CN111211309A - Phosphorus-doped graphene-coated iron oxide composite material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a phosphorus-doped graphene-coated iron oxide composite material and a preparation method and application thereof. Compared with the prior art, the invention improves the cycle life and stability by doping phosphorus, the phosphorus atoms are combined with the graphene carbon atoms to enable lithium ions to be better embedded, and the graphene carbon atoms have rich stress buffering nanometer spaces, effective charge transmission and stable structural stability in the electrochemical process; the invention has the advantages of simple process, mild condition, low cost and the like; the phosphorus-doped graphene-coated iron oxide composite material prepared by the invention has excellent electrochemical performance when being used as a lithium ion battery cathode.
Description
Technical Field
The invention belongs to the technical field of material science and electrochemistry, and particularly relates to a phosphorus-doped graphene-coated iron oxide composite material as well as a preparation method and application thereof.
Background
With the rapid development of the electric automobile industry, Lithium Ion Batteries (LIBs) as electronic products become one of the important technologies for promoting future development with their high energy density, and have become an important component of technological innovation. The key of the comprehensive performance of the lithium ion battery is that the most widely applied cathode material of the electrode material at present is graphite, but the electrode material has low theoretical capacity, low stability and poor cycle ratio performance, can not meet the requirements of continuously changing novel electrode materials with good comprehensive performance, safety and convenience in development of the electronic and electrical industry, and has important significance for continuous innovation of the lithium ion battery. The metal oxides are receiving more and more attention from scholars due to their high theoretical capacity, and at present, Sn, Fe, Co, Cu and Ti are the main metal oxides of LIBs anode materials.
Fe2O3The method has the advantages of high theoretical capacity, abundant resources, environmental friendliness and the like, and is one of the research hotspots of novel high-capacity anode materials. However, Fe2O3The problems of large volume effect, poor cycle stability and the like of the anode material still need to be optimized. The currently known improvement methods are mainly multidimensional nano-structure composite materials, shell-core structures, hybrid porous crystalline metal-organic frameworks (MOFs), pore structures and the likeIn order to prevent the volume effect of iron oxide, the addition of graphene is one of the most promising methods at present, and can improve the stability and electrochemical performance while effectively controlling the volume expansion.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a phosphorus-doped graphene-coated iron oxide composite material and a preparation method and application thereof.
According to the invention, hetero atoms (particularly phosphorus) are introduced into graphene crystal lattices to further improve the electrochemical performance of graphene, and the graphene crystal lattice is applied to super capacitors and fuel cells, so that good performance is obtained. Due to the low electronegativity of phosphorus, the introduction of phosphorus into the graphene and metal oxide composite material is of great significance.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a preparation method of a phosphorus-doped graphene-coated iron oxide composite material, which comprises the steps of converting Prussian blue MOF (metal organic framework) growing on a graphene sheet in situ into graphene-coated iron oxide aerogel, and doping phosphorus atoms into graphene lattices in a calcining manner to obtain the phosphorus-doped graphene-coated iron oxide composite material.
Preferably, the method comprises the steps of:
(1) dissolving potassium ferrocyanide into a graphene oxide solution;
(2) centrifuging the solution obtained in the step (1) to remove supernatant, adding deionized water, adding ferric chloride hexahydrate, and continuing centrifuging to remove supernatant;
(3) adding the precipitate obtained in the step (2) into deionized water, carrying out hydrothermal reaction to obtain a reduced graphene oxide hydrogel composite material, and freeze-drying to obtain a graphene Prussian blue composite material;
(4) calcining the graphene Prussian blue composite material obtained in the step (3) at high temperature in an air atmosphere to obtain graphene-coated iron oxide aerogel;
(5) and (5) calcining the graphene-coated iron oxide aerogel obtained in the step (4) together with a phosphorus source in a nitrogen atmosphere to obtain the phosphorus-doped graphene-coated iron oxide composite material.
Preferably, in the step (1), the mass ratio of potassium ferrocyanide to graphene oxide is 8-12: 1.
Preferably, in the step (1), the potassium ferrocyanide is a 0.5M potassium ferrocyanide solution, and the concentration of the graphene oxide solution is 3 mg/ml.
Preferably, the solution is dark blue after the ferric chloride hexahydrate is added in step (2).
Preferably, in the step (2), the rotation speed of the centrifugation is 9000-.
Preferably, in the step (3), the temperature of the hydrothermal reaction is 160-.
Preferably, in the step (4), the high-temperature calcination is carried out in an air atmosphere at a temperature of 200-300 ℃ for 2-6 hours.
Preferably, in the step (5), the calcination conditions in the nitrogen atmosphere are as follows: the temperature rise speed is 1-3 ℃/min, the temperature rises to 200-300 ℃ for calcination, and the time is 2-6 h.
Preferably, in step (5), the phosphorus source is sodium hypophosphite.
Preferably, in step (5), flowing nitrogen is used to form a nitrogen atmosphere, and when calcining in the nitrogen atmosphere, the phosphorus source is upstream and the graphene-coated iron oxide aerogel is downstream. It is further preferred that the phosphorus source and the graphene-coated iron oxide aerogel are placed in small quartz boats, respectively, and one large quartz boat is covered over the two small quartz boats.
