CN101000954A - Zinc cathode electrode material, preparation method and application - Google Patents
Zinc cathode electrode material, preparation method and application Download PDFInfo
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Abstract
The invention relates to a zinc cathode electrode material, a preparation method and application thereof. The zinc nanoflower, the nanospheres and the hexagonal structure microspheres are prepared by adopting a vapor deposition method through regulating test conditions such as heating temperature, gas flow rate, reaction time, deposition temperature and the like in a controllable manner. The method is characterized in that: the nanometer flower radiates a plurality of nanometer branches from a nanometer core (40-300 nm), the diameter of a single nanometer branch is 10-200nm, and the length can reach 0.3-1.0 mu m; the diameter of the nanosphere is 80-200nm; the microspheres have a typical hexagonal crystal structure with well-defined edges and corners and diameters of 0.5-5 μm. Because the zinc nano/micron material has high specific surface area and chemical activity, the zinc nano/micron material has higher electrochemical capacity and good high-power and high-rate discharge performance in a zinc/air battery and a zinc/manganese battery.
Description
[ technical field ]: the invention relates to the technical field of nano materials and preparation thereof, in particular to a zinc cathode electrode material, a preparation method and application thereof.
[ background Art ] A method of: with the miniaturization of household appliances, instruments, mobile communication equipment, portable electronic equipment, and defense equipment, the demand of people for batteries with high specific energy is rapidly increasing. As a new high-performance green energy source, the metal-air battery has the characteristics of high specific energy, long service life, safety, no pollution, no need of charging equipment, capability of quickly supplementing energy and the like, can be widely applied to the fields of small and medium-sized mobile power supplies, power supplies of small portable electronic devices, power supplies of underwater military devices and the like, and is expected to become an ideal updating product for replacing the conventional battery in the 21 st century. The zinc/air battery has high theoretical energy (the theoretical specific energy is 1350W. H.kg) -1 ) The advantages of high instantaneous output power, stable working voltage, cheap and easily available raw materials and the like gradually become hot spots for research and development in recent years. However, since the commercial zinc-based battery employs a zinc sheet or electrolytic zinc as a negative electrode, its market and application range are limited due to its low discharge current density. In recent years, with the development of material science and nanotechnology, nanomaterials gradually show incomparable advantages in performance due to their unique microstructures. Compared with the conventionalCompared with the bulk electrode material, the nano electrode material has small particle size and large specific surface area, can increase the contact between the active substance and the electrode, reduce the internal resistance of the battery and improve the diffusion performance of protons, thereby effectively improving the electrochemical performance of the battery and having potential application prospect. Therefore, the key material zinc in the traditional zinc/air battery is subjected to nanocrystallization and the electrochemical performance of the zinc/air battery is comprehensively considered, and the method has very important meaning for improving the comprehensive performance of the zinc/air battery.
At present, the preparation method of the metal zinc nano-material mainly comprises a gas phase transport method [ Synthesis of Ultrathin Zinc nanoparticles and N anothesbsbyVaporTransport. XiaoogangWen, yuejingFang, shiheYang, angew, chem, int.Ed. 2005, 44,2-5]Electrodeposition [ luminescences propertiesof Znnanowiepreprepared byyelectriceelementing, sung-sikchong, sangOkYoon, hyeJeong park, akirasaka. Materials letters53 (2002) 432-436]Mechanical ball milling method [ exotic of microbiological industry of insulation solid solution of ultra-fine-grain and nanocrystalline Znprepard of byballming. X. Zhang, h.wang, r.o.scantergood, j.narayan, c.c.koch, mater.sci.eng.344 (2003) 175-181.]And the like. However, in domestic and foreign literature reports, no literature report on zinc nanoflowers, nanospheres and hexagonal-structure microspheres is found, and few reports are made on applying nano-zinc materials to high-end chemical power sources and systematically researching electrochemical behaviors of the zinc nanomaterials in green zinc/air fuel cells and zinc-manganese cells. Thus: the exploration of the controllable preparation method of the zinc nano material and the research on the electrochemical performance of the zinc nano material have important value for improving the comprehensive performance of the zinc/air battery and the zinc-manganese battery. In addition, the electrochemical performance of nano/micron zinc is researched, and the research on the electrochemical performance of nano/micron zinc is aimed at developing novel Zn-MnO2, zn-Ag 2 O, zn-Ni and Zn-Br 2 The zinc-based battery has important guidanceAnd (5) defining.
[ summary of the invention ]: the invention aims to solve the problems of low discharge current density and the like of a zinc electrode in a zinc-based battery due to the defects of the zinc electrode, thereby improving the utilization rate of the zinc electrode, improving the high-rate discharge performance of an alkaline zinc/air battery and a zinc-manganese battery, and providing a zinc negative electrode material, a preparation method and application for developing and developing a novel high-specific-energy zinc-based battery.
