CN113809288B - MnO (MnO) 2 /C composite material and preparation method and application thereof - Google Patents
MnO (MnO) 2 /C composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to MnO 2 A/C composite material and a preparation method and application thereof belong to the technical field of new materials. MnO of the present invention 2 the/C composite material is synthesized by taking biological cell tissues as a structure directing agent through a simple hydrothermal method. Prepared MnO 2 MnO in/C composite samples 2 The growth of the MnO is guided and limited by the biochar, and the shape of the MnO is single 2 More regular sample, less agglomeration and MnO 2 Vertically grown to the biochar structure. MnO of 2 the/C composite material is used in lithium battery, compared with pure MnO 2 Materials, mnO prepared 2 the/C sample has good electrochemical behavior and reaches high specific capacity of 530mAh/g after circulating for 120 circles. The existence of the biochar is not only beneficial to guiding crystal growth, but also can improve the conductivity of the material, and in addition, the layered biochar can also improve the structural stability of the material, so that structural collapse caused by volume expansion in the circulation process is avoided.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to MnO 2 a/C composite material, a preparation method and application thereof.
Background
MnO 2 Is a very attractive anode material and is expected to be an effective graphite anode substitute because the graphite anode material has large theoretical specific capacity (1230 mAh/g) and a wider voltage window. Meanwhile, the natural mineral water has the advantages of low price, wide natural abundance, environmental friendliness and the like. Usually, mnO 2 Exist in various crystal forms (alpha-, beta-, gamma-, lambda-, delta-and the like). MnO (MnO) 2 PolycrystalThe basic unit of the crystal structure is formed by Mn 4+ Ions make up and occupy octahedral holes formed by hexagonal close-packed oxide ions. In addition, mnO due to different reaction conditions 2 Showing different morphologies (nanowires, nanospheres, nanosheets, nanorods, etc.). MnO due to its high density and purity and sufficient electrochemical activity 2 As electrode materials for electrochemical energy storage systems (supercapacitors, batteries) are widely studied. However, bulk MnO 2 Exhibit very limited surface active sites, thereby hindering electron and ion transport. Thus, by preparing nanostructured MnO 2 The material can increase the specific surface area of the material, provide more active sites, shorten the transmission distance of electrons and ions, and further effectively improve the reaction kinetics of the material. But its wide application is limited by capacity loss and poor stability during cycling. To address these issues, a great deal of work has focused on the most popular approach at present to build nanostructured composites with a variety of carbon-based nanomaterials, including carbon nanotubes, graphene, carbon fibers, amorphous carbon, and non-graphitic carbon.
Biotemplating is an effective strategy to obtain morphologically controllable materials with structural specificity, complexity and corresponding unique functions. Biological systems are an elegant model of natural assembly. In contrast, the ability of material scientists to design self-assembled structures with multi-scale precision remains very limited. However, engineering to precisely tailor new functional materials with structural and synthetic functions on the nanoscale has attracted a growing tremendous interest. The study of biological templates has been generated during the development of biological self-assembly and nanostructured inorganic materials. In nature, various biological systems direct the growth of complex hierarchical inorganic mineral structures through the process of biomineralization, the crystalline and multi-scale structure of which is determined by the underlying template composed of biomolecules.
Although MnO is present 2 Many studies have been made on the composition of C material, but the carbon material with special structure is prepared by using plant tissue structure as template and carbon source, so as to construct MnO based on the carbon material 2 Nano meterMnO with vertically grown sheets in biochar frame structure 2 the/C composite material is not reported.
Disclosure of Invention
In order to solve the technical problem, the invention provides MnO 2 MnO with nanosheets vertically grown in biological carbon framework structure 2 a/C composite material, a preparation method and application thereof. The invention prepares MnO by a biological template through a hydrothermal method 2 the/C composite material shows good lithium storage performance as an electrode material of a lithium ion battery.
