CN113213542A - Manganese sesquioxide multi-shell nano hollow sphere material and preparation and application thereof - Google Patents
Manganese sesquioxide multi-shell nano hollow sphere material and preparation and application thereof Download PDFInfo
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- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 title description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012697 Mn precursor Substances 0.000 claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000002077 nanosphere Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 239000011686 zinc sulphate Substances 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000013239 manganese-based metal-organic framework Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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Abstract
The invention discloses Mn suitable for preparing a water-based zinc ion battery anode2O3The multi-shell nano hollow sphere material comprises Mn combined by a mode of sleeving a large spherical shell and a small spherical shell2O3The inner surface of each shell layer is provided with a plurality of holes and Mn2O3And (3) nanoparticles. The invention also discloses the Mn2O3The preparation method of the multi-shell nano hollow sphere material comprises the following steps: firstly synthesizing Mn precursor metal organic framework microspheres, and then obtaining the Mn precursor metal organic framework microspheres by simple oxidation and calcination in airAnd (4) obtaining a final product. The invention can improve Mn2O3The electrochemical activity and the structural stability of the composite lead the discharge specific capacity, the cycle performance and the rate capability of the composite lead to be obviously improved. Mn2O3The multi-shell nano hollow sphere material has high application value as a zinc ion battery anode material.
Description
Technical Field
The invention relates to the technical field of water-system zinc ion batteries, in particular to a zinc ion battery suitable for preparing water-system zinc ionsManganese sesquioxide (Mn) of battery positive electrode2O3) A multi-shell nano hollow sphere material, and preparation and application thereof.
Background
Rechargeable aqueous batteries have the advantages of high safety, low cost, environmental friendliness, and the like, and are considered to be the most promising alternatives to lithium ion batteries. More importantly, the ionic conductivity of the aqueous electrolyte is 2-3 orders of magnitude higher than that of the organic electrolyte. Among various aqueous batteries, Zinc Ion Batteries (ZIBs) have received great attention because they: (1) has the advantages of low cost, high safety, rich resources and the like. (2) The lower redox potential of Zn is beneficial for obtaining high output voltage. (3) The high stability of Zn in water ensures the high reversibility of the battery. (4) The two electron transfer reaction can store more energy. For ZIBs, the positive electrode material is a critical factor in determining its electrochemical performance. Among the promising positive electrode materials, manganese-based oxides, in particular MnO2It is receiving increasing attention due to its high reversible capacity and operating voltage, as well as its variety of morphologies. MnO2The extensive research and great progress made in this area has promoted other manganese-based oxides such as Mn2O3Further study of (1). Unfortunately, challenges still exist. Poor conductivity, slow redox kinetics, large volume changes, resulting in Mn2O3The specific capacity and the rate capability of the Mn-Mn alloy are lower, the structure is unstable, the capacity attenuation is fast, and the Mn is prevented2O3The practical application of (1).
To solve the above problems, Mn is increased2O3Zinc storage property of (2) Mn2O3Material nanocrystallization is a major strategy. The invention patent with the publication number of CN111682178A discloses nitrogen-doped graphene oxide/Mn2O3Composite materials, but graphene oxide and Mn in this technique2O3The material is only simply mixed, and the bonding strength of the material is not high; the invention patent publication No. CN111115688A discloses sintering manganese carbonate to obtain manganese carbonate MnO2And Mn2O3The composite material of (1). The invention patent publication No. CN109616624A discloses that Mn is coated with indium oxide2O3Indium oxide is very expensive. In addition, Z.G.ZHao et al synthesized flexible three-dimensional vertically stacked Mn by direct annealing of Mn-based metal-organic frameworks Mn-MIL-1002O3@ C nanosheet (C.L.Liu, Q.L.Li, H.Z.Sun, Z.Wang, W.B.Gong, S.Cong, Y.G.Yao, Z.G.ZHao, MOF-derived vertical stack Mn2O3@ C flaps for fiber-shaped drawing-on batteries, J.Mater.chem.A., 2020,8, 24031-24039.). At present, Mn2O3The application of nano materials in the field of zinc ion batteries is still deficient, so that the development of Mn with a new structure is urgently needed2O3And (3) nano materials.
