Bionic grape form Mo / Eu co-modified MnO-NaMnO composite material and preparation method thereof
By preparing biomimetic grape-shaped Mo/Eu co-modified Mn2O3-Na2Mn8O16 composite material, the problems of low conductivity and structural instability of manganese-based oxides in aqueous zinc-ion batteries were solved, thereby improving material performance and battery performance.
Patent Information
- Application Number
- CN202511468910.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-15
- Publication Date
- 2026-01-30
AI Technical Summary
Manganese-based oxide cathode materials suffer from low electronic conductivity, poor structural stability, and manganese dissolution and loss in aqueous zinc-ion batteries, which limits their large-scale application.
A biomimetic grape-shaped Mo/Eu co-modified Mn2O3-Na2Mn8O16 composite material was prepared by a one-step hydrothermal method. The electronic and crystal structures were improved and the electrical conductivity and stability were enhanced through the co-modification of Mo and Eu.
It improves the electrochemical performance of the material, increases the specific surface area, forms unique electron transport channels and ion diffusion paths, promotes rapid charge transport, and enhances the cycle stability and battery performance of the material.
Smart Images
Figure CN121439731A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The application discloses a biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The composite material and a preparation method thereof belong to the technical field of aqueous zinc-ion batteries in inorganic materials. BACKGROUND
[0002] Under the dual pressures of the continuous rise in global energy demand and the depletion of fossil energy, developing efficient, sustainable and environmentally friendly new energy storage and conversion systems has become a key research topic in today's scientific and technological fields. Due to the scarcity and uneven distribution of lithium resources, the large-scale application and long-term development of lithium-ion batteries are severely limited, forcing researchers to turn their attention to new battery systems that are rich in resources, low in cost and environmentally friendly. Among the many alternative solutions, aqueous zinc-ion batteries have attracted considerable attention due to their unique advantages. Zinc has a high theoretical specific capacity, a low redox potential and abundant earth reserves, making aqueous zinc-ion batteries exhibit significant advantages in terms of cost and safety. At the same time, the use of aqueous electrolytes avoids the safety hazards of flammability and explosion associated with organic electrolytes, further enhancing the safety and environmental compatibility of the battery. However, the development of aqueous zinc-ion batteries still faces many challenges, with the performance bottleneck of the positive electrode material being one of the key factors restricting its large-scale application.
[0003] Manganese-based oxides have become a research hotspot for aqueous zinc-ion battery positive electrode materials due to their abundant resources, low cost and diverse crystal structures. However, manganese-based oxides still face severe challenges in practical applications. First, their intrinsic low electronic conductivity severely limits the charge transport dynamics, resulting in poor rate performance. Second, the inherent Jahn-Teller effect causes severe structural distortion during charge and discharge cycles, leading to decreased cycle stability. More problematic is that manganese dissolves in the electrolyte, causing irreversible loss of active material and rapid capacity decay. 3+ The inherent Jahn-Teller effect causes severe structural distortion during charge and discharge cycles, leading to decreased cycle stability. More problematic is that manganese dissolves in the electrolyte, causing irreversible loss of active material and rapid capacity decay.
[0004] To overcome the above bottlenecks, researchers have proposed various strategies, among which element doping and heterostructure construction are two effective methods. Element doping can effectively regulate the electronic structure of manganese oxides, enhance electronic conductivity by introducing defects, and stabilize the crystal framework through charge compensation. Molybdenum and europium, as two elements with unique electronic structures, exhibit great potential in material modification. Molybdenum has a high valence state, which can improve the conductivity by adjusting the electronic cloud distribution of the material. Europium, as a rare earth element, has rich electronic energy levels and a unique 4f electronic configuration, which can adjust the crystal structure and surface properties of the material through interaction with the host material, thereby improving the stability and electrochemical activity of the material. SUMMARY
[0005] In order to overcome the above technical defects, the present application provides a biomimetic grape morphology Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The composite material and a preparation method thereof belong to the field of inorganic materials. Sodium molybdate dihydrate, europium nitrate hexahydrate, 50% manganese nitrate solution and urea are dissolved in deionized water, and constant temperature reaction is carried out in a hydrothermal reaction kettle; after reaction, the precursor is dried in an oven, and then calcined in a muffle furnace, so that the biomimetic grape morphology Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The composite material. The present application improves the electrochemical performance of the composite material by one-step hydrothermal method, and the biomimetic grape morphology is observed in microcosm. The synthesis method is simple, low in cost and suitable for large-scale industrial production.
