CN107579241B - Preparation method of three-dimensional tent type graphene-metal oxide nano composite material - Google Patents
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Abstract
The invention discloses a preparation method of a three-dimensional tent type graphene-metal oxide nano composite material, which comprises the steps of firstly preparing three-dimensional nano porous graphene by adopting a sol-gel method; and then, soaking the prepared three-dimensional nano porous graphene into sol-gel containing an initiator and metal ions, and drying and calcining the obtained product by supercritical carbon dioxide or directly drying the product by supercritical carbon dioxide to obtain the three-dimensional tent type graphene-metal oxide nano composite material. The preparation method has the advantages of simple process, no need of adding an additive, low cost, easiness in large-scale production, good appearance structure, excellent electrochemical performance and the like of the obtained product, particularly, the porous structure in the obtained three-dimensional graphene does not appear randomly, the average pore diameter is less than 10nm, and the phenomenon that the three-dimensional graphene is easy to collapse and pile when being compounded with a metal oxide is avoided.
Description
Technical Field
The invention relates to a preparation method of a three-dimensional tent type graphene-metal oxide nano composite material capable of being used as an electrode material of a lithium ion battery, and belongs to the technical field of material preparation.
Background
Since the lithium ion battery has the advantages of high energy density and good cycle performance, the lithium ion battery has been widely applied to the fields of portable electronic products, electric vehicles and power grids since the commercialization of the lithium ion battery, and particularly, the lithium ion battery has gained more and more attention in the development of new energy industry along with the highlighting of energy and environmental problems. Electrode materials are key to improving the performance of lithium ion batteries. Graphene, whose english name is Graphene, has a two-dimensional honeycomb crystal structure formed by close packing of single-layer carbon atoms, and the unique two-dimensional structure enables the Graphene to have a large specific surface area, excellent conductivity and good mechanical properties, thereby enabling the Graphene to have a good application prospect in lithium ion battery materials. However, due to the existence of the two-dimensional structure, the graphene layers have strong van der waals force and are easy to agglomerate and accumulate into graphite sheets, and the defect of the agglomerated and accumulated graphene seriously hinders the application of the graphene in the aspect of electrode materials.
The three-dimensional graphene is formed by integrating and assembling two-dimensional graphene, so that the excellent physical and mechanical properties of the two-dimensional graphene are continued, and in addition, compared with the two-dimensional graphene, the three-dimensional porous structure unique to the three-dimensional graphene avoids the phenomenon of agglomeration and accumulation, so that the three-dimensional graphene has a wider application prospect in electrode materials. However, when the three-dimensional graphene is used as an electrode material, the three-dimensional graphene has a high power density and a high cycling stability, but the energy density is low, so the three-dimensional graphene and the metal oxide are usually compounded with metal oxides (such as manganese oxide, iron oxide, cobalt oxide, nickel oxide and the like) to prepare the three-dimensional graphene-metal oxide nanocomposite for the electrode material of the lithium ion battery.
When the three-dimensional graphene-metal oxide nanocomposite (GMOs) is applied to a lithium ion battery, the nanoscale metal oxide particles and the high-conductivity graphene can effectively shorten the diffusion path of lithium ions, so that the ohmic polarization effect at the electrode is reduced, and better performance is obtained; meanwhile, the porous structure can also effectively solve the defects of poor rate capability and cycle performance caused by volume expansion of the metal oxide in the lithiation process; moreover, GMOs serving as an electrode material has high conductivity, high mechanical strength, excellent chemical stability and high energy density, and the capacitance of the GMOs is improved by 2-5 times compared with that of a traditional graphite electrode. The advantages enable the three-dimensional graphene-metal oxide nanocomposite material to have great potential in the field of lithium ion batteries, and attract the attention of a large number of researchers.