The invention provides a zinc negative electrode material, which comprises: the nanometer flower comprises nanometer flowers, nanometer balls and micrometer balls with a hexagonal structure, wherein the nanometer flowers radiate 3-20 nanometer branches from a nanometer core with the diameter of 40-300nm, the diameter of each nanometer branch is 10-200nm, the length of each nanometer branch is 0.3-1.0 mu m, and each nanometer branch is of a typical flower-shaped structure; the nanospheres have uniform size, the diameter of the nanospheres is 80-200nm, and the nanospheres have good dispersibility; the microspheres have a typical hexagonal crystal structure and are well-defined in edges and corners (the spheres have smooth surfaces and regular geometric shapes, indicating that the microspheres have good crystallinity) and have diameters of 1-5 μm.
The preparation method of the zinc negative electrode material comprises the following steps:
1) Flatly placing a quartz boat containing high-purity zinc (99.99%) in the center of a quartz tube, sealing related connecting pieces, introducing high-purity Ar (99.995%) for half an hour at a flow rate of 200 cubic centimeters per minute to remove oxygen in the system, keeping the temperature of a tube furnace at 500-660 ℃ for two hours under the protection of Ar gas at the flow rate of 200 cubic centimeters per minute, naturally cooling to room temperature, then guiding a uniform grey film of tricholoma on a nano deposition end substrate, and collecting a sample to prepare a battery cathode material;
2) Soaking the quartz tube in 100-500 ml of 0.5mol/L HCl for half an hour, washing with water, washing with alcohol and drying; the treated quartz tube reactor can be repeatedly used for preparing the zinc nano material.
The usage amount of the metal zinc is 4.0-6.0 g.
The invention provides a special device for a preparation method of a zinc cathode electrode material, which comprises an Ar gas cylinder, a gas dryer, a gas flowmeter, a quartz tube reactor and a cooling dust removal device which are sequentially connected in series; the quartz tube reactor was passed through a tube furnace with a thermocouple program temperature controller and the substrate was placed at the cooling end of the quartz tube.
The size of the quartz tube reactor is phi Inner diameter 1.2cm, wall thickness 0.2cm, length 80.0cm; the length of the tube furnace is 66.0cm, and the diameter is 40.0cm.
The high-purity Ar gas cylinder is tightly connected with a gas drying device through a stainless steel pipeline and then passes through a gas flowmeter; the dried gas flows through a valve at the left side of the tube furnace and enters the quartz tube reactor; when the temperature of the tube furnace rises to the set temperature, the gas will transport the metallic zinc vapor in the reactor to the cooling end substrate. The tubular furnace is the main body of the whole heating system, and the heating temperature is controlled by a program temperature controller through a thermocouple; the cooling dust-removing device removes the superfine metal powder possibly contained in the reaction tail gas by water cooling so as to reduce the solid dust pollution.
The application of the zinc negative electrode material is applied to zinc-based batteries, including zinc/air, zinc/manganese, zinc/silver, zinc/nickel and zinc/bromine batteries.
1. Use in zinc/air cells:
the zinc metal can be used as zinc-based batteries (e.g. Zn-air, zn-MnO) 2 、Zn-Ag 2 O, zn-Ni, etc.). Due to the outstanding characteristics of the metal-air battery, the electrochemical behavior of the nano/micron zinc electrode in the zinc/air battery is preferentially considered. The zinc/air battery consists of a zinc cathode, a diaphragm and an air electrode; wherein the zinc cathode sample is obtained by vapor depositionZinc m/m (nanoflower, nanospheres and microspheres), electrodentritic zinc and commercial molten zinc; the negative electrode zinc paste was composed of 50.0wt% nano/micro zinc, 36.0wt% carbon black, 2.0wt% ZnO and 2.0wt% in 2 O 3 And 10wt% Polytetrafluoroethylene (PTFE) emulsion. The zinc paste was applied to a current collector and vacuum dried at 80 ℃ for 30 minutes. The air battery (anode) mainly comprises a waterproof breathable layer and a catalytic conductive layer, wherein the waterproof breathable layer, a current collecting net and the catalytic conductive layer are sequentially arranged from outside to inside; wherein the waterproof breathable layer is prepared from acetylene black, PTFE emulsion and Na 2 SO 4 Mixing, ultrasonically treating to paste, and rolling to form the product with a thickness of 200-400 μm; one side of the catalyst layer close to the electrolyte is made of perovskite La 0.6 Ca 0.4 CoO 3 Mixing the nanotube, acetylene black and PTFE emulsion, performing ultrasonic treatment to obtain a pasty state, and rolling to obtain a formed catalytic membrane with the thickness of 100-400 μm; la 0.6 Ca 0.4 CoO 3 The nanotube electrocatalyst is prepared by comprehensively utilizing a sol-gel method and an alumina template method, has the diameter of 200nm, the length consistent with the thickness of the template of 50-60 mu m and the wall thickness of 15nm; the electrolyte was 2.5wt% KOH solution.
