AU2020294319B1 - Transition metal ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth, and preparation method and application thereof - Google Patents

Transition metal ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth, and preparation method and application thereof Download PDF

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AU2020294319B1
AU2020294319B1 AU2020294319A AU2020294319A AU2020294319B1 AU 2020294319 B1 AU2020294319 B1 AU 2020294319B1 AU 2020294319 A AU2020294319 A AU 2020294319A AU 2020294319 A AU2020294319 A AU 2020294319A AU 2020294319 B1 AU2020294319 B1 AU 2020294319B1
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carbon cloth
transition metal
metal ions
trimanganese tetraoxide
nanosheet
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Jinxia Duan
Jie JI
Guokun MA
Liangping Shen
Houzhao WAN
Hanbin WANG
Hao Wang
Jun Zhang
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Hubei University
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Abstract

The present invention relates to transition metal ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth, and preparation method and application thereof. The present invention utilizes merit of high potential window of the Mn-based materials and on this basis modify the Mn-based materials by doping them with the transition metal ions, thereby improving the overall electrochemical performance of the ZIBs. Basic steps are as follows: pretreating a carbon cloth; growing transition metal ions doped trimanganese tetraoxide nanosheet arrays on the surface of the pretreated carbon cloth by electrochemical deposition process; and finally cleaning and drying. The present invention is convenient and simple by using a one-step method, and the raw materials of the present invention are convenient to obtain, low in cost, and non-toxic, so the problems of excessive impurities in materials and tedious operation in traditional process are solved. As cathode materials for ZIBs, the present invention optimizes the structure to improve the electrochemical performance of the batteries by doping Mn-based oxides with transition metal ions, which provides a good idea for the selection or improvement of cathode materials for ZIBs in the future. Drawing for Abstract Electrodeposition Carbon Cloth (CC) M- MnaO4/CC (M=Co, Ni, Cu)

Description

Transition metal ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth, and preparation method and application thereof
TECHNICAL FIELD The present invention belongs to the field of new energy materials, and relates to structure materials as cathode for energy storage. More particularly, the present invention relates to transition metal ions doped trimanganese tetraoxide (M-Mn 3 0 4/CC) nanosheet arrays grown based on carbon cloth, preparation method thereof and application thereof in ZIBs (zinc ion batteries).
BACKGROUND It is well known that Mn-based oxides are used as cathode materials for AZIBs (aqueous zinc ion batteries) due to their high energy density has always been a hot research topic, however, the instability of their structures leads to poor cycle stability. For example, the dissolution of the cathode during charging and discharging process, irreversible lattice distortion and electrostatic interaction make the battery capacity decrease seriously and cycle stability being poor, thereby severely restrict the development and promotion of ZIBs. Based on above reasons, the present invention is provided.
SUMMARY OF THE PRESENT INVENTION Aiming at above problems or defects in the prior art, objects of the present invention are to provide transition metal ions doped trimanganese tetraoxide (M-Mn 30 4/CC) nanosheet arrays grown based on carbon cloth, a preparation method thereof and an application thereof in ZIBs. Currently, the existing methods for solving the irreversible dissolution problem of Mn-based materials comprise: surface coating, element doping and electrolyte compensation. Among them, both surface coating and electrolyte compensation methods carry out structural modification on the surface of Mn-based materials from outside, while doping element (non-metal or metal) is mainly embedded in main body of the Mn-based materials in form of ions, and changing part of the crystal lattice position so as to form new chemical bonds to modify the internal structure. After considering structures of above modify Mn-base materials, the inventors of the present invention have selected doping trimanganese tetraoxide (Mn 3 0 4 ) with transition metal
