CN112374545A - Transition metal ion doped manganous-manganic oxide nanosheet array based on carbon cloth growth and preparation method and application thereof - Google Patents

Transition metal ion doped manganous-manganic oxide nanosheet array based on carbon cloth growth and preparation method and application thereof Download PDF

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CN112374545A
CN112374545A CN202011257579.1A CN202011257579A CN112374545A CN 112374545 A CN112374545 A CN 112374545A CN 202011257579 A CN202011257579 A CN 202011257579A CN 112374545 A CN112374545 A CN 112374545A
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transition metal
carbon cloth
nanosheet array
metal ion
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CN112374545B (en
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王浩
季杰
万厚钊
张军
汪汉斌
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Hubei University
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Abstract

The invention relates to a transition metal ion doped manganous-manganic oxide nanosheet array based on carbon cloth growth and a preparation method and application thereof. The invention takes the advantage of the high potential window of the manganese-based material as well as dopes transition metal ions to modify the manganese-based material, thereby integrally improving the electrochemical performance of the zinc ion battery. The method comprises the following basic steps: firstly, pretreating the empty carbon cloth; then growing a transition metal ion doped manganous-manganic oxide nanosheet array on the hollow carbon cloth by adopting an electrodeposition method; and finally, cleaning and drying. The invention adopts a one-step method, is convenient and simple, has convenient raw material acquisition, low cost and no toxicity, and solves the problems of excessive impurities in the materials, complex operation and the like in the traditional process. For the cathode material of the zinc ion battery, the structure is optimized by doping the transition metal ions with the manganese-based oxide, so that the electrochemical performance of the battery is improved. This provides a good idea for selecting or improving the cathode material of the zinc ion battery in the future.

Description

Transition metal ion doped manganous-manganic oxide nanosheet array based on carbon cloth growth and preparation method and application thereof
Technical Field
The invention belongs to the field of new energy materials, relates to a cathode energy storage structure material, and more particularly relates to transition metal ion doped manganous-manganic oxide (M-Mn) based on carbon cloth growth3O4a/CC) nanosheet array, a preparation method thereof and application thereof in a zinc ion battery.
Background
It is known that manganese-based oxides have been the subject of intense research as cathode materials for aqueous Zinc Ion Batteries (ZIBs) due to their high energy density, but their structural instability has led to poor cycle stability. For example, the dissolution of the cathode, irreversible lattice distortion and electrostatic interaction during the charge and discharge process lead to serious battery capacity attenuation and poor cycle stability, which all seriously restrict the development and popularization of Zinc Ion Batteries (ZIBs).
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or disadvantages of the prior art, it is an object of the present invention to provide a transition metal ion doped manganous-manganic oxide (M-Mn) based on carbon cloth growth3O4a/CC) nanosheet array, a preparation method thereof and application thereof in a zinc ion battery.
Currently, the prior art methods for solving the irreversible dissolution of manganese-based materials include: surface coating, element doping and electrolyte compensation; the surface coating and the electrolyte compensation are both used for carrying out structural modification on the surface of the manganese-based material from the outside, and element doping (nonmetal or metal) is mainly embedded into the manganese-based material main body in an ion form, so that partial lattice positions in the manganese-based material main body are changed, and a new chemical bond is formed to play a role in internal structural modification.
Based on the consideration of the above improved manganese-based material structure, the invention selects the transition metal ion M2+/3+(M2+/3+＝Co2+/3+、Ni2+/3+、Cu2+/3+Etc.) doped with trimanganese tetroxide (Mn)3O4) The manganese-based material is used as a cathode material for improving the electrochemical performance of the zinc ion battery, such as widening the potential window of the zinc ion battery, improving the cycling stability, improving the charge-discharge specific capacity and the like.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
transition metal ion doped manganous-manganic oxide (M-Mn) based on carbon cloth growth3O4the/CC) nanosheet array is formed by growing transition metal ion-doped M-Mn on the surface of Carbon Cloth (CC) by using the carbon cloth as a matrix and utilizing an electrochemical deposition method3O4And (4) obtaining a nanosheet array.