There are many reports on three-dimensional graphene-metal oxide nanocomposites, such as: dong et al (Dong X, Wang X, Wang J, et al. Synthesis of MnO a2-graphene foam hybrid with controlled MnO2particle shape and its use as a supercapacitor electrode[J]Carbon,2012,50(13): 4865) adopts a chemical vapor deposition method to prepare three-dimensional graphene, then the three-dimensional graphene and potassium permanganate are subjected to hydrothermal reaction for 6 hours at 150 ℃, and MnO with different shapes is grown by controlling the acidity of the solution during hydrothermal reaction2To prepare three-dimensional graphene/MnO2A composite material; wang et al (Wang C, Xu J, Yuen M F, et al. high compositional impurities of nickel oxide of lake3D grams for high-performance microorganisms [ J]Adv Funct Mater,2014,24(40): 6372) growing NiO nano-sheets on the surface of the three-dimensional graphene by using microwave plasma chemical vapor deposition and a hydrothermal method by taking foamed nickel as a template to prepare a three-dimensional graphene/NiO nano-sheet composite material; dong et al (Dong C X, Xu H, Wang X W, et al.3D graphics cobalt oxide electrode for high-performance supercapacitor and enzyme glucose detection [ J)]ACS Nano,2012,6(4): 3206) three-dimensional graphene/Co is prepared by chemical vapor deposition and hydrothermal method3O4A composite material; yu et al (Yu X, Lu B, Xu Z. super Long-Life Supercapacitors Based on the Construction of Nanohycemob-Like Stronggly Coupled CoMoO4–3D Graphene Hybrid Electrodes[J]Advanced Materials,2014,26(7):1044-1051.) Co (NO)3)2·6H2O and NaMoO4·7H2Compounding the O mixed solution with the three-dimensional graphene prepared by the CVD method under the hydrothermal condition to prepare the honeycomb three-dimensional graphene/CoMoO4A composite material.
Although scholars at home and abroad make a great deal of research on the application of the three-dimensional graphene/metal oxide nanocomposite in the lithium ion battery, the preparation process of the three-dimensional graphene/metal oxide nanocomposite is complex and complicated, various additional additives (conductive agents, binders and the like) are required to be added in the preparation process, the production cost is high, impurities are easily introduced to influence the product quality, and the large-scale production is not facilitated. In addition, in the current preparation process of the three-dimensional graphene/metal oxide nanocomposite, the porous structure of the three-dimensional graphene mostly appears randomly, the size of pores mainly depends on the size of a template or appears randomly in the self-assembly process, the diameter of the pores is usually between hundreds of nanometers and hundreds of micrometers, and the pores with larger diameters reduce the mechanical property of the three-dimensional graphene, so that the three-dimensional graphene is very easy to collapse and pile when being compounded with metal oxide, the performance of the finally prepared three-dimensional graphene/metal oxide nanocomposite is influenced, and the application of the three-dimensional graphene/metal oxide nanocomposite in electrode materials is limited.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a method for preparing a three-dimensional tent type graphene-metal oxide nanocomposite material that can be used as an electrode material of a lithium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a three-dimensional tent type graphene-metal oxide nano composite material comprises the following steps:
a) uniformly stirring and mixing ammonia water and a graphene oxide aqueous solution, then placing the mixture in a closed reactor, carrying out heat preservation reaction at 80-90 ℃ until graphene gel is formed, washing the obtained graphene gel, drying the washed graphene gel by using supercritical carbon dioxide, and finally carrying out calcination treatment to obtain three-dimensional nano porous graphene;
b) and (2) soaking the prepared three-dimensional nano porous graphene into sol-gel containing an initiator and metal ions, and drying and calcining the obtained product by supercritical carbon dioxide or directly drying the product by supercritical carbon dioxide to obtain the three-dimensional tent graphene-metal oxide nano composite material.
Preferably, the concentration of the graphene oxide aqueous solution in the step a) is 1-2 wt%.
Preferably, the aqueous solution of ammonia and graphene oxide in step a) is formedAmmonium hydroxide (NH) in the mixed solution4OH) is 0.3 to 0.6 wt.%.
Preferably, the graphene gel in the step a) is washed by deionized water and acetone to remove ammonia water on the surface and in the pores, and then is dried by supercritical carbon dioxide.
