CN112382747B - Carbon layer coated nano mangano-manganic oxide shell-core structure material and preparation method thereof - Google Patents

Carbon layer coated nano mangano-manganic oxide shell-core structure material and preparation method thereof Download PDF

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CN112382747B
CN112382747B CN202110062154.3A CN202110062154A CN112382747B CN 112382747 B CN112382747 B CN 112382747B CN 202110062154 A CN202110062154 A CN 202110062154A CN 112382747 B CN112382747 B CN 112382747B
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carbon
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CN112382747A (en
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吴正颖
俞明浩
陈志刚
陈丰
钱君超
林艳
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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
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to carbon-coated nano Mn3O4A shell-core structure material, a preparation method and application thereof. The nano Mn of the invention3O4The @ C material is synthesized by taking plant cell tissues as a structure directing agent through impregnation and step-by-step calcination. The synthesized material retains the biological form of the template, oxide nanoparticles and a thin layer of biochar are formed in the step-by-step calcination process, and the retention of the biochar promotes Mn3O4Nano dispersion and grain growth, and the obtained material is uniform and has no obvious agglomeration phenomenon. In the process of charging and discharging of the battery, the biological carbon can effectively relieve structural collapse caused by lattice shrinkage in the process of lithium ion deintercalation, support and protection are provided for volume change, and in the cycle process, the carbon layer can limit aggregation and volume expansion of nano particles, so that the performance of the battery is improved. When the material is used as a lithium ion battery cathode material, the material is stabilized at 840 mAhg after 250 cycles‑1High specific capacity and stable circulating coulombic efficiency of 99%.

Description

Carbon layer coated nano mangano-manganic oxide shell-core structure material and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, in particular to carbon-coated nano Mn3O4A shell-core structure material, a preparation method and application thereof.
Background
The transition metal oxide has the characteristics of high theoretical specific capacity, abundant resources, relative greenness, environmental protection and the like, so the transition metal oxide has a good development prospect in the lithium ion battery cathode material. Poizot et al first proposed in 2000 that transition metals could be mixed with Li+To perform a reversible reaction therebetween, thereby realizing Li+Storage and release of (1). Among the numerous transition metal oxides, manganese oxide is due to its theoryThe graphite has the advantages of high specific capacity, abundant reserves, wide distribution, no toxicity and the like, is widely concerned and is considered to be a very promising graphite substitute. Mn according to the charge-discharge storage mechanism of the present transition metal oxides3O4Voids/interstices in the spinel structure can provide more electrically active sites and higher electrolyte ion intercalation/delamination capability, and are one of the most attractive electrode materials.
Of course, Mn3O4There are two major problems in practical electrochemical applications: (1) in the charging and discharging process, the reduced metal simple substance is easy to agglomerate, and the stability of the material structure is greatly influenced by volume expansion, so that the capacity of the material is reduced and the cycle performance is deteriorated in the charging and discharging process; (2) mn3O4The conductivity is low, the electron transmission rate is low in the charging and discharging process, and the volume pulverization in the circulating process further influences the electron transmission, so that the low rate performance is caused.
In order to solve the above problems, Mn is added3O4Modification is often needed for battery electrode materials, and there are two main common methods: (1) synthesizing Mn with special shapes and structures such as mesopore and hollow structure3O4The volume change is relieved, so that the lithium storage performance is improved; (2) the conductivity of the material is increased by compounding with a carbon material. Preparation of Mn at present3O4The methods are various and mainly divided into the following methods: solid phase method, precipitation method, hydrothermal/solvothermal method, electrochemical method, sonochemical method, and the like, wherein the hydrothermal/solvothermal method and the precipitation method are two methods used by researchers at most. By the two methods, Mn with various morphologies can be prepared3O4And the obtained material has very excellent electrochemical performance. Another lifting Mn3O4The method of performance is to nanocrystallize the material. The nanometer material has five major effects, so the nanometer Mn3O4With conventional bulk Mn3O4Compared with the prior art, the method is superior in performance. The size and controllable preparation of nano material are always important difficulties in research, and the synthesis of nano material by biological template methodThe material has the advantages of low preparation condition and controllable temperature in the reaction process, so that the material is unique.
In recent years, with the continuous and deep understanding of nature, more and more unique biological structures are developed, simulated and utilized, and the obtained bionic material is widely applied to various fields. The biological template method is that natural biological material is used as a template, inorganic ions are diffused in the biological template, and the template is removed by other methods such as calcination and the like to obtain the material with a unique morphology structure. However, the method for preparing Mn by adopting a biological template method is not adopted at present3O4The report of (1).
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a carbon-coated nano-Mn3O4A shell-core structure material, a preparation method and application thereof. The invention successfully synthesizes a novel shell-core structure nano Mn by taking the cell tissue of cabbage leaves as a structure directing agent through simple impregnation and step-by-step calcination3O4The @ C material shows good lithium storage performance as an electrode material of a lithium ion battery.
