CN113809288A - 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 PDF

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CN113809288A
CN113809288A CN202110779972.5A CN202110779972A CN113809288A CN 113809288 A CN113809288 A CN 113809288A CN 202110779972 A CN202110779972 A CN 202110779972A CN 113809288 A CN113809288 A CN 113809288A
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mno
composite material
biochar
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CN113809288B (en
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吴正颖
俞明浩
陈志刚
陈丰
张琪
林艳
钱君超
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Suzhou University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to MnO2A/C composite material and a preparation method and application thereof belong to the technical field of new materials. MnO of the present invention2the/C composite material is synthesized by taking biological cell tissues as a structure directing agent through a simple hydrothermal method. Prepared MnO2MnO in/C composite samples2The growth of the MnO is guided and limited by the biochar, and the shape of the MnO is single2More regular sample, less agglomeration and MnO2Vertically grown to the biochar structure. MnO of2the/C composite material is used in lithium battery, compared with pure MnO2Materials, MnO prepared2the/C sample has good electrochemical behavior and reaches 5 after circulating for 120 circlesHigh specific capacity of 30 mAh/g. 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

MnO (MnO)2/C composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of new materials, in particular to MnO2a/C composite material, a preparation method and application thereof.
Background
MnO2Is a very attractive anode material and is expected to be an effective graphite anode substitute because the graphite anode has large theoretical specific capacity (1230mAh/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, MnO2In various crystal forms (alpha-, beta-, gamma-, lambda-, delta-and the like). MnO2The basic unit of the polymorphic crystal structure consists of Mn4+Ions make up and occupy octahedral holes formed by hexagonal close-packed oxide ions. In addition, MnO due to different reaction conditions2Showing different morphologies (nanowires, nanospheres, nanosheets, nanorods, etc.). MnO due to its high density and purity and sufficient electrochemical activity2As electrode materials for electrochemical energy storage systems (supercapacitors, batteries) are widely studied. However, bulk MnO2Exhibit very limited surface active sites, thereby hindering electron and ion transport. Thus, by preparing nanostructured MnO2The 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 problems, a great deal of work has been focused on the most popular methods currently using various carbon-based nanomaterials (including carbon nanotubes, graphene, carbon fibers, amorphous carbon, and non-graphite)Carbon) to construct a nanostructured composite material.
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 materials 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 nanometer scale has attracted a growing and enormous interest. The study of biological templates has been generated during the development of biological self-assembly and nanostructured inorganic materials. In nature, through the process of biomineralization, various biological systems direct the growth of complex hierarchical inorganic mineral structures whose crystalline and multi-scale structures are determined by underlying templates composed of biomolecules.
Although MnO2There have been many studies on the composition with C material, but the carbon material with special structure is prepared by using plant tissue structure as template and carbon source, and MnO is constructed based on the carbon material2MnO with nanosheets vertically grown in biological carbon framework structure2the/C composite material is not reported.
Disclosure of Invention
In order to solve the technical problem, the invention provides MnO2MnO with nanosheets vertically grown in biological carbon framework structure2a/C composite material, a preparation method and application thereof. The invention prepares MnO by a biological template through a hydrothermal method2the/C composite material is used as an electrode material of a lithium ion battery and shows good lithium storage performance.
It is a first object of the present invention to provide a MnO2The preparation method of the/C composite material comprises the following steps:
s1, calcining the biological template after soaking, washing and airing in an inert gas atmosphere to obtain biochar inheriting the appearance and the structure of the biological template;
s2, immersing the biochar obtained in the S1 step in KMnO4And MnSO4Performing 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 MnO2a/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 soaking is performed with an ethanol solution with a concentration of 40% to 60%, and the pH of the ethanol solution is 1 to 2.
In one embodiment of the present invention, the soaking time is 2 to 4 weeks in the step of S1.
In one embodiment of the present invention, in the step of S1, the calcination temperature is 600-800 ℃, and the calcination time is 2-4 h.
In one embodiment of the present invention, in the step of S2, KMnO is present in the mixed solution4And MnSO4The mass ratio of (A) to (B) is 2-3: 1; KMnO4The concentration of (b) is 0.004-0.02 g/mL.
In one embodiment of the present invention, in the step S2, the temperature of the hydrothermal reaction is 130-150 ℃ and the time is 0.5-2 h.
In one embodiment of the present invention, in the step of S2, the concentration of the biochar is 0.004-0.016 g/mL.
The second purpose of the invention is to provide MnO prepared by the method2a/C composite material.
It is a third object of the present invention to provide a lithium battery using the MnO for a negative electrode2the/C composite material is prepared.
