CN109742350B - Preparation method of nitrided ferroferric oxide/graphene composite material - Google Patents
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Abstract
The invention provides nitrided Fe3O4The preparation method of the/graphene composite material is characterized by comprising the following steps: adopting ferrocene as raw material, carrying out thermal cracking for 4-6h at 500-600 ℃ to obtain Fe2O3Of Fe2O3And the graphene oxide according to the mass ratio of 5-10: 1 mixing and grinding to obtain Fe2O3A mixture with graphene oxide; the resulting mixture is reacted in NH3Under the condition of flow rate of 80-100mL/min and NH3Carrying out auto-oxidation reduction reaction and nitridation treatment in the atmosphere at the temperature of 500-600 ℃, reacting for 4-8h, and then carrying out reaction on NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material. The resulting Fe3O4‑XThe Nx/Ny-graphene composite material has higher specific surface area up to 150m2The composite material has good charge and discharge performance in 0.1Ag‑1The discharge capacity is 1500mAhg‑1The material has high stability and is 0.5Ag after 250 cycles‑1The discharge capacity can be kept to be 850mAhg‑1。
Description
Technical Field
The invention belongs to the field of photoelectricity, and relates to an electrode material, in particular to Fe3O4A preparation method of an-xNx/N-graphene composite material.
Background
The carbon material is the most widely used lithium ion battery negative electrode material so far, but the biggest defect is that the theoretical specific capacity is only 372mAh g-1And the requirement of the modern society on the portable high-energy mobile power supply cannot be met. Therefore, it is important to search for new substitute materials having excellent properties. The oxides of transition metals such as Fe, Co, Ni and Cu have high specific capacities (generally 700mAh g)-1Above), becomes a type of negative electrode material of lithium ion batteries that has received attention. In the transition metal oxide-based lithium ion negative electrode material, Fe3O4Is one of the negative electrode materials with comparative application potential, and the theoretical capacity of the material is 926mAh g-1In addition, the method has the characteristics of low price, rich resources, environmental friendliness and the like, so that great attention is paid to the method. However, when ferroferric oxide is used as an electrode material, the electronic conductivity of the ferroferric oxide is poor, and large volume change can be generated in the charging and discharging processes, so that the structure of particles and the whole electrode is damaged, and the cycle life is poor. Thirdly, Fe3O4The magnetic particles are easily agglomerated and the number of reactive sites is reduced, so that improvement of Fe is required3O4The performance of (c).
In the past few years, great efforts have been made to solve these problems, and it is a common method to synthesize various nanostructures by changing surface morphology, reducing particle size, building porous structures, and incorporating conductive agents such as carbon-based and graphene-based materials. Recently, a three-dimensional graphene network structure containing a metal oxide has attracted a wide attention due to its unique properties. Application number CN 106935830A discloses a lithium ion battery composite anode material and a preparation method and application thereof. Li [ Ni ] disclosed in the application1-x-yCoxMny]O2The three-dimensional graphene anode material has larger capacity, the method for preparing the anode material is simple to operate, but the electrochemical performance of the lithium ion battery prepared by the technical method is not obviously improved, and certain limitation exists. Application number CN107293710A discloses a preparation method of a transition metal oxide/graphene composite material. The lithium ion battery prepared by the method has good cycle stability,but the battery capacity is slightly insufficient. The highest is ferric oxide/graphene composite material, and the battery capacity is 1252.7mAhg-1However, under the conditions of high current density and complex synthesis, the iron oxide composite material has poor cycle stability.
Disclosure of Invention
Aiming at the defects of low initial coulomb efficiency, quick cycle attenuation and poor rate capability of the ferroferric oxide as the electrode cathode material, the invention aims to improve the charge-discharge performance of the ferroferric oxide as the electrode cathode material.
In order to achieve the above object, the present invention provides a nitrided Fe3O4A preparation method of a graphene composite material. The invention innovatively provides that the nitrided graphene is used as a carrier and embedded with the iron tetroxide, so that the conductivity can be improved on the one hand, and the Fe problem is solved on the other hand3O4The preparation method mainly utilizes a mode that the autooxidation reduction reaction of iron oxide and graphene oxide and the nitridation treatment process of ammonia gas are synchronously carried out, and is simple and easy to operate. The invention innovatively provides the method for synthesizing Fe by using the graphite thermal method3O4Graphene nanocomposite, Fe3O4The graphene composite electrode has good cycling stability in charge-discharge cycles.
