CN1581567A - Solid polymer Zinc-air cell preparing method - Google Patents
Solid polymer Zinc-air cell preparing method Download PDFInfo
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Abstract
In the disclosed battery, oxygen in air is as active material of anode; zinc powder is as active material of cathode; alkali solid-state polyelectrolyte replaces traditional PP/PE barrier film made from nonwoven fabric and KOH electrolyte. Oxygen in air dissolved in KOH electrolyte is diffused and adsorbed by 'carbon electrode'. Electrochemical reaction is generated in interface between catalyst from 'carbon electrode' and electrolyte so that reduction reaction happens. Current can be generating continuously since oxygen is supplied from air. Alkali solid-state polyelectrolyte prevents issues of leakage and short circuit. The invention raises discharge capacity, use rate and energy density.
Description
Technical Field
The invention relates to a manufacturing technology of a battery, in particular to a manufacturing method of a solid-state air battery.
Background
The energy is the power of national economicdevelopment, and also is an important index for measuring comprehensive national power, the development degree of national civilization and the standard of people's living, and the history of social progress shows that each innovative breakthrough of energy technology brings great and profound revolution to the development of productivity and social progress, and proves that the energy technology is very important and has important influence on emerging industries in the future.
For the twenty-first century, environmental protection has become a topic of great concern to human society, is the core of a continuous development strategy, is a key factor influencing energy decision and technology guidance of countries in the world at present, and is a great driving force for promoting energy technology development, a huge energy system established in the 20 th century cannot meet the requirements of the future society on efficient, clean, economic and safe energy bodies, and energy development faces a great challenge.
The production and consumption of energy and global climate change are closely related to the global greenhouse effect. The greenhouse effect is caused by more than half of the current energy sources from the world, namely carbon dioxide released after the carbon-containing petroleum fuel is combusted. The energy provided by such fuels accounts for approximately four fifths of the world's energy, and is currently increasing continuously at 3% per year. Therefore, the emission amount of carbon dioxide also increases at the same rate. It is expected that this will increase nearly 2-fold by 2002 and 3-fold by 2025. Therefore, the improvement of the utilization rate of energy and the development of alternative energy are important issues in the 21 st century.
The human society has developed to date, and most of the energy conversion is achieved by a heat engine process. The heat engine process is limited by the Carnot cycle, not only the conversion rate is low, and the energy waste is caused, but also a large amount of dust, carbon dioxide, nitrogen oxide, sulfur oxide and other harmful substances and dry noise are generated. The pollution of the atmosphere, water quality, soil and the like caused by the pollution seriously threatens the living environment of human beings.
Disclosure of Invention
In order to solve the problems, the invention provides a solid polymer zinc-air battery which is based on an electrochemical process and is the most effective energy conversion method for converting chemical energy into electric energy.
Another objective of the present invention is to replace the conventional liquid KOH electrolytic solution and isolation film with the solid polymer electrolyte in the present invention, so that the battery will not leak, and can be applied to the characteristic requirements of 3C electronic products, i.e. light, thin, short, and small.
The zinc powder material used by the zinc electrode is used for preparing the high-surface-area dendritic zinc powder by an electrolysis method, and has the advantages of higher power, large-current discharge, high zinc utilization rate and the like; the solid polymer zinc-air battery has very high volume energy and weight energy density under various condition tests.
Drawings
FIG. 1 is a scanning electron microscope for observing the microscopic state of the solid-state PVA-glass fiber polyelectrolyte prepared by the present invention;
FIG. 2 is a process of preparing glass fiber cloth and polyvinyl alcohol polyelectrolyte;
FIG. 3 shows the electroplating current density of 250mA/cm2, SEM magnification of 200X;
FIG. 4 shows the electroplating current density 250mA/cm2, SEM magnification 500X;
FIG. 5 shows the electroplating current density of 250mA/cm2, SEM magnification of 3000X;
FIG. 6 is a graph showing the X-ray diffraction absorption spectrum of anodic zinc powder in a typical zinc/air cell;
FIG. 7 is an X-ray optical diffraction absorption spectrum of the electrolytic dendritic anode zinc powder of the present invention;
FIG. 8 is a flow chart of the preparation of the dendritic zinc powder of the present invention;
FIG. 9 shows a process for preparing zinc anode colloid according to the present invention;
FIG. 10 is a schematic view of an air electrode configuration of the present invention;
FIG. 11 is a flow chart of the preparation of the diffusion layer in the air electrode according to the present invention;
FIG. 12 is a simplified flow chart of the preparation of the air electrode (including the active layer) according to the present invention;
FIG. 13 is a schematic diagram of an electrical test of the air electrode of the present invention;
FIG. 14 is a schematic structural view of a solid-state polymer zinc-air battery according to the present invention;
FIG. 15 is a graph showing the AC resistance of solid alkaline polyvinyl alcohol polyelectrolyte under different temperature environments;
FIG. 16 is an Arrhenius diagram of a solid basic polyvinyl alcohol polyelectrolyte;
FIG. 17 is a voltammogram of electrochemical cycling of solid polyvinyl alcohol polyelectrolyte at different temperatures;
FIG. 18 is a graph showing the effect of placement time on the conductivity of a solid polyvinyl alcohol polyelectrolyte;
FIG. 19 is a graph of the potential versus time for electrolytic zinc for the preparation of zinc powder (at constant current density);
FIG. 20 is a plot of polarization for an air electrode at different temperatures;
FIG. 21 is a graph comparing the AC resistance and impedance of air electrodes at different ambient temperatures;
fig. 22 is a graph comparing the discharge curves of different air cells (using different separators);
FIG. 23 is a scanning electron microscope for observing the microscopic state of PP/PE separator used in a conventional Zn-air battery;
FIG. 24 is a scanning electron microscope for observing the microscopic state (15,000 times) of the solid polyvinyl alcohol alkaline polyelectrolyte film prepared by the present invention;
FIG. 25 is a graph of the discharge of a polymeric zinc-air cell at different rates;
fig. 26 is a graph of discharge curves of a solid polymer zinc-air battery under different temperature environments;
fig. 27 is an ac resistance impedance analysis chart of the solid polymer zinc-air battery at different temperatures.
