CN113371688A - Preparation method of novel iron nitride and porous carbon composite anode material - Google Patents

Preparation method of novel iron nitride and porous carbon composite anode material Download PDF

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CN113371688A
CN113371688A CN202110635456.5A CN202110635456A CN113371688A CN 113371688 A CN113371688 A CN 113371688A CN 202110635456 A CN202110635456 A CN 202110635456A CN 113371688 A CN113371688 A CN 113371688A
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carbon composite
porous carbon
iron nitride
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anode material
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张丹
杨奇超
张纯燕
李玉珠
刘光印
刘小娣
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Nanyang Normal University
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Abstract

The invention discloses a preparation method of a novel iron nitride and porous carbon composite anode material, and belongs to the technical field of lithium ion batteries. The method comprises the following steps: adding non-ionic polyacrylamide, urea and sodium chloride into deionized water, adding ferric nitrate under the condition of stirring after completely dissolving, heating the obtained mixed solution in a water bath to be viscous, freeze-drying, calcining the dried product under the inert atmosphere, and finally washing with deionized water and carrying out suction filtration to obtain the product. The iron nitride and porous carbon composite cathode material prepared by the preparation method provided by the invention has excellent cycling stability and rate capability, the synthesis method is green and simple, the cost is low, and the iron nitride and porous carbon composite cathode material is expected to become a novel cathode material for large-scale use.