ions M2+/3+ (the M 2+/3+ is any one of C02+/3+, Ni2+/3+, Cu2+/3+and the like) to modify internal structure of the Mn-base materials, and using them as cathode materials for improving electrochemical properties of ZIBs, such as widening the potential window of ZIBs, and improving cycling stability and charge-discharge specific capacity and the like. In order to achieve one of the above objects, the present invention adopts the following technical solutions: Transition metal ions doped trimanganese tetraoxide (M-Mn 30 4/CC) nanosheet arrays grown based on carbon cloth are obtained by using carbon cloth (CC) as a substrate and growing transition metal ions doped M-Mn 3 04nanosheet arrays on the surface of the carbon cloth by electrochemical deposition method. A method for preparing the above transition metal ions doped trimanganese tetraoxide (M-Mn 30 4/CC) nanosheet arrays grown based on carbon cloth, comprising the following steps: pretreating a carbon cloth; placing the pretreated carbon cloth in a uniformly mixed aqueous solution containing manganese salt, sodium sulfate and a small amount of transition metal salt as an electrolyte; growing M-Mn 304 nanosheet arrays on the surface of the pretreated carbon cloth by electrochemical deposition process; and upon the completion of the electrochemical deposition reaction, the resultants are cleaned repeatedly with deionized water, and then dried naturally at room temperature, wherein: the M is doped transition metal ions. Specifically, in the above technical solution, the pretreating primarily aimed at dirt and oil removal. The process for pretreating the carbon cloth is as follows: an empty carbon cloth is cut to a proper size. The carbon cloth is placed in concentrated nitric acid and transfered in a constant temperature water bath of 80°C, and then soaked for 1~2 h, taken out, cleaned repeatedly in anhydrous ethanol and deionized water, and finally dried to obtain the pretreated carbon cloth for use. Preferably, in the above technical solution, the concentrated nitric acid has a concentration of 6~12 mol/L. Further, in the above technical solution, the M is any one of Co, Ni, Cu and the like. Further, in the above technical solution, the M-Mn 304 is any one of Co-Mn 30 4 ,
Ni-Mn 30 4, Cu-Mn 3 04 and the like. Further, in the above technical solution, the M-Mn 304 nanosheets have a thickness of ~80 nm. Further, in the above technical solution, the M-Mn 3 04 nanosheets are about 1~2 m.
Specifically, the size of the Co-Mn 3 04 nanosheets is about 1~2 m; the size of the Ni-Mn 304 nanosheets is about 1~2 m; and the size of the Cu-Mn 304 zigzag nanosheets is about 1~2 Itm. Further, in the above technical solution, the manganese salt is any one of manganese acetate, manganese sulfate, manganese chloride and the like. For example, the manganese salt may be manganese(II) acetate tetrahydrate. Further, in the above technical solution, the transition metal salt is any one of cobalt salt, nickel salt, copper salt and the like. Preferably, in the above technical solution, the cobalt salt is any one of cobalt acetate, cobalt sulfate, cobalt chloride and the like. Preferably, in the above technical solution, the nickel salt is any one of nickel acetate, nickel sulfate, nickel chloride and the like. Preferably, in the above technical solution, the copper salt is any one of copper acetate, copper sulfate, copper chloride and the like. Further, in the above technical solution, the manganese salt and sodium sulfate in the mixed aqueous solution have the same concentration. 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, in the above technical solution, the molar concentration of the transition metal salt in the mixed aqueous solution is 0.002~0.08 mol/L. Further, in the above technical solution, the electrochemical deposition process adopts potentiostatic electrodeposition or cyclic voltammetry electrodeposition. Because the polarization potentials of transition metal (Co, Ni or Cu) are relatively close, the inventors of the present invention have selected the same potential for potentiostatic oxidation deposition. Moreover, the active qualities of the three deposited materials are consistent. Specifically, in the above technical solution, the electrochemical deposition process is conducted at room temperature using a three-electrode system, namely, the empty carbon cloth as working electrode, platinum electrode or graphite electrode as counter electrode, and saturated silver chloride electrode as reference electrode, and electrodepositing at a constant potential of -2.5~-1.3 V for 10~30 min or using linear cyclic voltammetry (CV) method to cycle 20~50 cycles under a potential window of -1.3~0 V with a scanning rate of 20~100 mV/s to obtain target resultants. Preferably, in the above technical solution, the scanning rate is 50~100 mV/s. A second object of the present invention is to provide the transition metal ions doped trimanganese tetraoxide (M-Mn 30 4/CC) nanosheet arrays grown based on carbon cloth prepared by the method described above. A third object of the present invention is to provide use of the transition metal ions doped trimanganese tetraoxide (M-Mn 30 4/CC) nanosheet arrays grown based on carbon cloth prepared by the method described above in a electrode material for ZIBs. A cathode material for ZIBs, comprising the transition metal ions doped trimanganese tetraoxide (M-Mn 30 4/CC) nanosheet arrays grown based on carbon cloth prepared by the above described method. Compared with pure trimanganese tetraoxide Mn 3 0 4 , the principle and advantages of the present invention are as follows: The transition metal is doped in the Mn3 04 crystal structure in form of ions according to the present invention. The present invention utilizes merit of high potential