Compared with the prior art, the technical scheme of the invention has the following advantages:
MnO of the invention2the/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. MnO2The growth of the MnO is guided and limited by the biochar, and the shape of the MnO is single2The sample is more regular, the agglomeration phenomenon is less, and the sample is vertically grown on a biological carbon framework. MnO of the present invention2Composite material/CThe presence of mesobiochar affects MnO2Growth orientation resulting in MnO2The 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 and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which
FIG. 1 shows carbonization and MnO of cabbage in example 1 of the present invention2And MnO2SEM image of/C, wherein, a is SEM image after the cabbage is carbonized; b is MnO2SEM image of (a); c is MnO2Macroscopic SEM images of/C; d is MnO2Magnified SEM image of/C.
FIG. 2 shows MnO in example 1 of the present invention2、MnO2TEM image of/C composite material, where a is MnO2A TEM image of (a); b to d are MnO2(ii)/C TEM images of different magnifications.
FIG. 3 shows MnO synthesized in example 1 of the present invention2Cycle performance diagram of the/C composite.
FIG. 4 shows MnO synthesized in example 1 of the present invention2A rate performance graph of the/C composite material.
FIG. 5 shows MnO obtained in example 2 of the present invention2SEM image of/C composite material.
FIG. 6 shows MnO obtained in example 3 of the present invention2SEM image of/C composite material.
FIG. 7 shows MnO in comparative examples 1 and 2 of the present invention2Wherein a is MnO2SEM image of-0.5, b is MnO2SEM image of (d).
FIG. 8 shows MnO in example 1, comparative example 1 and comparative example 2 of the present invention2Composite material of/C, MnO2-0.5 and MnO2XRD 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)2The 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)2O1: 1) and pH 2 adjusted with hydrochloric acid, pre-treated for two weeks to remove organic substances and pigments from the leaves of the cabbage.
(2) Taking out the pretreated cabbage leaves, washing with distilled water, filtering, and calcining at 800 deg.C under nitrogen atmosphere for 2 h.
(3) Weighing 0.5g KMnO4Solids and 0.2g MnSO4Dissolving 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 2 h. Finally obtaining MnO2a/C composite material.
MnO obtained by the following Synthesis with reference to examples2composite/C material, we further analyzed MnO in the present invention2The 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 MnO2SEM image of (a); c is MnO2Macroscopic SEM images of/C; d is MnO2Magnified 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 MnO2In a corner region of the/C sample, MnO was observed2B is grown on biochar, and delta-MnO can be seen by observing c under a high-power scanning electron microscope2Growing 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 view2Panel d, this is different from the common delta-MnO morphology of nanoflower2All MnO of2Oriented vertical growth of nanosheetsIn the frame structure of biochar, this is in contrast to MnO2Induction of biochar during growth is relevant.
In FIG. 2, a is MnO2TEM image of (b) to d are MnO2TEM image of the/C composite. From a comparison of fig. a and b, simple MnO2Sample thickness, MnO2The number of layers of the/C sample is less, and the thickness is thinner. In MnO2Under 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 invention2The electrochemical performance of the/C composite material is tested: test conditions MnO obtained in example2the/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 MnO2The material/C, conductive carbon black (Super P) and binder (PVDF) were ground at a ratio of 7:2:1 for half an hour, then an appropriate amount of N-was added to methyl pyrrolidone (NMP) until the solution became a fluid state, and stirred for half an hour using an emulsifying machine to obtain a slurry, which was uniformly coated on a copper foil sheet to a thickness of 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 MnO2Cycling 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. MnO2The 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, MnO2Although the material has better cycling stability, the specific capacity of the material is only about 85 mAh/g. MnO2The outstanding stability of the material has a close and inseparable relationship with the micro-morphology, delta-MnO2The unique nanoflower morphology provides a larger specific surface for lithium ion deintercalation, but due to MnO2The material has the characteristic of poor conductivity inherent in metal oxides, and therefore, the specific capacity of the material is low. AndMnO2material comparison, MnO2The 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/g2The rate performance graph of the/C sample. MnO at a current density of 50mA/g2The 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 shows that MnO2the/C material has good cycle reversibility and stability.
Example 2:
MnO (MnO)2The 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)2O1: 1) and pH 2 adjusted with hydrochloric acid, pre-treated for two weeks to remove organic substances and pigments from the leaves of the cabbage.
(2) Taking out the pretreated cabbage leaves, washing with distilled water, filtering, and calcining at 800 deg.C under nitrogen atmosphere for 2 h.