It is a first object of the present invention to provide a MnO 2 The preparation method of the/C composite material comprises the following steps:
s1, soaking, washing and airing a biological template, and calcining the biological template in an inert gas atmosphere to obtain biological carbon inheriting the appearance and the structure of the biological template;
s2, immersing the biochar obtained in the step S1 in KMnO 4 And MnSO 4 Performing hydrothermal reaction in the mixed solution;
s3, taking out the biochar reacted in the step S2, carrying out suction filtration, washing and drying to obtain the MnO 2 a/C composite material.
In one embodiment of the invention, the biological template is cabbage leaves or camellia petals.
In one embodiment of the present invention, in the step S1, the ethanol solution with a concentration of 40% to 60% is adopted for the soaking, and the pH of the ethanol solution is 1 to 2.
In one embodiment of the present invention, in the step S1, the soaking time is 2 to 4 weeks.
In one embodiment of the present invention, in the step S1, the calcination temperature is 600 to 800 ℃ and the calcination time is 2 to 4 hours.
In one embodiment of the invention, in the step S2, KMnO in the mixed solution 4 And MnSO 4 The mass ratio of (A) is 2-3:1; KMnO 4 The concentration of (b) is 0.004-0.02g/mL.
In one embodiment of the present invention, in the step S2, the temperature of the hydrothermal reaction is 130 to 150 ℃ and the time is 0.5 to 2 hours.
In one embodiment of the present invention, in the S2 step, the concentration of the biochar is 0.004-0.016g/mL.
The second purpose of the invention is to provide MnO prepared by the method 2 a/C composite material.
It is a third object of the present invention to provide a lithium battery using the MnO for a negative electrode 2 the/C composite material is prepared.
Compared with the prior art, the technical scheme of the invention has the following advantages:
MnO of the invention 2 the/C composite material is successfully synthesized by taking biological tissue cells widely existing in nature as a structure directing agent and a biological template in a hydrothermal mode. MnO 2 Guided and limited by biochar, and has a single shape 2 The sample is more regular, the agglomeration phenomenon is less, and the sample is vertically grown on a biological carbon framework. MnO of the present invention 2 The presence of biochar in the/C composite affects the MnO 2 Growth orientation resulting in MnO 2 The layer thickness is reduced. When the material is used as a lithium ion battery cathode material, after 120 times of circulation, the high specific capacity of 530mAh/g is stabilized, and the circulating coulomb efficiency is stabilized at 99%.
Drawings
In order that the present disclosure may be more readily understood, a more particular description of the disclosure will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings
FIG. 1 shows carbonization and MnO of cabbage in example 1 of the present invention 2 And MnO 2 An SEM image of/C, wherein a is an SEM image of the carbonized cabbage; b is MnO 2 SEM image of (a); c is MnO 2 Macroscopic SEM images of/C; d is MnO 2 Magnified SEM image of/C.
FIG. 2 shows MnO in example 1 of the present invention 2 、MnO 2 TEM image of/C composite material, where a is MnO 2 A TEM image of (a); b to d are MnO 2 (ii)/C TEM images of different magnifications.
FIG. 3 is a drawing of the present inventionMnO synthesized in example 1 2 Cycle performance diagram of the/C composite.
FIG. 4 shows MnO synthesized in example 1 of the present invention 2 A rate performance graph of the/C composite material.
FIG. 5 shows MnO obtained in example 2 of the present invention 2 SEM image of/C composite material.
FIG. 6 shows MnO obtained in example 3 of the present invention 2 SEM image of/C composite material.
FIG. 7 shows MnO in comparative examples 1 and 2 of the present invention 2 Wherein a is MnO 2 SEM image of 0.5, b is MnO 2 SEM image of (d).
FIG. 8 shows MnO in example 1, comparative example 1 and comparative example 2 of the present invention 2 Composite material of/C, mnO 2 -0.5 and MnO 2 XRD pattern of (a).
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1:
MnO (MnO) 2 The preparation method of the/C composite material comprises the following steps:
(1) Washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H) 2 O = 1:1) and pH =2 adjusted with hydrochloric acid, pre-treated for two weeks to remove organic matter and pigments from the leaves of the brassica campestris.