[0006] The biomimetic grape morphology Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The composite material, wherein: the XRD diffraction peaks are 23.07°, 28.53°, 32.86°, 37.25° and 55.32°; the XPS peaks are 231.84 eV, 234.99 eV, 530.52 eV, 531.36 eV, 641.48 eV, 653.02 eV, 1070.95 eV, 1134.27 eV, 1164.09 eV, Mo is +6 valence, and Eu is +3 valence.
[0007] The biomimetic grape morphology Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The preparation method of the composite material comprises the following steps:
[0008] In the first step, sodium molybdate dihydrate and europium nitrate hexahydrate are dispersed in deionized water, and urea and 50% manganese nitrate solution are sequentially added and uniformly stirred;
[0009] In the second step, the uniformly stirred solution is placed in a hydrothermal reaction kettle, and constant temperature reaction is carried out in an oven, and then natural cooling is carried out;
[0010] In the third step, the product is taken out from the hydrothermal reaction kettle, washed and filtered, and then dried in an oven;
[0011] In the fourth step, calcination is carried out in a muffle furnace, and the biomimetic grape morphology Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The composite material.
[0012] Further, in the above technical solution, in the first step, the molar ratio of sodium molybdate dihydrate to europium nitrate hexahydrate is 5:1; and the molar ratio of urea to sodium molybdate dihydrate is 11:1.
[0013] Further, in the above technical solution, in the first step, the molar ratio of europium nitrate hexahydrate to manganese nitrate is 1:19.
[0014] Further, in the above technical solution, in the second step, the constant temperature reaction temperature is 160 DEG C, and the reaction time is 8 hours.
[0015] Further, in the above technical solution, in the third step, the reaction product is washed with pure water, the reaction product is placed in pure water to form a suspension, and ultrasonic cleaning is carried out in an ultrasonic cleaner for 3 minutes, and the suspension is then suction filtered, and the total washing is 4 times.
[0016] Further, in the above technical solution, in the third step, the drying temperature is 90 DEG C, and the drying time is 1.5 hours.
[0017] Further, in the above technical solution, in the fourth step, the calcination temperature is 450 DEG C, and the constant temperature calcination time is 5 hours, wherein the temperature rising program is set to 2 hours, and the temperature is lowered to below 200 DEG C for 2 hours.
[0018] The application also provides the above-mentioned Mo / Eu co-modified Mn2O3-Na2Mn8O 16 Composite material in water-based zinc ion battery.
[0019] The application has the following beneficial effects:
[0020] 1. The Mo / Eu co-modified Mn2O3-Na2Mn8O 16 Composite material is prepared, the raw materials are cheap and easy to obtain, the synthesis method is simple, the preparation process is also relatively environmentally friendly, and the environmental pollution is relatively small.
[0021] 2. The method co-modifies the Mn2O3-Na2Mn8O 16 Composite material by Mo and Eu, improves the electrochemical performance of the material, and the bionic grape-like spherical morphology is observed microscopically, and the surface of the spherical particles presents a wrinkled structure. The wrinkled structure can significantly increase the specific surface area of the material, increase the contact surface of the composite material and the electrolyte, thereby providing more active sites for the penetration of the electrolyte, which is beneficial to the full interaction between the ions in the electrolyte and the surface of the material. At the same time, the interface interaction is enhanced, a unique electron transport channel and ion diffusion path are formed, and the rapid transmission of electric charge is promoted. BRIEF DESCRIPTION OF DRAWINGS
[0022] Figure 1 The XRD pattern of the Mo / Eu co-modified Mn2O3-Na2Mn8O 16 Composite material in Example 4 is shown in the following figure:
[0023] Figure 2 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 4 16 SEM images of the composite; wherein: a is a trinuclear spherical morphology, b is a multinuclear spherical morphology; c is a grape-like morphology
[0024] Figure 3 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 4 16 XPS images of the composite;
[0025] Figure 4 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 4 16 EDS images of the composite;
[0026] Figure 5 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 4 16 Elemental distribution maps of the composite; wherein: a is the Mn element distribution map, b is the O element distribution map, c is the Na element distribution map, d is the Mo element distribution map; e is the Eu element distribution map;
[0027] Figure 6 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 4 16 Infrared spectrum of the composite;
[0028] Figure 7 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 4 16 Raman spectrum of the composite;
[0029] Figure 8 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 5 16 Cyclic charge-discharge diagram of the composite;
[0030] Figure 9 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 5 16 Cyclic voltammogram of the composite;
[0031] Figure 10 Mn2O3-Na2Mn8O with Mo / Eu co-modification in the form of grape-like morphology in Example 5 16 Impedance diagram of the composite. DETAILED DESCRIPTION
[0032] The present application is further described by the following examples. However, these examples are merely exemplary and are not intended to limit the scope of the present application, which is defined solely by the appended claims, merely by way of example.