Preferably, the calcination treatment in step a) is to keep the dried product at 1000-1100 ℃ for 2-5 hours under the protection of inert gas (such as nitrogen).
Preferably, step b) comprises the following steps: stirring an alcohol aqueous solution of a metal ion precursor and an initiator at room temperature until the alcohol aqueous solution and the initiator are uniformly mixed to form sol, then immersing the three-dimensional nano porous graphene into the sol, then aging at 30-70 ℃ until the sol in a reaction system forms gel, then directly drying the reaction system by using supercritical carbon dioxide, or directly drying the reaction system by using supercritical carbon dioxide and then calcining, thus obtaining the three-dimensional tent type graphene-metal oxide nano composite material.
More preferably, the alcohol-water solution in step b) is formed by ethanol and water, the concentration of metal ions in the sol is 0.05-1.4M, and the molar ratio of the initiator to the metal ions is 15: 1-1: 1 (preferably 15: 1-5: 1).
Preferably, the metal oxide is selected from Fe2O3、SnO2、TiO2At least one of (1).
As a further preferred embodiment, when the metal oxide is Fe2O3Or TiO2When the initiator in step b) is propylene oxide (i.e. propylene oxide); when the metal oxide is SnO2, the initiator of step b) is oxetane (i.e., 1, 3-propylene oxide).
As a further preferred embodiment, when the metal oxide is Fe2O3In the step b), the calcination treatment refers to heat preservation of the dried product at 500-600 ℃ for 2-5 hours under the protection of inert gas (such as nitrogen).
As a further preferred embodiment, when the metal oxide is TiO2When the calcination treatment in step b) isAnd (3) preserving the heat of the dried product at 300-400 ℃ for 3-7 hours in a normal atmosphere.
As a further preferred embodiment, when the metal oxide is SnO2In this case, no calcination is required in step b).
Compared with the prior art, the invention has the following remarkable beneficial effects:
according to the preparation method, ammonia water and a graphene oxide aqueous solution are used as raw materials, a sol-gel method is adopted to prepare the three-dimensional nano porous graphene, and then the three-dimensional nano porous graphene is immersed into sol-gel containing an initiator and metal ions to prepare the three-dimensional tent type graphene-metal oxide nano composite material, so that the preparation process is simple, additives (a conductive agent, a binder and the like) are not required to be additionally added, the interference of impurities on the performance of the composite material is avoided, the production cost is low, and the large-scale production is easy to realize; the prepared three-dimensional tent type graphene-metal oxide nano composite material avoids the agglomeration of crystals, has the advantages of good morphology structure, excellent electrochemical performance and the like, and has good use value and application prospect on the electrode material of the lithium ion battery; particularly, the three-dimensional nano porous graphite prepared by the method has the advantages of good morphology structure, large specific surface area, excellent electrochemical performance and the like, the porous structure does not appear randomly, the repeatability and stability are good, the average pore diameter is less than 10nm, the mechanical property is good, the phenomenon that the three-dimensional graphene is easy to collapse and pile when being compounded with metal oxide is avoided, the three-dimensional graphene and the metal oxide in the prepared composite material have excellent synergistic effect, and the composite material has excellent electrochemical performance.
Drawings
Fig. 1 is a process flow diagram of the present invention for preparing a three-dimensional tent graphene-metal oxide nanocomposite;
fig. 2 is a TEM image of three-dimensional nanoporous graphene prepared in example 1;
fig. 3 is an SEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2;
fig. 4 is a TEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2;
fig. 5 is a TEM image of another angle of the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2;
fig. 6 is a high resolution TEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2;
fig. 7 is a schematic macroscopic cross-sectional view of the three-dimensional tent-type graphene-iron oxide nanocomposite prepared in example 2;
fig. 8 is a particle size distribution diagram of the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2;
fig. 9 is a diffraction pattern of the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2;
fig. 10 is a TEM image of a three-dimensional tent graphene-iron oxide nanocomposite material in a lithiated state after 30 cycles;
fig. 11 is a TEM image of the three-dimensional tent graphene-titanium oxide nanocomposite prepared in example 3;
fig. 12 is a pore distribution diagram of the three-dimensional nanoporous graphene prepared in example 1, the three-dimensional tent graphene-iron oxide nanocomposite prepared in example 2, and the three-dimensional graphene-titanium oxide nanocomposite prepared in example 3;
fig. 13 is a TEM image of the three-dimensional tent graphene-tin oxide nanocomposite prepared in example 4.