(2) Taking out the pretreated cabbage leaves, washing with distilled water, filtering, and calcining at 800 deg.C under nitrogen atmosphere for 2h.
(3) Weighing 0.5g KMnO 4 Solids and 0.2g MnSO 4 Dissolving in 50mL deionized water, and stirring the solution in a magnetic stirrer for half an hour to fully dissolve.
(4) And (3) while transferring the solution to a reaction kettle, weighing 0.5g of the biochar, adding the biochar into the reaction kettle, and placing the biochar in an oven for hydrothermal reaction. The hydrothermal temperature is 140 ℃ and the hydrothermal time is 2h. Finally obtaining MnO 2 a/C composite material.
MnO obtained by the following Synthesis with reference to examples 2 composite/C material, we further analyzed MnO in the present invention 2 The shape structure and performance characteristics of the/C composite material are as follows:
FIG. 1 is an SEM image of a material related to example 1, wherein a is an SEM image of a cabbage after carbonization; b is MnO 2 SEM image of (a); c is MnO 2 Macroscopic SEM images of/C; d is MnO 2 Magnified SEM image of/C. From a, the carbon template obtained by the cabbage at the high temperature of 800 ℃ has clear plant veins and biological appearance. Selecting MnO 2 In a corner region of the/C sample, mnO was observed 2 B is grown on biochar, and delta-MnO can be seen by observing c under a high-power scanning electron microscope 2 Growing along the plane of the carbon layer, and partially existing in a flower ball state on the surface. The delta-MnO in the planar state can be more clearly observed in the further enlarged view 2 Panel d, this is different from the common delta-MnO morphology of nanoflowers 2 All MnO of 2 The nano-sheet is directionally and vertically grown in a frame structure of biological carbon, which is similar to MnO 2 The induction of biochar during growth is relevant.
In FIG. 2, a is MnO 2 TEM image of (b) to d are MnO 2 TEM image of the/C composite. From a comparison of fig. a and b, simple MnO 2 Sample thickness, mnO 2 The number of layers of the/C sample is smaller, and the thickness is thinner. In MnO 2 Under the high-power scanning electron microscope c and d of the sample, the lattice lines at the edge of the sample can be clearly observed, which indicates that the sample has a small amount of crystals.
MnO synthesized for the present invention 2 The electrochemical performance of the/C composite material is tested: test conditions MnO obtained in example 2 the/C composite material is used as a negative electrode, the lithium sheet is used as a counter electrode and a reference electrode, and a CR2032 button cell is mounted to test the electrochemical performance of the battery. Specifically, the obtained nano MnO 2 material/C, conductive carbon black (Super P) and binder (PVDF) were ground in a ratio of 7The degree was 100. Mu.m. Then the mixture is placed in a vacuum oven at 80 ℃ for 24 hours for drying. The material was removed and sliced with a microtome and finally mounted in a glove box as button cells. The battery performance test was performed by a multi-channel battery tester (LAND CT 2001A). The test results were as follows:
FIG. 3 is MnO 2 Cycling performance plot of the/C composite at 100mA/g, with a current density of 50mA/g for the first three cycles used to activate the cell. MnO 2 The circulation curve of the/C sample shows a less obvious activation phenomenon, after the circulation is carried out for 120 circles, the specific capacity reaches and is stabilized to be about 530mAh/g, and the circulation efficiency is 99%. Under the same conditions, mnO 2 Although the material has better cycling stability, the specific capacity of the material is only about 85 mAh/g. MnO 2 The outstanding stability of the material has a close and inseparable relationship with the microscopic appearance thereof, delta-MnO 2 The unique nanoflower morphology provides a larger specific surface for lithium ion deintercalation, but due to MnO 2 The material has the characteristic of poor conductivity inherent in metal oxides, and therefore, the specific capacity of the material is low. With MnO 2 Material comparison, mnO 2 The excellent electrochemical performance of the/C sample is attributed to the tight combination with the biological carbon material, the conductivity of the sample is improved, and in addition, the layered structure of the biological carbon is also beneficial to relieving the volume expansion phenomenon in the circulation process and enhancing the structural stability of the sample.
