CN111377476A - Micro-nano material ZnMn2O4Preparation method of (1) - Google Patents

Micro-nano material ZnMn2O4Preparation method of (1) Download PDF

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CN111377476A
CN111377476A CN201811641213.7A CN201811641213A CN111377476A CN 111377476 A CN111377476 A CN 111377476A CN 201811641213 A CN201811641213 A CN 201811641213A CN 111377476 A CN111377476 A CN 111377476A
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许雪棠
王凡
苏海艳
刘素英
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Guangxi University
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    • C01G9/00—Compounds of zinc
    • C01G9/06—Sulfates
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
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    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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    • C—CHEMISTRY; METALLURGY
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C01P2006/17—Pore diameter distribution

Abstract

The invention discloses a micro-nano material ZnMn2O4By reacting Zn (NO)3)2·6H2O and MnCl2·4H2Dissolving O in ethylene glycol and adding Na2CO3And (3) preparing a precursor serving as a precipitator by adopting a low-temperature coprecipitation method, and grinding the precursor in a muffle furnace to calcine the precursor to obtain a target product. The method has simple process, and the prepared micro-nano material ZnMn2O4Has larger surface area and larger pore size of about 10nm, and has practical significance.

Description

Micro-nano material ZnMn2O4Preparation method of (1)
Technical Field
The invention belongs to the technical field of micro-nano material preparation, and particularly relates to a micro-nano material ZnMn2O4The preparation method of (1).
Background
The low-temperature coprecipitation method is an application of the coprecipitation method in a low-temperature environment. Under the condition of low temperature, the nucleation and nucleus growth speed of the precipitate becomes slow, and the Ostwald ripening process is slowed down, so that the precipitate particles have different structural characteristics from the normal-temperature precipitate product. The low-temperature coprecipitation method inherits the advantages of the coprecipitation method, and the nano powder material with uniform chemical components can be obtained through reasonable precipitation time. The product particles can present the characteristics of small particle size and uniform size through the limitation of low-temperature reaction environment. Through aging for a certain time, the primary particles can be assembled into multi-stage assembled structures with different appearances according to the growth habit of the primary particles. Similar to the conventional coprecipitation method, the influencing factors of the low-temperature coprecipitation method are complicated, such as: the selection of metal salt and precipitant, the concentration of solution, the temperature of precipitation, the feeding mode and the stirring intensity. Since the low-temperature coprecipitation method is difficult to obtain a product with high crystallinity, the post-treatment mode also has an influence on the performance of the product.
Since water is difficult to maintain a liquid phase at a relatively low temperature, organic solvents are commonly used in the low-temperature co-precipitation method. However, the organic solvent has a limited ability to dissolve inorganic salt materials, and some researchers have used a mixed system of an organic solvent and water. Among them, alcohol-water systems are common. For example, Qiu et al prepared Co-Mn-O, Fe-Mn-O and Ni-Mn-O series composite oxides by low temperature coprecipitation in a mixed solvent of ethylene glycol and water and tested their NOxReducing the catalytic activity. The results show that, in a low-temperature environment, the carbonate precursor grows in a crystal splitting mode to form dumbbell-shaped particles with branched ends. The Co-Mn-O particles after calcination show good catalytic performance. By NH3Is a reducing agent, NO is in the range of 100 ℃ to 225 ℃XThe conversion rates were all 100%.
Disclosure of Invention
The invention aims to provide a micro-nano material ZnMn2O4The preparation method prepares the ZnMn with larger surface area by a low-temperature coprecipitation method and auxiliary post-calcination treatment2O4The material has good application prospect in the field of charge storage.
The invention is realized by the following technical scheme:
micro-nano material ZnMn2O4The preparation method specifically comprises the following steps:
1) weighing Zn (NO)3)2·6H2O and MnCl2·4H2Dispersing O in glycol, and stirring to fully dissolve the O;
2) the resulting solution was placed in a cryostat under nitrogenStirring and dripping Na in the atmosphere2CO3After the solution is obtained, aging is carried out for 1 h;
3) centrifugally separating the aged sample, and sequentially washing obtained precipitates with deionized water and absolute ethyl alcohol;
4) drying the washed sample for 10h, and grinding the dried product into powder;
5) and (3) placing the powder in a muffle furnace, heating, calcining for 4 hours, and naturally cooling to room temperature to obtain a final product.
Further, Zn (NO) in step (1)3)2·6H2O and MnCl2·4H2The mass ratio of O is 1: 2.
