CN110611096B - MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material - Google Patents

MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material Download PDF

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CN110611096B
CN110611096B CN201910887790.2A CN201910887790A CN110611096B CN 110611096 B CN110611096 B CN 110611096B CN 201910887790 A CN201910887790 A CN 201910887790A CN 110611096 B CN110611096 B CN 110611096B
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吴正颖
林艳
陈志刚
刘谢
查振龙
钱君超
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Suzhou University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • H01—ELECTRIC ELEMENTS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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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Abstract

The invention discloses a MnO/C composite material with excellent electrochemical performance, the microstructure of which presents a sandwich structure of a C layer-MnO particles-C layer, and a preparation method of the composite material comprises the following steps: 1) washing camellia petals with deionized water for several times; 2) soaking the washed petals in an ethanol solution for 2-4 weeks to remove pigments and other organic substances in the petals; 3) cleaning the soaked petals with deionized water, and filtering in the air; 4) immersing the filtered petals into the prepared manganese source concentrationC Mn=0.05～0.1 mol L‑1Soaking in the manganese acetate aqueous solution for 48-96 hours, washing with deionized water, and naturally drying in the air to obtain dried petals; 5) calcining at 600-800 ℃ in nitrogen atmosphere to obtain the composite material. Meanwhile, the invention provides the application of the composite material as a lithium ion battery cathode material.

Description

MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material
Technical Field
The invention relates to a MnO/C composite material, a preparation method thereof and application of the MnO/C composite material as a lithium ion battery cathode material.
Background
The material has high theoretical capacity (756 mAhg)-1) Low voltage hysteresis (<0.8V), low switching potential (1.032V) Vs Li/Li+) The advantage of (1). Meanwhile, MnO becomes a good candidate material for a high-performance lithium ion battery due to the advantages of relative cheapness, rich properties, environmental protection and the like. However, pure MnO materials have problems such as inherent low conductivity and structural collapse due to lattice shrinkage during lithium ion deintercalation. Therefore, carbonaceous materials are generally used as a matrix for transition metal oxides to alleviate the above-mentioned drawbacks because they have high electrical conductivity and elasticity. Some MnO/carbon composites have been reported as lithium battery negative electrode materials, such as MnO/carbon fibers, MnO @ C hollow nanospheres, porous MnO @ C nanocomposites and MnO/carbon core shell nanorods. The above results indicate that the electrical properties of carbon-based materials depend largely on their size and structure. For example, the RGO-MnO-RGO sandwich nano-structured material synthesized by Yuan et al shows excellent performance when being used as a negative electrode material of a lithium battery. The unique layered structure provides excellent support and protection for volume changes, resulting in structural strain and improved lithium storage capability of the electrode. However, most of these synthetic methods are relatively complicated, and simpler and more direct methods are required for preparing the MnO/C layered nanocomposite.
The biomateplate method has been widely used to prepare transition metal oxide materials. Natural biomaterials can provide a variety of architectures with complex morphologies and specialized functions. Especially plant leaves, are often used to make layered structure materials due to their unique natural cellular structure. For example, Yang et al synthesized Co by using rose petals as a biological template3O4The sample, which exhibits a specific nanosheet morphology, with a thickness similar to the original petals. Compared with an artificial template, the biological material has the advantages of low cost, reproducibility, easy removal and the like. This motivated us to use petals as templates to prepare the structure of MnO particles grown in the carbon layer by using their natural lamellar structure.
Disclosure of Invention
The invention aims to: provides a new MnO/C composite material with a special structure and a preparation method thereof, and the MnO/C composite material can be used as an electrode material of a lithium ion battery to show good lithium storage performance.
In order to solve the technical problems, the technical scheme of the invention is as follows: the MnO/C composite material is characterized in that the microstructure of the MnO/C composite material is a sandwich structure of a C layer, MnO particles and a C layer.
Further, the MnO particles of the present invention have a diameter of 20 to 40 nm.
Furthermore, when the MnO/C composite material is used as a lithium ion battery cathode material, the reversible specific capacity of the electrode reaches and is stabilized at 445-563 mAhg after 300 cycles-1The coulomb efficiency was 99%.