FIG. 4 shows MnO cycles of 40 at different current densities of 50 to 1500mA/g 2 Rate performance graph of the/C sample. MnO at a current density of 50mA/g 2 The specific capacity of the/C material is 491mAh/g, and when the current density is increased continuously, the specific capacity is reduced gradually. When the current density is recovered to 100mA/g again, the reversible specific capacity of the material is recovered to about 308mAh/g rapidly, which indicates that MnO is 2 the/C material has good cycle reversibility and stability.
Example 2:
MnO (MnO) 2 The preparation method of the/C composite material comprises the following steps:
(1) Washing cabbage leaf with distilled water, and soaking in EtOH solution (EtOH: H) 2 O = 1:1) and pH =2 adjusted with hydrochloric acid, pre-treated for two weeks to remove the wrapOrganic matters and pigments in vegetable leaves.
(2) Taking out the pretreated cabbage leaves, washing with distilled water, filtering, and calcining at 800 deg.C under nitrogen atmosphere for 2h.
(3) Weighing 0.5g KMnO 4 Solids and 0.2g MnSO 4 Dissolving in 50mL deionized water, and stirring the solution in a magnetic stirrer for half an hour to fully dissolve.
(4) And (3) while transferring the solution to a reaction kettle, weighing 0.2g of the biochar, adding the biochar into the reaction kettle, and placing the biochar in an oven for hydrothermal reaction. The hydrothermal temperature is 140 ℃ and the hydrothermal time is 2h respectively. Finally obtaining MnO 2 a/C composite material.
FIG. 5 shows MnO obtained in example 2 2 SEM image of/C composite material. As can be seen from the graph, when the amount of biochar added during hydrothermal synthesis is reduced, mnO is obtained 2 MnO in/C composites 2 Although highly dispersed on the surface of the biochar, mnO was formed because the content of carbon as a support structure was relatively small 2 Agglomeration is more likely to occur and the particle size is reduced.
Example 3:
MnO (MnO) 2 The preparation method of the/C composite material comprises the following steps:
(1) Washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H) 2 O = 1:1) and pH =2 adjusted with hydrochloric acid, pre-treated for two weeks to remove organic matter and pigments from the leaves of brassica oleracea.
(2) Taking out the pretreated cabbage leaves, washing with distilled water, filtering, and calcining at 800 deg.C under nitrogen atmosphere for 2h.
(3) Weighing 0.5g KMnO 4 Solids and 0.2g MnSO 4 Dissolving in 50mL deionized water, and stirring the solution in a magnetic stirrer for half an hour to fully dissolve.
(4) And (3) while transferring the solution to a reaction kettle, weighing 0.8g of the biochar, adding the biochar into the reaction kettle, and placing the biochar in an oven for hydrothermal reaction. The hydrothermal temperature is 140 ℃ and the hydrothermal time is 2h respectively. Finally obtaining MnO 2 a/C composite material.
FIG. 6 showsShows MnO obtained in example 3 2 SEM image of/C composite material. As can be seen from the graph, when the content of biochar in the synthesis system is high, mnO was obtained 2 MnO in/C composites 2 Although highly dispersed on the surface of the biochar and vertically grown on the frame of the biochar, similar to example 1.
Comparative example 1
(1) Weighing 0.5g of KMnO 4 Solids and 0.2g MnSO 4 Dissolving in 50mL of deionized water, and stirring the solution in a magnetic stirrer for half an hour to fully dissolve.
(2) Transferring the solution to a reaction kettle and placing the reaction kettle in an oven for hydrothermal reaction. The hydrothermal temperature is 140 ℃ and the hydrothermal time is 0.5h. Finally obtaining MnO 2 Material, denominated MnO 2 -0.5。
Comparative example 2
(1) Weighing 0.5g KMnO 4 Solids and 0.2g MnSO 4 Dissolving in 50mL deionized water, and stirring the solution in a magnetic stirrer for half an hour to fully dissolve.