Detailed Description
[ preparation of solid alkaline polyelectrolyte]
With the development of polymer batteries, new technologies are developed, so that different types of polymer batteries are increased. Meanwhile, due to the expansion of the field of 3C products, thinner, lighter and smaller batteries also become the mainstream of the market. The battery using solid polymer as solid electrolyte has good advantages in safety, processability and high temperature use, because there is no worry that the reduction of electrolyte in the isolating film affects the battery performance because of improper packaging of the electrolyte or because of too long storage time of the battery, and the battery can have better performance when used at high temperature, which is the important breakthrough of the future battery development of the solid polymer battery.
Polyvinyl alcohol (PVA) is a water-soluble polymer compound.
The glass fiber cloth is silicon dioxide (SiO)2) The fused body of (2) has a soft property and the tensile strength is increased by tens of times. The reinforcing material for the composite material is usually in the form of very fine fibers, which are not sufficient to secure strength and impart excellent flexibility, becauseNo residual stress is generated in any shape of the product.
The reinforcing material of the glass fiber material has the following characteristics:
1) has extremely high tensile strength: at the same mass, the tensile strength is twice that of steel wire.
2) Dimensional stability: under the action of maximum stress, the elongation change of the unit size is only 3-4%.
3) Higher thermal resistance: at the temperature of 343 ℃, the tensile strength of the material still keeps 50 percent of the original tensile strength.
4) Excellent in resistance to chemical corrosion: has excellent erosion resistance when reacting with most chemicals.
5) Fire resistance: will not burn (generate heat) and will not smolder (smoke).
The polyvinyl alcohol alkaline polymer electrolyte has high ionic conductivity after being processed, but has the defects of relatively tough structure and poor mechanical strength compared with the common PP/PE isolating membrane. Therefore, the glass fiber is added during the preparation process, so as to greatly improve the mechanical strength and the thermal stability of the polyvinyl alcohol alkaline polymer film, the strength is more than five times of the mechanical strength of a common isolation membrane, and the glass fiber cloth has no influence on the conductivity of the polymer, so that the problem of long-term storage shrinkage of the polyvinyl alcohol alkaline polymer film can be solved in terms of time variation. The polyvinyl alcohol alkaline polymer film added with the glass fiber cloth has relatively high mechanical strength, is not easy to deform in processing, battery charging and discharging and battery packaging, and has no large holes on the surface but many small holes of 0.1-0.2 mm as shown in figure 1 after being discovered by a scanning electron microscope. Therefore, when the zinc-air battery is applied to the zinc-air battery, the short circuit caused by the fact that zinc ions penetrate through the isolating membrane and enter the cathode air electrode to cause the reduction of the service life of the battery can be isolated when anode zinc is discharged. Moreover, since the KOH electrolyte is impregnated in the PVA polymer structure and maintains the solid gel state, the problem of battery leakage corrosion caused by the leakage of the common liquid electrolyte can be solved, and the solid alkaline polymer electrolyte has high conductivity and electrochemical stability.
The preparation method of polyvinyl alcohol solid electrolyte of the invention is that under the condition of specific polymerization reaction, potassium hydroxide, water and glass fiber cloth are added to prepare solid alkaline electrolyte, and at normal temperature, the conductivity of PVA polymer solid electrolyte can reach 10-1S/cm, also shows that the alkaline solid polymer electrolyte is applied to zinc-air batteries, the battery performance effect is better than that of the PP/PE isolating membrane used in the zinc-air batteries on the market, and the application range can be used for preparing electrolyte membranes with different thicknesses, sizes and shapes according to different required sizes, capacities, voltages and the like.
The program comprises five steps: selecting raw materials of polyvinyl alcohol and potassium hydroxide, and respectively reacting the polyvinyl alcohol and the potassium hydroxide with water; adding a potassium hydroxide aqueous solution according to the complete water dissolution degree of the polyvinyl alcohol, and controlling certain reaction temperature and time; (III) according to the reaction time and the dissolution situation of the mixed solution, terminating the reaction, taking out the polymer solution which is polymerized into different quantities, coating the polymer solution on a bearing container or a fiber cloth, and controlling the required film thickness; fourthly, controlling the film forming time, temperature and humidity of the polymer film so as to control the proper water content in the polymer electrolyte film; and (V) testing the electrochemical properties of the solid alkaline polymer electrolyte membrane.
The procedure for the preparation of the polyvinyl alcohol polyelectrolyte is described below:
(I) selection and pretreatment of raw materials
The raw material is polyvinyl alcohol polymer with purity of 80-99%, the average molecular weight is 2,000-120,000, preferably 5,000-100,000, and it can participate in the reaction no matter it is granular or powder. The purity of the potassium hydroxide is 85%, and the potassium hydroxide can participate in the reaction whether the potassium hydroxide is granular or powdery.
(II) reaction sequence of reactants
The reaction proportion and the reaction sequence of reactants can directly influence the property of the polymer film, and whether the polymer film is formed or not is critical, if the weight percentage of the polyvinyl alcohol is too high, the dissolution is difficult and the conductivity is reduced, and if the weight percentage is too low, the polymer film cannot be formed. If the weight percentage of potassium hydroxide is too high, the structure is deteriorated and even the film cannot be formed. Feeding both at the same time will result in both being insoluble. Therefore, the ratio of the reactants and the order of dissolving the reactants are important for the production of the polymer film. The invention selects 10-20 wt% polyvinyl alcohol, stirs and mixes with 50-60 wt% water under normal temperature and closed environment, can dissolve completely in about two hours, adds 15-25 wt% potassium hydroxide water solution, and adds 10-20 wt% pure water under normal temperature and closed environment to fully mix and dissolve.