The invention also provides a preparation method of the composite material, which is characterized by comprising the following steps:
1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2-4 weeks to remove pigments and other organic substances in the petals;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the prepared manganese source concentration CMn＝0.05～0.1mol L-1Soaking in the manganese acetate aqueous solution for n hours, washing with deionized water, and naturally airing in the air to obtain dried petals, wherein n is 48-96; it should be noted here that the draining in the previous step is a different concept from the airing in the previous step, the draining means to filter the deionized water on the petal surface by using a common net bag or sieve, and the airing means to make the petals reach the cell dehydration state in the natural state.
5) Calcining the dried petals obtained in the step 4) in a nitrogen atmosphere at the temperature of 600-800 ℃ to obtain the required MnO/C composite material.
Further, in the ethanol solution of step 2) of the present invention, the volume ratio V of ethanol to waterEtOH/VH2OThe pH value of the ethanol solution is adjusted to 2-3 by hydrochloric acid, wherein the pH value is 1: 1-4: 1.
Further, the volume ratio V of the ethanol to the water isEtOH/VH2O1:1, allThe pH was 2.
Further, the calcination temperature in step 5) of the present invention is 800 ℃.
Further, the concentration of the manganese source in the step 5) of the invention is CMn＝0.1mol L-1。
An application of the MnO/C composite material as a lithium ion battery cathode material.
In this work, a new type of MnO/C nanomaterials was designed and prepared by uniformly embedding MnO particles ranging in size from about 20 to 40nm in diameter into a carbon layer to form a special "layer-particle-layer" sandwich structure. Accordingly, the synthesized nanocomposite shows good lithium storage performance as a negative electrode material of a lithium ion battery. And the influence of the concentration and the calcination temperature on the material performance is researched.
Compared with the prior art, the invention has the following advantages:
1. the MnO/C composite material is successfully synthesized by taking camellia petals as a biological template through processes of infiltration, permeation, calcination and the like, and when the material is used as a negative electrode material of a lithium ion battery, the reversible specific capacity of an electrode reaches and is stabilized at 445-563 mAhg after 300 cycles-1The coulomb efficiency was 99%.
2. The morphology structure and the composition of the material are respectively analyzed by SEM and TEM, and the obtained composite material not only replicates the micro morphology of petals, but also presents a special sandwich structure of C/MnO/C, namely 'layer-particle-layer', and the size of MnO nano particles in the composite material is 20-40 nm.
3. The MnO/C composite material has better electrochemical performance.
When the calcining temperature is constant, the concentration of the manganese source is 0.1mol L-1The obtained composite material has better electrochemical performance, and MnO/C (0.1) -800 material reaches 563mAhg after 300 cycles-1The reversible specific capacity of the material (469 mAhg) is measured under the same condition compared with MnO/C (0.05) -800 material-1) High. The MnO concentration in the material is high, so that the material can exert the characteristics of manganese oxide, and the electrochemical performance of the material is improved.
When the concentration is constant, the composite material obtained at a calcination temperature of 800 ℃ (MnO/C (0.1) -800) has better electrochemical performance than the composite material obtained at a calcination temperature of 600 ℃ (MnO/C (0.1) -600), and after 300 cycles, two samples respectively reach 563mAhg-1And 449mAh g-1The reversible specific capacity of (a). This is because the higher the temperature, the higher the crystallinity of the template-derived carbon contained in the material, which is favorable for ion conduction, and the higher the electrode cycling performance of the material.
Drawings
The invention is further described with reference to the following figures and examples.
FIG. 1 is an SEM image of a MnO/C composite material (MnO/C (0.1) -600 samples) prepared according to the present invention;
FIGS. 2 to 3 are TEM images (resolution increased stepwise) of MnO/C composites (MnO/C (0.1) -600 samples) prepared according to the present invention;
FIG. 4 is a TEM image of a MnO/C composite material prepared according to the present invention (MnO/C (0.1) -800 sample);
FIG. 5 is a schematic diagram of the mechanism of formation of a MnO/C composite of the present invention;
FIG. 6 is a graph of MnO/C (0.05) -600 samples, MnO/C (0.1) -600 samples, MnO/C (0.05) -800 samples, MnO/C (0.1) -800 samples, MnO samples and biochar at a current density of 100mAg-1Comparative graph of cycle performance of the following.