window of the Mn-based materials and on this basis modify the Mn-based materials by doping them with the transition metal ions, thereby improving the overall electrochemical performance of the ZIBs. Transition metal ions M2+/3+(the M2 +/3+is any one of C02+/3+, Ni 2 +/3+, Cu 2 +/3+and the like) are used to dope trimanganese tetraoxide (Mn 30 4) according to the present invention, and M-Mn 304nanosheet arrays are grown on the surface of carbon cloth by electrodeposition, which are used as electrode materials for ZIBs to improve the structural stability and conductivity of the electrode materials, while the two-dimensional nanosheet array structure of the M-Mn 304nanosheet arrays can provide a larger specific surface area to promote the rapid transfer of ions, thereby improving the rate capability and cycle stability of the ZIBs. Moreover, the novel electrodeposition process for preparing transition metal ions doped trimanganese tetraoxide nanosheet arrays is cheap and simple. Compared with the prior art, the beneficial effects of the present invention are described as follows: (1) The good conductivity of the carbon cloth according to the present invention can ensure the uniform deposition of active materials, and can also provide a considerable surface area for the effective contact between the electrolyte and the surface of the cathode materials, so the overall electrochemical performance of the ZIBs is improved by the prepared M-Mn 3 0 4/CC nanosheet arrays. (2) The transition metal ions doped trimanganese tetraoxide(M-Mn 30 4)nanosheet arrays grown based on carbon cloth according to the present invention comprising carbon cloth (CC) and M-Mn 3 0 4/CC nanosheet arrays, wherein the two-dimensional nanosheet arrays can short ion diffusion pathways and promote ions to transfer rapidly, because these array morphologies are very beneficial for ions embedding/stripping process in ZIBs. (3) Compared with the Mn3 04nanosheet arrays prepared by methods in the prior art, the M-Mn 3 0 4/CC nanosheet arrays prepared by the present invention have higher potential window, better cycle stability, higher capacity, and better rate capability when they are applied in ZIBs. (4) The M-Mn 3 0 4/CC nanosheet arrays prepared by the present invention have intact morphology and larger specific surface area in structure. (5) The preparation process of the present invention is convenient and simple by using a one-step method, and the raw materials of the present invention are convenient to obtain, low in cost, and non-toxic, so the problems of excessive impurities in materials and tedious operation in traditional process are solved. As cathode materials for ZIBs, the present invention optimizes the structure to improve the electrochemical performance of the batteries by doping Mn-based oxides with transition metal ions, which provides a good idea for the selection or improvement of cathode materials for ZIBs in the future.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is schematic diagram of the M-Mn 3 0 4 /CC (M is Co, Ni or Cu) nanosheet arrays prepared by the electrodeposition method according to the present invention; In figure 2, (a) and (b) are SEM (scanning electron microscope) images of Co-Mn 30 4/CC nanosheet arrays at different magnification, respectively, prepared according to Example 1 of the present invention; (c) and (d) are SEM images of Ni-Mn 3 04/CC nanosheet arrays at different magnification, respectively, prepared according to Example 2 of the present invention; (e) and (f) are SEM images of Cu-Mn 3 0 4/CC nanosheet arrays at different magnification, respectively, prepared according to Example 3 of the present invention; (g) and (h) are SEM images of Mn 3 04/CC nanosheet arrays at different magnification, respectively, prepared according to Comparative Example 1 of the present invention. Figure 3 is an XRD (X-Ray Diffraction) spectrogram of cobalt ions doped trimanganese tetraoxide (Co-Mn 3 0 4/CC) nanosheet arrays grown based on carbon cloth, prepared according to Example 1 of the present invention. Figures 4 (a), (b), (c) and (d) are CV (cyclic voltammetry) curves of Mn3 04/CC nanosheet arrays, Co-Mn 30 4/CC nanosheet arrays, Ni-Mn 30 4/CC nanosheet arrays, and Cu-Mn 30 4/CC nanosheet arrays at a low scanning rate, respectively, prepared according to
Comparative Example 1, Example 1, Example 2, and Example 3. Figure 5 is capacity performance comparison diagram of Co-Mn 30 4/CC nanosheet arrays, Ni-Mn 30 4/CC nanosheet arrays, Cu-Mn 3 0 4/CC nanosheet arrays, and undoped trimanganese tetraoxide (Mn 30 4/CC), respectively, prepared according to Example 1, Example 2, Example 3 and Comparative Example 1. Figure 6 is cycle performance comparison diagram of Co-Mn 30 4/CC nanosheet arrays, Ni-Mn 30 4/CC nanosheet arrays, a Cu-Mn 30 4/CC nanosheet arrays, and undoped trimanganese tetraoxide (Mn 30 4/CC), respectively, prepared according to Example 1, Example 2, Example 3 and Comparative Example 1. Figure 7 is XPS (X-Ray Photoelectron Spectroscopy) analysis of the valence states of each element of Co-Mn 3 0 4/CC nanosheet arrays prepared in Example 1 according to the present invention.