The first purpose of the invention is to provide nano Mn coated by a carbon layer3O4The preparation method of the shell-core structure material comprises the following steps:
s1, soaking and washing the biological template, and airing for later use;
s2, placing the air-dried biological template in a manganese nitrate solution, soaking for 48-96 hours, cleaning and air-drying to obtain a dried manganese nitrate infiltration biological template;
s3, heating the manganese nitrate infiltrated biological template to 550-650 ℃ under a protective atmosphere, and carrying out heat preservation and calcination for 1-3 hours;
s4, taking out the manganese nitrate soaked biological template calcined in the step S3, and heating to 650-750 ℃ in the air atmosphere to obtain the carbon layer coated nano Mn3O4A shell-core structural material.
Further, the biological template is cabbage leaves, Chinese rose petals or camellia petals.
Further, in the step S1, an ethanol solution with the concentration of 40% -60% is adopted for soaking the biological template, and the pH value of the ethanol solution is 2-4.
Further, in the step S1, the soaking time is 2 to 4 weeks.
Further, in the step S2, the concentration of the manganese nitrate solution is 0.01-0.1 mol/L.
Further, in the step S3, the temperature rising rate is 8-12 ℃ min-1。
Further, in the step S3, the protective atmosphere is nitrogen or an inert gas.
Further, in the step S4, the temperature rising rate is 8-12 ℃ min-1。
The second purpose of the invention is to provide the carbon-coated nano Mn prepared by the method3O4A shell-core structural material.
The third purpose of the invention is to provide a lithium battery electrode, wherein the lithium battery electrode is coated with nano Mn by the carbon layer3O4Preparing the shell-core structure material.
The fourth purpose of the invention is to provide a lithium battery, the negative electrode of which adopts the carbon layer to coat the nano Mn3O4Preparing the shell-core structure material.
By the scheme, the invention at least has the following advantages:
the nano Mn of the invention3O4The @ C material is successfully synthesized by taking the cell tissue of cabbage leaves as a structure directing agent through simple impregnation and step-by-step calcination. The nano Mn synthesized by the invention3O4The @ C material well retains the biological form of the template, oxide nanoparticles and thin-layer biochar are formed in the step-by-step calcination process, and the retention of the biochar promotes Mn3O4The nanometer dispersion and the grain growth, and the obtained material is uniform and has no obvious agglomeration phenomenon. During the process of charging and discharging the battery,the biological carbon can effectively relieve structural collapse caused by lattice contraction in the lithium ion deintercalation process, support and protection are provided for volume change, and the carbon layer can limit aggregation and volume expansion of nano particles in the circulating process, so that the performance of the battery is improved. When the material is used as a lithium ion battery cathode material, the material is stabilized at 840 mAhg after 250 cycles-1The specific capacity is high, and the circulating coulombic efficiency is stabilized at 99%.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 shows the nano-Mn synthesized in example 13O4SEM image of @ C material;
FIG. 2 shows the nano-Mn synthesized in example 13O4A TEM image of the material @ C, wherein (a) is a TEM image under a low-power transmission electron microscope and (b) is a TEM image under a high-power transmission electron microscope;
FIG. 3 shows the nano-Mn synthesized in example 13O4A plot of the cycling performance of the @ C material;
FIG. 4 shows the nano-Mn synthesized in example 13O4Rate performance plot of @ C material;
FIG. 5 shows the nano Mn synthesized in comparative example 13O4A TEM image of the material @ C, wherein (a) is a TEM image under a low-power transmission electron microscope and (b) is a TEM image under a high-power transmission electron microscope;
FIG. 6 shows the nano Mn synthesized in comparative example 23O4A TEM image of the material @ C, wherein (a) is a TEM image under a low-power transmission electron microscope and (b) is a TEM image under a high-power transmission electron microscope.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1:
nano Mn3O4The synthesis method of the @ C material comprises the following steps:
(1) washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H)2O =1: 1) and adjusting pH = 2-4 with hydrochloric acid, and pre-treating for two weeks to remove organic matter and pigments in the leaf of the cabbage.
(2) Taking out pretreated cabbage leaf, washing with distilled water, filtering, soaking in 50% Mn (NO)3)2The solution is prepared with Mn (NO) with the concentration of 0.05 mol/L3)2And (5) dissolving in the aqueous solution for 72 h.
(3) Taking out the soaked leaves, washing with distilled water, and air drying at room temperature.
(4) Calcining the dried leaves, namely firstly calcining the leaves in N2Heating to 600 deg.C in atmosphere at a heating rate of 10 deg.C/min-1Keeping the temperature for 2 h, taking out, heating to 700 ℃ in air atmosphere at a heating rate of 10 ℃ min-1Finally obtaining the nano Mn3O4@ C material.