Detailed Description
Example 1: a preparation method of MnO/C composite material comprises the following steps:
1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2 weeks to remove pigments and other organic substances in the petals; in the ethanol solution, the volume ratio V of ethanol to waterEtOH/VH2O1:1 and the acidity of the ethanol solution was adjusted to pH 2 by hydrochloric acid;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the solutionConcentration C of manganese sourceMn＝0.05molL-1Soaking in manganese acetate water solution for n hours, washing with deionized water, and naturally drying in the air to obtain dried petals;
5) calcining the dried petals obtained in the step 4) at the temperature of 600 ℃ in a nitrogen atmosphere to obtain the required MnO/C composite material, and naming the composite material as a MnO/C (0.05) -600 sample.
Example 2: a preparation method of MnO/C composite material comprises the following steps:
1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2 weeks to remove pigments and other organic substances in the petals; in the ethanol solution, the volume ratio V of ethanol to waterEtOH/VH2O1:1 and the acidity of the ethanol solution was adjusted to pH 2 by hydrochloric acid;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the prepared manganese source concentration CMn＝0.1mol L-1Soaking in manganese acetate water solution for n hours, washing with deionized water, and naturally drying in the air to obtain dried petals;
5) calcining the dried petals obtained in the step 4) at the temperature of 600 ℃ in a nitrogen atmosphere to obtain the required MnO/C composite material, and naming the composite material as a MnO/C (0.1) -600 sample.
Example 3: a preparation method of MnO/C composite material comprises the following steps:
1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2 weeks to remove pigments and other organic substances in the petals; in the ethanol solution, the volume ratio V of ethanol to waterEtOH/VH2O1:1 and the acidity of the ethanol solution was adjusted to pH 2 by hydrochloric acid;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the prepared manganese source concentration CMn＝0.05mol L-1Soaking in manganese acetate water solution for n hours, washing with deionized water, and naturally drying in the air to obtain dried petals;
5) calcining the dried petals obtained in the step 4) at the temperature of 800 ℃ in a nitrogen atmosphere to obtain the required MnO/C composite material, and naming the composite material as a MnO/C (0.05) -800 sample.
Example 4: a preparation method of MnO/C composite material comprises the following steps:
1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2 weeks to remove pigments and other organic substances in the petals; in the ethanol solution, the volume ratio V of ethanol to waterEtOH/VH2O1:1 and the acidity of the ethanol solution was adjusted to pH 2 by hydrochloric acid;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the prepared manganese source concentration CMn＝0.1mol L-1Soaking in manganese acetate water solution for n hours, washing with deionized water, and naturally drying in the air to obtain dried petals;
5) calcining the dried petals obtained in the step 4) at the temperature of 800 ℃ in a nitrogen atmosphere to obtain the required MnO/C composite material, and naming the composite material as a MnO/C (0.1) -800 sample.
Comparative example 1: a small amount of pure manganese acetate solid is independently and directly taken and calcined at 800 ℃ in nitrogen atmosphere, and the obtained material is named as a MnO sample.
Comparative example 2: the camellia petals treated in the steps 1) to 3) in the embodiment 1 are directly calcined at 800 ℃ in a nitrogen atmosphere to obtain a biological carbon material named as 'biological carbon'.
The MnO/C composite samples prepared in example 2 and example 4 were MnO/C (0.1) -600 (C)Mn＝0.1mol L-1At a calcination temperature of 600 ℃) and MnO/C (0.1) -800 (C)Mn＝0.1mol L-1At 800 ℃ calcination temperature), we further analyzed the formation and structural features of the MnO/C material of the present invention as follows:
scanning electron microscope (Quanta400FEG), transmission electron microscope (JEOL 2100F), for observing the morphology, structure and composition of the sample.