DETAILED DESCRIPTION OF THE PRESENT INVENTION The above content of the present invention will be further illustrated in detail below in the form of examples, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples. Any technology implemented based on the above content of the present invention shall fall within the scope of the present invention. In the following examples, the test methods used are conventional methods unless otherwise specified; the raw materials, reagents, and the like used can be obtained from commercial channels such as conventional commercial purchases, unless otherwise specified. The transition metal ions doped trimanganese tetraoxide (M-Mn 30 4) prepared by the method of the present invention are mainly used as a cathode material for ZIBs. The preparation process comprises: cleaning a carbon cloth substrate, growing transition metal ions doped trimanganese tetraoxide (M-Mn 3 0 4) nanosheet arrays by three-electrode electrodeposition method, and cleaning and drying the resultants. The structure of pure trimanganese tetraoxide (Mn 30 4) eventually collapses and the capacity decreases, due to its irreversible dissolution phase transition during the electrochemical cycling process. Therefore, transition metal ions are used to dope trimanganese tetraoxide (M-Mn 30 4) to optimize the material structure, so as to improve the electrochemical performance of the electrode materials. A used method is potentiostatic deposition or cyclic voltammetry (CV) electrodeposition. Specifically, electrodeposition at a constant temperature and a constant voltage or cyclic voltammetry electrodeposition at a constant temperature are conducted in a mixed aqueous solution composed of 0.05~0.2 mol/L manganese salt, 0.05~0.2 mol/L sodium sulfate and 0.002~0.08mol/L transition metal salt, and finally transition metal ions doped trimanganese tetraoxide (M-Mn 30 4 ) nanosheet arrays are obtained. The preparation process of the present invention is convenient and simple, green and environmental-friendly, and low in cost, so the problems of excessive impurities in materials and tedious operation in traditional process are solved. Moreover, a good idea for solving some electrode materials with poor structural stability is provided. Example 1 In this example, the method for preparing cobalt ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth (Co-Mn 3 0 4 /CC), comprising the following steps: (1) Pretreation of carbon cloth A 3x3 cm2 empty carbon cloth was prepared. The carbon cloth was immersed in 12 mol/L concentrated nitric acid and heated in a constant temperature water bath of 80°C for 1 ~2 h, then the empty carbon cloth was ultrasonically cleaned with anhydrous ethanol and deionized water for several times, and finally dried overnight in a drying oven for use. (2)Preparation of materials Preparation of electrolyte: a 100 mL mixed aqueous solution containing 0.1 mol/L manganese acetate tetrahydrate (Mn(CH 3COO) 2 -4H20), 0.1 mol/L sodium sulfate (Na2 SO 4
) and 0.005 mol/L cobalt acetate tetrahydrate (Co(CH 3COO) 2 -4H20) was prepared. (3)Potentiostatic electrodeposition Potentiostatic electrodeposition was conducted in the prepared mixed electrolyte at room temperature and at a constant potential of -1.8 V for 20 min, namely, the pretreated empty carbon cloth as working electrode. (4) Cleaning and drying The electrodeposition resultants were repeatedly cleaned with deionized water, and dried overnight at room tempeture to obtain the cobalt ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth (Co-Mn 3 0 4 /CC). Example 2 In this example, the method for preparing nickel ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth (Ni-Mn3 0 4 /CC), comprising the following steps: (1) Pretreation of carbon cloth A 3x3 cm2 empty carbon cloth was prepared. The carbon cloth was immersed in 12 mol/L concentrated nitric acid and heated in a constant temperature water bath of 80°C for 1 ~2 h, then the empty carbon cloth was ultrasonically cleaned with anhydrous ethanol and deionized water for several times, and finally dried overnight in a drying oven for use. (2)Preparation of materials Preparation of electrolyte: a 100 mL mixed aqueous solution containing 0.1 mol/L manganese acetate tetrahydrate (Mn(CH 3COO)2-4H 20), 0.1 mol/L sodium sulfate (Na2 SO 4