(III) control of the conditions of the polymerization reaction
The temperature and time control of the polymerization reaction will affect the moisture composition of the polymer electrolyte membrane, the higher the moisture content is, the higher the ionic conductivity is, but the polymerization reaction must be carried out at a certain reaction temperature without phase separation, and the shorter polymerization time and the loss of moisture are controlled. The invention mixes two completely dissolved polyvinyl alcohol aqueous solutions and potassium hydroxide aqueous solutions at normal temperature, white solid is generated at the moment, the white solid and the solutions are fully stirred, the two mixed solutions are heated in a closed container at 50-100 ℃, oxides with small particle size, such as g-Al2O3, TiO2, ZrO2, SiO2 and the like, can also be added at the moment to improve the physical property and the chemical property of high molecules, the reaction lasts for about 30 minutes, the solid is completely dissolved, and the solution can be cooled in the atmosphere. The cooled alkaline polymer electrolyte is coated on a carrier film (such as glass fiber cloth or PTFE film) according to the desired film thickness.
(IV) film Forming conditions
Cutting glass fiber cloth into a proper size, placing on a bearing plate, paving, pouring the solution containing the polymer liquid into the bearing plate, and coating by a coating rod according to the required film thickness. And placing the bearing disc into a constant temperature and humidity box, and controlling the temperature to be between 40 and 80 ℃ and the humidity to be between 30 and 50RH percent. The optimum film forming conditions are 50-60 ℃ and 20-30 RH% humidity for about 30-60 minutes to form the solid polymer electrolyte film. Taking out the bearing disc and placing the bearing disc in the atmosphere, and after heat balance is carried out for 30 minutes, the solid polymer film can be easily taken down.
(V) testing the Electrical Properties of the Polymer films
(1) And (3) testing the conductivity:
the solid polymer electrolyte is analyzed by an Autolab FRA alternating current impedance analyzer, and the resistance is measured by a two-pole stainless steel electrode. The frequency sweep range is between 100kHz and 0.1Hz, and the amplitude (amplitude) is 10 mV. The film thickness was measured and the conductivity was measured with an electrical impedance measuring instrument (AUTOLAB FRA). The calculation formula is [ σ ═ 1/(Rb × a)]. The impedance value of the left high-frequency region in the Nyquist diagram is zero on the-Z "axis (Capacitance) and intersects the Z '-axis, (Z' ═ Rb), which is the resistance value of the polymer film.
(2) Electrochemical stability test
The cyclic voltammogram of the polyelectrolyte and different types of isolation membranes was scanned by Autolab GPES with a potential range of-1.5 to 1.5V and a scanning rate of 1mV/s, and a stainless steel electrode (SS-316) was used as the working electrode.
(3) Battery electrical property test
The solid polyvinyl alcohol polyelectrolyte prepared by the method is matched with a zinc electrode (-) and an air electrode (+) to assemble the zinc-air battery, and the area of the electrode is about (2 multiplied by 3cm, 6 cm)2) And respectively carrying out discharge tests at constant currents of 50mA, 100mA and 200mA, and simultaneously carrying out performance comparison analysis by matching with different isolating membranes and solid electrolytes.
(4) Calculation of chemical composition of PVA film
And calculating the chemical composition ratio of the PVA film before and after reaction by using a weight difference method.
(5) Calculation of activation energy
From the Arrhenius Plot (Plot log (. sigma.) vs.1/T), the slope was determined and the activation energy (Ea) was calculated.
σ＝σoexp(-Ea/RT)
logσ＝logσo-′Ea/(2.303×1000R)×1/T (1)
The whole process flow of preparing the solid alkaline PVA (containing glass fiber cloth) electrolyte is shown in FIG. 2.
[ preparation of Zinc Anode]
Zinc-air cells can replace existing alkaline cells by a high energy density primary cell, where zinc powder plays the most important role, and factors such as capacity, high current density, flat discharge voltage, cell self-discharge rate, and cell cost determine the conditions for cell performance. In order to improve the utilization rate of the existing zinc powder, the invention aims to develop the dendritic zinc powder, because the dendritic zinc powder has the advantages of good ductility, large specific surface area, small particle size of particles and the like. The zinc electrode is converted into zinc oxide by the zinc powder after discharging, and the dendritic zinc powder can also be recycled and prepared, so that the discharging power and energy of the battery can be improved, the zinc powder is recycled by electrolyzing the zinc oxide, the raw material cost can be reduced, and the pollution to the environment can be reduced. In view of the above, the present invention provides a zinc powder plated with a dendritic form, which is obtained by dissolving zinc oxide in an alkaline potassium hydroxide solution and electrolyzing the zinc powder under specific conditions. The process control variables are many: such as current density, concentration of zinc oxide in the electrolyte, temperature, mass transfer conditions, additives and drying time, it is necessary to obtain zinc powder active material with the most suitable characteristics under specific operating conditions.
In order to make zinc-air cells amenable to this development, zinc powder is the key to determining the maximum lifetime and performance of the cell. Because the zinc powder applied to the battery in the market has the particle size of about 300-600 microns and wide distribution, the battery cannot work under the heavy current load state and the utilization rate is obviously reduced. The method for preparing the dendritic zinc powder with high specific surface area and low density is provided, the preparedzinc powder can be applied to alkaline batteries, zinc-air batteries, batteries of zinc systems (such as nickel zinc and the like), and the like, and zinc oxide of the zinc powder can be recycled into the dendritic zinc powder, so that the improvement of the battery performance, the reduction of the battery production cost, the environmental protection and the like are facilitated.
[ PRODUCTION PROCESS OF GRADED ZINC POWDER]
Solubility test of zinc oxide
The method comprises the steps of dissolving zinc oxide with different percentages in 1-10M KOH solution, measuring the solubility of the zinc oxide at the temperature of 25-60 ℃ and under the humidity of 50-80 RH%, wherein the solubility of ZnO in KOH is limited by thermodynamic balance and has a certain solubility, and the solubility of ZnO in the KOH solution is about 7% according to experimental results, so that the dendritic zinc electroplating is prepared by using 7 wt% of ZnO electrolyte in the zinc electrolysis experiment.
Solubility of (di) zinc oxide
Taking out oxidized zinc anode from zinc-air cell, mechanically separating zinc oxide powder from current collector, dissolving the zinc oxide in KOH solution to obtain K2Zn(OH)4An aqueous solution.
(III) preparation of dendritic zinc powder
Will K2Zn(OH)4Aqueous solution, in specific different stripsElectrolyzing the zinc powder into dendritic zinc powder at different temperatures (30 ℃, 50 ℃ and 70 ℃) at a constant current density of 100-250 mA/cm2Electroplating is carried out, and the temperature has great influence on the structure of the electroplated zinc powder. When the temperature is higher, the powder particles are larger, and the electrolysis efficiency is higher.