The transition metal ion doped mangano-manganic oxide (M-Mn) based on carbon cloth growth3O4The preparation method of the/CC) nanosheet array comprises the following specific steps:
firstly, pretreating carbon cloth, then placing the pretreated carbon cloth in a uniformly mixed aqueous solution (electrolyte) containing manganese salt, sodium sulfate and a small amount of transition metal salt, and then growing M-Mn on the surface of the pretreated carbon cloth by adopting an electrochemical deposition process3O4A nanosheet array; after the electrochemical deposition reaction is finished, repeatedly cleaning the obtained product by using deionized water, and naturally drying the product at room temperature; wherein: and M is doped transition metal ions.
Specifically, in the above technical scheme, the pretreatment mainly aims at decontamination and oil removal. The carbon cloth pretreatment process comprises the following steps: cutting an empty carbon cloth with a proper specification, placing the empty carbon cloth in concentrated nitric acid, transferring the empty carbon cloth into a constant-temperature water bath kettle at 80 ℃, soaking for 1-2 h at a constant temperature, taking out, sequentially and repeatedly cleaning in absolute ethyl alcohol and deionized water, and finally drying to obtain the pretreated carbon cloth for later use.
Preferably, in the technical scheme, the concentration of the concentrated nitric acid is 6-12 mol/L.
Further, in the above technical means, the M is any one of Co, Ni, Cu, and the like.
Further, in the above technical scheme, the M-Mn3O4Is Co-Mn3O4、Ni-Mn3O4、Cu-Mn3O4And the like.
Further, in the above technical scheme, the M-Mn3O4The thickness of the nano-sheet is 40-80 nm.
Further, in the above technical scheme, the M-Mn3O4The size of the nano sheet is 1-2 μm. Specifically, the Co-Mn3O4The size of the nano-sheet is between 1 and 2 mu m; the Ni-Mn3O4The size of the nano sheet is 1-2 μm; the Cu-Mn3O4The size of the sawtooth-shaped nano sheet is 1-2 μm.
Further, in the above technical solution, the manganese salt is any one of manganese acetate, manganese sulfate, manganese chloride, or the like, and for example, the manganese salt may be manganese acetate tetrahydrate.
Further, in the above technical solution, the transition metal salt is any one of a cobalt salt, a nickel salt, a copper salt, or the like.
Preferably, in the above technical solution, the cobalt salt is any one of cobalt acetate, cobalt sulfate, cobalt chloride, or the like.
Preferably, in the above technical solution, the nickel salt is any one of nickel acetate, nickel sulfate, nickel chloride, or the like.
Preferably, in the above technical solution, the copper salt is any one of copper acetate, copper sulfate, copper chloride, or the like.
Further, according to the technical scheme, the concentration of the manganese salt in the mixed water solution is the same as that of the sodium sulfate. Preferably, the molar concentration of the manganese salt in the mixed aqueous solution is 0.05-0.2 mol/L; the molar concentration of the sodium sulfate in the mixed aqueous solution is 0.05-0.2 mol/L.
Further, according to the technical scheme, the molar concentration of the transition metal salt in the mixed water solution is 0.002-0.08 mol/L.
Further, according to the above technical solution, the electrochemical deposition process is any one of potentiostatic electrodeposition or cyclic voltammetry electrodeposition. Because the polarization potentials of the transition metals (Co, Ni and Cu) are relatively close, the constant potential oxidation deposition is carried out by selecting the same potential. Furthermore, the active mass of the three materials prepared by deposition is consistent.