Detailed Description
The technical scheme of the invention is further detailed and completely explained in the following by combining specific examples and comparative examples.
Example 1
Firstly, preparing a graphene oxide aqueous solution
And ultrasonically dispersing graphene oxide in deionized water to prepare a graphene oxide aqueous solution with the concentration of 1-2 wt% for later use.
Secondly, preparing three-dimensional nano porous graphene
Taking 3.5g of graphene oxide aqueous solution with the concentration of 1.5 wt%, adding a proper amount of ammonia water (high-purity ammonia water with the concentration of more than 25 wt%), stirring and mixingHomogenizing to obtain ammonium hydroxide (NH) in the mixed solution4OH) is 0.5 wt%, then the mixed solution is placed in a closed reactor, the temperature is kept at 85 ℃ for reaction for 7.5 hours to form graphene gel, the reaction is finished, and the obtained graphene gel is washed by deionized water and acetone to remove ammonium hydroxide (NH) on the surface and in the holes4OH), then drying with supercritical carbon dioxide, and finally calcining the obtained dried gel at 1050 ℃ for 4 hours under the protection of nitrogen to obtain the three-dimensional nano porous graphene. The preparation process can be seen in figure 1.
In this embodiment, the concentration of the graphene oxide aqueous solution may be any one of 1 to 2 wt%; in the mixed solution of the graphene oxide and the ammonia water, the concentration of the ammonium hydroxide can be any value of 0.3-0.6 wt%; the temperature of the heat preservation reaction can be 80-90 ℃; the reaction time can be 7-8 hours; the calcination temperature can be 1000-1100 ℃, and the calcination time can be 3-5 hours.
Fig. 2 is a TEM image of the three-dimensional nanoporous graphene prepared in this example; as can be seen from the figure, the graphene prepared in this example is a three-dimensional porous structure.
Through tests, the density of the three-dimensional nano porous graphene prepared in the embodiment is 65-70 mg-cm-3The specific surface area is 1500-1600 m2·g-1Has better appearance structure.
In addition, the three-dimensional nanoporous graphene prepared by the embodiment has a stable porous structure, does not randomly appear, has small pore size, has an average pore diameter of about 3-8.5 nm and less than 10nm, and has no collapse and accumulation phenomena when being subsequently compounded with materials such as oxides compared with the traditional three-dimensional graphene with the pore diameter of hundreds of nanometers to hundreds of micrometers.
Through tests, the conductivity of the three-dimensional nano-porous graphene prepared in the embodiment is about 2S-cm-1When the material is used as a lithium ion electrode material, the current density is 100mA g-1The first discharge and charge capacities were 2603mAh · g, respectively-1And 633 mAh. g-1Coulombic efficiency of about 24%, whichThe medium discharge capacity is reduced to 850mAh g after the second cycle-1And stabilized at about 405mAh g after 30 cycles-1(Current Density 100 mA. g)-1) The method has excellent electrochemical performance, and lays a good foundation for the excellent electrochemical performance of the subsequent three-dimensional graphene-metal oxide nano composite material.
The three-dimensional nanoporous graphene prepared by the embodiment can be prepared by the following three-dimensional tent graphene-metal oxide nanocomposite according to the process flow shown in fig. 1.