Disclosure of Invention
Aiming at the technical problems and the defects in the field, the invention provides Mn suitable for preparing the anode of the water-based zinc-ion battery2O3And (3) a multi-shell nano hollow sphere material. The invention can obviously improve Mn2O3The electrochemical activity and the structural stability of the composite material, and further the specific discharge capacity, the cycle performance and the rate capability of the composite material are improved. Mn as a positive electrode material for zinc ion batteries2O3The multi-shell nano hollow sphere material has high application value.
Mn suitable for preparing anode of water-based zinc ion battery2O3The multi-shell nano hollow sphere material comprises Mn combined by a mode of sleeving a large spherical shell and a small spherical shell2O3The inner surface of each shell layer is provided with a plurality of holes and Mn2O3And (3) nanoparticles.
Preferably, the Mn is2O3The outer diameter of the multi-shell hollow nanosphere is 0.5-3.5 μm, the shell thickness is 5-50nm, and the number of shells is 2-7.
Preferably, the pores and Mn2O3The size of the nanoparticles was 10 nm.
The invention also provides the Mn2O3The preparation method of the multi-shell nano hollow sphere material comprises the following steps:
dissolving manganese nitrate tetrahydrate and isophthalic acid in a molar ratio of 1:1 in N, N-dimethylformamideStirring the mixed solution of acetone for 6 hours at room temperature, transferring the solution into a reaction kettle, heating the solution to 150-200 ℃ for solvothermal reaction for 0.5-5 hours, cooling the solution to room temperature, then centrifugally separating the product, washing the product with ethanol for several times, and drying the product at 80 ℃ to obtain Mn precursor microspheres; heating the Mn precursor microspheres in the air at a heating speed of 4-10 ℃ for min-1Heating to 350-2O3And (3) a multi-shell nano hollow sphere material.
The preparation method of the invention comprises the steps of firstly synthesizing Mn precursor metal organic framework microspheres, and then obtaining the final product through oxidizing and calcining in air. Because the valence state form and the structural morphology of the manganese oxide exist in a plurality of forms which are difficult to predict and regulate, in order to ensure that the Mn provided by the invention is obtained2O3The inventor strictly controls the following parameter conditions in the preparation method of the multi-shell hollow nanosphere material: 1. the molar ratio of the manganese nitrate tetrahydrate to the isophthalic acid is 1: 1; 2. and the heating rate, the heating final temperature and the heat preservation time of the Mn precursor microsphere in the air atmosphere are simultaneously controlled within the ranges. The two should be absent, otherwise, Mn with the structural morphology and valence state of the invention is difficult to obtain2O3And (3) a multi-shell nano hollow sphere material. Preferably, the Mn precursor microspheres are heated at a heating speed of 5 ℃ for min in the air-1Heating to 450 deg.C, and maintaining the temperature for 10min to obtain Mn2O3And (3) a multi-shell nano hollow sphere material.
The concentration of the manganese nitrate tetrahydrate in the solvothermal reaction system has certain influence on the size and the shape of the product. Preferably, the amount of the acetone is 10mL and the amount of the manganese nitrate tetrahydrate is 0.05-0.4mmol relative to 10mL of the N, N-dimethylformamide.
The invention also provides the Mn2O3The application of the multi-shell nano hollow sphere material in the preparation of the anode of a water system zinc ion battery.
The anode of the zinc ion battery is made of the material of the invention: respectively weighing Mn with the mass ratio of 70:15:152O3Multi-shell nano hollow sphere material, acetylene black conductive agent and polyvinylidene fluoride (PVDF) binderDissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground active material and acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a stainless steel foil wafer (with the diameter of 12mm), and drying in a vacuum oven at 100 ℃ to obtain the electrode slice.