The invention provides a phosphorus-doped graphene-coated iron oxide composite material obtained by the preparation method.
The third aspect of the invention provides application of the phosphorus-doped graphene-coated iron oxide composite material as a negative electrode material of a lithium ion battery.
For the phosphorus-doped graphene composite material, the cycle life and the stability are improved by doping phosphorus, lithium ions are better embedded by combining phosphorus atoms with graphene carbon atoms, and the composite material has rich stress relaxationNanometer space, effective charge transport and robust structural stability in electrochemical processes. The phosphorus-doped graphene-coated iron oxide composite material obtained by the method has the advantages of simple process, mild conditions, low cost and the like. The phosphorus-doped graphene-coated iron oxide composite material prepared by the invention has excellent electrochemical performance as a lithium ion battery cathode and has the electrochemical performance of 100 mA-g-1The capacity of the battery can reach 900 mAh.g under charging and discharging current-1At 4A · g-1The lower capacity is 200mAh g-1Excellent rate capability. The method provides good experimental data and theoretical support for the research and application of the graphene-based metal oxide heteroatom doped material in the field of electrochemistry.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the phosphorus-doped graphene-coated iron oxide composite material is prepared by a calcination method, and in the calcination process, effective doping is carried out in a mode of combining three quartz boats, phosphorus atoms can be well doped, and the method is safe and simple;
2. according to the invention, the composite material is prepared by taking the metal oxide of iron as an active component, coating the active component by using the three-dimensional structure of graphene and doping phosphorus atoms, and the raw material is designable and low in cost;
3. the phosphorus-doped graphene-coated iron oxide composite material prepared by the method has high reversible capacity, very good cycle stability and rate capability, and has wide application prospect in the field of rechargeable batteries.
Drawings
FIG. 1 is an SEM topography of the phosphorus-doped graphene-coated iron oxide composite material obtained in example 1;
fig. 2 is a cycle performance diagram of the phosphorus-doped graphene-coated iron oxide composite material obtained in example 1 as a negative electrode material of a lithium ion battery;
fig. 3 is a graph of rate performance of the iron oxide-doped phosphorus atom composite materials obtained in example 1 and comparative example 1 as a negative electrode material of a lithium ion battery.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Firstly, preparing a graphene Prussian blue composite material:
(1) dissolving 2.25mL of 0.5M potassium ferrocyanide into 15mL of 3mg/mL graphene oxide solution;
(2) centrifuging the obtained solution to remove supernatant, adding 15mL of deionized water, adding 2.7g of ferric chloride hexahydrate into the solution, and then continuously centrifuging to remove the supernatant;
(3) finally, adding a proper amount of deionized water into the precipitate, and filling the precipitate into a hydrothermal kettle for hydrothermal reaction under the hydrothermal condition of 180 ℃ for 12 hours. And (4) obtaining the reduced graphene oxide hydrogel composite material, and freeze-drying to obtain the graphene Prussian blue composite material.
Step two, preparing the phosphorus-doped graphene-coated iron oxide composite material:
(1) putting the obtained material into a tubular furnace to be calcined at high temperature in the air atmosphere, keeping the temperature at 250 ℃ for 2-6 hours, then putting the material into the tubular furnace to be calcined together with a phosphorus source in the nitrogen atmosphere to finally obtain the phosphorus-doped graphene-coated iron oxide composite material, raising the temperature to 300 ℃ at the temperature raising speed of 1-3 ℃/min, keeping the temperature for 2-6 hours, wherein an SEM photograph of the phosphorus-doped graphene-coated iron oxide composite material is shown in figure 1; it is evident from fig. 1 that the iron oxide nanoparticles are distributed on and encapsulated in the graphene lamellar structure.
Comparative example 1
(1) Dissolving 2.25mL of 0.5M potassium ferrocyanide into 15mL of 3mg/mL graphene oxide solution;
(2) centrifuging the obtained solution to remove supernatant, adding 15mL of deionized water, adding 2.7g of ferric chloride hexahydrate into the solution, and then continuously centrifuging to remove the supernatant;
(3) finally, adding a proper amount of deionized water into the precipitate, and filling the precipitate into a hydrothermal kettle for hydrothermal reaction under the hydrothermal condition of 180 ℃ for 12 hours. And (4) obtaining the reduced graphene oxide hydrogel composite material, and freeze-drying to obtain the graphene Prussian blue composite material. And finally calcining in an air atmosphere, and keeping the temperature at 250 ℃ for 2-6 hours to obtain the graphene coated iron oxide composite material.