Example 2
Three-dimensional tent type graphene-iron oxide (Fe)2O3) Preparation of nanocomposites
2.27g of FeCl3(0.014mol) was dissolved in 10mL of a 60 wt% ethanol aqueous solution, 0.89g (0.015mol) of propylene oxide was added thereto, and the mixture was stirred at room temperature to be mixed uniformly to form a sol, and then 1g of the three-dimensional nanoporous graphene obtained in example 1 was immersed in a solution containing Fe3+And an initiator, aging at 40 ℃ until the sol in the reaction system forms gel, and then directly reacting three-dimensional graphene and Fe3+The obtained dried product is calcined for 3 hours at 550 ℃ under the protection of nitrogen, and the three-dimensional tent type graphene-iron oxide nano composite material is obtained. The preparation process can be seen in figure 1.
Fig. 3 is an SEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in the present example; fig. 4 is a TEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example; fig. 5 is a TEM image of another angle of the three-dimensional tent-type graphene-iron oxide nanocomposite prepared in the present example; fig. 6 is a high-resolution TEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example; graphene in fig. 6 refers to three-dimensional graphene; as can be seen from fig. 3 to 6, in the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example, iron oxide crystals are uniformly fixed on the surface of a graphene sheet along a three-dimensional graphene framework, and no crystal agglomeration phenomenon occurs, no collapse or accumulation phenomenon occurs, and the three-dimensional tent graphene-iron oxide nanocomposite has a good morphology structure; in particular, as can be seen from fig. 5, the three-dimensional graphene-iron oxide nanocomposite particles are in a polygonal state in the two-dimensional projection direction, and taking two examples of the composite materials marked by straight lines in fig. 5 as an example, it can be seen that the iron oxide particles are effectively wrapped by the three-dimensional graphene, and the formed three-dimensional graphene-iron oxide nanocomposite is in a tent shape as a whole.
Fig. 7 is a schematic macroscopic cross-sectional view of the three-dimensional tent-type graphene-iron oxide nanocomposite prepared in the present example; as can be seen from the figure, the iron oxide particles are wrapped by the three-dimensional graphene and are uniformly fixed on the surface of the graphene sheet layer along the three-dimensional graphene framework, and the composite material is integrally tent-shaped. As can be seen from fig. 5 and 7, the nanocomposite prepared in this example was tent-type.
Fig. 8 is a particle size distribution diagram of the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example; as can be seen from the figure, the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example has a small particle size, is in the nanometer level, has an average particle size of 12.5 ± 5.5nm, and is relatively uniformly distributed.
Fig. 9 is a diffraction pattern of the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example; as can be seen from the figure, Fe in the composite2O3Consisting of alpha and gamma phases.
Through tests, when the three-dimensional tent type graphene-iron oxide nanocomposite prepared in the embodiment is used as a lithium ion electrode material, the current density is 100mA · g < -1 >, and the first discharge capacity and the first charge capacity are 1365mAh · g respectively-1And 740 mAh. g-1The coulombic efficiency is about 54 percent, and the reversible capacity is stabilized at 777mAh g after 30 cycles-1And has excellent electrochemical performance.
Fig. 10 is a TEM image of the three-dimensional tent graphene-iron oxide nanocomposite prepared in this example after 30 cycles when the three-dimensional tent graphene-iron oxide nanocomposite is used as a lithium ion electrode material (i.e., a lithiated three-dimensional tent graphene-iron oxide nanocomposite); the three-dimensional graphene-iron oxide nanocomposite particles are circled in the figure, the depth of each single particle is clear, and the dark points with relative depth represent the iron oxide particles, and as can be seen from the figure, after 30 cycles, the original polygonal shape (as shown in fig. 5) of the nanocomposite particles is changed into an elliptical or circular shape, but the lithium-state composite particles do not have an agglomeration phenomenon, which shows that the three-dimensional graphene in the tent-type composite material can effectively wrap the iron oxide particles and play a role in preventing the agglomeration of the nanoparticles.