Assembling the prepared electrode slice, a metal zinc slice and a glass fiber membrane into a CR2025 button type zinc ion battery, wherein the electrolyte is 2mol L-1ZnSO4And 0.1mol L-1MnSO4The mixed aqueous solution adopts a Xinwei battery test system to test the charge-discharge performance and the cycle performance of the zinc ion battery.
Compared with the prior art, the invention has the main advantages that:
(1) the hollow nanospheres have the advantages of large specific surface area, more active sites and high electrochemical activity, and are beneficial to releasing higher specific discharge capacity of the material. The spherical shell has the advantages of thin thickness, short zinc ion diffusion path, good reaction kinetics and high material utilization rate. The combined structure of the plurality of nano hollow spherical shells improves the space utilization rate of the material, and is beneficial to improving the energy density of the manufactured electrode. The hollow structure facilitates the permeation and diffusion of electrolyte ions, is beneficial to the internal material to fully contact the electrolyte, and meets the requirement of the electrochemical reaction of the internal material. The inner and outer surfaces of each spherical shell can be contacted with electrolyte, which can increase Mn2O3The charge-discharge reaction efficiency of the material is very favorable for improving the specific capacity.
(2) The hollow ball structure is beneficial to adjusting Mn2O3The volume of the material expands in the charge-discharge cycle process, and the cycle stability of the material can be obviously improved. More importantly, a plurality of holes and nano particles are hidden under the shell layer of the hollow sphere, and the holes can be well adapted to Mn2O3The expansion/contraction of the material can further enhance the structure and the cycling stability of the hollow spherical shell. The pores and the nano particles further increase the specific surface area of the material, and are beneficial to enhancing the electrochemical activity and specific capacity of the material.
(3) The method for synthesizing the multi-shell nano hollow sphere material by oxidizing the Mn precursor metal organic framework microspheres is simple and efficient, and is suitable for industrial mass production.
Drawings
FIG. 1 shows Mn prepared in example 12O3SEM photo of the multi-shell nanometer hollow sphere;
FIG. 2 shows Mn prepared in example 12O3TEM photo of the multi-shell nano hollow sphere;
FIG. 3 shows Mn prepared in example 12O3Local TEM photographs of the multi-shell nano hollow spheres;
FIG. 4 shows Mn prepared in example 12O3Multiplying power performance diagram of the multi-shell nano hollow sphere material;
FIG. 5 shows Mn prepared in example 12O3The multi-shell nano hollow sphere material has the current density of 1A g-1Cycle performance map of (c).
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Dissolving 0.2mmol of manganese nitrate tetrahydrate and 0.2mmol of isophthalic acid in a mixed solution of 10mL of N, N-dimethylformamide and 10mL of acetone, stirring for 6h at room temperature, transferring the solution into a reaction kettle, heating to 160 ℃, preserving heat for 4h, cooling to room temperature, centrifugally separating a product, washing with ethanol for several times, and drying at 80 ℃ to obtain the Mn precursor microsphere. The Mn precursor microspheres are heated for 5 ℃ min at a heating speed in the air-1Heating to 450 deg.C, and maintaining the temperature for 10min to obtain Mn2O3The multi-shell layer nanometer hollow sphere.
FIG. 1 is Mn prepared2O3SEM photograph of the multi-shell nanometer hollow sphere. Individual spheres were seen, with a very rough surface showing many folds, with a sphere diameter of about 1.4 μm. FIG. 2 is a TEM photograph thereof clearly showing the hollow and multi-shell structure therein, the shell having 4 layersThe thickness of the shell is 10-15 nm. Fig. 3 is a partially enlarged TEM photograph of the shell, in which many pores and nanoparticles having a size of about 10nm exist on the inner surface of the corrugated shell.