Description

Preparation method of novel iron nitride and porous carbon composite anode material
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a novel iron nitride and porous carbon composite anode material.
Background
Lithium ion batteries are widely used due to their advantages of less environmental pollution, longer cycle life, etc., but large-scale applications of electric vehicles and hybrid electric vehicles have a strong demand for higher power density and energy density of lithium ion batteries. At present, the graphite cathode of a commercial lithium ion battery reaches the theoretical limit, and the iron nitride has the advantages of no toxicity, low price, higher conductivity, excellent electrochemical performance and the like. However, iron nitride has problems such as rapid capacity fading due to large volume change during charge and discharge.
In order to solve the above problems, two effective methods are proposed. One approach is to reduce the particle size of the iron nitride to the nanometer level; in the other method, iron nitride and a carbon material are compounded, so that the volume change in the charge and discharge process can be relieved, the conduction speed of electrons and lithium ions is obviously increased, and the electrochemical performance is improved. It is clear that combining the advantages of the two methods, namely the construction of a composite of iron nitride nanoparticles and carbon, allows to achieve excellent electrochemical performances. In recent years, scientists report that a series of composite materials of iron nitride nanoparticles and carbon as negative electrode materials of lithium ion batteries show better electrochemical performance. However, the synthesis methods in the prior art are complex, long in period and high in cost; worse, the products are obtained by calcining in ammonia atmosphere, and the safety is poor. In order to avoid the above technical problems, it is necessary to provide a method for preparing a novel iron nitride and porous carbon composite anode material to overcome the above-mentioned drawbacks in the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a novel iron nitride and porous carbon composite cathode material, aiming at solving the problems that the synthesis methods of the iron nitride and porous carbon composite cathode material in the prior art are complex, long in period and high in cost; worse, the products are obtained by calcining in ammonia atmosphere, and the safety is poor.
The invention is realized in such a way that a preparation method of a novel iron nitride and porous carbon composite anode material comprises the following steps:
1) dissolving nonionic polyacrylamide, urea and sodium chloride in deionized water, adding ferric nitrate nonahydrate under the stirring condition, and stirring to be viscous under the water bath condition;
2) cooling the sample obtained in the step 1) by liquid nitrogen, freezing and drying the sample, and calcining the dried sample in argon atmosphere;
3) washing and filtering the sample obtained in the step 2) by using deionized water, and drying the washed sample in a vacuum oven to obtain the iron nitride and porous carbon composite cathode material.
The further technical scheme comprises the following specific steps: in the step 1), 1.6g of nonionic polyacrylamide, 0.1-2 g of urea and 0.1-5 g of sodium chloride are weighed and dissolved in 100mL of deionized water, 0.8g of ferric nitrate nonahydrate is added under the stirring condition, and the mixture is stirred for 1-8 hours under the water bath condition of 60-95 ℃ until the mixture is sticky;
in the step 2), the sample obtained in the step 1) is cooled by liquid nitrogen and then is freeze-dried for 6-72 hours, and the dried sample is calcined for 0.5-4.5 hours at the high temperature of 450-750 ℃ in an argon atmosphere;
in the step 3), the sample obtained in the step 2) is washed and filtered by deionized water, and the washed sample is placed into a vacuum oven to be dried for 2-72 hours at the temperature of 40-90 ℃ to obtain the iron nitride and porous carbon composite cathode material.
According to a further technical scheme, in the step 1), the mass ratio of the nonionic polyacrylamide to the ferric nitrate nonahydrate is 1: (0.2-2).
In the step 1), ferric chloride hexahydrate or ferrous chloride tetrahydrate is used for replacing ferric nitrate nonahydrate, and other conditions are kept the same.
The novel iron nitride and porous carbon composite anode material is prepared by the preparation method of the novel iron nitride and porous carbon composite anode material, and the novel iron nitride and porous carbon composite anode material is Fe24N10And porous carbon composite negative electrode material.
A method for preparing a lithium ion battery by using the novel iron nitride and porous carbon composite negative electrode material comprises the following steps:
mixing Fe24N10Mixing with porous carbon composite negative electrode material and 20% of conductive agent, mixing with N-methyl pyrrolidone solution containing 10% of binder, stirring uniformly, coating on copper foil, and drying in a vacuum oven at 100 deg.C; then, cutting out the electrode slice by using a slicer with the diameter of 14mm, and drying the electrode slice in a vacuum oven at the temperature of 80 ℃ for 6-12 hours; and then transferring the mixture into a glove box filled with argon, and assembling the button cell by taking a metal lithium sheet as a counter electrode, a polypropylene porous membrane as a diaphragm and 1mol/L mixed solution of ethylene carbonate and dimethyl carbonate of lithium hexafluorophosphate as electrolyte.
According to a further technical scheme, the novel iron nitride and porous carbon composite anode material comprises the following components in percentage by weight: the mass ratio of the binder is 7: 1, said Fe24N10And porous carbon composite anode material: the mass ratio of the conductive agent is 7: 2.
according to a further technical scheme, the binder is polyvinylidene fluoride, and the conductive agent is conductive carbon black.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a preparation method of a novel iron nitride and porous carbon composite anode material, which comprises the following steps:
1. the method is realized by simple stirring, freeze drying, calcining and water washing, the whole process is green and simple, the consumed time is short, the controllability is strong, the cost is low, and the method is suitable for industrial production;
2. compared with the synthesis of other iron nitrides, the nitrogen source used by the invention is polyacrylamide and a small amount of urea, and compared with ammonia gas, the nitrogen source has the advantages of less pollution and higher safety;
3. the lithium ion battery prepared from the novel iron nitride and porous carbon composite cathode material has excellent cycle stability and rate capability.
Drawings
FIG. 1 is Fe provided in the examples of the present invention24N10And a flow chart of a preparation method of the porous carbon composite anode material.
FIG. 2 is Fe provided in the examples of the present invention24N10XRD, Raman, nitrogen adsorption and pore distribution of the porous carbon composite negative electrode material. 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 is Fe provided in the examples of the present invention24N10XPS spectra of the region with the porous carbon composite anode material N1 s.