) and 0.005 mol/L nickel acetate tetrahydrate (Ni(CH 3COO)2-4H 20) was prepared. (3)Potentiostatic electrodeposition Potentiostatic electrodeposition was conducted in the prepared mixed electrolyte at room temperature and at a constant potential of -1.4 V for 25 min, namely, the pretreated empty carbon cloth as working electrode. (4) Cleaning and drying The electrodeposition resultants Ni-Mn 3 0 4 /CC was repeatedly cleaned with deionized water, and dried overnight at room tempeture to obtain the nickel ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth (Ni-Mn 3O 4/CC)
. Example 3 In this example, the method for preparing copper ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth (Cu-Mn 3 0 4 /CC), comprising the following steps: (1) Pretreation of carbon cloth A 3x3 cm2 empty carbon cloth was prepared. The carbon cloth was immersed in 12 mol/L concentrated nitric acid and heated in a constant temperature water bath of 80°C for 1 ~2 h, then the empty carbon cloth was ultrasonically cleaned with anhydrous ethanol and deionized water for several times, and finally dried overnight in a drying oven for use. (2)Preparation of materials Preparation of electrolyte: a 100 mL mixed aqueous solution containing 0.1 mol/L manganese acetate tetrahydrate (Mn(CH 3COO) 2 -4H20), 0.1 mol/L sodium sulfate (Na2 SO 4 )
and 0.005 mol/L copper acetate monohydrate (Cu(CH 3 COO)2-H 2 0) was prepared. (3) Cyclic voltammetry (CV) scanning electrodeposition Electrodeposition was conducted in the prepared mixed aqueous solution using a cyclic voltammetry method, namely, the pretreated empty carbon cloth as working electrode, and a range of scanning window was -1.3~0 V, a scanning rate was 50 mV/s, and 50 cycles were performed at room temperature. (4) Cleaning and drying
The electrodeposition resultants Cu-Mn 3 0 4 /CC was repeatedly cleaned with deionized water, and dried overnight at room tempeture to obtain the copper ions doped trimanganese tetraoxide nanosheet arrays grown based on carbon cloth (Cu-Mn 3 0 4 /CC). Comparative Example 1 In this comparative example, the method for preparing trimanganese tetraoxide grown based on carbon cloth(Mn 3 0 4 /CC), comprising the following steps: (1) Pretreation of carbon cloth A 3x3 cm2 empty carbon cloth was prepared. The carbon cloth was immersed in 12 mol/L concentrated nitric acid and heated in a constant temperature water bath of 80°C for 1 ~2 h, then the empty carbon cloth was ultrasonically cleaned with anhydrous ethanol and deionized water for several times, and finally dried overnight in a drying oven for use. (2)Preparation of materials Preparation of electrolyte: a 100 mL mixed aqueous solution containing 0.1 mol/L manganese acetate tetrahydrate (Mn(CH 3COO)2-4H 20) and 0.1 mol/L sodium sulfate (Na 2 SO4 ) was prepared. (3) Cyclic voltammetry (CV) scanning electrodeposition Electrodeposition was conducted in the prepared mixed aqueous solution using a three -electrode cell cyclic voltammetry method, namely, the pretreated empty carbon cloth as working electrode, and a range of scanning window was -1.3~0 V, a scanning rate was 50 mV/s, and 20 cycles were performed at room temperature. (4) Cleaning and drying The electrodeposition resultants were repeatedly cleaned with deionized water, and dried overnight at room tempeture to obtain the trimanganese tetraoxide grown based on carbon cloth (Mn 3 0 4 /CC). In figure 2, (a) and (b) are SEM images of Co-Mn 30 4/CC nanosheet arrays at different magnification, respectively, prepared according to Example 1 of the present invention. It can be seen that: the Co-Mn 304nanosheets are uniformly coated on the surface of the carbon rods in a vertical state, and they have a size of about 1~2 m. In figures 2, (c) and (d) are SEM images of Ni-Mn 30 4/CC nanosheet arrays at different magnification, respectively, prepared according to Example 2 of the present invention. It can be seen that: the Ni-Mn 3 04 nanosheets are uniformly coated on the surface of the carbon rods in a vertical state, and they have a size of about 2 m and a rough morphology. In figure 2, (e) and (f) are SEM images of Cu-Mn 3 0 4/CC nanosheet arrays at different magnification, respectively, prepared