Example 3
Three-dimensional tent type graphene-titanium oxide (TiO)2) Preparation of nanocomposites
Dissolving 1g of butyl titanate (0.0029mol) and 71.4 muL of 37 wt% hydrochloric acid in 5mL of 95 wt% ethanol aqueous solution, stirring at room temperature to mix uniformly, adding 0.357g of propylene oxide (0.0061mol), stirring at room temperature to mix uniformly to form sol, and then soaking 1g of the three-dimensional nanoporous graphene prepared in example 1 in Ti-containing solution4+And an initiator, aging at 40 ℃ until the sol in the reaction system forms gel, and then directly reacting three-dimensional graphene and Ti4+The obtained dried product is calcined for 5 hours at 350 ℃ (the calcination is carried out in the air without nitrogen protection), and the three-dimensional tent type graphene-titanium oxide nano composite material is obtained.
Fig. 11 is a TEM image of the three-dimensional tent graphene-titanium oxide nanocomposite prepared in this example; in the figure, titanium oxide particles are arranged in white circles, and it can be seen from the figure that in the three-dimensional graphene-titanium oxide nanocomposite prepared in the embodiment, titanium oxide crystals are uniformly fixed on the surface of a graphene sheet layer along a three-dimensional graphene skeleton, no crystal agglomeration phenomenon occurs, no collapse or accumulation phenomenon occurs, and the three-dimensional graphene-titanium oxide nanocomposite has a good morphology structure. The nanocomposite material prepared in this example was also tent-shaped like the nanocomposite material prepared in example 2.
Through the test: the three-dimensional graphene-titanium oxide nanocomposite prepared by the embodiment has a small particle size, belongs to a nanometer level, has an average particle size of 5.5 +/-0.6 nm, and is relatively uniform in distribution.
The pore distribution of the composite nanomaterial prepared in this example, the nanocomposite prepared in example 2, and the three-dimensional graphene prepared in example 1 were tested by BJH method under the same conditions, and the test results are shown in fig. 12, where it can be seen from fig. 12 that the pore size distribution of the composite material is not changed much through the process of attaching the metal oxide particles (iron oxide particles, titanium oxide particles), and the pore size distribution of the graphene-metal oxide (iron oxide, titanium oxide) composite material is more uniform than that of graphene.
Through tests, when the three-dimensional tent type graphene-titanium oxide nanocomposite prepared in the embodiment is used as a lithium ion electrode material, the current density is 100mA · g < -1 >, and the first discharge capacity and the first charge capacity are 1472mAh · g respectively-1492 mAh. g-1The coulombic efficiency is about 31 percent, and the reversible capacity is stabilized at 241 mAh.g after 30 cycles-1And has excellent electrochemical performance.
Example 4
Three-dimensional tent type graphene-tin oxide (SnO)2) Preparation of nanocomposites
0.65g of SnCl4(0.0025mol) and 1.03g of oxetane (0.018mol) were dissolved in 14mL of 58 wt% ethanol aqueous solution, and the mixture was stirred at room temperature to be mixed uniformly to form a sol, and then 1g of the three-dimensional nanoporous graphene obtained in example 1 was immersed in a solution containing Sn4+And an initiator, aging at 40 ℃ until the sol in the reaction system forms a gel, and then directly reacting the three-dimensional graphene and Sn4+The reaction system is directly dried by supercritical carbon dioxide to obtain the three-dimensional tent type graphene-tin oxide nano composite material.
Fig. 13 is a TEM image of the three-dimensional tent graphene-tin oxide nanocomposite prepared in this example; as can be seen from the figure, in the three-dimensional graphene-tin oxide nanocomposite prepared in this embodiment, tin oxide crystals are uniformly fixed on the surface of a graphene sheet along a three-dimensional graphene skeleton, and the three-dimensional graphene-tin oxide nanocomposite has a good morphology structure without crystal agglomeration or collapse and accumulation. The nanocomposite material prepared in this example was also tent-shaped like the nanocomposite material prepared in example 2.
Through the test: the three-dimensional tent type graphene-tin oxide nano composite material prepared by the embodiment has a small particle size, belongs to a nano level, has an average particle size of 4.6 +/-0.5 nm, and is relatively uniformly distributed. When the three-dimensional tent type graphene-tin oxide nanocomposite prepared in the embodiment is used as a lithium ion electrode material, the current density is 100mA · g-1, and the first discharge capacity and the first charge capacity are 1875mAh · g-1679 mAh. g-1The coulombic efficiency is about 45 percent, and the reversible capacity is stabilized at 747 mAh.g after 30 cycles-1And has excellent electrochemical performance.