Specifically, according to the technical scheme, the electrochemical deposition process specifically adopts a three-electrode system, uses empty carbon cloth as a working electrode, uses a platinum electrode or a graphite electrode as a counter electrode, uses a saturated silver chloride electrode as a reference electrode, and performs electrodeposition for 10-30 min under the constant potential condition of-2.5-1.3V at room temperature or circulates for 20-50 circles at a scanning rate of 20-100 mV/s under a potential window of-1.3-0V by using a linear Cyclic Voltammetry (CV) method to obtain a target product.
Preferably, in the technical scheme, the scanning speed is 50-100 mV/s.
The second purpose of the invention is to provide transition metal ion doped mangano-manganic oxide (M-Mn) based on carbon cloth growth prepared by the method3O4/CC) nanosheet array.
The third purpose of the invention is to provide transition metal ion doped manganomanganic oxide (M-Mn) based on carbon cloth growth prepared by the method3O4and/CC) the nanosheet array is used as an electrode material in a zinc ion battery.
The cathode material of the zinc ion battery comprises transition metal ion doped manganous-manganic oxide (M-Mn) based on carbon cloth growth prepared by the method3O4/CC) nanosheet array.
The principle and advantages of the invention are as follows (note: manganese manganic oxide Mn mainly and pure)3O4For comparison):
the transition metal of the invention is doped into Mn in the form of ions3O4In the crystal structure. The invention utilizes the high potential window of the manganese-based material as the advantage, and modifies the manganese-based material by a method of doping transition metal ions on the basis, thereby integrally improving the electrochemical performance of the zinc ion battery.
The invention utilizes transition metal ions M2+/3+(M2+/3+＝Co2+/3+、Ni2+/3+、Cu2+/3+Etc.) doped with trimanganese tetroxide (Mn)3O4) Which grows M-Mn by electrodeposition on the surface of carbon cloth3O4The nanosheet array is used as an electrode material of the zinc ion battery, so that the structural stability and the conductivity of the electrode material can be improved, and meanwhile, the two-dimensional nanosheet array structure can provide a larger specific surface area so as to promote the rapid transfer of ions and further improve the rate characteristic and the cycle stability of the zinc ion battery; in another aspect, the invention uses an electrodeposition process to prepare transition metal ion doped manganomanganic oxide (M-Mn)3O4) The nano-sheet array has low preparation cost and simple method.
Compared with the prior art, the invention has the following beneficial effects:
(1) the good conductivity of the carbon cloth can ensure the uniform deposition of active substances and provide considerable surface area for the effective contact of electrolyte and the surface of a cathode material, and the prepared M-Mn3O4the/CC nanosheet array can improve the overall electrochemical performance of the zinc ion battery.
(2) The transition metal ion doped mangano-manganic oxide (M-Mn) based on carbon cloth growth3O4) Nanosheet array comprising Carbon Cloth (CC), M-Mn3O4a/CC nanosheet array; the two-dimensional nanosheet array can shorten an ion diffusion path and promote rapid ion transfer, and the array morphology is very beneficial to the ion embedding/extracting process in the zinc ion battery.
(3) M-Mn prepared by the technique of the invention3O4Compared with Mn prepared by the prior art by using a CC nanosheet array3O4When the nanosheet array is applied to a zinc ion battery, the potential window is higher, the cycling stability is better, the capacity is higher, and the multiplying power characteristic is better.
(4) M-Mn prepared by the technique of the invention3O4the/CC nanosheet array is complete in shape and has a larger specific surface area structurally.
(5) The preparation process of the invention adopts a one-step method, so the method is convenient and simple, and simultaneously, the raw materials of the invention are convenient to obtain, the cost is low, and the invention has no toxicity, thus solving the problems of excessive impurities in the materials, complex operation and the like in the traditional process. For the cathode material of the zinc ion battery, the structure is optimized by doping the transition metal ions with the manganese-based oxide, so that the electrochemical performance of the battery is improved. This provides a good idea for selecting or improving the cathode material of the zinc ion battery in the future.