La as described above 0.6 Ca 0.4 CoO 3 The electrocatalyst adopts (La (NO 3) 3.6H 2O), (Ca (NO 3) 2.4H 2O), (Co (NO 3) 2.6H 2O) asRaw materials are added with citric acid which is 1 to 2 times of the total mole number of the metal ions according to the mole ratio of 3: 2: 5, and gel-sol is prepared by heating treatment; then introducing a template substrate, and carrying out high-temperature sintering treatment at 650-800 ℃ for 3-10 hours to obtain the template.
The electrochemical test of the zinc electrode adopts a three-electrode system, the prepared zinc electrode is taken as a working electrode, and a Pt sheet (1 cm) 2 ) A saturated calomel electrode is selected as a counter electrode and a reference electrode; the electrode testing instrument used was a Parstat2273 type electrochemical workstation (Princeton applied Research)&Amtech company); the electrolytes of the linear scanning and alternating current impedance test are both alkaliProperty 2.5wt% KOH solution.
The discharge performance of the air battery adopts a special battery test system.
2. Application in zinc-based cells:
since zinc can be used as the negative electrode material of various zinc-based batteries, the zinc-manganese battery can also be applied to zinc-manganese batteries. The alkaline zinc-manganese battery has the characteristics of low price, mature manufacturing process and the like, and is widely applied to various small portable electronic products. The invention provides a zinc-manganese battery taking a zinc nano/micron material as a negative active material, and comprehensively inspects the electrochemical behavior of the zinc-manganese battery. The alkaline zinc-manganese dioxide battery of the invention comprises: a nano/micron zinc cathode, a diaphragm, a manganese dioxide anode, an alkaline electrolyte and a battery container; the preparation method of the nano/micron zinc cathode is the same as the preparation process of the zinc electrode in the zinc/air battery; the manganese dioxide positive electrode material comprises gamma-MnO 2 Nanotube/nanowire, activated carbon, said gamma-MnO 2 The nanotube content in the nanotube/nanowire is 40-50%, the length of a single nanotube/nanowire is 2-4 μm, and the diameter is 75-85nm. The formula of the anode material is as follows: 85% (all by mass) of gamma-MnO 2 Nanotube/nanowire, 8% activated carbon and 7% electrolyte. The instrument used was a Parstat2273 type electrochemical workstation (Princeton applied research)&Amtech company) and Arbin (2001-T) charge and discharge systems in the united states, the electrolyte of the zinc-manganese cell was alkaline 2.5wt% koh solution.
The invention has the advantages and effects that:
the invention has the advantages that the high-purity zinc nanospheres, nanoflowers and hexagonal-structure microspheres are obtained by adopting a vapor deposition method; by adjusting the test conditions such as heating temperature, deposition temperature, reaction time and the like, the morphology of the material is effectively controlled. The invention is characterized in that the nano/micron zinc material can obviously improve the physical and chemical properties, in particular toAlong with the increase of the crystallinity of zinc and the atomic number ratio of the surface, the electrochemical activity of the material is obviously increased, so that the utilization rate of a zinc electrode is obviously improved, and the energy density, the electrochemical capacity, the high-power and high-rate discharge performance of a zinc/air battery and a zinc-manganese battery are improved, thereby having important theoretical and practical significance for improving the comprehensive performance of the zinc/air and zinc-manganese batteries. In addition, the nano/micron zinc material is also Zn-Ag 2 O, zn-Ni and Zn/Br 2 The zinc-based battery has wide application prospect.
The preparation method is characterized in that: 1) The instrument and equipment are simple, the investment is low, the effect is quick, and the method is suitable for popularization and research; 2) Various ultra-pure zinc nano and micron materials with typical shapes are prepared by evaporating high-purity zinc powder and adopting a vapor deposition method, the raw materials are cheap and easy to obtain, the whole experimental device is reasonable in design, and no environmental pollution is caused; 3) The proportion of the zinc nano/micron material can be effectively controlled by adjusting test conditions such as heating temperature, heating time, deposition temperature and the like, and the method has the advantages of strong process controllability, simple operation and high reproducibility.