[0033] In the following examples, the reagents, materials and instruments used are conventional reagents, conventional materials and conventional instruments, which are commercially available, and the reagents involved can also be synthesized by conventional synthesis methods.
[0034] Example 1
[0035] First step, disperse 11.6136 g of sodium molybdate dihydrate and 0.5353 g of europium nitrate hexahydrate in deionized water, stir for 0.5 hours;
[0036] Second step, add 1.4414 g of urea and 8.1601 g of manganese nitrate solution (mass fraction 50%) to the mixed uniform solution, and stir for 1.5 hours;
[0037] Third step, after continuously stirring the above mixed solution for 1.5 hours, put it into a hydrothermal reaction kettle, and react at a constant temperature of 160°C in an oven for 8 hours, and then naturally cool down.
[0038] Fourth step, take out the reaction product from the hydrothermal reaction kettle, perform cleaning operation, use pure water to clean and filter the reaction product, put the reaction product into pure water to form a suspension, and perform ultrasonic cleaning in an ultrasonic cleaner for 3 minutes, then perform suction filtration on the suspension, a total of 4 times.
[0039] Fifth step, put the cleaned and filtered product into an oven, dry at 90°C for 1.5 hours.
[0040] Sixth step, put the dried product into a muffle furnace for calcination, after the calcination is completed, cool down with the furnace to obtain the biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O 16 composite. The calcination temperature is 450°C, the temperature rising program is set to 2 hours, the temperature is lowered to below 200°C for 2 hours, and the constant temperature calcination time is 5 hours.
[0041] Example 2
[0042] First step, disperse 11.6136 g of sodium molybdate dihydrate and 0.5353 g of europium nitrate hexahydrate in deionized water, stir for 0.5 hours;
[0043] Second step, add 1.4414 g of urea and 8.1601 g of manganese nitrate solution (mass fraction 50%) to the mixed uniform solution, and stir for 1.5 hours;
[0044] The third step involves continuously stirring the above mixed solution for 1.5 hours and then placing it in a hydrothermal reactor. The mixture is then kept at a constant temperature of 160°C in an oven for 8 hours, followed by natural cooling.
[0045] The fourth step is to remove the reaction product from the hydrothermal reactor and perform a cleaning operation. Use pure water to clean and filter the reaction product, place the reaction product in pure water to form a suspension, and sonicate it in an ultrasonic cleaner for 3 minutes. Then filter the suspension. A total of 4 cleaning operations are performed.
[0046] Fifth step: Place the cleaned and filtered product into an oven and dry at 90°C for 1.5 hours.
[0047] The sixth step involves calcining the dried product in a muffle furnace. After calcination, the furnace is cooled to obtain biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O. 16 Composite material. The calcination temperature is 450℃, with the heating program set for 2 hours, cooling to below 200℃ for 2 hours, and the constant temperature calcination time for 5 hours.
[0048] Example 3
[0049] The first step is to disperse 2.9034g of sodium molybdate dihydrate and 0.5353g of europium nitrate hexahydrate in deionized water and stir for 0.5 hours;
[0050] The second step is to add 3.6036g of urea and 8.1601g of manganese nitrate solution (50% by mass) to the well-mixed solution and stir for 1.5 hours.
[0051] The third step involves continuously stirring the above mixed solution for 1 hour and then placing it in a hydrothermal reactor. The mixture is then kept at a constant temperature of 160°C in an oven for 8 hours, followed by natural cooling.
[0052] The fourth step is to remove the reaction product from the hydrothermal reactor and perform a cleaning operation. Use pure water to clean and filter the reaction product, place the reaction product in pure water to form a suspension, and sonicate it in an ultrasonic cleaner for 3 minutes. Then filter the suspension. A total of 4 cleaning operations are performed.
[0053] Fifth step: Place the cleaned and filtered product into an oven and dry at 90°C for 1.5 hours.