Drawings
FIG. 1 shows the preparation of M-Mn by electrodeposition3O4Schematic diagram of/CC nanosheet array (M ═ Co, Ni, Cu);
in FIG. 2, (a) and (b) show Co-Mn prepared in example 1 of the present invention, respectively3O4The different magnifications of the/CC nanosheet array are Scanning Electron Microscope (SEM) images; (c) and (d) respectively represent Ni-Mn prepared in example 2 of the invention3O4The different magnifications of the/CC nanosheet array are Scanning Electron Microscope (SEM) images; (e) and (f) are Cu-Mn prepared in example 3 of the invention3O4The different magnifications of the/CC nanosheet array are Scanning Electron Microscope (SEM) images. (g) And (h) Mn prepared in comparative example 1 of the present invention3O4The different magnifications of the/CC nanosheet array are Scanning Electron Microscope (SEM) images.
FIG. 3 shows cobalt ion doped manganous-manganic oxide (Co-Mn) based on carbon cloth growth prepared in example 1 of the present invention3O4/CC) XRD pattern corresponding to the nanosheet array.
FIGS. 4(a), (b), (c), (d) are Mn prepared in comparative example 1, respectively3O4/CC, examples1 Co-Mn prepared3O4/CC nanosheet array, Ni-Mn prepared in example 23O4/CC nanosheet array, Cu-Mn prepared in example 33O4CV curve diagram of CC nano sheet array under small scanning speed.
FIG. 5 shows Co-Mn prepared in example 1 of the present invention3O4/CC nanosheet array, Ni-Mn prepared in example 23O4/CC nanosheet array, Cu-Mn prepared in example 33O4/CC nanosheet array and undoped mangano-manganic oxide (Mn) prepared in comparative example 13O4/CC) capacity performance versus graph.
FIG. 6 shows Co-Mn prepared in example 1 of the present invention3O4/CC nanosheet array, Ni-Mn prepared in example 23O4/CC nanosheet array, Cu-Mn prepared in example 33O4/CC nanosheet array and undoped mangano-manganic oxide (Mn) prepared in comparative example 13O4/CC) cycle performance versus graph.
FIG. 7 shows Co-Mn prepared in example 1 of the present invention3O4And analyzing the valence state of each XPS element of the/CC nanosheet array.
Detailed Description
The foregoing aspects of the present invention are described in further detail below by way of examples, but it should not be construed that the scope of the subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above aspects of the present invention are within the scope of the present invention.
The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials and reagents used are, unless otherwise specified, those commercially available from ordinary commercial sources.
The transition metal ion doped manganous-manganic oxide (M-Mn) prepared by the method of the invention3O4) The preparation method is mainly applied to the cathode material of the zinc ion battery, and the preparation process comprises the following steps: cleaning carbon cloth substrate, growing transition metal ion doped manganomanganic oxide (M-Mn) by three-electrode electrodeposition method3O4) Nanoplate arrays and productsAnd (4) cleaning and drying. Due to simple mangano-manganic oxide (Mn)3O4) Irreversible solution phase changes can occur during electrochemical cycling, eventually leading to structural collapse and resulting capacity fade. Thus, the mangano-manganic oxide (M-Mn) can be doped by transition metal ions3O4) The material structure is optimized, and the electrochemical performance of the electrode material is further improved. The specific method comprises the following steps: potentiostatic deposition or Cyclic Voltammetric (CV) electrodeposition. Carrying out constant-temperature and constant-pressure electrodeposition or constant-temperature cyclic voltammetry electrodeposition by using a mixed aqueous solution consisting of 0.05-0.2 mol/L manganese salt, 0.05-0.2 mol/L sodium sulfate and 0.002-0.08 mol/L transition metal salt to finally obtain transition metal ion doped manganous-manganic oxide (M-Mn)3O4) A nanosheet array. The preparation method is convenient and simple in preparation process, environment-friendly and low in cost, solves the problems of excessive impurities in materials, complex operation and the like in the traditional process, and improves a good idea for solving certain electrode materials with poor structural stability from another aspect.