[ description of drawings ]:
FIG. 1 is a schematic diagram of an experimental apparatus for preparing zinc nano-materials;
FIG. 2 is a scanning electron micrograph of different samples prepared according to examples 1 to 3: (a, b) hexagonal structure microspheres, (c, d) nanoflower/microspheres, (e, f) nanospheres/microspheres;
fig. 3 is an XRD pattern of zinc of different morphologies: melting zinc, (b) electrolyzing zinc, and (c) preparing zinc by a vapor deposition method;
FIG. 4 is a Transmission Electron Microscope (TEM) image of various samples made according to examples 1-3: (a) Microspheres, (b) nanoparticles/microspheres, (c, d, e) nanoflowers; the inset is a Fourier transform (FFT) of the nanoparts that make up the nanoflower;
FIG. 5 is a linear scan of different zinc electrodes in a 2.5wt% KOH electrolyte of saturated ZnO at a sweep rate of 20mV/s;
FIG. 6 is La 0.6 Ca 0.4 CoO 3 Scanning electron microscopy analysis and transmission electron microscopy analysis of nanotube catalyst;
FIG. 7 is a graph of the constant current (1 mA) discharge curves for zinc/air cells made according to examples 5 and 7 using different zinc materials;
FIG. 8 is a discharge curve at different discharge currents (2 mA, 4 mA) for a zinc/air cell made according to examples 5, 7 using micro/nano zinc and electrolytic zinc;
fig. 9 is a discharge curve at 20 ℃ at constant resistance (20 Ω) of an LR6 type alkaline zinc-manganese dioxide cell made in accordance with example 9;
fig. 10 is a discharge curve of LR6 type alkaline zinc-manganese dioxide battery made in example 9 at 20 ℃ at different resistances;
fig. 11 is a discharge curve of LR6 type alkaline zinc-manganese dioxide battery made according to example 9 at 20 ℃ at different powers.
[ embodiments ] of the present invention:
example 1:
preparation of zinc hexagonal structure micro-spheres
1. The device comprises the following steps: FIG. 1 is a schematic diagram of an experimental apparatus for preparing various zinc nanomaterials by a vapor deposition method. 1-high-purity Ar protective gas, 2-gas drying system, 3-gas flowmeter, 4-quartz tube reactor, 5-heating and temperature control system, 6-substrate and 7-cooling dust-removing device.
The Ar gas cylinder, the gas dryer, the gas flowmeter, the quartz tube reactor and the cooling dust removal device are sequentially connected, the quartz tube reactor penetrates through the tube furnace with the thermocouple program temperature controller, the substrate is placed at the cooling end of the quartz tube, and the outlet end of the reactor is sequentially connected with the pressure gauge, the valve and the cooling dust removal device.
The high-purity Ar gas cylinder is tightly connected with a gas drying device through a stainless steel pipeline and then passes through a gas flowmeter; the dried gas flows through a valve at the left side of the tube furnace and enters the quartz tube reactor; when the temperature of the tube furnace is raised to a high temperature, the gas will transport the metal vapor in the reactor to the cooling end substrate. The tube furnace is a main body of the whole heating system, the heating temperature is controlled by a program temperature controller through a thermocouple, the heating temperature of the tube furnace is controlled by an artificial intelligent temperature controller and a thermocouple in the center of the furnace body, and the error between the actual furnace temperature and the set temperature is less than 2 ℃; the cooling dust removal device removes superfine zinc powder contained in reaction tail gas by water cooling, reduces solid dust pollution and avoids injury to operators.
The size of the quartz tube reactor is phi Inner diameter 1.2cm, 0.2cm wall thickness and 80.0cm length; the tube furnace has a length of 66.0cm and a diameter of 40.0cm.
2. The preparation method comprises the following steps: placing a quartz boat containing 4.0 g Gao Chunxin (99.99%) in the center of a quartz tube, sealing the relevant connecting pieces, and sealing by 200cm 3 Permin flow rate of high purity Ar (99.995%) for 0.5 hr to remove oxygen from the system at a flow rate of 200cm 3 And (3) keeping the temperature of the tubular furnace at 660 ℃ for 2 hours under the protection of Ar gas for/min, naturally cooling to room temperature, obtaining a uniform grey film of the tricholoma matsutake on the nano deposition end substrate, and collecting a sample with the deposition temperature of 180 ℃ for later use. Soaking the quartz tube in 0.5mol/LHCl for 30min, washing with water, washing with alcohol, and drying.
Scanning electron microscopy analysis (figure 2a, b) of the zinc deposition product prepared by the method indicated: a large amount of product regular hexagonal structure microspheres are uniformly distributed on the surface of the substrate; the surface of the microsphere is in a regular geometric structure, the edges and corners of the hexagonal stacked layer are clearly visible, and the diameter of the central part of the microsphere is about 2-4 mu m.
Analysis of the XRD contrast spectrum (as shown in fig. 3) of the vapour-deposited zinc prepared by the method with electrolytic zinc and commercial molten zinc shows that: the peak shapes of the vapor deposited zinc were very similar to those of the other two zinc types, and the intensity and position of the diffraction peaks were consistent with the data of JCDPS card No. (No. 04-0831). The diffraction peak of the hetero-phase zinc oxide is not present in the figure, which shows that the introduction of oxygen is avoided in the process of preparing the sample, and the prepared samples are all high-purity zinc, thereby further proving the feasibility of the design and the operation of the test device.
Example 2
Preparation of zinc nanoflower/micron ball
The apparatus was as described in example 1, a quartz boat containing 6.0 g Gao Chunxin (99.99%) was placed flat in the center of the quartz tube, the associated connections were sealed, and 200cm was used first 3 Permin flow rate of high purity Ar (99.995%) for 0.5 hr to remove oxygen from the system at a flow rate of 200cm 3 And (3) keeping the temperature of the tubular furnace at 660 ℃ for 2 hours under the protection of Ar gas for/min, naturally cooling to room temperature, obtaining a uniform grey film of the tricholoma matsutake on the nano deposition end substrate, and scraping a sample with the deposition temperature of 360 ℃ for later use. Soaking the quartz tube in 0.5mol/LHCl for 30min, washing with water, washing with alcohol, and drying.