[0054] The sixth step involves calcining the dried product in a muffle furnace. After calcination, the furnace is cooled to obtain biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O. 16 Composite material. The calcination temperature is 450℃, with the heating program set for 2 hours, cooling to below 200℃ for 2 hours, and the constant temperature calcination time for 5 hours.
[0055] Example 4
[0056] The first step is to disperse 1.4517g of sodium molybdate dihydrate and 0.5353g of europium nitrate hexahydrate in deionized water and stir for 0.5 hours;
[0057] The second step is to add 3.9640g of urea and 8.1601g of manganese nitrate solution (50% by mass) to the well-mixed solution and stir for 1.5 hours.
[0058] The third step involves continuously stirring the above mixed solution for 1 hour and then placing it in a hydrothermal reactor. The mixture is then kept at a constant temperature of 160°C in an oven for 8 hours, followed by natural cooling.
[0059] The fourth step is to remove the reaction product from the hydrothermal reactor and perform a cleaning operation. Use pure water to clean and filter the reaction product, place the reaction product in pure water to form a suspension, and sonicate it in an ultrasonic cleaner for 3 minutes. Then filter the suspension. A total of 4 cleaning operations are performed.
[0060] Fifth step: Place the cleaned and filtered product into an oven and dry at 90°C for 1.5 hours.
[0061] The sixth step involves calcining the dried product in a muffle furnace. After calcination, the furnace is cooled to obtain biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O. 16 Composite material. The calcination temperature is 450℃, with the heating program set for 2 hours, cooling to below 200℃ for 2 hours, and the constant temperature calcination time for 5 hours.
[0062] Figure 1 Demonstrates biomimetic grape-like morphology with Mo / Eu co-modified Mn2O3-Na2Mn8O 16 XRD pattern of the composite material. The positions of the main diffraction peaks are related to Mn₂O₃ (standard card PDF#04-007-0856) and Na₂Mn₈O₃. 16 (Standard card PDF#00-029-1244) The standard spectrum matches well, indicating that the composite material is mainly composed of Mn2O3 and Na2Mn8O 16 The composition is two-phase. By performing full-spectrum fitting on the XRD patterns, the mass fractions of each phase were determined to be 66.6% Mn₂O₃ and 66.6% Na₂Mn₈O₃. 16 33.4%. Among them, the Mn2O3 phase belongs to the orthorhombic crystal system, and its characteristic diffraction peaks are located at 23.07°, 32.86°, and 55.32°, corresponding to the (211), (222), and (404) crystal planes, respectively. Na2Mn8O 16 The phase belongs to the tetragonal crystal system. Its diffraction peak at 28.53° corresponds to the (310) crystal plane, and it exhibits a strong diffraction peak at 37.25°, which belongs to the (211) crystal plane.
[0063] Figure 2 Mn2O3-Na2Mn8O3 co-modified with Mo / Eu to mimic the shape of a biomimetic grape 16 SEM images of the composite material clearly show spherical particles arranged in a specific pattern, exhibiting three-unit spherical morphologies, multi-unit spherical morphologies, and biomimetic grape-like interconnected spherical morphologies. This interconnected structure likely results from the fusion or connection of adjacent spherical particles during material growth, creating a surface with numerous wrinkles. This morphology significantly increases the specific surface area of the material, providing more active sites for electrolyte penetration and facilitating sufficient interaction between ions in the electrolyte and the material surface.
[0064] Figure 3 Mn2O3-Na2Mn8O3 co-modified with Mo / Eu to mimic the shape of a biomimetic grape 16 XPS full spectrum of the composite material. Characteristic peaks for Mo3d, Eu3d, Na1s, Mn2p, and O1s can be observed in the image. The double peaks at 231.84 eV (Mo 3d5 / 2) and 234.99 eV (Mo3d3 / 2) confirm that Mo is present in the form of Mo2+. 6+ The Eu element exists in its normal form. The main Eu peaks at 1134.27 eV (3d⁵ / ²) and 1164.09 eV (3d³ / ²), and the distinct satellite peak at 1143.56 eV, exhibit typical Eu characteristics. 3+ Characteristics: The binding energy of the Na 1s spectrum is located at 1070.95 eV. The binding energies of Mn2p3 / 2 and Mn2p1 / 2 are located at 641.48 eV and 653.02 eV, respectively. The main peak at 529.23 eV belongs to lattice oxygen, mainly originating from Mn–O and Na–O bonds. The peak at 531.36 eV belongs to oxygen associated with surface-adsorbed hydroxyl groups (–OH) or oxygen vacancies. The component at 530.52 eV belongs to oxygen associated with high-valence metal cations (Mo). 6+ ) bonded oxygen, Mo 6+ It has extremely high electronegativity, which strongly attracts the electron cloud of oxygen atoms, causing its O1s binding energy to increase relative to ordinary Mn-O bonds.