The anode of the zinc ion battery is made of the material of the invention: respectively weighing Mn with the mass ratio of 70:15:152O3The preparation method comprises the steps of dissolving PVDF in a proper amount of 1-methyl-2-pyrrolidone (NMP), stirring until the PVDF is completely dissolved, adding the uniformly ground active material and acetylene black into the solution, and continuously stirring to ensure that the slurry is uniformly mixed. And then uniformly coating the slurry on a stainless steel foil wafer (with the diameter of 12mm), and drying in a vacuum oven at 100 ℃ to obtain the electrode slice.
Assembling the prepared electrode slice, a metal zinc slice and a glass fiber membrane into a CR2025 button type zinc ion battery, wherein the electrolyte is 2mol L-1ZnSO4And 0.1mol L-1MnSO4The mixed aqueous solution adopts a Xinwei battery test system to test the charge-discharge performance and the cycle performance of the zinc ion battery.
FIG. 4 is Mn2O3Multiplying power performance diagram of the multi-shell nano hollow sphere. At a current density of 0.1A g-1The specific capacity is particularly high and reaches 267-453mAh g-1Showing Mn2O3Has high electrochemical activity. At current densities of 0.5, 1 and 1.5A g-1The discharge capacity is stabilized at 316, 184 and 107mAh g-1，Mn2O3The multi-shell nano hollow sphere shows excellent high-current charge and discharge capacity. When the current drops to 0.1A g-1The discharge capacity can be restored to 467mAh g-1Description of Mn2O3The multi-shell nano hollow sphere has good stability. Mn2O3The multiplying power Performance of the multi-shell nano hollow sphere is superior to that of N.N.Liu (N.N.Liu, X.Wu, Y.Y.Yin, A.S.Chen, C.Y.ZHao, Z.K.Guo, L.S.Fan, N.Q.Zhang, construction of the Efficient Ion Diffusion by induced Oxygen Defects in Mn2O3 for High-Performance air nitride Batteries, ACS.Mater.Interfaces 2020,12,28199-28205.) and M.Mao (M.Mao, X.X.Wu, Y.Hu, Q.H.H.Yuan, Y.B.He, F.Y.Kang, Charge storage mechanism of MOF-derived Mn2O3 as high performance cathode of aqueous zinc baths, Journal of Energy Chemistry 52(2021) 277) 283), and the like.
FIG. 5 shows Mn2O3The multi-shell nano hollow sphere has the current density of 1A g-1And the voltage range is 1.0-1.85V. Except for the initial decrease of 13 cycle discharge capacities, the cycle discharge capacity after the decrease slowly rises, and the discharge capacity is stabilized at 157mAh g at 100-400 cycles-1. The discharge capacity was 152.8mAh g by 500 th cycle-1。Mn2O3The specific capacity and the cycle performance of the multi-shell nano hollow sphere exceed CN111115688A and M.Mao (M.Mao, X.X.Wu, Y.Hu, Q.H.Yuan, Y.B.He, F.Y.kang, Charge storage mechanism of MOF-derived Mn)2O3as high performance category of aquouus zinc-ion batteries, Journal of Energy Chemistry,2021, 52.277-283), etc.
Example 2
Dissolving 0.2mmol of manganese nitrate tetrahydrate and 0.2mmol of isophthalic acid in a mixed solution of 10mL of N, N-dimethylformamide and 10mL of acetone, stirring for 6h at room temperature, transferring the solution into a reaction kettle, heating to 190 ℃, preserving heat for 4h, cooling to room temperature, centrifugally separating a product, washing with ethanol for several times, and drying at 80 ℃ to obtain the Mn precursor microsphere. The Mn precursor microspheres are heated for 5 ℃ min at a heating speed in the air-1Heating to 450 deg.C, and maintaining the temperature for 10min to obtain Mn2O3The multi-shell layer nanometer hollow sphere.