Scanning electron microscopy analysis of the zinc nanoflower deposit prepared by the method described (figure 2, c, d) shows: a large number of nanoflowers are distributed on the surfaces of the hexagonal structure microspheres, and a plurality of nanoflowers are in a network cross-linked state. The nanoflower is composed of 3-20 dendritic nanorods radiated by a central core (40-300 nm), wherein the length of the nanorods can reach 0.3-1.0 μm, the diameter is only 10-50nm, and the nanoflower is a typical flower-shaped structure;
example 3
Preparation of zinc nanosphere/microsphere
Apparatus as in the examples1, a quartz boat containing 5.0 g Gao Chunxin (99.99%) is placed in the center of a quartz tube, and the relevant connecting pieces are sealed, wherein the quartz boat is firstly placed by 200cm 3 Permin flow rate of high purity Ar (99.995%) for 0.5 hr to remove oxygen from the system at a flow rate of 200cm 3 And (3) keeping the temperature of the tubular furnace at 500 ℃ for 2 hours under the protection of Ar gas for min, naturally cooling to room temperature, obtaining a uniform grey film of the tricholoma matsutake on the nano deposition end substrate, and scraping a sample with the deposition temperature of 360 ℃ for later use. Soaking the quartz tube in 0.5mol/LHCl for 30min, washing with water, washing with alcohol, and drying.
Scanning electron microscopy analysis of zinc nanosphere/microsphere deposits prepared by the method (fig. 2, e, f) shows: a large number of nanospheres are uniformly dispersed around the hexagonal structure microsphere with the diameter of only 1-2 mu m; analysis by a high power scanning electron microscope (figure 2,f) shows that the diameters of the nanospheres are distributed in the range of 150-200nm, and the nanospheres are agglomerated into a network structure due to high specific surface area. The test proves that: when the heating temperature of the tubular furnace is lower, the zinc nano or micro spheres are easy to grow at the proper deposition temperature, and the proportion of nano and micro materials can be effectively changed by adjusting the necessary reaction conditions.
Example 4
Transmission electron microscope testing of zinc microspheres, nanoflowers and nanospheres/microspheres
The microstructures and morphologies of the zinc hexagonal structure microspheres, nanoflower/microspheres, nanospheres/microspheres described in examples 1-3 are shown in transmission electron microscopy and high resolution transmission electron microscopy (TEM and HRTEM) of fig. 4: the diameter of the hexagonal structure micro-sphere (as shown in fig. 4 a) in example 1 is about 2-4 μm, the upper and lower planes of the hexagonal sphere are parallel to each other, and the edge angle is clearly visible; nanospheres/microspheres described in example 3 (as in figure 4 b) show that: a large number of nanospheres are dispersed around the microspheres with the diameter of 1-3 μm, and a plurality of nanospheres are gathered together due to the large specific surface area of the nanospheres (the diameter is about 150 nm); the nanoflower/microspheric samples described in example 2 (see figure 4c, d, e) demonstrate that: the diameter of the nanoflower is only 20-30nm, and the length is 200-500nm, which is consistent with the analysis result of the Scanning Electron Microscope (SEM) of example 2; fig. 4e demonstrates that the nanopacle radiated from the nanoflower does not have a distinct oxide layer. High Resolution Transmission Electron Microscopy (HRTEM) of a single nanotree showed a lattice spacing of 0.247nm for zinc (fig. 4 f); since the lattice fringes of zinc are perpendicular to the crystal axis direction, the nano-branches of the nanoflower are grown along the (001) crystal plane, which is consistent with the results of fourier transform (FFT) analysis in fig. 4 f.
Example 5
Preparation of zinc electrode
The zinc electrode samples selected from the nano/micro zinc (nanospheres, nanoflowers and microspheres), electrolytic dendritic zinc and commercial molten zinc prepared in examples 1-3; characterized in that the negative electrode calamine paste is composed of 50.0wt% nano/micro zinc, 36.0wt% carbon black, 2.0wt% ZnO and 2.0wt% in 2 O 3 And 10wt% Polytetrafluoroethylene (PTFE) emulsion. The zinc paste was applied to the current collector and vacuum dried at 80 ℃ for 30 minutes. The electrochemical test of the zinc electrode adopts a three-electrode system, and the prepared zinc electrode is taken as a working electrode and a Pt sheet (1 cm) 2 ) A saturated calomel electrode is selected as a counter electrode and a reference electrode; the instrument used was a Parstat2273 electrochemical workstation (princetonappplied research)&Amtech company); the electrolytes of both the linear sweep and the AC impedance test were alkaline 2.5wt% KOH solution.