Further, the low-temperature constant temperature in the step (2) is specifically-10 ℃.
Further, Na is dropwise added in the step (2)2CO3The concentration of the solution was 0.225 mol. L-1The dropping rate was 1.2 mL/min-1。
Further, the temperature of the deionized water in the step (3) is 60 ℃.
Further, the drying condition in the step (4) is 60 ℃.
Further, the temperature rise rate of the muffle furnace in the step (5) is 1 ℃ min-1The temperature is raised to 400 ℃.
The invention has the beneficial effects that:
the invention can obtain the composite oxide ZnMn with larger specific surface area by a low-temperature coprecipitation method and auxiliary post-calcination treatment2O4. Experiments show that the prepared ZnMn2O4The powder is a nano-particle accumulation body with a porous structure, the size of a pore channel is larger and is about 10nm, and no obvious agglomeration phenomenon exists among the accumulation bodies, so that the product is formed mainly through the assembly behavior of particles, and the agglomeration phenomenon of the particles can be eliminated in the low-temperature coprecipitation process.
Drawings
FIG. 1 shows ZnMn at different calcination temperatures2O4XRD spectrogram of the sample;
FIG. 2 is ZnMn2O4SEM and TEM images of the sample;
FIG. 3 is ZnMn2O4Nitrogen sorption/desorption curves for the samples;
FIG. 4 is ZnMn2O4Pore size distribution curve of the sample;
FIG. 5 is sample ZnMn2O4XPS spectra of (a);
FIG. 6 is a ZnMn calcined at 400 deg.C2O4Cyclic voltammetry of the electrode;
FIG. 7 is ZnMn2O4A charge-discharge curve of the electrode;
FIG. 8 is ZnMn2O4The Nyquist curve for the electrode;
FIG. 9 is ZnMn2O4Electrode at 5A g-1Current density of (d).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of ZnMn by Low temperature Co-precipitation2O4
Weighing 1.1155g Zn (NO)3)2·6H2O and 1.4843g MnCl2·4H2O is dispersed in 30mL of ethylene glycol and is dissolved completely by magnetic stirring for 30 min. The resulting solution was transferred to a 250mL three-necked flask, placed in a low-temperature constant temperature bath at-10 ℃ and mechanically stirred under nitrogen atmosphere for 30min, and then stirred at 1.2 mL/min-10.225 mol. L is added dropwise at a rate of- 1Na2CO3The solution was 100 mL. After the dropwise addition, the stirring speed is slowed down, and the aging is started for 1 h. Centrifuging the aged sample, washing the obtained precipitate with 60 deg.C deionized water for 5 times and anhydrous ethanol for 2 times, oven drying at 60 deg.C for 10 hr, grinding the dried product into powder, placing in a muffle furnace, and heating at 1 deg.C for min-1Is raised to a specific temperatureCalcining for 4h, and naturally cooling to room temperature to obtain the final product.
Example 2 ZnMn2O4Characterization of micro-nano materials
1) X-ray diffraction (XRD)
The samples were characterized for phase structure on an X-ray powder diffractometer model D8 ADVANCE.A 10 ° -80 ° range scan was performed using a Cu target, K α radiation, at a tube pressure of 40kV, a tube flow of 40mA current, and a scan speed of 8 °/min.
2) Electronic scanning microscope (SEM)
The morphology and the size of the sample are characterized on an S-3400N type electron scanning microscope (SEM) by an accelerating voltage of 15 KV.
3) Transmission Electron Microscope (TEM)
A transmission electron microscope of the sample can be used to observe its morphology and lattice fringes. The product prepared herein was observed under the acceleration voltage of 300KV using a transmission electron microscope Tecnai G2F30 manufactured by FEI, USA.
4) Specific surface and pore size distribution test (BET, BJH)
Samples were tested on a TriStar type II 3020 specific surface area and pore size analyzer. The samples tested had a mass of about 0.1g, a pretreatment temperature of 90 ℃ and a duration of 1h, and were measured under liquid nitrogen conditions at 77K.
5) X Photoelectron Spectrometer (XPS)
The sample is tested on PHI 5000Versa Probe type X-ray photoelectron spectrum, and C1s peak (284.8eV) is selected for correction standard of binding energy peak to analyze valence state of element.