Product Mn2O3The multi-shell hollow nanospheres have a structure similar to that of example 1, with the main difference being Mn2O3The outer diameter of the multi-shell hollow nanosphere is 2.5 mu m, and the number of the shells is 5-6.
The same procedure as in example 1 was used to fabricate a positive electrode of a zinc ion battery, which was assembled into a zinc ion battery at a current density of 1A g-1And carrying out cyclic charge and discharge test in the voltage range of 1.0-1.85V. The variation trend of the cycle performance is similar to that of the example 1, and the discharge capacity is stabilized at 178mAh g at 100-300 cycles-1. In the following cycleRing, the discharge capacity decreased gradually. The discharge capacity was 150.3mAh g by 500 th cycle-1。
Example 3
Dissolving 0.1mmol of manganese nitrate tetrahydrate and 0.1mmol of isophthalic acid in a mixed solution of 10mL of N, N-dimethylformamide and 10mL of acetone, stirring for 6h at room temperature, transferring the solution into a reaction kettle, heating to 160 ℃, keeping the temperature for 2h, cooling to room temperature, centrifugally separating the product, washing with ethanol for several times, and drying at 80 ℃ to obtain the Mn precursor microsphere. The Mn precursor microspheres are heated for 5 ℃ min at a heating speed in the air-1Heating to 450 deg.C, and maintaining the temperature for 10min to obtain Mn2O3The multi-shell layer nanometer hollow sphere.
Product Mn2O3The multi-shell hollow nanospheres have a structure similar to that of example 1, with the main difference being Mn2O3The outer diameter of the multi-shell hollow nanosphere is 0.91 mu m, and the number of the shells is 2-3.
The same procedure as in example 1 was used to fabricate a positive electrode of a zinc ion battery, which was assembled into a zinc ion battery at a current density of 1A g-1And carrying out cyclic charge and discharge test in the voltage range of 1.0-1.85V. The variation trend of the cycle performance is similar to that of the example 1, and the discharge capacity is stabilized at 143mAh g at 100-400 cycles-1. At subsequent cycles, the discharge capacity decreased slightly. The discharge capacity was 139.2mAh g by 500 th cycle-1。
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (6)
1. Mn suitable for preparing anode of water-based zinc ion battery2O3The multi-shell nano hollow sphere material is characterized by comprising Mn combined by a mode of sleeving a large spherical shell and a small spherical shell2O3The inner surface of each shell layer is provided with a plurality of holes and Mn2O3And (3) nanoparticles.
2. Mn according to claim 12O3The multi-shell nano hollow sphere material is characterized in that the Mn2O3The outer diameter of the multi-shell hollow nanosphere is 0.5-3.5 μm, the shell thickness is 5-50nm, and the number of shells is 2-7.
3. Mn according to claim 12O3The multi-shell nano hollow sphere material is characterized in that the holes and Mn2O3The size of the nanoparticles was 10 nm.
4. A Mn according to any one of claims 1 to 32O3The preparation method of the multi-shell nano hollow sphere material is characterized by comprising the following steps:
dissolving manganese nitrate tetrahydrate and isophthalic acid in a molar ratio of 1:1 in a mixed solution of N, N-dimethylformamide and acetone, stirring for 6 hours at room temperature, transferring the solution into a reaction kettle, heating to the temperature of 150-; heating the Mn precursor microspheres in the air at a heating speed of 4-10 ℃ for min-1Heating to 350-2O3And (3) a multi-shell nano hollow sphere material.
5. The method according to claim 4, wherein the acetone is used in an amount of 10mL and the manganese nitrate tetrahydrate is used in an amount of 0.05 to 0.4mmol, relative to 10mL of the N, N-dimethylformamide.
6. A Mn according to any one of claims 1 to 32O3The application of the multi-shell nano hollow sphere material in the preparation of the anode of a water system zinc ion battery.
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