Example 1
Cobalt ion doped manganous-manganic oxide (Co-Mn) based on carbon cloth growth of the embodiment3O4The preparation method of the/CC) nanosheet array comprises the following steps:
(1) carbon cloth pretreatment
Firstly, 3X 3cm is prepared2Soaking the specified empty carbon cloth in concentrated nitric acid with the concentration of 12mol/L, heating the cloth in water bath for 1-2 h at the constant temperature of 80 ℃, then ultrasonically cleaning the empty carbon cloth with absolute ethyl alcohol and deionized water for multiple times in sequence, and finally drying the cloth in a drying oven overnight for later use.
(2) Stock preparation
Preparing electrolyte: 100mL of manganese acetate (Mn (CH) containing 0.1mol/L tetrahydrate3COO)2·4H2O), 0.1mol/L sodium sulfate (Na)2SO4) And 0.005mol/L cobalt acetate tetrahydrate (Co (CH)3COO)2·4H2O) is added.
(3) Constant potential electrodeposition
And performing constant potential electrodeposition in the prepared mixed electrolyte by taking the treated empty carbon cloth as a working electrode, wherein the constant potential is controlled at-1.8V, and the electrodeposition is performed for 20min at room temperature.
(4) Cleaning and drying
Repeatedly cleaning the product obtained by electrodeposition with deionized water, and finally drying overnight in a room temperature environment to obtain the cobalt ion-doped manganous manganic oxide (Co-Mn) based on carbon cloth growth3O4/CC) nanosheet array.
Example 2
Nickel ion doped mangano-manganic oxide (Ni-Mn) based on carbon cloth growth of the embodiment3O4The preparation method of the/CC) nanosheet array comprises the following steps:
(1) carbon cloth pretreatment
Firstly, 3X 3cm is prepared2Soaking the specified empty carbon cloth in concentrated nitric acid with the concentration of 12mol/L, heating the cloth in water bath for 1-2 h at the constant temperature of 80 ℃, then ultrasonically cleaning the empty carbon cloth with absolute ethyl alcohol and deionized water for multiple times in sequence, and finally drying the cloth in a drying oven overnight for later use.
(2) Stock preparation
Preparing electrolyte: 100mL of manganese acetate (Mn (CH) containing 0.1mol/L tetrahydrate3COO)2·4H2O), 0.1mol/L sodium sulfate (Na)2SO4) And 0.005mol/L of nickel acetate tetrahydrate (Ni (CH)3COO)2·4H2O) is added.
(3) Constant potential electrodeposition
And performing constant potential electrodeposition in the prepared mixed electrolyte by taking the treated empty carbon cloth as a working electrode, wherein the constant potential is controlled at-1.4V, and the electrodeposition is performed for 25min at room temperature.
(4) Cleaning and drying
Electrodeposit Ni-Mn3O4the/CC is repeatedly washed by deionized water and finally is dried overnight in a room temperature environment to obtain the nickel ion doped manganous-manganic oxide (Ni-Mn) based on the growth of the carbon cloth3O4/CC) nanosheet array.
Example 3
Copper ion doped manganous-manganic oxide (Cu-Mn) based on carbon cloth growth of the embodiment3O4Preparation of/CC) nanosheet arrayThe method comprises the following steps:
(1) carbon cloth pretreatment
Firstly, 3X 3cm is prepared2Soaking the specified empty carbon cloth in concentrated nitric acid with the concentration of 12mol/L, heating the cloth in water bath for 1-2 h at the constant temperature of 80 ℃, then ultrasonically cleaning the empty carbon cloth with absolute ethyl alcohol and deionized water for multiple times in sequence, and finally drying the cloth in a drying oven overnight for later use.