At 250mA/cm2The zinc powder has a dendritic structure at the lower current density, as shown in fig. 3 to 5. Fig. 6 and 7 compare XRD analysis patterns of a typical zinc powder and a dendritic zinc powder.
(IV) treatment after electrolysis
The treatment after electrolysis has a great influence on the dendritic zinc powder, if the KOH electrolyte remained on the surface of the zinc powder is not cleaned, the zinc powder is oxidized into zinc oxide in the drying process, the previous work is abandoned, therefore, the treatment after electroplating needs to be carefully treated, the zinc powder after electroplating is scraped from a cathode, is cleaned by ultrapure water, is vibrated for 30 minutes by ultrasonic waves and filtered, and is repeatedly washed, so that the zinc powder is fully cleaned to avoid the oxidation problem caused by the remaining electroplating solution remained in the zinc powder. And packaging the dried zinc powder by a chain belt, and placing the packaged zinc powder in a drying box to avoid zinc oxidation. FIG. 8 is a flow chart of the preparation of the whole porous high surface area dendritic zinc powder.
(V) preparation of Zinc Anode gel
Weighing a proper amount of indium acetate (in (Ac)3) inhibitor, adding the inhibitor into the KOH solution, and stirring to uniformly disperse the inhibitor. And adding dendritic zinc powder in a proper proportion into the colloidal solution prepared in the step. Adding proper amount of zinc oxide powder (ZnO) according to the design requirement of the experiment. The solution was placed in a sonic shaker for one hour. A proper amount of polyacrylic acid-based polymer gelling agent (gelling agent) was added and stirred uniformly to form a high-viscosity gel, and the completed zinc anode was prepared for battery assembly electrical property test, and the manufacturing flow is shown in fig.9.
[ preparation of air electrode]
The zinc-air cell needs an effective air electrode to function, and the present invention aims toThe technology of thin solid polymer air electrode with high efficiency is mainly researchedIncluding development of better catalysts, longer life electrode structures, low manufacturing costs, etc. FIG. 10 is a schematic view of an air electrode. The air electrode is made by pressing active carbon as diffusion layer, nickel net and catalyst layer together, and the anode is separated by isolating film to avoid short circuit. The diffusion layer is composed of hydrophobic activated carbon and a nickel net power collecting net, and the catalyst layer is made of hydrophilic carbon powder and a catalyst (KMnO)4Or MnO2) And (4) preparing.
Since oxygen in the air itself cannot be used as an electrode to accept electrons for cathodic reduction, the reaction is carried out by a carbon electrode made of activated carbon as a carrier. The carrier activated carbon does not participate in the electrode reaction but provides a site for cathodic reduction with oxygen. Oxygen molecules dissolved in the solution diffuse to the surface of the carbon electrode, and then electrochemical reduction is carried out on the carbon surface three-phase region. Air electrodes are less active in acidic and neutral media, and electrode materials and catalysts are easily corroded in acidic materials, so air electrodes working in alkaline electrolytes are widely used at present.
The electrochemical reduction reaction of oxygen in alkaline electrolyte is as follows:
since the exchange current density io of the oxygen electrode is small, it is difficult to establish an equilibrium potential, and thus the electric polarization is severe when a load is applied.
The air electrode takes a carbon electrode as a main body, oxygen is dissolved and adsorbed on the surface of the carbon electrode to carry out electrochemical reaction, but because the solubility of the oxygen in an alkaline solution is very low, in order to improve the working current density of the zinc-air battery and reduce polarization, on one hand, the real surface area of the electrode is increased, and on the other hand, the thickness of a boundary layer of liquid phase transfer is reduced. Porous diffusion electrodes have been developed to meet this requirement. It is a very important issue that the stability of the reaction zone (usually called the three-phase interface) should be maintained inside the porous gas diffusion electrode. In the bonded gas diffusion electrode, a three-phase interface is stabilized by using a water repellent agent (e.g., polytetrafluoroethylene) in order to impart a certain level of water repellency to the electrode. The content of polytetrafluoroethylene is usually 5 to 10 wt%. However, the addition of the hydrophobic agent in too large an amount will reduce the conductivity of the electrode and affect the performance of the battery. For zinc-air batteries using solid electrolytes, such as polyvinyl alcohol alkaline solid polymer electrolytes, solid oxides can be added to the electrolyte to improve the interfacial stability.
The gas diffusion electrode is an electrode which has a certain porosity and a high specific surface area and can form a stable gas, liquid and solid three-phase interface system, so that the reaction mechanism is relatively complex and generally comprises the following steps:
dissolution of gas → diffusion → adsorption → electrochemical reaction → diffusion of reactants into solution.
Generally speaking, one side of the air electrode is gas, the other side is electrolyte, the liquid of the three-phase interface forms a meniscus on the capillary on the electrode, and the meniscus is adhered to the electrode surface to form an extremely thin film, the solubility and diffusivity of the gas in the liquid are very low, but the liquid film is extremely thin, so the oxygen can penetrate through the film to reach the electrode at normal speed, the gas, liquid and solid three-phase interface inside the electrode is stable, the capillary of the electrode is required not to be completely filled with the electrolyte, and the electrolyte is prevented from being blocked and not entering the capillary.
However, in order to establish a stable three-phase interface region by making the pores on the electrode surface neither completely "dry" nor completely "wet", a water-proof material is added to the electrode to change the contact angle of the electrode surface, so that the "gas diffusion electrode" has a three-layer structure including at least a "water-proof layer", a "power collecting network" and an "active layer".