Example 6
Electrochemical study of Zinc electrodes
The linear scan of three types of zinc electrodes described in example 5 (see fig. 5) is mainly composed of three parts: an anodic dissolution process (a → b), an anodic diffusion process (b → c), and a passivation process (c → d). The anode dissolution and diffusion process voltages were-1.36V and-1.24V, respectively. Among the three types of zinc electrodes, the peak generated in the dissolving process of the molten zinc anode has no nano/micron zinc and the peak generated by electrolytic zinc is obvious; the anode dissolution potential of the nano/micron zinc sample is only-1.45V, while the initial potentials of electrolytic zinc and molten zinc are slightly more positive, and the more electronegativity of the anode material is, the more beneficial the open-circuit voltage of the battery is. The descending order of the current density of anode dissolution and diffusion is as follows: the nano ball/micro ball is more than nano flower/micro ball is more than electrolytic zinc is more than hexagonal structure micro ball is more than molten zinc. This result indicates that: the electrochemical activity of vapour deposited zinc and electrolytic zinc is significantly higher than that of molten zinc. For molten zinc, when the voltage is increased to-1.20V, the current density of the zinc electrode is suddenly reduced, which indicates that a thin passivation film is formed on the surface of the zinc electrode, and the further occurrence of the electrochemical reaction is influenced; the passivation potential of nano/micron zinc prepared by a vapor deposition method and electrolytic zinc is only-1.10V, which shows that the passivation of the zinc electrode in the system is effectively inhibited, and the occurrence of electrochemical reaction is facilitated, and the characteristic is favorable for improving the capacity and high-rate discharge performance of a zinc-based battery.
Example 7
Manufacture of alkaline zinc/air cell
The invention provides an alkaline zinc/air battery, which comprises a zinc cathode, a diaphragm and an air electrode. The zinc electrode was prepared as described in example 5, with the electrode areas all being 2.0X 2.0cm; the air electrode mainly comprises a waterproof breathable layer and a catalytic conductive layer, and the waterproof breathable layer, a current collecting net (a foamed nickel or copper net) and the catalytic conductive layer are sequentially arranged from outside to inside; wherein the waterproof breathable layer is prepared from acetylene black, PTFE emulsion and Na 2 SO 4 Mixing, ultrasonically mixing to paste, and rolling to form the paste with the thickness of 200-400 μm; one side of the catalytic layer close to the electrolyte consists of perovskite La 0.6 Ca 0.4 CoO 3 Mixing the nanotube, acetylene black and PTFE emulsion, ultrasonically treating to obtain paste, and rolling to obtain a catalytic membrane with a thickness of 100-400 μm; la 0.6 Ca 0.4 CoO 3 The nanotube electrocatalyst is prepared by comprehensively utilizing a sol-gel method and an alumina template method, and comprises the following specific steps: 1) Firstly, mixing three salts (La (NO 3) 3.6H 2O), (Ca (NO 3) 2.4H 2O) and (Co (NO 3) 2.6H 2O) according to the molar ratio of 3: 2: 5, adding a proper amount of citric acid, and heating to prepare gel-sol; 2) Placing the mixture into a template, dipping, drying and sintering at 650-800 ℃; 3) Perovskite La0.6Ca0.4CoO obtained by removing aggregates 3 A nanotube catalyst. The diameter is 200nm, the length is consistent with the thickness of the template (50-60 μm), and the wall thickness is 15nm (as shown in figure 6). The electrolyte is alkaline 2.5wt% KOH solution.
Example 8
Electrochemical performance study of alkaline zinc-air cell
FIG. 7 is a constant current discharge curve at 20 ℃ at 1mA constant current for alkaline zinc/air cells assembled with different zinc materials according to examples 5, 7: battery 1) micro-and nanospheres, battery 2) electrolytic zinc, and battery 3) high purity molten zinc. As can be seen from the figure: the nano/micron zinc provided by the invention has stable discharge performance in a discharge process, and the discharge time is obviously longer than that of the traditional electrolytic dendritic zinc and commercial molten zinc. The method has important guiding significance for developing nano/micron zinc to be applied to other zinc-based batteries.
Fig. 8 is a discharge curve of a zinc/air cell assembled from 7 nm/μm zinc and electrolytic zinc according to example 5 at different discharge currents (2 mA, 4 mA): battery 1) micro-and nanospheres, battery 2) electrolytic zinc. As can be seen from the figure: the nano/micron zinc can respectively and continuously discharge for 14.2 h and 7.5h under the larger currents of 2mA and 4mA, and also has higher discharge capacity and energy, which shows that the alkaline zinc/air battery has good large-current discharge performance.