Nitrided Fe of the invention3O4The preparation method of the/graphene composite material is characterized by comprising the following steps: adopting ferrocene as raw material, carrying out thermal cracking for 4-6h at 500-600 ℃ to obtain Fe2O3Of Fe2O3And the graphene oxide according to the mass ratio of 5-10: 1 mixing and grinding to obtain Fe2O3A mixture with graphene oxide; the resulting mixture is reacted in NH3Under the condition of flow rate of 80-100mL/min and NH3Carrying out auto-oxidation reduction reaction and nitridation treatment in the atmosphere at the temperature of 500-600 ℃, reacting for 4-8h, and then carrying out reaction on NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material.
Preferably, said nitrided Fe3O4The molecular formula of the graphene composite material is Fe3O4-XNx/Ny-graphene, wherein x is 0.1-0.25, and y is 1% -8%.
Preferably, the graphene oxide is prepared by a modified hummer method.
Preferably, the nitriding and the auto-redox processes occur simultaneously.
Preferably, the resulting nitrided Fe3O4The specific surface area of the graphene composite material reaches 150m2More than g.
Preferably, the resulting nitrided Fe3O4The graphene composite material is 0.1Ag-1The discharge capacity is 1500mAhg-1After 250 cycles, at 0.5Ag-1The discharge capacity can be kept to be 850mAhg-1。
The invention firstly obtains Fe with controllable shape by a thermal cracking method2O3And Fe is reduced by carbothermic reduction of iron oxide with graphene oxide2O3Reduction to Fe3O4And the graphene oxide is subjected to self-reduction in the heating process to form graphene. Meanwhile, in the ammonia atmosphere, in the dynamic process of the reduction reaction, Fe3O4Introducing a nitrogen source into the surface of the graphene to form nitrided Fe3O4A graphene composite material. The self-oxidation-reduction reaction and the nitridation treatment process lead the nanoscale nitrided Fe3O4The particles are encapsulated in the space and dispersed on the surface of the nitrided graphene nanoplatelets, which not only effectively promotes the electron transport between the two, but also significantly enhances the electrical conductivity of the composite containing the two. On one hand, the composite material is characterized in that a single carbon atom layer has strong flexibility and can deform along with the change of an external force under the condition of not destroying the internal structure of an internal carbon atom, so that the structural stability of the composite material is maintained, and as a result, the composite material shows excellent electrode rate and stability in the aspect of electrochemistry, which is mainly because (1) a large amount of oxygen-containing functional groups Fe exist on a graphene sheet3O4The nano material can be compounded with graphene through chemical bonds to preventStopping the falling and damage of materials in the reaction process; (2) the excellent conductivity of the azotized graphene can ensure good electrochemical contact among ferroferric oxide particles, and the interaction among graphene sheet layers can form a three-dimensional nano-network structure, so that the contact resistance is reduced, and the rate capability in electrochemistry is improved. The advantages enable the composite electrode to have great application value in the anode material of the lithium ion battery.
The invention provides a method for synchronously carrying out the autoxidation reduction reaction of iron oxide and graphene oxide and the nitridation treatment process of ammonia gas, and Fe for realizing nitridation treatment3O4And preparation of the graphene composite material. The preparation process is simple and easy to operate, and the obtained product has the advantages of large specific surface area, large specific capacity and high stability.
The present invention is a significant improvement over the prior inventions. The method makes full use of the auto-oxidation reduction reaction of the iron oxide and the graphene oxide, and simultaneously realizes the nitridation process. The resulting nitrided Fe3O4The graphene composite material has a high specific surface area which can reach 150m2The composite material has good charge and discharge performance in 0.1Ag-1The discharge capacity is 1500mAhg-1The material has high stability and is 0.5Ag after 250 cycles-1The discharge capacity can be kept to be 850mAhg-1。
Drawings
FIG. 1 SEM photograph of example 1;
FIG. 2 TEM image of example 2;
FIG. 3 a TEM image of example 3;
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The graphene oxide in the following examples is prepared by an improved hummer method, and the specific method is as follows:
step a) 0.6g of graphite and 1.0g of NaNO were weighed out separately3Putting the mixture into a 250ml beaker, and slowly adding 35ml of H with the mass concentration of 95-98% under the conditions of ice-water bath and stirring2SO4Stirring for 1 h;
step b) slowly add 3g KMnO4After 1 hour of addition, stirring for 4 hours;
and c) removing the ice water bath, heating to 35 ℃, and continuing stirring for 30 min. 150ml of distilled water is slowly added, and after the reaction is finished, the temperature is raised to 98 ℃, and the stirring is carried out for 15 min.
Step d) preheating 200ml of pure distilled water at 60 ℃ in advance, slowly pouring the solution reacted in the step c) into hot water under stirring, and adding 10ml of H with the mass concentration (30%)2O2Added to the solution. At this point the solution turned yellow and was allowed to stand overnight.
And e) centrifugally washing to obtain the graphene oxide.