The preparation method of the air electrode of the present invention is explained as follows:
(I) diffusion layer preparation process
1. Firstly, weighing proper amount of Triton-X, PTFE-30 and H2O, mixing them uniformly, and putting the mixture and the container into an ultrasonic oscillator to vibrate for 10 minutes (to make the PTFE and H mix)2Mixing O and Triton X uniformly);
2. adding AB50 carbon powder, stirring by hand, and drying in oven at 120 deg.C (H is required) after ultrasonic vibration for 30min2O is completely expelled);
3. the dried raw materials are tangled together, are uniformly ground and weighed, and the diffused raw materials are weighed according to the air requirement;
4. placing the nickel screen on a mould, and uniformly coating the raw materials on the nickel screen;
5. and (3) placing the die in a hot press, and sintering under constant pressure according to parameter requirements (time, temperature and thickness). After the completion, the high-temperature die is sent to a cooling machine to be kept under pressure for cooling, and the diffusion layer is taken out to be sprayed with the catalyst layer. (refer to FIG. 11)
(II) preparation of air electrode active layer
1. XC-72R carbon powder is weighed firstly, and proper amount of KMnO is added4A catalyst.
2. Weighed PTFE-30 and H2O, ultrasonic vibration for 5 minutes (reacting PTFE with H)2O mixed well).
3. Adding the step 1 into the step 2, and stirring with the assistance of ultrasonic oscillation.
4. Adding proper amount of Methanol and Propanol. And stirred by hand and shaken with ultrasonic assistance for 30 minutes (liquid, for spraying). Sprayed on the diffusion layer according to the required amount.
5. And (4) sintering at high temperature after drying, cooling under constant pressure, and taking out the air electrode. (refer to FIG. 12)
(III) testing the electrical properties of the air electrode
The electrical property of the air electrode can be scanned from E DEG C V to the cathode potential direction to obtain the electrode polarization curve (I-V polarization curve). The test is set to seal two ABS plates on the two outer sides of the air electrode respectively, so that the reaction area is controlled to be 1cm2The current density (mA/cm) of theair electrode at different potentials was measured2) The test structure of the three-pole air half-electrode is shown in fig. 13.
[ Assembly of solid Polymer Zinc-air Battery]
The solid alkaline polyvinyl alcohol polymer electrolyte, the cathode zinc gel and the anode air electrode which are developed by the invention are assembled into a polymer zinc-air battery. The solid polymer zinc-air battery assembled by the invention is assembled into a flat plate type (passive type), and can be applied to 3C electronic products such as mobile phones, PDA, PHS and the like. In order to determine the performance of the developed zinc-air polymer battery, the present invention will discuss the electric effect of temperature effect on the battery, the electric effect of different isolating films on the battery and the influence of discharge rate on the battery performance. Fig. 14 is a schematic structural diagram of a homemade solid polymer zinc-air battery.
The electrochemical reaction formulas of the positive electrode and the negative electrode in the solid polymer zinc-air battery are as follows:
negative electrode:
and (3) positive electrode:
the battery full reaction:
examples
Example 1 Synthesis of glass fiber polyvinyl alcohol solid Polymer electrolyte
Accurately weighing 8.0g of PVA and 40g of water according to different proportion formulas, putting the PVA and the water into a reactor, weighing and recording the PVA, the water and a stirrer together, and stirring for one hour at normal temperature to completely dissolve the PVA and the water. 12.5g of KOH were dissolved in 10g of water and poured into the reactor. The reactor was warmed to 70 ℃ and polymerization time was controlled within 30 minutes. The reacted reactor together with the polymer therein is weighed and recorded, and the viscous polymer solution is coated on glass fiber, the weight is fixed (about 5-10 g of polymer solution), and the reactor is placed in a constant temperature and humidity box (controlled at 40 RH% and 60 ℃) for one hour. Taking out and placing in the atmosphere for one hour, taking down the polymer film, weighing, calculating the proportion of the components after drying, and storing in a chain clamping belt.
Taking the PVA composite polymer film, measuring the film thickness by a thickness meter, measuring the conductivity by an electrochemical impedance analyzer AUTOLAB FRA (two-pole stainless steel electrode), and measuring a cyclic voltammogram by AUTOLABFRA. The results of the electrical impedance analysis are shown in FIG. 15, while the results of Arrhenius Plot are shown in FIG. 16. As can be seen from FIG. 8, the conductivity of the polyvinyl alcohol polyelectrolyte obtained in this example at room temperature was about 0.1408S/cm, and the activation energy of the reaction was about 10kJ/mole, which is much lower than the activation energy of polyethylene oxide polyelectrolytes proposed by M.B. Armand, which is 22-30 kJ/mole. The results are shown in Table 1 as the change in conductivity of the compounded polyvinyl alcohol at different temperatures. From the cyclic voltammogram scanned in FIG. 17, it can be seen that the PVA polyelectrolyte obtained in this example has no oxidation and reduction reaction within the working voltage stability range of-1.4 to 1.4V, i.e. no Faraday current flow, and has very good electrochemical stability, and is more stable than the commercially available PP/PE separation film (voltage stability range of-1.0V to 1.0V) and cellulose separation film (voltage stability range of-1.2 to 1.2V), and has a wider electrochemical voltage range (2.8V window range).
TABLE 1 values of conductivity of solid polyvinyl alcohol polyelectrolyte at different temperatures
| Parameter T (. degree. C.) | Impedance (ohm) | Conductivity (S/cm) |
| -20 | 1.1663 | 0.0765 |
| -10 | 1.1201 | 0.0796 |
| 0 | 1.0542 | 0.0846 |
| 10 | 0.9294 | 0.0959 |
| 20 | 0.6335 | 0.1408 |
| 30 | 0.5616 | 0.1588 |
| 40 | 0.4829 | 0.1847 |
| 50 | 0.4364 | 0.2043 |
| 60 | 0.3925 | 0.2272 |
| 70 | 0.3474 | 0.2567 |
| 80 | 0.3324 | 0.2683 |
The PVA composite polymer film is put into a chain clamping belt and placed in an environment with the temperature of 25 ℃ and the RH of 60 percent to test the influence of the change of time on the conductivity every other week under the environment condition of fixed room temperature. As is clear from FIG. 18, the change in conductivity was not significantly affected by the change with time, and was maintained at about 0.1S/cm. Therefore, the result shows that the polyvinyl alcohol polyelectrolyte containing glass fiber cloth has excellent stability. Table 2 lists the conductivity of the PVA solid electrolyte at different times.