Example 9
An LR6 (AA) alkaline zinc-manganese battery is manufactured: mixing manganese dioxide positive electrode materials, granulating, pressing a ring, filling into a steel shell, coating a sealant, then inserting a diaphragm, adding an electrolyte and a negative electrode zinc paste, then inserting a negative electrode current collector assembly, welding a negative electrode terminal, rolling a wire, curling and then welding a positive electrode terminal to obtain the finished product of the alkaline zinc-manganese dioxide battery. The negative electrode zinc paste was composed of 50.0wt% nano/micro zinc, 36.0wt% carbon black, 2.0wt% ZnO and 2.0wt% in% 2 O 3 And 10wt% Polytetrafluoroethylene (PTFE) emulsion; the positive electrode material comprises: 85% (all by mass) of gamma-MnO 2 Nanotube/nanowire, 8% activated carbon and alkaline 2.5% koh electrolyte.
Example 10
Electrochemical performance research of nano/micron zinc in zinc-manganese battery
The constant resistance discharge curve (fig. 9) of an LR6 type (i.e., A.A type) alkaline zinc manganese cell gives a discharge curve that is continuously discharged to 0.8V at constant resistance (12 ohms) at 20 ℃ with the nanospheres/microspheres, electrolytic zinc, and molten zinc of example 3. The results show that: the discharge time of the nanosphere/microsphere, the electrolytic zinc and the molten zinc is 315 hours, 30.0 hours and 28.0 hours respectively, and the discharge time of the nanosphere/microsphere is obviously superior to that of the electrolytic zinc and the molten zinc.
Figure 10 shows the constant resistance discharge curve of the alkaline zn-mn cell assembled from nanospheres/microspheres and electrolytic zinc according to example 3 at 20 ℃ discharging continuously to 0.8V at different resistances (1.5,3.0,6.0 ohm). As can be seen from the figure: when the battery is discharged under 6.0 ohm, the alkaline zinc-manganese battery assembled by the nanosphere/microsphere has longer discharge time and higher discharge platform under the conditions of low load and high load.
Figure 11 shows the constant resistance discharge curve of the nano/micro spheres and electrolytic zinc assembled alkaline zn-mn cell according to example 3 at 20 ℃ with continuous discharge to 0.8V at different powers (2.0,1.0,0.5,0.25 watts). In combination with the data in table 1, it was found that: the alkaline zinc-manganese dioxide battery has good discharge performance under different powers, but the nano/micron zinc material has better high-power discharge performance compared with electrolytic zinc.
By comparing the electrochemical performance of nano/micro zinc with that of zinc/air cell assembled by traditional electrolytic zinc and dendritic zinc and alkaline zinc-manganese cell, it can be seen that: the zinc-based battery has higher electrochemical capacity, high power and high-rate discharge performance. The method mainly results from the fact that the physical and chemical properties of the battery material after the nano-crystallization are changed to a considerable extent, and the electrochemical activity of the material is increased along with the reduction of the particle size of the material; therefore, the two types of batteries have higher electrochemical capacity and good high-power and high-rate discharge performance.
TABLE 1 electrochemical performance of LR6 type alkaline Zn-Mn battery at 20 deg.C in different discharge modes
| Load(s) | Capacity of (Ah) | (Energy) (Wh) | Specific energy (Wh·Kg -1 ) | Energy density (Wh·L -1 ) | ||||
| Cell-1 | Cell-4 | Cell-1 | Cell-4 | Cell-1 | Cell-4 | Cell-1 | Cell-4 | |
| 1.5Ω 3.0Ω 6.0Ω 12Ω 0.25W 0.5W 1.0W 2.0W | 3.00 3.03 3.10 3.15 3.13 3.06 2.98 2.97 | 2.95 2.98 2.99 3.00 3.03 3.01 3.00 2.99 | 3.60 3.64 3.72 3.78 3.76 3.67 3.58 3.56 | 3.54 3.58 3.59 3.60 3.64 3.61 3.60 3.59 | 150.0 151.7 155.0 157.5 156.7 152.9 149.2 148.3 | 147.5 149.2 149.6 150.0 151.7 150.4 150.0 149.6 | 480.0 485.3 496.0 504.0 501.3 489.3 477.3 474.7 | 472.0 477.3 478.7 480.0 485.3 481.3 480.0 478.7 |
* The weight of the battery is as follows: 24g of the total weight of the mixture, ** battery volume: 7.5cm 3 .
Claims (9)
1. A zinc negative electrode material, characterized in that it comprises: the nanometer flower comprises nanometer flowers, nanometer balls and micrometer balls with a hexagonal structure, wherein the nanometer flowers radiate 3-20 nanometer branches from a nanometer core with the diameter of 40-300nm, and the diameter and the length of a single nanometer branch are 10-50nm and 0.3-1.0 mu m respectively; the diameter of the nanosphere is 80-200nm; the microspheres have a typical hexagonal crystal structure with well-defined edges and corners and a diameter of 0.5-5.0 μm.