(2) Stock preparation
Preparing electrolyte: 100mL of manganese acetate (Mn (CH) containing 0.1mol/L tetrahydrate3COO)2·4H2O), 0.1mol/L sodium sulfate (Na)2SO4) And 0.005mol/L of copper acetate monohydrate (Cu (CH)3COO)2·H2O) is added.
(3) Electrodeposition by CV scanning method
And performing electrodeposition by using the treated empty carbon cloth as a working electrode in the prepared mixed aqueous solution by using a cyclic voltammetry method, wherein the scanning window range is-1.3-0V, and the scanning rate is 50mV/s and the electrodeposition is performed for 50 circles at room temperature.
(4) Cleaning and drying
Electrodeposit Cu-Mn3O4the/CC is repeatedly cleaned by deionized water and finally is dried overnight in a room temperature environment to obtain the copper ion doped manganomanganic oxide (Cu-Mn) based on the carbon cloth growth3O4/CC) nanosheet array.
Comparative example 1
Trimanganese tetroxide (Mn) based on carbon cloth growth of this comparative example3O4The preparation method of/CC) comprises the following steps:
(1) carbon cloth pretreatment
Firstly, 3X 3cm is prepared2Soaking the specified empty carbon cloth in concentrated nitric acid with the concentration of 12mol/L, heating the cloth in water bath for 1-2 h at the constant temperature of 80 ℃, then ultrasonically cleaning the empty carbon cloth with absolute ethyl alcohol and deionized water for multiple times in sequence, and finally drying the cloth in a drying oven overnight for later use.
(2) Stock preparation
Preparing electrolyte: 100mL of manganese acetate (Mn (CH) containing 0.1mol/L tetrahydrate3COO)2·4H2O), 0.1mol/L sodium sulfate (Na)2SO4) The mixed aqueous solution of (1).
(3) Electrodeposition by CV scanning method
And taking the treated empty carbon cloth as a working electrode, performing electrodeposition in the prepared mixed aqueous solution by using a three-electrode-tank cyclic voltammetry, wherein the scanning window range is-1.3-0V, the scanning rate is 50mV/s, and the operation is performed by circulating for 20 circles at room temperature.
(4) Cleaning and drying
Repeatedly washing the product obtained by electrodeposition with deionized water, and finally drying overnight in a room temperature environment to obtain the trimanganese tetroxide (Mn) based on carbon cloth growth3O4/CC)。
In FIG. 2, (a) and (b) show Co-Mn prepared in example 1 of the present invention, respectively3O4Scanning Electron Microscope (SEM) images of CC nanosheet arrays at different magnifications; it can be seen that Co-Mn3O4The nano-sheets are uniformly coated on the surface of the carbon rod in a vertical state, and the size of the nano-sheets is about 1-2 mu m.
In FIG. 2, (c) and (d) show Ni-Mn prepared in example 2 of the present invention3O4Scanning Electron Microscope (SEM) images of CC nanosheet arrays at different magnifications; as can be seen, Ni-Mn3O4The nano-sheet is uniformly coated on the surface of the carbon rod in a vertical state, the size of the nano-sheet is about 2 mu m, and the appearance of the nano-sheet is rough.
In FIG. 2, (e) and (f) show Cu-Mn prepared in example 3 of the present invention, respectively3O4Scanning Electron Microscope (SEM) images of CC nanosheet arrays at different magnifications; as can be seen, Cu-Mn3O4The nano-sheet is uniformly coated on the surface of the carbon rod in a vertical state, and the size of the nano-sheet is kept about 1 mu m. From the appearance, Cu-Mn3O4Compared with the two electrode materials, the nano sheet array has brittle physical strength and reduced stability.
In FIG. 2, (g) and (h) are Mn prepared in comparative example 1 of the present invention3O4Scanning Electron Microscope (SEM) images of CC nanosheet arrays at different magnifications; as can be seen, Mn3O4Is a sheet-like nano structure with particlesThe carbon rod is uniformly coated on the surface of the carbon rod in a vertical state, and the size of the carbon rod is kept about 1-2 mu m.