(2) The obtained composite material is used as a lithium ion battery cathode material to assemble a lithium ion button type half battery (the counter electrode is metal lithium), the obtained composite material aerogel is physically pressed to prepare a cathode, and a pure lithium sheet is used as the counter electrode. Mixing 1M NaPF6The electrolyte is prepared by dissolving the electrolyte in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC) (volume ratio is 1:1), and electrochemical tests are carried out by using a button type half cell, and the cycle performance diagram and the rate performance diagram are respectively shown in figures 2 and 3. In FIG. 2, P-Fe2O3@ RG denotes the composite material obtained in example 1, Fe2O3@ RG denotes the composite material prepared in comparative example 1, and it is apparent from fig. 2 that the cycle performance stability of the composite material is greatly improved after doping with the P element. And it can be seen from fig. 3 that the capacity of the rate capability is also significantly improved after the P element is introduced. (P-Fe in the figure)2O3@ RG denotes P element doped graphene-based iron oxide composite material)
Example 2
The present embodiment is substantially the same as embodiment 1, except that the mass ratio of potassium ferrocyanide to graphene oxide is 8:1 in the present embodiment.
Example 3
The present embodiment is substantially the same as embodiment 1, except that the mass ratio of potassium ferrocyanide to graphene oxide is 12:1 in the present embodiment.
Example 4
This example is substantially the same as example 1 except that the hydrothermal reaction temperature was 160 ℃ and the hydrothermal reaction time was 24 hours.
Example 5
This example is substantially the same as example 1 except that the hydrothermal reaction temperature was 200 ℃ and the hydrothermal reaction time was 6 hours.
Example 6
This example is substantially the same as example 1 except that the high-temperature calcination was carried out in an air atmosphere at a temperature of 300 ℃ for 2 hours.
Example 7
This example is substantially the same as example 1 except that the high-temperature calcination was carried out in an air atmosphere at a temperature of 200 ℃ for 6 hours.
Example 8
This example is substantially the same as example 1, except that in this example, the temperature was raised to 200 ℃ at a temperature raising rate of 1 to 3 ℃/min and the calcination was carried out for 6 hours.
Example 9
This example is substantially the same as example 1, except that in this example, the temperature was raised to 250 ℃ at a temperature raising rate of 1 to 3 ℃/min and the calcination was carried out for 2 hours.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The preparation method of the phosphorus-doped graphene-coated iron oxide composite material is characterized by converting Prussian blue MOF growing on a graphene sheet in situ into graphene-coated iron oxide aerogel, and doping phosphorus atoms into graphene lattices in a calcining manner to obtain the phosphorus-doped graphene-coated iron oxide composite material.
2. The preparation method of the phosphorus-doped graphene-coated iron oxide composite material according to claim 1, comprising the following steps:
(1) dissolving potassium ferrocyanide into a graphene oxide solution;
(2) centrifuging the solution obtained in the step (1) to remove supernatant, adding deionized water, adding ferric chloride hexahydrate, and continuing centrifuging to remove supernatant;
(3) adding the precipitate obtained in the step (2) into deionized water, carrying out hydrothermal reaction to obtain a reduced graphene oxide hydrogel composite material, and freeze-drying to obtain a graphene Prussian blue composite material;
(4) calcining the graphene Prussian blue composite material obtained in the step (3) at high temperature in an air atmosphere to obtain graphene-coated iron oxide aerogel;
(5) and (5) calcining the graphene-coated iron oxide aerogel obtained in the step (4) together with a phosphorus source in a nitrogen atmosphere to obtain the phosphorus-doped graphene-coated iron oxide composite material.
3. The preparation method of the phosphorus-doped graphene-coated iron oxide composite material according to claim 2, wherein in the step (1), the mass ratio of potassium ferrocyanide to graphene oxide is 8-12: 1.
4. The method for preparing the phosphorus-doped graphene-coated iron oxide composite material according to claim 2 or 3, wherein in the step (1), the potassium ferrocyanide is a 0.5M potassium ferrocyanide solution, and the concentration of the graphene oxide solution is 3 mg/ml.
5. The method for preparing the phosphorus-doped graphene-coated iron oxide composite material according to claim 2, wherein the solution obtained after adding the ferric chloride hexahydrate in the step (2) is dark blue.
6. The method for preparing the phosphorus-doped graphene-coated iron oxide composite material as claimed in claim 2, wherein in the step (3), the hydrothermal reaction is carried out at a temperature of 160-200 ℃ for 6-24 h.
7. The method for preparing the phosphorus-doped graphene-coated iron oxide composite material according to claim 2, wherein in the step (4), the high-temperature calcination is carried out in the air atmosphere at a temperature of 200-300 ℃ for 2-6 hours.
8. The preparation method of the phosphorus-doped graphene-coated iron oxide composite material according to claim 2, wherein the step (5) comprises any one or more of the following conditions:
(a) the calcination conditions in a nitrogen atmosphere were: the temperature rising speed is 1-3 ℃/min, the temperature rises to 200-300 ℃ for calcination, and the time is 2-6 h;
(b) the phosphorus source is sodium hypophosphite;
(c) and (3) forming a nitrogen atmosphere by adopting flowing nitrogen, wherein a phosphorus source is arranged at the upstream and the graphene-coated iron oxide aerogel is arranged at the downstream during calcination in the nitrogen atmosphere.
9. The phosphorus-doped graphene-coated iron oxide composite material obtained by the preparation method according to any one of claims 1 to 8.
10. The application of the phosphorus-doped graphene-coated iron oxide composite material according to claim 9, wherein the phosphorus-doped graphene-coated iron oxide composite material is used as a lithium ion battery negative electrode material.
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