XRD analysis of the sample: XRD spectra of samples obtained at different calcination temperatures from precursors prepared by low-temperature co-precipitation using ethylene glycol/water as a solvent are shown in fig. 1. It can be seen that the XRD diffraction peaks of the obtained product are all the same as those of spinel type ZnMn2O4The JCPDS standard spectra (PDF #24-1133) show that after calcination at 400 ℃, the carbonate precursor has been converted into ZnMn2O4. No hetero-phase peak appears in the spectrogram, and the obtained product has higher purity. Intensity of diffraction peak with increasing calcination temperatureAnd gradually increased, the crystallinity of the product increased. The relative intensity of each diffraction peak of the sample is basically consistent with that of the standard spectrum, which indicates that the obtained sample has no obvious fast-growing crystal face, namely the sample grows in an isotropic mode in the alcohol/water solvent. Calcination at 400 ℃ gave a sample with an average size of 16.7nm, calculated according to the scherrer equation.
And (3) analyzing the appearance of the sample: the shape of the product obtained by the precursor prepared by the low-temperature coprecipitation method at different calcining temperatures is basically consistent, and the product is a nano-particle accumulation body with a porous structure. The effect of calcination temperature cannot be effectively distinguished from SEM and TEM characterization, and only ZnMn prepared at 400 ℃ is shown here2O4SEM and TEM spectra of the samples. As can be seen from FIG. 2a, the samples obtained were all approximately round uniform submicron spheres with a size of about 200-500 nm. No obvious agglomeration phenomenon exists among the small balls, and the precursor prepared by the low-temperature coprecipitation method can be inferred to be the submicron small ball. Figure 2b is a high magnification SEM image of the calcined product. It can be clearly seen that the calcined product is formed by stacking approximately elliptical particles, and larger gaps are formed among the particles, so that the surfaces of the small spheres are rough and present a characteristic porous structure. Fig. 2c is a TEM image of the calcined product, demonstrating that the calcined product is a porous structure and has a large pore size of about 10nm, consistent with SEM results. The high power TEM profile (fig. 2d) further confirms the formation of the porous structure. Meanwhile, the calcined product is formed by stacking irregular nano-crystals with the diameter of about 20nm, the edges of the nano-crystals are smooth, and clear lattice stripes can be seen. The nanocrystal stacks form a large number of random stacking holes.
Specific surface analysis of the sample: FIGS. 3 and 4 show ZnMn produced2O4N of the sample2Adsorption-desorption isotherms and BJH pore size distribution curves. As can be seen from FIG. 3, the adsorption/desorption isotherms obtained at the different calcination temperatures all exhibit a substantially uniform change, i.e., at P/PoIn the pressure range of 0.4-0.8, there is no significant adsorption, when P/PoWhen the vapor pressure reached 0.8, capillary condensation began to occur, and the adsorption isotherm was delayed and the vapor pressure was not reached until the saturated vapor pressure was reachedThe adsorption saturation phenomenon is shown, which indicates that the sample contains a certain amount of mesopores and macropores. The sharp rise of the isotherm appears at the inflection point at P/Po>0.9 region, which conforms to the multi-layer adsorption characteristics, mainly the adsorption behavior of larger-sized pores. The curve of the desorption portion generally belongs to the hysteresis loop type H1. The pore diameters of the samples at different calcination temperatures are all within<Distributions appear at 5nm and 10-20 nm. The porous structure results mainly from two factors, i.e. the packed pores of the particles and the gas channels created by the conversion of carbonate to oxide. The pore size distribution of the sample is shown in fig. 4, where the smaller pore size distribution should be formed by decomposition of carbonate or hydroxide, and the larger pore size distribution is the stacking pores of the particles, consistent with SEM and TEM results. With the increase of the calcination temperature, the specific surface area of the product is changed from 95.8m2·g-1Down to 52.3m2·g-1And 49.6m2·g-1. The specific surface areas of the samples at the calcination temperatures of 450 ℃ and 500 ℃ are similar, indicating ZnMn built up from larger nanoparticles2O4Spherical particles with a certain structural thermal stability.