FIG. 3 shows cobalt ion-doped manganous-manganic oxide (Co-Mn) based on carbon cloth growth prepared in example 13O4/CC) XRD pattern corresponding to the nanosheet array. (note: since transition metal ions are doped in the mangano-manganic oxide, the transition metal ions are mixed with standard mangano-manganic oxide (Mn)3O4) Compared with the XRD patterns, the position of each crystal face is not obviously shifted. ) Therefore, the invention only selects cobalt ion doped manganous-manganic oxide (Co-Mn)3O4) And simple mangano-manganic oxide (Mn)3O4) And performing comparative analysis.
FIGS. 4(a), (b), (c), (d) are Mn prepared in comparative example 1, respectively3O4/CC, Co-Mn prepared in example 13O4/CC nanosheet array, Ni-Mn prepared in example 23O4/CC nanosheet array, Cu-Mn prepared in example 33O4CV curve diagram of CC nano sheet array under small scanning speed. As can be seen from the figure, Co-Mn3O4The response current embodied by the/CC nano-sheet array is the highest and is close to 0.006A. Meanwhile, as the number of scanning turns is increased, the coincidence rate of CV curves is better. As a result, the capacity and cycle stability exhibited is also the best. As shown in fig. 5 and 6. (Note: CV Curve was measured by linear cyclic voltammetry using Chenghua CHI760E electrochemical workstation)
FIG. 5 shows Co-Mn prepared in example 1 of the present invention3O4/CC nanosheet array, Ni-Mn prepared in example 23O4/CC nanosheet array, Cu-Mn prepared in example 33O4/CC nanosheet array and undoped mangano-manganic oxide (Mn) prepared in comparative example 13O44/CC) capacity performance versus graph. It can be seen from the figure that compared to Mn which is only undoped3O4/CC, transition metal ion doped manganomanganic oxide (M-Mn)3O4the/CC) has obvious improvement on the performance. Wherein Co-Mn3O4The multiplying power performance of/CC is better, and reaches 362 mA-h g under the current density of 0.1A/g-1The ultra-high specific capacity. This is strongly related to the specific doping mechanism and good physical morphology of the Co metal ions. (Note: Rate Performance Curve is measured using New NeWARE eight channel device)
FIG. 6 shows Co-Mn prepared in example 1 of the present invention3O4/CC nanosheet array, Ni-Mn prepared in example 23O4/CC nanosheet array, Cu-Mn prepared in example 33O4/CC nanosheet array and undoped mangano-manganic oxide (Mn) prepared in comparative example 13O4/CC) cycle performance versus graph. It can be seen that compared to Mn which is only undoped3O4/CC, transition metal ion doped manganomanganic oxide (M-Mn)3O4the/CC) has obvious improvement on the cycle stability. Wherein Co-Mn3O4The circulation stability of the/CC is better, and after 500 cycles of charge and discharge, the capacity retention rate is as high as 94%. Such excellent properties are greatly related to the special doping mechanism and good physical morphology of the Co metal ions. Thus, overall, trimanganese tetroxide (Mn) is modified by transition metal ion doping3O4) The electrochemical performance is improved to various degrees. Such as improving the structural stability and conductivity of the material (note: the battery cycle life performance curve is measured by using the new Wei NEWARE eight-channel device)
FIG. 7 shows Co-Mn prepared in example 1 of the present invention3O4And analyzing the valence state of each XPS element of the/CC nanosheet array. It can be seen that, in Co-Mn3O4In the/CC electrode material, the valence state of Mn is mainly Mn2+And Mn3+The valence state of the doped Co is also mainly Co2+And Co3+Indicating that the Co doping form is ion doping by in-situ substituting Mn lattice position, and the whole crystal form still maintains Mn3O4Of spinel crystal form. (note: the doping pattern of other metal ions (Ni, Cu) is the same as that of Co, and Co-Mn is selected here3O4For example, analysis of
The above tests were all based on packaging into button cells: cathode material (M-Mn prepared by the invention)3O4a/CC nanosheet array), a glass fiber diaphragm, a commercial zinc sheet cathode and a mixed electrolyte of 2mol/L zinc sulfate and 0.2mol/L manganese sulfate.

