims 1 to 3, wherein the mass ratio of the carbon source, the nitrogen source and the molten salt is 1: 0.5-4: 3-30, preferably 1: 0.5-2: 3-10.
5. The method for preparing two-dimensional porous nitrogen-doped carbon according to any one of claims 1 to 3, wherein the carbon source is one of glucose, fructose, sucrose, lignin and cellulose;
the nitrogen source is one of melamine, urea and dicyandiamide;
the molten salt is one or more of salts composed of alkali metal cations and halide anions;
preferably, the molten salt is one or more of lithium bromide, zinc chloride, potassium bromide, cobalt chloride, ferric chloride, sodium chloride and nickel chloride.
6. The method for preparing two-dimensional porous nitrogen-doped carbon according to any one of claims 1 to 3, wherein the calcination temperature is 500-1000 ℃, and the calcination time is 0.5-5 h;
preferably, the temperature rise rate during the calcination is 0.5-10 ℃/min.
7. A two-dimensional porous nitrogen-doped carbon, which is produced by the production method for a two-dimensional porous nitrogen-doped carbon according to any one of claims 1 to 6.
8. The two-dimensional porous nitrogen-doped carbon according to claim 7, wherein the thickness of the two-dimensional porous nitrogen-doped carbon is 60-500nm, preferably 100-200 nm;
the nitrogen content of the two-dimensional porous nitrogen-doped carbon is 7-18%, and the nitrogen content is preferably 13%.
9. Use of the two-dimensional porous nitrogen-doped carbon of claim 7 or 8 in a lithium ion battery.
10. A lithium ion battery comprising a lithium ion battery electrode fabricated using the two-dimensional porous nitrogen-doped carbon of claim 7 or 8;
the lithium ion battery electrode is prepared by uniformly mixing the two-dimensional porous nitrogen-doped carbon of claim 7 or 8 with a conductive agent, a binder and a solvent;
preferably, the conductive agent is selected from acetylene black;
preferably, the binder is selected from polyvinylidene fluoride;
preferably, the solvent is selected from N-methylpyrrolidone.
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