TABLE 2 conductivity values of solid polyvinyl alcohol polyelectrolyte
| Number of days
Degree of | 7 | 14 | 21 | 28 | 35 | 42 | 49 | 56 |
| s (S/cm) | 0.1413 | 0.1394 | 0.1402 | 0.1387 | 0.1396 | 0.1411 | 0.1408 | 0.1401 |
EXAMPLE two preparation of dendritic Zinc powders
Selecting nickel plate as cathode and anode plates, dissolving 7 wt% ZnO in 8M KOH aqueous solution, and heating at different temperatures (30 deg.C, 50 deg.C, 70 deg.C) at different current densities of 50mA/cm2、100mA/cm2、200mA/cm2、250mA/cm2Electroplating was carried out for one hour. The influence of post-treatment of the electroplated zinc powder on the dendritic zinc powder is great, and the electroplated zinc powder is scraped from a cathode, cleaned by ultra-pure water and cleaned by ultrasonic wavesVibrating for 30 minutes, filtering, repeatedly washing, and fully cleaning the zinc powder to avoid the oxidation problem caused by the residual electrolyte remaining in the zinc powder. And packaging the dried zinc powder by a chain belt, and placing the packaged zinc powder in a vacuum drying oven to avoid zinc oxidation.
FIG. 19 is a graph showing the change of potential with respect to time of a zinc powder at a constant current. The VS time diagram of the electrolysis potential shows that the higher the current density of the electrolysis, the more the potential drop is, i.e. the more the polarization is, the more the energy consumption is. Table 3 shows the results of (%) comparison of the efficiencies of zinc powders at different current densities, which werefound to be 200mA/cm2The efficiency (84.70%) of lower electrolytic zinc powder is highest, and the energy consumption is also lower. The density of the zinc powder is less than 7.13 (g/cm)3) At 4.8 to 5.4 (g/cm)3) In between, mainly the porous dendritic zinc powder structure has very high specific surface area.
TABLE 3 comparison of the efficiencies (%) of zinc powders at different current densities
| Parameter(s) I(mA/cm2 ) | Theoretical zinc Powder weight (g) | Actual zinc Powder weight (g) | Faraday Coulomb efficiency | Zinc powder density (g/cm3) |
| 100 | 0.7308 | 0.3745 | 51.24％ | 4.76 |
| 166 | 1.2180 | 0.7046 | 57.85％ | 5.08 |
| 200 | 1.8270 | 1.5482 | 84.70％ | 5.26 |
| 250 | 1.4616 | 1.1239 | 76.89％ | 5.42 |
EXAMPLE III preparation of Zinc gel electrode
Weighing 1% indium acetate inhibitor, adding 7MKOH solution, and stirring to uniformly disperse the inhibitor. Mixing 20 wt% of dendritic zinc powder and 80 wt% of zinc alloy powder, and adding the solution prepared in the step. The solution was placed in a sonic shaker for one hour. Adding proper amount of polyacrylic acid as high molecular gelling agent (such as CMC, PVA and Capobol) into the above solution, stirring to obtain colloid, and preparing the finished zinc anode for zinc-air battery assembly and electrical property test.
EXAMPLE four preparation of air electrode
Firstly, weighing proper amounts of Triton-X, PTFE-30 and H2O, mixing them uniformly, and putting the mixture and the container into an ultrasonic oscillator to vibrate for 10 minutes (to make the PTFE and H mix)2O, Triton X mixed well). Adding weighed acetylene black AB50 carbon powder, stirring, assisting ultrasonic vibration for 30 minutes, and placing in an oven for drying at 120 ℃ (H is required)2O is completely expelled). The dried raw materials are tangled together at this time, and are uniformly ground and then uniformly coated on a nickel screen placed in a die. And (3) placing the die in a hot press, and sintering under constant pressure according to parameter requirements (time, temperature and thickness). And after the diffusion layer is finished, the high-temperature die is conveyed to a cooling machine to be kept under pressure for cooling, and the prepared diffusion layer is taken out. Weighing XC-72R carbon powder and adding a proper amount of KMnO4Or MnO2A catalyst. At the same time weighing PTFE-30 and H2O and are reacted withUltrasonic vibration for 5 minutes (reacting PTFE with H)2O mixed well) to form an aqueous PTFE solution. Mixing carbon powder and KMnO4The powder is poured into PTFE aqueous solution, and is stirred with the assistance of ultrasonic vibration. Adding proper amount of methanol and isopropanol. Stirring and ultrasonic-assisted shaking for 30 minutes (liquid state for spraying). Sprayed on the diffusion layer according to the required amount. And (3) placing the sprayed test piece in an oven, sintering at 350 ℃ for 20-30 min, cooling under constant pressure, and taking out the air electrode.
And (4) carrying out electrical test on the air electrode to know the performance of the air electrode. The electrical property of the air electrode is scanned from the open circuit voltage (E DEG C V) to the cathode potential direction to obtain the polarization curve (I-V curve) of the electrode. When the test is carried out, two ABS plates are respectively sealed on the two outer sides of the air electrode, so that the reaction area is controlled to be 1cm2, and the current density (mA/cm2) of the air electrode under different potentials can be expected to be more accurately measured. The results are shown in fig. 20 and 21. The higher the temperature, the higher the polarization current of the air electrode and the lower the resistance (Rb), which represents the better performance of the electrode, and the Rb value is about 0.6-0.7 ohm.