(2) Transferring the solution to a reaction kettle and placing the reaction kettle in an oven for hydrothermal reaction. The hydrothermal temperature is 140 ℃ and the hydrothermal time is 2h. Finally obtaining MnO 2 Material named MnO 2 。
As can be seen from the SEM image of FIG. 7, in MnO 2 Typical delta-MnO can be observed in-0.5 samples 2 The cauliflower-like morphology of (a) but with agglomeration. MnO (MnO) 2 MnO can also be seen in the scanned image of the sample 2 High degree of formation, but with a small amount of MnO in the form of rods 2 Note that although MnO has been formed well 2 However, the phases are not pure enough and the samples still have significant agglomeration. As can be seen from the two graphs c and d in FIG. 1, by introducing biochar obtained by high-temperature calcination of cabbage leaves into the system, the cauliflower-like delta-MnO with regular morphology 2 Uniformly distributed on the biochar, indicating that the presence of biochar helps to direct the MnO 2 To reduce agglomeration and to increase the MnO content 2 The purity of the phases.
It can also be seen from the XRD pattern in FIG. 8 that hydrothermal processing is in progressMnO of 0.5h 2 The characteristic peaks of the-0.5 sample at 2 theta of 12.4 degrees, 24.8 degrees, 36.7 degrees and 65.7 degrees respectively correspond to delta-MnO 2 The (001), (002), (111) and (020) crystal planes (JCPDS NO. 42-1317). Prolonging the hydrothermal time to 2h to obtain MnO 2 XRD pattern of sample and MnO 2 The-0.5 sample was similar but had a sharper diffraction peak, indicating that increasing the reaction time can increase the crystallinity of the material. Adding biochar obtained by calcining cabbage leaves at a high temperature of 800 ℃ in the sample preparation process with the hydrothermal time of 2h to obtain MnO 2 XRD pattern of/C sample and single MnO 2 Comparison of samples, mnO 2 The XRD pattern of the/C sample still presents standard delta-MnO 2 The characteristic peak, and the (002) plane diffraction peak became wider, it is likely that MnO was affected by the presence of biochar 2 Growth orientation, resulting in MnO 2 The layer thickness is reduced.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. MnO (MnO) 2 The preparation method of the/C composite material is characterized by comprising the following steps:
s1, calcining a biological template in an inert gas atmosphere after soaking, washing and airing to obtain biochar inheriting the appearance and structure of the biological template; the biological template is cabbage leaves;
s2, immersing the biochar obtained in the step S1 in KMnO 4 And MnSO 4 Performing hydrothermal reaction in the mixed solution;
s3, taking out the biochar reacted in the step S2, carrying out suction filtration, washing and drying to obtain the MnO 2 a/C composite material.
2. The method of claim 1MnO of 2 The preparation method of the/C composite material is characterized by comprising the following steps: in the step S1, ethanol solution with the concentration of 40% -60% is adopted for soaking, and the pH value of the ethanol solution is 1-2.
3. The MnO of claim 1 2 The preparation method of the/C composite material is characterized by comprising the following steps: in the step S1, the soaking time is 2-4 weeks.
4. The MnO of claim 1 2 The preparation method of the/C composite material is characterized by comprising the following steps: in the step S1, the calcining temperature is 600-800 ℃, and the calcining time is 2-4h.
5. The MnO of claim 1 2 The preparation method of the/C composite material is characterized by comprising the following steps: in the step S2, KMnO in the mixed solution 4 And MnSO 4 The mass ratio of (A) is 2-3:1; KMnO 4 The concentration of (b) is 0.004-0.02g/mL.
6. The MnO of claim 1 2 The preparation method of the/C composite material is characterized by comprising the following steps: in the S2 step, the hydrothermal reaction is carried out for 0.5-2h at 130-150 ℃.
7. The MnO of claim 1 2 The preparation method of the/C composite material is characterized by comprising the following steps: in the S2 step, the concentration of the biochar is 0.004-0.016g/mL.
8. MnO obtainable by a process according to any one of claims 1 to 7 2 a/C composite material.
9. A lithium battery characterized in that the MnO of claim 8 is used for the negative electrode 2 the/C composite material is prepared.
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