FIG. 4 is Fe provided in the examples of the present invention24N10SEM, TEM, and HRTEM images of the anode material with porous carbon composite. In the figure: (a) and (b) is an SEM image; (c) is a nitrogen TEM image; (d) HRTEM image.
FIG. 5 shows Fe provided in the examples of the present invention24N10Porous carbon composite anode material and Fe24N10And the electrochemical performance of the carbon composite anode material. In the figure: (a) is a CV curve; (b) is a voltage curve; (c) a cycle performance and coulombic efficiency chart of a lithium ion battery assembled by the lithium ion battery with a current density of 100mA/g and a voltage range of 3-0.01V; (d) the multiplying power performance graph under different current densities is shown; (e) the cycle performance at a current density of 2000mA/g is shown.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and 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.
1): weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under the stirring condition, and stirring for 4 hours at 80 ℃ in a water bath to be viscous;
2): cooling the sample obtained in the step 1) by liquid nitrogen, freeze-drying and drying for 24 hours, and calcining the dried sample at the high temperature of 700 ℃ for 1 hour in the argon atmosphere;
3): washing the product obtained by the sample obtained in the step 2) with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at the temperature of 60 ℃ for 6 hours to obtain the iron nitride and porous carbon composite negative electrode material;
in the step 1), the adding amount of the urea is 0.1-2 g, the adding amount of the sodium chloride is 0.1-5 g, and the mass ratio of the nonionic polyacrylamide to the ferric nitrate nonahydrate is 1: (0.2-2);
the calcining conditions in the step 2) comprise: the calcining temperature is 450-750 ℃, the calcining time is 0.5-4.5 h, 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 60-95 ℃, and the water bath time is 1-8 h;
the freeze-drying conditions of step 3) include: the drying time is 6-72 h;
taking the iron nitride and porous carbon composite cathode material as a lithium ion battery cathode material;
ferric chloride hexahydrate or ferrous chloride tetrahydrate is used for replacing ferric nitrate nonahydrate, and other conditions are the same, so that the ferric nitride and porous carbon composite negative electrode material can be prepared;
the application principle of the present invention is further described below with reference to specific embodiments:
example 1
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
The implementation effect is as follows: the novel Fe prepared in this example24N10And (3) assembling the porous carbon composite negative electrode material into a battery for charge and discharge tests, wherein a cycle performance diagram of the lithium ion battery assembled in a voltage range of 3-0.01V at a current density of 100mA/g is shown in figure 5 c. The first discharge capacity is 1081mAh/g, the first reversible capacity is 607mAh/g, the first coulombic efficiency is 59%, and the circulation stability is good. FIG. 5d shows the rate capability at different current densities, and at a current density of 2000mA/g, the capacity of 356mAh/g still remains, and the rate capability is very good. FIG. 5e is a graph of cycling performance at a current density of 2000mA/g, and it can be seen that it still exhibits good cycling performance at high current densities.
Example 2
Weighing 1.6g of nonionic polyacrylamide and 0.2g of urea, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under the stirring condition, stirring for 4 hours under the water bath condition of 80 ℃ to be viscous, cooling by using liquid nitrogen, freeze-drying for 24 hours, treating a dried sample for 1 hour at 700 ℃ in an argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven for 6 hours at 60 ℃ to obtain the Fe24N10And carbon composite negative electrode material.
The implementation effect is as follows: the novel Fe prepared in this example24N10The carbon composite negative electrode material and the carbon composite negative electrode material are assembled into a battery to be subjected to charge and discharge tests, the charge and discharge tests are performed on the battery with the current density of 100mA/g, the first discharge capacity is 927mAh/g, the charge capacity is 506mAh/g, the first charge and discharge coulombic efficiency is 55%, and the discharge capacity is maintained to be 438mAh/g after 80 cycles of circulation.
Example 3
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours under the water bath condition of 60 ℃ to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating a dried sample in an argon atmosphere at 700 ℃ for 1 hour, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 4
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours under the condition of 70 ℃ water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 5
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 90 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 6
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 90 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 500 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 7
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 90 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating a dried sample at 600 ℃ for 1 hour in an argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and placing the washed sample in a vacuum oven at 60 DEG CDrying for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 8
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 48 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 9
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 72 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 10
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 2 hours in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 11
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, and dryingTreating the sample at 700 ℃ for 4 hours in argon atmosphere, washing the obtained product with deionized water, filtering, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 12
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 50 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 13
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 70 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 14
Weighing 1.6g of nonionic polyacrylamide, 0.5g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 15
Weighing 1.6g of nonionic polyacrylamide, 1.0g of urea and 1.0g of sodium chloride, dissolving in 100mL of deionized water, and stirringAdding 0.8g of ferric nitrate nonahydrate under the condition of 80 ℃ water bath, stirring for 4 hours until the mixture is viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, performing suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 16
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 2.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode material.
Example 17
Weighing 1.6g of nonionic polyacrylamide, 0.2g of urea and 4.0g of sodium chloride, dissolving in 100mL of deionized water, adding 0.8g of ferric nitrate nonahydrate under stirring, stirring for 4 hours at 80 ℃ in a water bath to be viscous, cooling by liquid nitrogen, freeze-drying for 24 hours, treating the dried sample at 700 ℃ for 1 hour in argon atmosphere, washing the obtained product with deionized water, carrying out suction filtration, and drying the washed sample in a vacuum oven at 60 ℃ for 6 hours to obtain the Fe24N10And porous carbon composite negative electrode 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.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (8)