The following examples are combined to synthesize nano Mn3O4@ C Material, we further analyzed Nano Mn in the present invention3O4The morphological structure and performance characteristics of the @ C material are as follows:
FIG. 1 shows Mn3O4Scanning Electron Microscope (SEM) images of the @ C material, the outline of hexagonal plant-like cells can be clearly seen from the SEM images, which indicates that the sample well retains the cell framework structure of the cabbage leaves. Meanwhile, Mn is also clearly seen from SEM image3O4The particles are arranged orderly, and no obvious agglomeration phenomenon of the particles is found.
FIG. 2 shows Mn3O4TEM image of @ C material. Under a low-power transmission electron microscope, (a) the full appearance of a sample, Mn3O4The particle size is about 24-32 nm, the particles are arranged closely, and no obvious agglomeration phenomenon occurs. Mn can be clearly observed under a high-power transmission electron microscope3O4The size of the nano-particles is 26.7 nm, Mn3O4 (211) And (112) interplanar spacings of approximately 0.249 nm and 0.309 nm. Careful observation of Mn revealed that3O4A layer of thin biological carbon is wrapped around the nano-particles, the biological carbon is similar to a shell-core structure formed by wrapping egg yolk with egg white, and the thickness of the carbon layer is 2.7 nm.
The following is for the nano Mn synthesized by the present invention3O4Electrochemical performance of the @ C material was tested: test conditions the nano Mn obtained in the examples3O4The material of @ C is used as a negative electrode, the lithium sheet is used as a counter electrode and a reference electrode, and the CR2032 button cell is mounted to test the electrochemical performance of the button cell. Specifically, the obtained nano Mn3O4Material @ 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 methylpyrrolidone (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 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 Mn3O4The graph of the cycling performance of the @ C material at 0.1A/g shows that the capacity of the sample decreases in the first 25 cycles and gradually increases after 25 cycles, which is related to the activation of the battery. After 250 circles, the specific capacity of the material is stabilized at 840 mAh/g, and the coulombic efficiency is stabilized at 99%. The Mn is3O4The excellent electrochemical performance of the @ C material is mainly due to the fact that nano Mn3O4Has a small grain size and is in the nanometer Mn range3O4Comprises a very thin layer of a biocarbon material around it, which makes the material in Li+The volume change of the material can be effectively relieved in the embedding and removing processes.
FIG. 4 shows a nano Mn3O4@ C material cycles 40 cycles of magnification plot at different current densities. Mn at a current density of 0.1A/g3O4The specific capacity of the @ C material is approximately 338 mAh/g. With increasing current densityThe specific capacity of the material in the charging and discharging processes of the lithium ion half battery is not obviously reduced, when the current density is increased to 1.0A/g, the specific capacity of about 353mAh/g is still reserved in the material, and the stability of the material under high current density is fully explained by the phenomenon. When the current density is again returned to 100 mA/g, the material likewise returns to a specific capacity of around 432 mAh/g.
Example 2:
(1) washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H)2O =1: 1) and adjusting pH = 2-4 with hydrochloric acid, and pre-treating for two weeks to remove organic matter and pigments in the leaf of the cabbage.
(2) Taking out pretreated cabbage leaf, washing with distilled water, filtering, soaking in 50% Mn (NO)3)2The solution is prepared with Mn (NO) with the concentration of 0.10mol/L3)2And (5) dissolving in the aqueous solution for 72 h.
(3) Taking out the soaked leaves, washing with distilled water, and air drying at room temperature.
(4) Calcining the dried leaves, namely firstly calcining the leaves in N2Heating to 600 deg.C in atmosphere at a heating rate of 10 deg.C/min-1Keeping the temperature for 2 h, taking out, heating to 700 ℃ in air atmosphere at a heating rate of 10 ℃ min-1Finally obtaining the nano Mn3O4@ C material.
Example 3:
(1) washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H)2O =1: 1) and adjusting pH = 2-4 with hydrochloric acid, and pre-treating for two weeks to remove organic matter and pigments in the leaf of the cabbage.
(2) Taking out pretreated cabbage leaf, washing with distilled water, filtering, soaking in 50% Mn (NO)3)2The solution prepared Mn (NO) with the concentration of 0.15mol/L3)2And (5) dissolving in the aqueous solution for 72 h.
(3) Taking out the soaked leaves, washing with distilled water, and air drying at room temperature.
(4) Calcining the dried leaves, namely firstly calcining the leaves in N2Rise under atmosphereThe temperature is increased to 600 ℃, and the temperature rising speed is 10 ℃ and min-1Keeping the temperature for 2 h, taking out, heating to 700 ℃ in air atmosphere at a heating rate of 10 ℃ min-1Finally obtaining the nano Mn3O4@ C material.