XPS analysis of the samples: in order to further research ZnMn prepared by a low-temperature coprecipitation method2O4Valence state information of each element in a sample is obtained by adopting an XPS (X-ray diffraction) characterization technology to obtain ZnMn under the condition of calcining at 400 DEG C2O4The samples were characterized and the results are shown in figure 5. In FIG. 5a it is clearly seen that the sample contains elements Zn, Mn and O. FIGS. 5 b-d are XPS spectra of Zn 2p, Mn 2p and O1 s. The binding energy peaks near 1044.4eV and 1021.3eV in FIG. 5b correspond to Zn 2p, respectively1/2And Zn 2p3/2Peak, indicating that the Zn element is present in the +2 valence state. The electron binding energies 653.4eV and 642.2eV in FIG. 5c correspond to Mn 2p1/2And Mn 2p3/2. Oxides of manganese, Mn 2p, hardly form single valence oxides1/2And Mn 2p3/2The energy interval between the peaks was 11.4eV, indicating that Mn exists mainly in the +3 valence state. Corresponding in FIG. 5d to the electron binding energies 531.0eV and 529.9eV are O1s, in which the peak at 531.0eV is derived from the Mn-O-H peak formed in the manganese oxide bulk, and the peak at 529.9eV is derived from Mn-O-Mn peak formed in the manganese oxide bulkEnergy peak.
Example 3 ZnMn2O4Electrochemical performance of micro-nano material
A three-electrode system is adopted, wherein an Hg/HgO electrode is used as a reference electrode, a nickel screen coated with a sample is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and 6 mol.L-1KOH solution is used as electrolyte, electrochemical performance is tested at constant temperature of 30 ℃, and a nickel net is cut into 1 × 1cm2The square with the handle is sequentially cleaned by acetone and distilled water in an ultrasonic mode to remove oil stains and dust on the surface of the nickel screen and in the grid, and the nickel screen and the grid are dried in an oven and weighed to obtain the mass of the current collector. Respectively weighing 0.2g of acetylene black, 5% of PVDF (polyvinylidene fluoride resin) and 75% of electrode material in mass ratio, carefully grinding for 20min to mix the conductive auxiliary agent, the organic binder and the active substance, transferring the electrode material into a beaker, adding 2mL of N-methyl-2-pyrrolidone, and magnetically stirring for 3h to obtain the electrode slurry. Uniformly coating the slurry on a dried nickel screen with a coating area of 1cm2Drying at 60 deg.C for 8 hr, and weighing the net weight difference to obtain the mass (0.8 mg. cm) of electrode material loaded on the nickel net-2). And obtaining the electrochemical information of the electrode by adopting a cyclic voltammetry method, a constant current charging and discharging technology and an impedance spectrum test.
1) Cyclic voltammetry tests (CV)
The cyclic voltammetry curve can be used for judging the redox reaction condition on the surface of the electrode, so that the charge storage performance of the electrode is deduced. Setting the voltage window (-0.05-0.45V) within different 10-100 mV.s by electrochemical workstation-1At the scanning rate of (2), the I-V curve of the working electrode measured over time was recorded.
2) Constant current charge and discharge test (CP)
The constant current charge and discharge test is a general method for calculating the discharge capacity of the super capacitor. In the invention, the voltage window of constant current charging and discharging of the working electrode is-0.05-0.45V, and the current density range is 0.5-5 A.g-1The specific capacitance per unit mass C of the active material was calculated by the following formula (3-1)p(F·g-1)：
Figure BDA0001931142890000091
Wherein I (A) represents a discharge current density,. DELTA.t(s) represents a discharge time,. DELTA.U (V) represents a potential window, and m (g) represents a mass of an active material on an electrode.
3) Electrochemical impedance test (EIS)
Electrochemical impedance spectroscopy is a powerful tool for electrochemical systems to evaluate charge transfer rates and charge transport processes, and is widely used for characterization of electrode materials. The electrode structure test interval of the sample material prepared by the method is 0.1Hz-100kHz, and the amplitude of disturbance voltage is +/-5.0 mV.
By a low-temperature coprecipitation method, a composite oxide with a large specific surface area can be obtained. The spinel type composite oxide has higher conductivity, and can improve the defect of poor performance caused by low conductivity of the oxide to a certain extent. Considering that manganese-based compounds are common electrode materials, to understand the ZnMn produced2O4The charge storage properties of the samples, we tested their electrochemical behavior. In general, the charge storage behavior of spinel-type composite oxides occurs mainly in alkaline solutions, and charge transfer is achieved by a rapid redox reaction at the surface. The CV curve is characterized by having obvious oxidation reduction peak, and the pseudo-capacitance behavior of the electrode can be known by judging the position of the oxidation reduction peak and the symmetry condition of the oxidation reduction peak. Since the redox peak is relatively concentrated in a certain voltage interval, its charge storage behavior is similar to that of an aqueous alkaline cell.