The material morphological structure in the process of preparing the MnO/C composite material by taking the camellia petals as the template is shown in figures 1-4. The MnO/C composite material obtained by taking the petals as the template presents a characteristic biological form similar to the camellia petals in a macroscopic view. In SEM images of MnO/C composite material, close periodic arrangement with petal cytoskeleton as structural support was observed (FIG. 1). The surface of the MnO/C composite was not very smooth and a small amount of large particles of MnO could be observed (FIG. 1). TEM images show that MnO nanoparticles ranging in size from about 20 to 30nm can be found uniformly incorporated into biochar in MnO/C (0.1) -600 composites (FIGS. 2 and 3). High resolution TEM images show that the nanoparticles are polycrystalline structures with a lattice spacing of about 0.22 nm, corresponding to the (200) plane of cubic MnO (fig. 3). MnO nanoparticles having a size of about 30 to 40nm can be found to be uniformly incorporated into biochar in the MnO/C (0.1) -800 composite (FIG. 4). The edge regions of the images shown in fig. 2, 3 and 4 indicate that MnO nanoparticles are embedded in the biocarbon layer of the MnO/C composite, forming a special C/MnO/C, i.e., a "layer-particle-layer" sandwich structure.
FIG. 5 is a schematic diagram showing the mechanism of formation of the MnO/C composite material of the present invention, which is a schematic diagram of the mechanism of formation of a special C/MnO/C, i.e. "layer-particle-layer" sandwich structure, using petal cells as a bioscaffold based on detailed analysis of the petal cells of camellia and the morphology and structure of the obtained MnO/C composite material. With reference to the preparation methods of examples 1 to 4, the following analyses were performed: first, petals of camellia are pretreated with an ethanol solution to remove impurity ions, pigments, chlorophyll and other organic substances from petal cells. In this step, plasmolysis occurs and the cell wall, which is composed mainly of lamellar cellulose, is retained as a support to maintain the original cell morphology after pretreatment (step 1 of fig. 5). Secondly, the pretreated petals are soaked in manganese acetate solution for 72 hours, and due to the difference of osmotic pressure inside and outside the cells, manganese ions can permeate into the lamellar fibers of the cell walls to form manganese acetate/cellulytic cellulose complex (such as step 2 in figure 5). And finally, carrying out heat treatment, and converting the manganese acetate/cellulytic cellulose compound into the MnO/C composite material in a nitrogen atmosphere. During pyrolysis, MnO crystals are confined between the cellular cellulose layers resulting in particle sizes of 20-40 nm. At the same time, the cellullose is converted to biochar coated on MnO nanoparticles, forming a unique C/MnO/C sandwich (e.g., step 3 of fig. 5), i.e., "C-layer-MnO particle-C-layer".
The electrochemical properties of the MnO/C composite material prepared by the present invention were tested as follows:
test conditions MnO/C composite materials (MnO/C (0.05) -600 sample, MnO/C (0.1) -600 sample, MnO/C (0.05) -800 sample and MnO/C (0.1) -800 sample) obtained in examples 1-4, MnO materials and biochar materials obtained in comparative examples 1-2 were used as negative electrodes, lithium plates were used as counter electrodes and reference electrodes, and CR2032 button cells were mounted to test electrochemical properties. Specifically, the obtained MnO/C composite material (or MnO material, biological carbon material), conductive carbon black (Super P) and adhesive (PVDF) are ground for half an hour in a ratio of 7:2:1, then a proper amount of N is added, methyl pyrrolidone (NMP) is added until the solution becomes a flowing state, an emulsifying machine is used for stirring for half an hour to obtain slurry, and the slurry is uniformly coated on a copper foil with the 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. 6 is at 100mAg-1Current density of MnO/C (0.05) -600 samples, MnO/C (0.1) -600 samples, MnO/C (0.05) -800 samples, MnO/C (0.1) -800 samples, MnO material and biochar material. First threeCircle 50 mAg-1For activating the battery. After 300 times of circulation, the reversible capacity of the MnO/C composite material (MnO/C (0.1) -800) gradually reaches and is stabilized at 563mAhg-1The coulomb efficiency was 99%. This capacity is much higher than pure MnO (243 mAhg)-1) And biochar (260 mAhg)-1) A material. The reason why the MnO/C composite can have a relatively high capacity is due to the structure of the composite. The MnO nanoparticles in this study were mainly incorporated in a biocarbon layer, forming a "layer-particle-layer" sandwich. During cycling, particle aggregation and volume expansion of MnO nanoparticles may be limited in the carbon layer, thereby improving cycling stability of the electrode. In addition, sandwich-structured MnO/C composites exhibit unique "U" shaped cycling behavior (capacity first decreases and then recovers and increases rapidly). This phenomenon was also observed in previously reported MnO nanoparticle encapsulated carbon composites, which may be attributed to a new electrochemical reaction to form high oxidation state products or to an uneven distribution of Mn cluster aggregation and improvement of reversibility.