Comparative example 1:
(1) washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H)2O =1: 1) and adjusting pH = 2-4 with hydrochloric acid, and pre-treating for two weeks to remove organic matter and pigments in the leaf of the cabbage.
(2) Taking out pretreated cabbage leaf, washing with distilled water, filtering, soaking in 50% Mn (NO)3)2The solution is prepared with Mn (NO) with the concentration of 0.05 mol/L3)2And (5) dissolving in the aqueous solution for 72 h.
(3) Taking out the soaked leaves, washing with distilled water, and air drying at room temperature.
(4) Calcining the dried leaves, namely firstly calcining the leaves in N2Heating to 700 deg.C in the atmosphere at a heating rate of 10 deg.C/min-1Keeping the temperature for 2 h, taking out, heating to 500 ℃ in air atmosphere at a heating rate of 10 ℃ for min-1Finally obtaining the nano Mn3O4@ C material.
As can be seen from the TEM image of FIG. 5, in the stepwise calcination process, after the calcination temperature of the second step was lowered, the biochar in the composite was not well removed, and a large amount of thin carbon remained in the composite and was not well wrapped in Mn3O4The surface of the nanoparticles. After the battery is assembled, the materials of the structure are prone to volume expansion, resulting in structural collapse, which affects the capacity and cycling stability of the battery.
Comparative example 2:
(1) washing cabbage leaves with distilled water, and soaking in EtOH solution (EtOH: H)2O =1: 1) and adjusting pH = 2-4 with hydrochloric acid, and pre-treating for two weeks to remove organic matter and pigments in the leaf of the cabbage.
(2) Taking out pretreated cabbage leaf, washing with distilled water, filtering, soaking in 50% Mn (NO)3)2The solution is prepared with Mn (NO) with the concentration of 0.05 mol/L3)2And (5) dissolving in the aqueous solution for 72 h.
(3) Taking out the soaked leaves, washing with distilled water, and air drying at room temperature.
(4) Calcining the dried leaves, namely firstly calcining the leaves in N2Heating to 900 deg.C in atmosphere at a heating rate of 10 deg.C/min-1Keeping the temperature for 2 h, taking out, heating to 700 ℃ in air atmosphere at a heating rate of 10 ℃ min-1To obtain nano Mn3O4@ C material.
FIG. 6 is a TEM image of the material obtained in the comparative example, and it can be seen that Mn is present after the calcination temperature of the first step is increased during the stepwise calcination3O4The grain size of the nano particles can be obviously increased, but at the same time, the thin carbon layer coated on the surface of the material is easily damaged or baked, and only large-size Mn is obtained3O4Nanoparticles. Pure Mn3O4When the material is used for battery electrode materials, the structure is unstable, volume expansion and structure pulverization are easy to occur, and the battery capacity is quickly attenuated and the cycling stability is poor. The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (9)

1. Carbon-coated nano Mn3O4The preparation method of the shell-core structure material is characterized by comprising the following steps:
s1, washing and soaking cabbage leaves, and airing for later use;
s2, placing the dried cabbage leaves in a manganese nitrate solution to be soaked for 48-96 hours, cleaning and drying the cabbage leaves to obtain dried manganese nitrate soaked cabbage leaves;
s3, soaking cabbage leaves with manganese nitrate in N2Heating to 550-650 ℃ in the atmosphere, and calcining for 1-3 hours in a heat preservation manner;
s4, calcining the nitric acid obtained in the step S3Taking out the cabbage leaves soaked with manganese, and heating to 650-750 ℃ in the air atmosphere to obtain the carbon-coated nano Mn3O4A shell-core structural material.
2. The preparation method of claim 1, wherein in the step S1, the cabbage leaves are soaked in an ethanol solution with a concentration of 40-60%, and the pH of the ethanol solution is 2-4.
3. The method according to claim 1, wherein the soaking step in S1 is carried out for 2-4 weeks.
4. The method according to claim 1, wherein in the step S2, the concentration of the manganese nitrate solution is 0.01-0.1 mol/L.
5. The method according to claim 1, wherein the temperature is increased at a rate of 8 to 12 ℃ min in the step S3-1。
6. The method according to claim 1, wherein the temperature is increased at a rate of 8 to 12 ℃ min in the step S4-1。
7. Carbon-coated nano Mn prepared by the preparation method of any one of claims 1 to 63O4A shell-core structural material.
8. A lithium battery electrode, characterized in that the lithium battery electrode is coated with nano Mn by the carbon layer of claim 73O4Preparing the shell-core structure material.
9. A lithium battery, characterized in that the negative electrode is coated with nano Mn by the carbon layer as claimed in claim 73O4Preparing the shell-core structure material.
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