(3) Weighing 0.5g KMnO4Solids and 0.2g MnSO4Dissolving 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 MnO2a/C composite material.
FIG. 5 shows MnO obtained in example 22SEM image of/C composite material. As can be seen from the graph, when the amount of biochar added during hydrothermal synthesis was reduced, MnO was obtained2MnO in/C composites2Although highly dispersed on the surface of the biochar, but because the content of carbon as a supporting structure is relativeLess, so MnO2Agglomeration occurs more easily and the particle size decreases.
Example 3:
MnO (MnO)2The 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)2O1: 1) and pH 2 adjusted with hydrochloric acid, pre-treated for two weeks to remove organic substances and pigments from the leaves of the cabbage.
(2) Taking out the pretreated cabbage leaves, washing with distilled water, filtering, and calcining at 800 deg.C under nitrogen atmosphere for 2 h.
(3) Weighing 0.5g KMnO4Solids and 0.2g MnSO4Dissolving 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 MnO2a/C composite material.
FIG. 6 shows MnO obtained in example 32SEM 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 obtained2MnO in/C composites2Although 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 KMnO4Solids and 0.2g MnSO4Dissolving 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 0.5 h. Finally obtaining MnO2Material, denominated MnO2-0.5。
Comparative example 2
(1) Weighing 0.5g KMnO4Solids and 0.2g MnSO4Dissolving in 50mL deionized water, and placing the solution under magnetic stirringThe mixer is stirred 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 2 h. Finally obtaining MnO2Material, denominated MnO2。
As can be seen from the SEM image of FIG. 7, in MnO2Typical delta-MnO can be observed in-0.5 samples2The cauliflower-like morphology of (a) but with agglomeration. MnO2MnO was also observed in the scanned image of the sample2High degree of formation, but with a small amount of rod-like MnO2Although MnO has been preferably formed2However, 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 morphology2Uniformly distributed on the biochar, indicating that the presence of biochar helps to direct the MnO2To reduce agglomeration and to increase the MnO content2The purity of the phases.
From the XRD pattern in FIG. 8, it can be seen that MnO was obtained at a hydrothermal time of 0.5h2The 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-MnO2The (001), (002), (111) and (020) crystal planes (JCPDS NO. 42-1317). Prolonging the hydrothermal time to 2h to obtain MnO2XRD pattern and MnO of sample2The-0.5 sample was similar but had a sharper diffraction peak, indicating that extended reaction time can improve 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 MnO2XRD pattern of/C sample and single MnO2Comparison of samples, MnO2The XRD pattern of the/C sample still shows standard delta-MnO2The characteristic peak, and the (002) plane diffraction peak became wider, it is likely that MnO was affected by the presence of biochar2Growth orientation resulting in MnO2The 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. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (10)

1. MnO (MnO)2The preparation method of the/C composite material is characterized by comprising the following steps:
s1, calcining the biological template after soaking, washing and airing in an inert gas atmosphere to obtain biochar inheriting the appearance and the structure of the biological template;
s2, immersing the biochar obtained in the S1 step in KMnO4And MnSO4Performing 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 MnO2a/C composite material.
2. The MnO of claim 12The preparation method of the/C composite material is characterized by comprising the following steps: the biological template is cabbage leaves or camellia petals.
3. The MnO of claim 12The 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.
4. The MnO of claim 12The preparation method of the/C composite material is characterized by comprising the following steps: in step S1, the soaking time is 2-4 weeks.
5. The MnO of claim 12The 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 2-4 h.
6. The MnO of claim 12The preparation method of the/C composite material is characterized by comprising the following steps: in step S2, KMnO in the mixed solution4And MnSO4The mass ratio of (A) to (B) is 2-3: 1; KMnO4The concentration of (b) is 0.004-0.02 g/mL.
7. The MnO of claim 12The preparation method of the/C composite material is characterized by comprising the following steps: in the step S2, the hydrothermal reaction is carried out at the temperature of 130 ℃ and 150 ℃ for 0.5-2 h.
8. The MnO of claim 12The preparation method of the/C composite material is characterized by comprising the following steps: in the step S2, the concentration of the biochar is 0.004-0.016 g/mL.
9. MnO obtainable by a process according to any one of claims 1 to 82a/C composite material.
10. A lithium battery characterized in that the MnO of claim 9 is used for the negative electrode2the/C composite material is prepared.
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US20140295278A1 (en) * 2013-03-26 2014-10-02 Toyota Motor Engineering & Manufacturing North America, Inc. Magnesium battery having a cathode containing manganese dioxide nanoparticles as active material
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