EXAMPLE V preparation and Performance testing of Zinc air cells
Comparison of different separators:
2.5g of zinc gel (zinc gel) containing 70 wt% of zinc powder is weighed as a negative electrode, a PP/PE isolating membrane and a cellulose isolating membrane are matched with the prepared air electrode as a positive electrode to assemble the zinc-air battery, meanwhile, the PVA-glass fiber film electrolyte of the embodiment is taken to replace the PP/PE and the cellulose isolating membrane to assemble the solid polymer zinc-air battery, and the discharge electrical property comparison is carried out. The theoretical capacity of the battery is 1500 mAh. At normal temperature, the discharge was carried out at a rate of C/10 (150mA), and the test results are shown in FIG. 22. Table 4 compares the results of the electrical tests of zinc-air cells for various electrolytes. From the C/10 discharge rate in FIG. 22, it can be seen that the discharge time of the zinc-air battery using PP/PE as the separator was 7.8 hours, and the utilization rate was 75%. The discharge time of the zinc-air battery using cellulose as the isolating film is 8.2 hours, and the utilization rate is only78.85% was obtained, but the discharge time of the zinc-air battery using the PVA-glass fiber membrane electrolyte of example one as the separator was 8.7 hours, and the utilization rate was as high as 83.65%. The utilization rate is so different because the pores of the PP/PE or cellulose isolating film used in the alkaline battery in the market have a size of about 20-30 μm as shown in FIG. 23, when the battery is discharged, Zn will expand to ZnO after the discharge of the zinc anode, and enter into the other electrode along the pores of the isolating film due to the expansion and extrusion of the electrodes to cause short circuit, but the pore size of the PVA solid electrolyte is about 0.1-0.2 μm as shown in FIG. 24. The pore diameter is small, and Zn (OH) can be blocked4 2-To avoid short circuits. However, when the composite PVA film electrolyte is used as a separator, it is formed by temporary coordination polymerization by dipole action force generated by polymer chains and metal ions, and then ion conduction by the flexibility of the chains, so the expansion of the zinc electrodeBecause of the PVA film, short circuit is not caused, and the utilization rate is higher than that of the common isolation film.
TABLE 4 comparison of the results of the electrical tests of zinc-air batteries with various electrolytes
| Battery item |
Zn-air+
PP/ | Zn-air+ Cellulose | Zn-air+ PVA(GF)Soli d polymer electroly te |
| Theoretical capacity (mAh) | 1560 | 1560 | 1560 |
| Discharge current (mA) | 150 | 150 | 150 |
| Time of discharge (hrs) | 7.8 | 8.2 | 8.7 |
| Actual capacity (mAh) | 1170 | 1230 | 1305 |
| Utilization (%) | 75 | 78.85 | 83.65 |
(II) comparison of Electrical Properties at different discharge rates
2.5g of zinc gel (zinc gel) containing 70 wt% of zinc powder was weighed as a negative electrode, the prepared air electrode was used as a positive electrode, and the PVA-glass fiber membrane electrolyte of the first example was used as an isolating membrane to assemble a zinc-air battery for comparison of discharge electrical characteristics. The theoretical electric quantity of the battery is 1500 mAh. At normal temperature, the discharge is carried out at a C/5 rate, the zinc electrode utilization rate can reach 82.88 percent, the discharge is carried out at a C/10 rate, the zinc electrode utilization rate can reach 89.9 percent, the discharge is carried out at a C/20 rate, and the zinc electrode utilization rate can reach 91.37 percent. There is fig. 25 which is a graph of battery discharge. Table 5 compares the results of the tests at different c-rates. The zinc-air battery prepared by the invention can achieve the utilization rate of more than 80% no matter at high discharge rate or low discharge rate, and is a primary battery with competitive power in the market.
TABLE 5 comparison of the results of the tests at different c-rates
| Rate item | C/5 | C/10 | C/20 |
| Theoretical capacity (mAh) | 1560 | 1560 | 1560 |
| Discharge current (mA) | 300 | 150 | 75 |
| Time of discharge (hrs) | 4.31 | 9.35 | 19.08 |
| Actual capacity (mAh) | 1293 | 1402.5 | 1431 |
| Utilization (%) | 82.88 | 89.90 | 91.37 |
(III) influence of different ambient temperatures
2.5g of zinc gel (zinc gel) containing 70 wt% of zinc powder is weighed as a negative electrode, the prepared air electrode is used as a positive electrode, and the PVA-glass fiber film electrolyte of the first embodiment is used as an isolating film to assemble a zinc-air battery, and the discharge electrical property comparison in different temperature environments (0 ℃, 20 ℃ and 50 ℃) is carried out. The theoretical capacity is 1500 mAh. Fig. 26 is a battery discharge curve chart of the battery at different temperatures. Table 6 shows the results of the utilization (%) of the batteries at different temperatures for comparison. The zinc utilization rate is 75% at 0 ℃, 78.65% at 20 ℃ and 83.65% at 50 ℃. When the environmental temperature is higher, the battery performance is better, and the battery prepared by the invention can also maintain the high utilization rate of more than 70 percent in a low-temperature environment.
TABLE 6 comparison of results of battery utilization (%) at different temperatures
| T (. degree. C.) | 0 | 20 | 50 |
| Theoretical capacity (mAh) | 1560 | 1560 | 1560 |
| Discharge current (mA) | 150 | 150 | 150 |
| Time of discharge (hrs) | 7.8 | 8.2 | 8.7 |
| Actual capacity (mAh) | 1170 | 1230 | 1305 |
| Utilization (%) | 75％ | 78.85％ | 83.65％ |
(IV) analysis of AC resistance impedance
2.5g of zinc gel (zinc gel) containing 70 wt% of zinc powder is weighed as a negative electrode, the prepared air electrode is used as a positive electrode, meanwhile, the PVA-glass fiber film electrolyte of the first embodiment is used as an isolating film to assemble a zinc-air battery, and an electrochemical impedance analyzer AUTOLAB FRA is used for carrying out comparative test experiments of alternating current resistance impedance in different temperature environments (0 ℃, 20 ℃ and 50 ℃). Fig. 27 is the electrochemical impedance analysis results of a solid state zinc-air cell. Table 7 shows comparative resistance values of the battery at different temperatures. The higher the ambient temperature, the lower the ac impedance of the battery, and this result shows that the battery has a lower impedance in a high temperature environment, so the performance of the battery is higher than that in a low temperature environment. The battery performance was poor in a low-temperature environment, as shown in table 7, because the PVA solid electrolyte had a high resistance in a low-temperature environment.
TABLE 7 comparison of resistance values of battery impedances at different temperatures
| T (. degree. C.) | 0 | 20 | 50 |
| Rb(ohm) | 0.32 | 0.225 | 0.125 |
It is intended that all such alterations and modifications in the preferred embodiment, and all such modifications and variations that fall within the true spirit and scope of the invention, are desired to be understood by those skilled in the art.