In summary, the three-dimensional nano-porous graphene is prepared by a sol-gel method, and then is immersed in the sol-gel containing the initiator and the metal ions to prepare the three-dimensional graphene-metal oxide nanocomposite material, so that the preparation method has the advantages of simple preparation process, no need of adding additives (such as conductive agents and binders), low production cost, easiness in large-scale production and the like; in addition, the prepared three-dimensional graphene-metal oxide nano composite material is tent-shaped, metal oxide particles in the composite material are uniformly fixed on the surface of a graphene sheet layer along a three-dimensional graphene framework and are effectively wrapped by graphene, so that the crystal agglomeration phenomenon is effectively prevented, the composite material has the advantages of good morphology structure, excellent electrochemical performance and the like, and has good use value and application prospect on the electrode material of a lithium ion battery; in particular, the prepared three-dimensional nano porous graphite not only has the advantages of good morphology structure, large specific surface area, excellent electrochemical performance and the like, but also has the advantages of non-random occurrence of porous structure, good repetition stability, average pore diameter smaller than 10nm and good mechanical property, avoids the phenomena of collapse and accumulation of the three-dimensional graphene when being compounded with metal oxide, and provides a good basis for the preparation of the subsequent three-dimensional graphene-metal oxide nano composite material; compared with the prior art, the method has significant progress and industrial application value.
Finally, it should be pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above description are intended to be covered by the present invention.
Claims (8)
1. A preparation method of a three-dimensional tent type graphene-metal oxide nano composite material capable of being used as an electrode material of a lithium ion battery is characterized by comprising the following steps:
a) uniformly stirring and mixing ammonia water and a graphene oxide aqueous solution, then placing the mixture in a closed reactor, carrying out heat preservation reaction at 80-90 ℃ until graphene gel is formed, washing the obtained graphene gel, drying the washed graphene gel by using supercritical carbon dioxide, and finally carrying out calcination treatment to obtain three-dimensional nano porous graphene;
b) stirring an alcohol-water solution of a metal ion precursor and an initiator at room temperature until the alcohol-water solution and the initiator are uniformly mixed to form sol, then immersing the three-dimensional nano porous graphene in the sol, then aging at 30-70 ℃ until the sol in a reaction system forms gel, then directly drying the reaction system by using supercritical carbon dioxide, or directly drying the reaction system by using supercritical carbon dioxide and then calcining to obtain the three-dimensional tent type graphene-metal oxide nano composite material;
wherein the metal oxide is selected from Fe2O3、SnO2、TiO2At least one of (1).
2. The method of claim 1, wherein: the concentration of the graphene oxide aqueous solution in the step a) is 1-2 wt%.
3. The method of claim 1, wherein: the concentration of ammonium hydroxide in the mixed solution formed by ammonia water and the graphene oxide aqueous solution in the step a) is 0.3-0.6 wt%.
4. The method of claim 1, wherein: the calcining treatment in the step a) is to preserve the temperature of the dried product at 1000-1100 ℃ for 2-5 hours under the protection of inert gas.
5. The method of claim 1, wherein: when the metal oxide is Fe2O3Or TiO2When the initiator in the step b) is propylene oxide; when the metal oxide is SnO2When the initiator of step b) is oxetane.
6. The method of claim 1, wherein: when the metal oxide is Fe2O3In the step b), the calcination treatment refers to heat preservation of the dried product at 500-600 ℃ for 2-5 hours under the protection of inert gas.
7. The method of claim 1, wherein: when the metal oxide is TiO2In the step b), the calcination treatment refers to heat preservation of the dried product at 300-400 ℃ for 3-7 hours in an air atmosphere.
8. The method of claim 1, wherein: when the metal oxide is SnO2In this case, no calcination is required in step b).
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