2. A method for preparing the zinc negative electrode material of claim 1, which is characterized by comprising the following steps:
1) Flatly placing a quartz boat containing high-purity zinc (99.99%) in the center of a quartz tube, sealing a tube opening connecting piece, introducing high-purity Ar (99.995%) for half an hour at a flow rate of 200 cubic centimeters per minute to remove oxygen in the system, keeping the temperature of a tube furnace at 500-660 ℃ for two hours under the protection of Ar gas at the flow rate of 200 cubic centimeters per minute, naturally cooling to room temperature to obtain a uniform grey film of tricholoma on a nano deposition end substrate, and collecting a sample to prepare a battery cathode material;
2) Soaking the quartz tube in 100-500 ml of 0.5mol/LHCl for half an hour, washing with water, washing with alcohol and drying; the treated quartz tube reactor can be repeatedly used to prepare the zinc nano material.
3. The method for preparing a zinc negative electrode material according to claim 2, wherein the amount of the metallic zinc used is 4.0 to 6.0 g.
4. The special device for the preparation method of the zinc cathode electrode material according to claim 2 is characterized by comprising an Ar gas cylinder, a gas dryer, a gas flowmeter, a quartz tube reactor and a cooling and dedusting device which are sequentially connected in series; the quartz tube reactor was run through a tube furnace with a thermocouple program temperature controller and the substrate was placed on the cool end of the quartz tube.
5. The apparatus as claimed in claim 4, wherein the reactor quartz tube has a length of 80.0cm and a diameter of Φ Inner diameter 1.2cm and a wall thickness of 0.2cm.
6. The use of the zinc negative electrode material of claim 1 in zinc-based batteries including zinc/air, zinc/manganese, zinc/silver, zinc/nickel, zinc/bromine batteries.
7. The use of the zinc negative electrode material of claim 6 in a zinc-based cell, wherein the zinc/air cell is comprised of a zinc negative electrode, a separator and an air electrode: wherein the zinc negative electrode is composed of 50.0wt% zinc (nano/micro zinc, electrolytic zinc and molten zinc), 36.0wt% carbon black, 2.0wt% ZnO and 2.0wt% in 2 O 3 And 10wt% Polytetrafluoroethylene (PTFE); spreading zinc paste on a current collector and vacuum drying at 80 ℃ for 30 minutes; the air electrode mainly comprises a waterproof breathable layer and a catalytic conductive layer, and the waterproof breathable layer, the current collecting net and the catalytic conductive layer are sequentially arranged from outside to inside; wherein the waterproof breathable layer is prepared from acetylene black, PTFE emulsion and Na 2 SO 4 Mixing, ultrasonically treating to paste, and rolling to form the paste with the thickness of 200-400 μm; one side of the catalytic layer close to the electrolyte consists of perovskite La 0.6 Ca 0.4 CoO 3 Mixing the nanotube, acetylene black and PTFE emulsion, ultrasonically treating to obtain paste, and rolling to obtain a catalytic membrane with a thickness of 100-400 μm; la 0.6 Ca 0.4 CoO 3 The nanotube electrocatalyst is prepared by comprehensively utilizing a sol-gel method and an alumina template method, has the diameter of 200nm, the length consistent with the thickness of the template of 50-60 mu m and the wall thickness of 15nm; the electrolyte solution was alkaline 2.5wt% KOH solution.
8. Use according to claim 7, characterized in that the positive electrode of the air cell, la 0.6 Ca 0.4 CoO 3 The electrocatalyst adopts (La (NO 3) 3.6H 2O), (Ca (NO 3) 2.4H 2O), (Co (NO 3) 2.6H 2O) as raw materials, the raw materials are dissolved in deionized water according to the molar ratio of 3: 2: 5, citric acid which is 1 to 2 times of the total molar number of the metal ions is added, and the gel-sol is prepared by heating treatment; then introducing a template substrate, and sintering at a high temperature of 650-800 DEG CProcessing for 3-10 hours.
9. The use of the zinc negative electrode material in a zinc-based cell according to claim 6, wherein the LR6 (i.e., AA) alkaline zinc/manganese cell is comprised of a nano/micro zinc negative electrode, a separator, a manganese dioxide positive electrode, an alkaline electrolyte and a cell container; wherein the zinc electrode consists of 50.0wt% zinc (nano/micro zinc, electrolytic zinc and molten zinc), 36.0wt% carbon black, 2.0wt% ZnO and 2.0wt% in 2 O 3 And 10wt% Polytetrafluoroethylene (PTFE) emulsion; the manganese dioxide positive electrode comprises gamma-MnO 2 Nanotube/nanowire, activated carbon, said gamma-MnO 2 The content of the nanotube in the nanotube/nanowire is 40-50%, the length of a single nanotube/nanowire is 2-4 μm, and the diameter is 75-85nm; the anode material formula is selected from the following components in percentage by mass: 85% gamma-MnO 2 Nanotube/nanowire, 8% of activated carbon and 7% of electrolyte; the instrument used was a Parstat2273 electrochemical workstation (princetonappplied research)&AMTECT company) and Arbin (2001-T) in the United states of America, the electrolyte for the batteries was 2.5wt% KOH solution.
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