according to Example 3 of the present invention. It can be seen that: the Cu-Mn 304 nanosheets are also uniformly coated on the surface of the carbon rods in a vertical state, and they have a size of about 1 m. In terms of morphology, Cu-Mn 304 nanosheet array is more brittle in physical strength and less stable than the above two electrode materials. In figure 2, (g) and (h) are SEM images of Mn 3 04/CC nanosheet arrays at different magnification, respectively, prepared according to Comparative Example 1 of the present invention. It can be seen that: Mn 3 04 are uniformly coated on the surface of the carbon rods in a vertical state of sheet-like nanostructure with particles, and their size remains around 1~2 Itm. Figure 3 is an XRD (X-Ray Diffraction) spectrogram of cobalt ions doped trimanganese tetraoxide (Co-Mn 3 0 4/CC) nanosheet arrays grown based on carbon cloth, prepared according to Example 1 of the present invention. Compared with the XRD pattern of standard trimanganese tetraoxide (Mn 3 0 4 ), the position of each crystal plane of trimanganese tetraoxide doped with transition metal ions do not move significantly, therefore, only cobalt ions doped trimanganese tetraoxide (Co-Mn 3 0 4) and pure trimanganese tetraoxide (Mn 3 0 4
) are used for comparative analysis according to the present invention. Figure 4 (a), (b), (c) and (d) are CV (cyclic voltammetry) curves of Mn3 04/CC nanosheet arrays, Co-Mn 30 4/CC nanosheet arrays, Ni-Mn 30 4/CC nanosheet arrays, and Cu-Mn 30 4/CC nanosheet arrays at a low scanning rate, respectively, prepared according to Comparative Example 1, Example 1, Example 2, and Example 3. It can be seen from the figure that: a response current reflected by the Co-Mn 3 0 4/CC nanosheet arrays is the highest, which is close to 0.006 A, while with the increase of scanning cycles, the coincidence rate of the CV curve is better. As a result, the best capacity and cycle stability are also performed. The details are shown in Figure 5 and Figure 6. (Note: CV curves were measured by linear cyclic voltammetry method using Chenhua (CHI760E) electrochemical workstation) Figure 5 is capacity performance comparison diagram of Co-Mn 30 4/CC nanosheet arrays, Ni-Mn 30 4/CC nanosheet arrays, Cu-Mn 3 0 4/CC nanosheet arrays, and undoped trimanganese tetraoxide (Mn 30 4/CC), respectively, prepared according to Example 1, Example 2, Example 3 and Comparative Example 1. It can be seen from the figure that: compared with pure undoped Mn 3 0 4 /CC, the properties of transition metal ions doped trimanganese tetraoxide (Mn 30 4/CC) are all significantly improved. Among them, Co-Mn 30 4/CC has the best rate performance, reaching an ultra-high specific capacity of 362 mA-h-g- at a current density of 0.1 A-g- , which is closely related to the special doping mechanism and good physical morphology of Co metal ions (Note: the rate performance curve was measured using a 8-channel NEWARE equipment.) Figure 6 is cycle performance comparison diagram of Co-Mn 30 4/CC nanosheet arrays, Ni-Mn 30 4/CC nanosheet arrays, Cu-Mn 3 0 4/CC nanosheet arrays, and undoped trimanganese tetraoxide (Mn 3 0 4/CC), respectively, prepared according to Example 1, Example 2, Example 3 and Comparative Example 1. It can be seen that: compared to pure undoped Mn 3 0 4/CC, the cycle stability of transition metal ions doped trimanganese tetraoxide (Mn 3 0 4/CC) are all significantly improved. Among them, Co-Mn 30 4/CC has the best cycle stability, and a capacity retention rate is as high as 94% after 500 cycles. Such excellent performance is closely related to the special doping mechanism and good physical morphology of Co metal ions. Therefore, the modification of trimanganese tetraoxide (Mn 3 0 4 ) with transition metal ions doping can improve electrochemical performance in different degrees, such as improve the stability of material structure, conductivity and the like. (Note: the cycle life performance curves of the batteries were measured using a 8-channel NEWARE equipment.) Figure 7 is XPS (X-Ray Photoelectron Spectroscopy) analysis of the valence states of each element of Co-Mn 3 0 4/CC nanosheet arrays prepared in Example 1 according to the present invention. It can be seen that: in electrode materials of Co-Mn 