[0065] Figure 4 Mn2O3-Na2Mn8O3 co-modified with Mo / Eu to mimic the shape of a biomimetic grape 16 The EDS chromatogram of the composite material showed characteristic peaks of Mn, O, Na, Eu, and Mo in all selected analytical regions, confirming that Eu and Mo elements were successfully introduced into the composite material system.
[0066] Figure 5Mn2O3-Na2Mn8O3 co-modified with Mo / Eu to mimic the shape of a biomimetic grape 16 The elemental distribution of the composite material shows that Mn and O have the highest signal intensities, followed by Na, whose spatial distribution highly overlaps with that of Mn and O, consistent with the characteristics of composite oxides. In contrast, Mo and Eu signals were also successfully detected, indicating the formation of a Mo / Eu co-modified composite material.
[0067] Figure 6 Mn2O3-Na2Mn8O3 co-modified with Mo / Eu to mimic the shape of a biomimetic grape 16 FTIR spectrum of the composite material. Located at 599 cm⁻¹. -1 The absorption peak at that location can be attributed to Mn in the MnO6 octahedron. 3+ The symmetric stretching vibration of the -O bond is a characteristic vibrational mode in Mn2O3 and Na2Mn8O. 16 Typical fingerprint signals of [MnO6] structural units in the phase. 515 cm⁻¹ -1 The absorption peak at that location exhibits a complex characteristic, primarily originating from Mn. 4+ The stretching vibration of the -O bond may also be superimposed with Na2Mn8O. 16 The vibrational contribution of the Na-O bond in the phase reflects the interaction between sodium ions and [Mn8O] 16 Interactions within the layered framework. 677cm -1 The band at this location corresponds to the asymmetric stretching vibration of the Mn-O-Mn bridging bonds in the manganese oxide framework. The sample at 3076 cm⁻¹... -1 A distinct broadened absorption band is observed at the point, which can be attributed to the stretching vibrations of the OH bonds in the physically adsorbed water molecules on the material surface.
[0068] Figure 7 Mn2O3-Na2Mn8O3 co-modified with Mo / Eu to mimic the shape of a biomimetic grape 16 The Raman spectrum of the composite material at 632.68 cm⁻¹ -1 The strong Raman peak observed at 335.82 cm⁻¹ is a typical characteristic peak of manganese oxides and belongs to the symmetric stretching vibration mode of the MnO₆ octahedron. -1 The Raman shift at the point can be clearly attributed to the bending vibration of the Mo-O-Mo bridging oxygen bond, indicating that MoO4 2- The MoO6 groups may have formed stable chemical bonds with the manganese-oxygen framework, which may contribute to enhancing the overall structural stability and electronic conductivity of the material. At a low frequency region of 159.71 cm⁻¹... -1 The Raman peak at this location typically originates from low-energy vibrational modes of the crystal lattice, including bending vibrations of Mn-O-Mn bonds and Na... + Ions in [Mn8O 16 Restricted migration vibrations in interlayer vacancies.
[0069] Example 5
[0070] The biomimetic grape-shaped Mn2O3-Na2Mn8O prepared in Examples 1-4 was co-modified with Mo / Eu. 16 Composite materials were used to prepare the positive electrode for aqueous zinc-ion batteries.
[0071] The first step is to weigh out the biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O 16 0.24g of the composite material and 0.03g of acetylene black were thoroughly ground using an agate mortar.
[0072] The second step involves mixing 0.03g of polyvinylidene fluoride and 0.6mL of N-methylpyrrolidone to form a binder, and then adding the ground product.
[0073] The third step is to coat the mixed slurry onto a 0.01mm thick stainless steel foil and dry it at a constant temperature of 80℃ for 1 hour.
[0074] The fourth step is to process the stainless steel foil into a positive electrode sheet with a diameter of 10mm after the active material is completely dried.