Claims (10)

1. Transition metal ion doped manganous-manganic oxide M-Mn based on carbon cloth growth3O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: the method comprises the following specific steps:
firstly, pretreating carbon cloth, then placing the pretreated carbon cloth in a uniformly mixed aqueous solution containing manganese salt, sodium sulfate and a small amount of transition metal salt, and then growing M-Mn on the surface of the pretreated carbon cloth by adopting an electrochemical deposition process3O4A nanosheet array; after the electrochemical deposition reaction is finished, repeatedly cleaning the obtained product by using deionized water, and naturally drying the product at room temperature; wherein: and M is doped transition metal ions.
2. Carbon cloth growth based transition metal ion doped manganomanganic oxide M-Mn according to claim 13O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: and M is any one of Co, Ni and Cu.
3. Carbon cloth growth based transition metal ion doped manganomanganic oxide M-Mn according to claim 13O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: the M-Mn3O4The thickness of the nano sheet is 40-80 nm, and the M-Mn content is3O4The size of the nano sheet is 1-2 μm.
4. Carbon cloth growth based transition metal ion doped manganomanganic oxide M-Mn according to claim 13O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: the manganese salt is any one of manganese acetate, manganese sulfate or manganese chloride; the transition metal salt is any one of cobalt salt, nickel salt or copper salt.
5. Carbon-based cloth according to claim 4Growing transition metal ion doped mangano-manganic oxide M-Mn3O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: the cobalt salt is any one of cobalt acetate, cobalt sulfate or cobalt chloride; the nickel salt is any one of nickel acetate, nickel sulfate or nickel chloride; the copper salt is any one of copper acetate, copper sulfate or copper chloride.
6. Carbon cloth growth based transition metal ion doped manganomanganic oxide M-Mn according to claim 13O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: the molar concentration of manganese salt in the mixed aqueous solution is 0.05-0.2 mol/L; the molar concentration of sodium sulfate in the mixed aqueous solution is 0.05-0.2 mol/L; the molar concentration of the transition metal salt in the mixed water solution is 0.002-0.08 mol/L.
7. Carbon cloth growth based transition metal ion doped manganomanganic oxide M-Mn according to claim 13O4The preparation method of the/CC nanosheet array is characterized by comprising the following steps: the electrochemical deposition process specifically comprises the steps of adopting a three-electrode system, taking empty carbon cloth as a working electrode, taking a platinum electrode or a graphite electrode as a counter electrode and taking a saturated silver chloride electrode as a reference electrode, carrying out electrodeposition for 10-30 min under the condition of room temperature and constant potential of-2.5 to-1.3V or circulating for 20-50 circles at a scanning rate of 20-100 mV/s under a potential window of-1.3 to 0V by using a linear cyclic voltammetry method to obtain the transition metal ion doped manganous manganic oxide M-Mn based on carbon cloth growth3O4a/CC nanosheet array.
8. Transition metal ion doped manganous-manganic oxide M-Mn prepared by the method of any one of claims 1 to 7 and based on carbon cloth growth3O4a/CC nanosheet array.
9. Transition metal ion doped manganous-manganic oxide M-Mn prepared by the method of any one of claims 1 to 7 and based on carbon cloth growth3O4Method for preparing zinc ion battery by using/CC nanosheet array as electrode materialApplication in a pool.
10. A zinc ion battery cathode material, which comprises transition metal ion doped manganous-manganic oxide M-Mn prepared by the method of any one of claims 1 to 7 and based on carbon cloth growth3O4a/CC nanosheet array.
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