3 0 4 /CC, valence states of Mn are mainly Mn2and Mn , and valence states of doped Co are mainly Co2and Co illustrating the doping form of Co is ions doping by replacing the lattice position of Mn in situ, and the overall crystal type still maintains the spinel crystal type of Mn3 0 4. (Note: the doping mode of other metal ions (Ni or Cu) is consistent with the doping mode of Co, so Co-Mn 304 is selected as an example for analysis here.) The above tests are all based on encapsulated button batteries: namely, M-Mn 3 0 4 /CC nanosheet arrays prepared by the present invention as the cathode material, glass fiber as diaphragm, commercial zincfoil as the anode, and 2 mol/L zinc sulfate and 0.2 mol/L manganese sulfate as mixed electrolyte.

Claims (10)

WHAT IS CLAIMED IS:
1. A method for preparing transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth, comprising the following steps: pretreating a carbon cloth; placing the pretreated carbon cloth in a uniformly mixed aqueous solution containing manganese salt, sodium sulfate and a small amount of transition metal salt; growing M-Mn 304 nanosheet arrays on the surface of the pretreated carbon cloth by electrochemical deposition process; and upon the completion of the electrochemical deposition reaction, the resultants are cleaned repeatedly with deionized water, and then dried naturally at room temperature, wherein: the M is doped transition metal ions.
2. The method for preparing transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth according to claim 1, wherein: the M is any one of Co, Ni, and Cu.
3. The method for preparing transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth according to claim 1, wherein: the M-Mn 3 04 nanosheets have a thickness of 40~80 nm and a size of 1~2 m.
4. The method for preparing transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth according to claim 1, wherein: the manganese salt is any one of manganese acetate, manganese sulfate, and manganese chloride; and the transition metal salt is any one of cobalt salt, nickel salt, and copper salt.
5. The method for preparing transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth according to claim 4, wherein: the cobalt salt is any one of cobalt acetate, cobalt sulfate, and cobalt chloride; the nickel salt is any one of nickel acetate, nickel sulfate, and nickel chloride; and the copper salt is any one of copper acetate, copper sulfate, and copper chloride.
6. The method for preparing transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth according to claim 1, wherein: a molar concentration of the manganese salt in the mixed aqueous solution is 0.05~0.2 mol/L; a molar concentration of the sodium sulfate in the mixed aqueous solution is 0.05~0.2 mol/L; and a molar concentration of the transition metal salt in the mixed aqueous solution is 0.002~0.08 mol/L.
7. The method for preparing transition metal ions doped trimanganese tetraoxide
M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth according to claim 1, wherein: the electrochemical deposition process is conducted at room temperature using a three-electrode system, namely, the empty carbon cloth as working electrode, platinum electrode or graphite electrode as counter electrode, and saturated silver chloride electrode as reference electrode, and electrodepositing at a constant potential of -2.5- -1.3 V for 10-30 min or using linear cyclic voltammetry method to cycle 20~50 cycles under a potential window of -1.3~0 V with a scanning rate of 20~100 mV/s to obtain the transition metal ion doped trimanganese tetraoxide M-Mn 30 4/CC nanosheet array grown based on carbon cloth.
8. Transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth prepared by the method according to any one of claims 1 to 7.
9. Use of the transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4 /CC nanosheet arrays grown based on carbon cloth prepared by the method according to any one of claims 1 to 7 in a electrode material for ZIBs.
10. A cathode material for ZIBs, comprising transition metal ions doped trimanganese tetraoxide M-Mn 3 0 4/CC nanosheet arrays grown based on carbon cloth prepared by the method according to any one of claims I to 7.
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