When the calcining temperature is constant, the concentration of the manganese source is 0.1mol L-1The obtained composite material has better electrochemical performance. The MnO/C (0.1) -800 sample has a reversible specific capacity of 563mAhg after 300 cycles-1The specific capacity of the sample is higher than that of MnO/C (0.05) -800 sample under the same test condition (469 mAhg)-1). The MnO concentration in the material is high, so that the material can exert the characteristics of manganese oxide, and the electrochemical performance of the material is improved.
When the concentration is constant, the composite material (MnO/C (0.1) -800) obtained at the calcination temperature of 800 ℃ has better electrochemical performance than the composite material (MnO/C (0.1) -600) obtained at the calcination temperature of 600 ℃, and the reversible specific capacity of the composite material after 300 cycles of the composite material is 563mAhg-1And the reversible specific capacity of the latter under the same condition is 449mAhg-1. This is because the higher the temperature, the more template-derived carbon defects are contained in the material, which is beneficial to ion conduction, and the higher the electrode cycling performance of the material is.
It should be understood that the above-mentioned embodiments are only illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All modifications made according to the spirit of the main technical scheme of the invention are covered in the protection scope of the invention.

Claims (9)

1. The MnO/C composite material is characterized in that the microstructure of the MnO/C composite material is a sandwich structure of a C layer, MnO particles and a C layer, wherein the diameter of the MnO particles is 20-40nm, and the preparation method of the MnO/C composite material comprises the following steps: 1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2-4 weeks to remove pigments and other organic substances in the petals;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the prepared manganese source concentrationC Mn = 0.05～0.1 mol L-1Soaking in the manganese acetate aqueous solution for n hours until n = 48-96, washing with deionized water, and naturally drying in the air to obtain dried petals;
5) calcining the dried petals obtained in the step 4) at the temperature of 600-800 ℃ in a nitrogen atmosphere to obtain the required MnO/C composite material.
2. The MnO/C composite as claimed in claim 1, wherein: when the MnO/C composite material is used as a lithium ion battery cathode material, the reversible specific capacity of the electrode reaches and is stabilized at 445-563 mAhg after 300 times of circulation-1The coulomb efficiency was 99%.
3. A method of making the MnO/C composite of claim 1 or 2, comprising the steps of:
1) washing camellia petals with deionized water for several times;
2) soaking the camellia petals washed in the step 1) in an ethanol solution for 2-4 weeks to remove pigments and other organic substances in the petals;
3) cleaning the petals soaked in the ethanol solution in the step 2) with deionized water, and filtering the petals in the air;
4) immersing the petals drained in the step 3) into the prepared manganese source concentrationC Mn = 0.05～0.1 mol L-1Soaking in the manganese acetate aqueous solution for n hours until n = 48-96, washing with deionized water, and naturally drying in the air to obtain dried petals;
5) calcining the dried petals obtained in the step 4) at the temperature of 600-800 ℃ in a nitrogen atmosphere to obtain the required MnO/C composite material.
4. The method according to claim 3, wherein the ethanol solution of step 2) has a volume ratio V of ethanol to waterEtOH/VH2O= 1:1 to 4:1, and the acidity of the ethanol solution is adjusted to pH = 2 to 3 by hydrochloric acid.
5. The process according to claim 4, wherein the volume ratio V of ethanol to water isEtOH/VH2O= 1:1, said pH = 2.
6. The method according to claim 3, wherein the calcination temperature in the step 5) is 800 ℃.
7. The method according to claim 3, wherein the manganese source is used in the step 4) at a concentration ofC Mn = 0.1 mol L-1。
8. The method according to claim 3, wherein n = 72.
9. Use of the MnO/C composite of claim 1 or 2 as a negative electrode material for a lithium ion battery.
CN201910887790.2A 2019-09-19 2019-09-19 MnO/C composite material, preparation method thereof and application of MnO/C composite material as lithium ion battery negative electrode material Active CN110611096B (en)

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