Example 1
Nitrided Fe3O4The preparation method of the graphene composite material comprises the following specific steps:
(1) fe is prepared by using ferrocene as a raw material and thermally cracking for 4 hours at 600 DEG C2O3；
(2) Preparing graphene oxide according to the improved hummer method;
(3) fe obtained from (1) and (2)2O3And the graphene oxide by mass ratio of 8: 1 mixing and grinding to obtain Fe2O3And graphene oxide.
(4) Mixing the homogeneous mixture obtained in step (3) in NH3At a flow rate of 80mL/min in NH3Performing auto-oxidation reduction reaction and nitridation treatment at 500 deg.C in the atmosphere, reacting for 6h, and reacting with NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material.
(5) The content of Fe was detected by ICP, the content of N in the composite material was quantitatively analyzed by elemental analysis and XPS, and the content of O was monitored by XPS. Of the composite materials obtained in the examplesThe molecular formula is: (Fe)3O3.85N0.15/N0.05-graphene).
The specific surface area is 180.5m by adopting a nitrogen adsorption and desorption method BET method2/g。
SEM morphology analysis of the obtained sample was carried out by Hitachi S-4800II of Japan, and it was found that Fe nitride was produced3O4The graphene is in a spindle shape, the size of the graphene is about 50nm, and the graphene is uniformly distributed on the surface of the graphene.
Nitriding the obtained Fe3O4Graphene composite material, acetylene black and polytetrafluoroethylene emulsion ((specific gravity 25 ℃ 1.52 g/cm)3Solid content of 60%) in a mass ratio of 8: 2: 1, weighing, mixing, coating on a processed foam nickel plate, flattening and drying to perform electrochemical performance test. The composite material has good charge and discharge performance, and the charge and discharge performance is 0.1Ag-1The discharge capacity is 1200mAhg-1The material has high stability and is 0.5Ag after 250 cycles-1The discharge capacity can be maintained at 780mAhg-1。
Example 2
Nitrided Fe3O4The preparation method of the graphene composite material comprises the following specific steps:
(1) fe is prepared by using ferrocene as a raw material and thermally cracking for 4 hours at 500 DEG C2O3；
(2) Preparing graphene oxide according to the improved hummer method;
(3) fe obtained from (1) and (2)2O3And the graphene oxide according to the mass ratio of 7: 1 mixing and grinding to obtain Fe2O3And graphene oxide.
(4) Mixing the homogeneous mixture obtained in step (3) in NH3At a flow rate of 100mL/min in NH3Performing auto-oxidation reduction reaction and nitridation treatment at 600 deg.C in the atmosphere, reacting for 4h, and reacting with NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material.
(5) The content of Fe was measured by ICP, and the content of N in the composite material was quantitatively analyzed by elemental analysis and XPSAmount, content of O was monitored by XPS. The molecular formula of the composite material obtained in the examples is: (Fe)3O3.80N0.2/N0.05-graphene).
The specific surface area is 200.2m by adopting a nitrogen adsorption and desorption method BET method2/g。
TEM morphology analysis of the obtained sample with Hitachi S-4800II of Japan revealed nitrided Fe having a diameter size of about 60nm3O4The nano-spherical particles are distributed on the surface of the graphene.
Nitriding the obtained Fe3O4Graphene composite material, acetylene black and polytetrafluoroethylene emulsion (specific gravity of 1.52g/cm at 25℃)3Solid content of 60%) in a mass ratio of 8: 2: 1, weighing, mixing, coating on a processed foam nickel plate, flattening and drying to perform electrochemical performance test. The composite material has good charge and discharge performance, and the charge and discharge performance is 0.1Ag-1The discharge capacity is 1500mAhg-1The material has high stability and is 0.5Ag after 250 cycles-1The discharge capacity can be kept to be 850mAhg-1。
Example 3
Nitrided Fe3O4The preparation method of the graphene composite material comprises the following specific steps:
(1) fe is prepared by using ferrocene as a raw material and thermally cracking for 5 hours at 550 DEG C2O3；
(2) Preparing graphene oxide according to the improved hummer method;
(3) fe obtained from (1) and (2)2O3And graphene oxide according to the mass ratio of 6: 1 mixing and grinding to obtain Fe2O3And graphene oxide.
(4) Mixing the homogeneous mixture obtained in step (3) in NH3At a flow rate of 90mL/min in NH3Performing auto-oxidation reduction reaction and nitridation treatment at 550 ℃ in the atmosphere at the same time, reacting for 8h, and then performing reaction on NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material.
(5) The content of Fe is detected by utilizing ICP,the content of N in the composite material was quantitatively analyzed by elemental analysis and XPS, and the content of O was monitored by XPS. The molecular formula of the composite material obtained in the examples is: (Fe)3O3.72N0.28/N0.06-graphene).