1. A preparation method of a novel iron nitride and porous carbon composite anode material is characterized by comprising the following steps:
1) dissolving nonionic polyacrylamide, urea and sodium chloride in deionized water, adding ferric nitrate nonahydrate under the stirring condition, and stirring to be viscous under the water bath condition;
2) cooling the sample obtained in the step 1) by liquid nitrogen, freezing and drying the sample, and calcining the dried sample in argon atmosphere;
3) washing and filtering the sample obtained in the step 2) by using deionized water, and drying the washed sample in a vacuum oven to obtain the iron nitride and porous carbon composite cathode material.
2. The preparation method of the novel iron nitride and porous carbon composite anode material according to claim 1, characterized by comprising the following specific steps:
in the step 1), 1.6g of nonionic polyacrylamide, 0.1-2 g of urea and 0.1-5 g of sodium chloride are weighed and dissolved in 100mL of deionized water, 0.8g of ferric nitrate nonahydrate is added under the stirring condition, and the mixture is stirred for 1-8 hours under the water bath condition of 60-95 ℃ until the mixture is sticky;
in the step 2), the sample obtained in the step 1) is cooled by liquid nitrogen and then is freeze-dried for 6-72 hours, and the dried sample is calcined for 0.5-4.5 hours at the high temperature of 450-750 ℃ in an argon atmosphere;
in the step 3), the sample obtained in the step 2) is washed and filtered by deionized water, and the washed sample is placed into a vacuum oven to be dried for 2-72 hours at the temperature of 40-90 ℃ to obtain the iron nitride and porous carbon composite cathode material.
3. The preparation method of the novel iron nitride and porous carbon composite anode material according to claim 1, wherein in the step 1), the mass ratio of the nonionic polyacrylamide to the ferric nitrate nonahydrate is 1: (0.2-2).
4. The preparation method of the novel iron nitride and porous carbon composite anode material according to claim 1, characterized in that in step 1), ferric chloride hexahydrate or ferrous chloride tetrahydrate is used instead of ferric nitrate nonahydrate, and other conditions are kept the same.
5. The iron nitride and porous carbon composite anode material prepared by the preparation method of the novel iron nitride and porous carbon composite anode material according to claim 1, wherein the novel iron nitride and porous carbon composite anode material is Fe24N10And porous carbon composite negative electrode material.
6. A method for preparing a lithium ion battery by using the novel iron nitride and porous carbon composite anode material as claimed in claim 5, wherein the method for preparing the lithium ion battery comprises the following steps:
mixing Fe24N10Mixing with porous carbon composite negative electrode material and 20% of conductive agent, mixing with N-methyl pyrrolidone solution containing 10% of binder, stirring uniformly, coating on copper foil, and drying in a vacuum oven at 100 deg.C; then, cutting out the electrode slice by using a slicer with the diameter of 14mm, and drying the electrode slice in a vacuum oven at the temperature of 80 ℃ for 6-12 hours; and then transferring the mixture into a glove box filled with argon, and assembling the button cell by taking a metal lithium sheet as a counter electrode, a polypropylene porous membrane as a diaphragm and 1mol/L lithium hexafluorophosphate mixed solution of ethylene carbonate and dimethyl carbonate as electrolyte.
7. The method for preparing a lithium ion battery according to claim 6, wherein the novel iron nitride and porous carbon composite anode material: the mass ratio of the binder is 7: 1, said Fe24N10And porous carbon composite anode material: the mass ratio of the conductive agent is 7: 2.
8. the method of claim 6, wherein the binder is polyvinylidene fluoride and the conductive agent is conductive carbon black.
CN202110635456.5A 2021-06-07 2021-06-07 Preparation method of novel iron nitride and porous carbon composite anode material Pending CN113371688A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114554819A (en) * 2022-02-25 2022-05-27 山东大学 Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof
CN114852974A (en) * 2022-04-14 2022-08-05 平顶山学院 Gram-level high oxidation state single atomic site FeN 5 Electrocatalyst and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004022484A1 (en) * 2002-09-05 2004-03-18 National Institute Of Advanced Industrial Science And Technology Carbon fine powder coated with metal oxide, metal nitride or metal carbide, process for producing the same, and supercapacitor and secondary battery using the carbon fine powder
CN105977458A (en) * 2016-05-09 2016-09-28 吉林大学 Nano diamond powder and graphene composite electrode material and preparation method thereof
CN107068994A (en) * 2017-01-17 2017-08-18 陕西科技大学 A kind of preparation method of the carbon load nitridation iron complexes anode material of lithium-ion battery of N doping
CN107768645A (en) * 2017-11-28 2018-03-06 吉林大学 A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof
CN110867565A (en) * 2019-07-26 2020-03-06 吉林大学 Preparation method of carbon-coated silicon and zinc oxide composite electrode material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004022484A1 (en) * 2002-09-05 2004-03-18 National Institute Of Advanced Industrial Science And Technology Carbon fine powder coated with metal oxide, metal nitride or metal carbide, process for producing the same, and supercapacitor and secondary battery using the carbon fine powder
CN105977458A (en) * 2016-05-09 2016-09-28 吉林大学 Nano diamond powder and graphene composite electrode material and preparation method thereof
CN107068994A (en) * 2017-01-17 2017-08-18 陕西科技大学 A kind of preparation method of the carbon load nitridation iron complexes anode material of lithium-ion battery of N doping
CN107768645A (en) * 2017-11-28 2018-03-06 吉林大学 A kind of porous nitrogen-doped carbon nanometer sheet composite negative pole material and preparation method thereof
CN110867565A (en) * 2019-07-26 2020-03-06 吉林大学 Preparation method of carbon-coated silicon and zinc oxide composite electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C ZHANG ET AL.: "Facile synthesis of Fe24N10/porous carbon as a novel high-performance anode material for lithium-ion batteries", 《MATERIALS LETTERS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114554819A (en) * 2022-02-25 2022-05-27 山东大学 Electromagnetic wave absorber based on iron-based metal organic framework material and preparation method thereof
CN114852974A (en) * 2022-04-14 2022-08-05 平顶山学院 Gram-level high oxidation state single atomic site FeN 5 Electrocatalyst and preparation method and application thereof

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