FIG. 6 shows the sample electrodes at 10, 20, 50 and 100 mV. multidot.s-1The CV curve is obtained under a potential window of-0.05-0.45V at the scanning speed of (1). As can be seen from the figure, the CV curve has a pair of redox peaks in the range of 0.25 to 0.4V, which is Mn3+/Mn4+Redox peaks of ion pairs. The oxidation peak occurring above 0.4V may be an oxidation process of metallic nickel. It can be seen that as the scan rate increases, the peak positions move away from each other in the direction of the high voltage and the response current increases, indicating that this is a surface electrochemical behavior controlled by the ion transport process. In the voltage region below 0.25V, the electrode also has a certain current response, which shows that the electric double layer capacitance behavior is more obvious because of the larger specific surface area.
The constant current charge and discharge test can better calculate the charge storage capacity of the obtained electrode. In alkaline solution, the electrochemical reaction of the spinel type composite oxide electrode is relatively concentrated in a certain voltage region, so that the obtained charge-discharge curve is not triangular, but has a large discharge platform. Fig. 7 is a charge and discharge curve of the prepared sample electrode. Under different current densities, a charge-discharge platform exists in a charge-discharge curve range of 0.3-0.4V. However, as reflected by the CV curve. The electrode has double electric layer behavior, the length of the charging and discharging platform is not obvious, and the curve is close to a triangular shape. The value of 0.5 A.g at the sample electrode can be calculated by the formula (3-1)-1、1A·g-1、2A·g-1And 5 A.g-1The mass specific capacitance at the current density was 53.7 F.g-1、39.9F·g-1、28.0F·g-1And 16.8 Fg-1. Obviously, the charge storage properties of the electrode are not ideal, probably because Zn element is not an electrochemically active element, while the electrochemical properties of Mn compounds in alkaline media are not outstanding.
Fig. 8 is an Electrochemical Impedance Spectroscopy (EIS) diagram of a sample electrode. Internal resistance (R)s) The value equal to the intersection of the Nyquist curve with the real part Z', shown as 1.48 Ω, illustrates a lower internal resistance of the electrode system, probably because of ZnMn2O4Due to the porous electrode structure of the sample. The slope of the curve in the low frequency region is larger, indicating that the diffusion resistance of the prepared sample electrode is smaller. Meanwhile, in the high frequency region, the curve does not appear to be semicircular, indicating the charge transfer resistance (R) of the sample electrode interfaceCt) Negligible, the sample electrode has a sufficiently large active surface.
The cycle life of the electrode material is also one of the important factors in measuring its electrochemical performance. Fig. 9 is a capacity curve of the prepared sample electrode. As can be seen from FIG. 9, at 5A g-1After 3000 cycles of charge and discharge at the current density of (1), the sampleThe capacitance of the product electrode compared to the initial capacity had a 77.3% retention.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. Micro-nano material ZnMn2O4The preparation method is characterized by comprising the following steps:
1) weighing Zn (NO)3)2·6H2O and MnCl2·4H2Dispersing O in glycol, and stirring to fully dissolve the O;
2) placing the obtained solution in a low-temperature constant-temperature tank, stirring and dropwise adding Na in a nitrogen atmosphere2CO3After the solution is obtained, aging is carried out for 1 h;
3) centrifugally separating the aged sample, and sequentially washing obtained precipitates with deionized water and absolute ethyl alcohol;
4) drying the washed sample for 10h, and grinding the dried product into powder;
5) and (3) placing the powder in a muffle furnace, heating, calcining for 4 hours, and naturally cooling to room temperature to obtain a final product.
2. The ZnMn micro-nano material of claim 12O4Characterized in that Zn (NO) in the step (1)3)2·6H2O and MnCl2·4H2The mass ratio of O is 1: 2.
3. The ZnMn micro-nano material of claim 12O4The preparation method is characterized in that the low-temperature constant temperature in the step (2) is-10 ℃.
4. The ZnMn micro-nano material of claim 12O4Characterized in that Na is added dropwise in the step (2)2CO3The concentration of the solution was 0.225 mol. L-1The dropping rate was 1.2 mL/min-1。
5. The ZnMn micro-nano material of claim 12O4The method for preparing (1), wherein the temperature of the deionized water in the step (3) is 60 ℃.
6. The ZnMn micro-nano material of claim 12O4The preparation method of (5) is characterized in that the drying condition in the step (4) is 60 ℃.
7. The ZnMn micro-nano material of claim 12O4Characterized in that the muffle furnace in the step (5) has a temperature rise rate of 1 ℃ min-1The temperature is raised to 400 ℃.
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