The specific surface area is 160m by adopting an ammonia adsorption and desorption method BET method2/g。
The TEM morphology analysis of the obtained sample by using Hitachi S-4800II of Japan shows that the nitrided Fe3O4 exists in the form of aggregates and is paved on the surface of graphene. However, careful observation revealed that the agglomerates consisted of a large number of small nanoparticles.
Mixing the composite material with acetylene black and polytetrafluoroethylene emulsion (specific gravity of 1.52g/cm at 25℃)3Solid content of 60%) in a mass ratio of 8: 2: 1, weighing, mixing, coating on a processed foam nickel plate, flattening and drying to perform electrochemical performance test. The composite material has good charge and discharge performance, and the charge and discharge performance is 0.1Ag-1The discharge capacity was 1300mAhg-1The material has high stability and is 0.5Ag after 250 cycles-1Still can keep the discharge capacity of 840mAhg-1。
Example 4
Nitrided Fe3O4The preparation method of the graphene composite material comprises the following specific steps:
(1) fe is prepared by using ferrocene as a raw material and thermally cracking for 4 hours at 600 DEG C2O3；
(2) Preparing graphene oxide according to the improved hummer method;
(3) fe obtained from (1) and (2)2O3And graphene oxide according to the mass ratio of 6: 1 mixing and grinding to obtain Fe2O3And graphene oxide.
(4) Mixing the homogeneous mixture obtained in step (3) in NH3At a flow rate of 90mL/min in NH3Performing auto-oxidation reduction reaction and nitridation treatment at 550 ℃ in the atmosphere at the same time, reacting for 6h, and then performing reaction on NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material.
(5) The content of Fe was detected by ICP, the content of N in the composite material was quantitatively analyzed by elemental analysis and XPS, and the content of O was monitored by XPS. The molecular formula of the composite material obtained in the examples is: (Fe)3O3.67N0.33/N0.06-graphene).
The specific surface area is 190.2m by adopting a nitrogen absorption and desorption method BET method2/g。
SEM morphology analysis was performed on the resulting sample using Hitachi S-4800II of Japan. Discovery of nitrided Fe3O4The graphene is spherical, the particle size is about 55nm, and the graphene is monodisperse on the surface of the graphene.
The composite material, acetylene black and polytetrafluoroethylene emulsion (specific gravity of 1.52g/cm at 25℃)3Solid content of 60%) in a mass ratio of 8: 2: 1, weighing, mixing, coating on a processed foam nickel plate, flattening and drying to perform electrochemical performance test. The composite material has good charge and discharge performance, and the charge and discharge performance is 0.1Ag-1The discharge capacity is 1425mAhg-1The material has high stability and is 0.5Ag after 250 cycles-1The discharge capacity can be still maintained to be 835mAhg-1。
Claims (5)
1. Nitrided Fe3O4The preparation method of the/graphene composite material is characterized by comprising the following steps: adopting ferrocene as raw material, carrying out thermal cracking for 4-6h at 500-600 ℃ to obtain Fe2O3Of Fe2O3And the graphene oxide according to the mass ratio of 5-10: 1 mixing and grinding to obtain Fe2O3A mixture with graphene oxide; the resulting mixture is reacted in NH3Under the condition of flow rate of 80-100mL/min and NH3Carrying out auto-oxidation reduction reaction and nitridation treatment in the atmosphere at the temperature of 500-600 ℃, reacting for 4-8h, and then carrying out reaction on NH3Cooling with the furnace in the atmosphere to obtain nitrided Fe3O4A graphene composite material; said nitrided Fe3O4The molecular formula of the graphene composite material is Fe3O4-xNx/Ny-graphene, wherein x is 0.1-0.25 and y is 1-8%; the self-oxidation reduction reactionComprises the following steps: fe is reduced by carbothermic-like action of graphene oxide on iron oxide2O3Reduction to Fe3O4And the graphene oxide is subjected to self-reduction in the heating process to form graphene.
2. Nitrided Fe according to claim 13O4The preparation method of the graphene/graphene composite material is characterized in that the graphene oxide is prepared by an improved hummer method.
3. Nitrided Fe according to claim 13O4The preparation method of the/graphene composite material is characterized in that the nitridation treatment and the auto-oxidation reduction process occur simultaneously.
4. Nitrided Fe according to claim 13O4The preparation method of the/graphene composite material is characterized in that the obtained nitrided Fe3O4The specific surface area of the graphene composite material reaches 150m2More than g.
5. Nitrided Fe according to claim 13O4The preparation method of the/graphene composite material is characterized in that the obtained nitrided Fe3O4The graphene composite material is 0.1A g-1The discharge capacity is 1500mAh g-1After 250 cycles, at 0.5A g-1The discharge capacity can be kept to be 850mAhg-1。
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