[0075] The fifth step involves assembling an aqueous zinc-ion battery using a zinc sheet as the negative electrode, glass fiber paper as the separator, and a mixture of 2 mol / L ZnSO4 and 0.2 mol / L MnSO4 solutions as the electrolyte. The battery is then left to stand for 24 hours before testing.
[0076] Figure 8 Mn2O3-Na2Mn8O modified with Mo / Eu in the form of biomimetic grapes 16 The composite material is used as the positive electrode in an aqueous zinc-ion battery cyclic charge-discharge test. The charge-discharge test currents were set at 50 mA / g, 100 mA / g, 200 mA / g, 300 mA / g, and 500 mA / g. The composite material prepared in Example 4 exhibited the highest discharge capacity of 355.81 mAh g at a current density of 50 mA / g. -1 .
[0077] Figure 9 Mn2O3-Na2Mn8O is a biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O 16 Cyclic voltammogram of an aqueous zinc-ion battery with the composite material as the positive electrode. The oxidation and reduction peaks are sharp and symmetrical, and the potential difference between them is small, indicating that the electrode reaction has high reversibility and fast kinetic characteristics, and low polarization. This is attributed to the modification effect of Mo and Eu elements on the composite material.
[0078] Figure 10Mn2O3-Na2Mn8O is a biomimetic grape-shaped Mo / Eu co-modified Mn2O3-Na2Mn8O 16 The AC impedance curve of the aqueous zinc-ion battery with the composite material as the positive electrode shows that both the solution resistance and charge transfer resistance are at a low level, indicating that the material synthesized under these conditions has better electronic conductivity and a more efficient interfacial charge transfer process, thus making the electrochemical performance of the material more stable.
[0079] Based on the disclosure in the foregoing specification, those skilled in the art can make appropriate changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention.
Claims
1. Multicatena biomimetic grape-like morphology Mo / Eu co-modified Mn2O3-Na2Mn8O 16 Composite material, characterized in that: The XRD diffraction peaks are 23.07°, 28.53, 32.86°, 37.25° and 55.32°; the XPS peaks are 231.84eV, 234.99eV, 530.52eV, 531.36eV, 641.48eV, 653.02eV, 1070.95eV, 1134.27, 1164.09eV, Mo is +6 valence, and Eu is +3 valence.
2. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 Method for producing a composite material, characterized in that The method comprises the following steps: In the first step, sodium molybdate dihydrate and europium nitrate hexahydrate are dispersed in deionized water, and urea and 50% manganese nitrate aqueous solution are added in sequence and stirred uniformly; In the second step, the uniformly stirred solution is placed in a hydrothermal reaction kettle and reacted in an oven at a constant temperature, and then naturally cooled; In the third step, the product is taken out from the hydrothermal reaction kettle, washed and filtered, and then placed in an oven for drying; Fourth step, calcination in muffle furnace, cooling to get Mo / Eu co-modified Mn2O3-Na2Mn8O 16 Composite material.
3. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 The method for producing a composite material, characterized by comprising: In the first step, the molar ratio of sodium molybdate dihydrate to europium nitrate hexahydrate is 5:1, and the molar ratio of urea to sodium molybdate dihydrate is 11:
1.
4. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 The method for producing a composite material, characterized by comprising: In the first step, the molar ratio of europium nitrate hexahydrate to manganese nitrate is 1:
19.
5. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 The method for producing a composite material, characterized by comprising: In the second step, the constant temperature reaction temperature is 160℃, and the reaction time is 8 hours.
6. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 Method for the production of a composite material, characterized in that In the third step, the reaction product is washed with pure water, the reaction product is placed in pure water to form a suspension, and ultrasonic cleaning is performed in an ultrasonic cleaner for 3 minutes, and then the suspension is suction filtered, and the total washing time is 4 times.
7. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 Process for the production of a composite material, characterized in that: In the third step, the drying temperature is 90℃, and the drying time is 1.5 hours.
8. The biomimetic grape-like morphology Mo / Eu co-modified Mn203-Na2Mn8O 16 Process for the production of a composite material, characterized in that: In the fourth step, the calcination temperature is 450℃, and the constant temperature calcination time is 5 hours, wherein the temperature rising program is set to 2 hours, and the temperature is lowered to below 200℃ for 2 hours.
9. The biomimetic grape-shaped Mo / Eu co-modified Mn203-Na2Mn8O 16 Application of composite materials in aqueous zinc ion battery.