Claims (14)
1. A method for preparing a solid polymer electrolyte is characterized by comprising the following steps:
(1) selecting polyvinyl alcohol with the molecular weight of 2,000-120,000, wherein the usage amount of the polyvinyl alcohol is 10-20 wt%, and stirring, mixing and reacting with water with the weight ratio of 50-60 wt% at normal temperature and in a closed environment;
(2) mixing and dissolving 15-25 wt% of alkali metal solution with 10-20 wt% of water under normal temperature and sealed environment;
(3) then mixing the two completely dissolved polyvinyl alcohol solutions and the alkali metal solution at normal temperature, fully stirring the mixed solution to generate a solid, reacting the solid and the solution at 50-100 ℃ in a closed container to copolymerize the solid, and cooling the solid in the atmosphere;
(4) and (3) controlling the thickness of the coating film coated on the bearing plate by the cooled polymer liquid according to the required film thickness, placing the bearing plate with the polymer liquid coating film into a constant temperature and humidity box, controlling the temperature to be 40-80 ℃ and the humidity to be 20-50 RH%, standing for 30-60 minutes to form a solid polymer film, taking out the bearing plate, and placing in the atmosphere to easily take down the film.
2. The method of claim 1, wherein the alkali metal is KOH, NaOH, LiOH or a mixture thereof.
3. The method of claim 1, wherein the polyvinyl alcohol has an average molecular weight of 50,000 to 100,000.
4. The method of claim 1, wherein Glass-Fiber Cloth (Glass-Fiber Cloth) with a thickness of 20 μm to 400 μm is added to the method, depending on the process, to improve the mechanical strength and thermo-chemical and electrochemical stability.
5. The method of claim 1, wherein the polyvinyl alcohol is supplemented with a nano-sized particulate oxide material, such as g-Al2O3、TiO2、ZrO2Or SiO2。
6. The method according to claim 1, wherein the optimum conditions of the constant temperature and humidity chamber in the step (4) are a temperature of 50 ℃ and a humidity of 30 RH.
7. The preparation method of the dendritic electrolytic zinc powder with high specific surface area is characterized by comprising the following steps:
(1) dissolving 5-15 wt% zinc oxide powder in an alkali metal solution at 30-90 ℃ and electrolyzing at a constant current density of 50-300 mA/cm2The cathode plate is a nickel plate, and is electrolyzed into dendritic zinc powder under specific conditions and environments;
(2) scraping the electroplated zinc powder from the cathode, cleaning with ultrapure water, oscillating with ultrasonic waves, filtering, and repeatedly washing for 5-10 times;
(3) the zinc powder is fully cleaned to avoid the residual electroplating solution remaining in the zinc powder to cause oxidation, and is dried and placed in a drying box by a vacuum sealing device to avoid oxidation.
8. The method of claim 7, wherein the alkali metal is NaOH, KOH, LiOH or a mixture thereof.
9. A preparation method of zinc anode gel is characterized by comprising the following steps:
(1) weighing a proper amount of hydrogen inhibitor, adding an alkali metal solution, and stirring to uniformly disperse the inhibitor;
(2) adding 1-7 wt% of dendritic zinc powder into the solution prepared in the step, placing the solution into an ultrasonic oscillator for oscillation, adding 0.5-10 wt% of high-molecular gelling agent, and uniformly stirring to obtain a colloid.
10. The method of claim 9, wherein the hydrogen inhibitor is zinc oxide, indium acetate, magnesium oxide, calcium oxide, or barium oxide.
11. The method of claim 9, wherein the gelling agent is CMC, PVA, starch, polyacrylic acid, a polymeric gelling agent, or cellulose.
12. The method of claim 9, wherein the gelling agent is preferably used in an amount of 1 to 2 wt%.
13. A method for manufacturing a diffusion layer in an air electrode, comprising:
(1) weighing a proper amount of dispersant Triton-X, polytetrafluoroethylene and water, uniformly mixing the dispersant Triton-X, the polytetrafluoroethylene and the water, and putting the mixture and a container into an ultrasonic oscillator to vibrate the mixture for uniform mixing;
(2) weighing hydrophobic acetylene black carbon powder, adding, stirring and assisting ultrasonic vibration, and placing in an oven for drying (H is required)2O is completely expelled);
(3) after drying, uniformly grinding and weighing the diffusion raw materials, and weighing the diffusion raw materials according to the size requirement of the air electrode;
(4) placing the nickel screen on a mould, uniformly coating the raw materials on the nickel screen, placing the mould in a hot press, carrying out pressure-sustaining sintering, sending the high-temperature mould to a cooling machine, carrying out pressure-sustaining cooling and taking out the diffusion layer.
14. A method of making an air electrode, comprising:
(1) firstly weighing hydrophilic carbon powder XC-72R, and adding a proper amount of potassium permanganate or MnO2 catalyst;
(2) weighing Polytetrafluoroethylene (PTFE) -30 and water, and uniformly mixing the PTFE-30 and the water by ultrasonic oscillation;
(3) mixing the above (1) and (2), stirring and assisting ultrasonic oscillation, adding an appropriate amount of alcohol solvent, stirring and assisting ultrasonic oscillation;
(4) and (3) spraying the required amount of the solution on the diffusion layer, drying the air electrode sprayed with the activation layer at 120 ℃, sintering at high temperature, and then keeping the pressure for cooling to finish the air electrode.
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| CN103515676B (en) * | 2013-09-29 | 2015-06-17 | 吉林大学 | All-solid-state separable aluminium-air cell |
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| CN104868166A (en) * | 2014-02-25 | 2015-08-26 | 常州优特科新能源科技有限公司 | Electrolyte additive for zinc-series battery |
| CN104167528A (en) * | 2014-08-19 | 2014-11-26 | 合肥献芝新能源有限公司 | Zinc electrode for zinc-air batteries and preparation method of zinc electrode |
| CN104167528B (en) * | 2014-08-19 | 2017-02-15 | 合肥献芝新能源有限公司 | Zinc electrode for zinc-air batteries and preparation method of zinc electrode |
| CN108539330A (en) * | 2018-02-06 | 2018-09-14 | 宁波大学 | A kind of all solid state zinc-air battery and its gel electrolyte |
| CN109860647A (en) * | 2018-12-19 | 2019-06-07 | 苏州柔能纳米科技有限公司 | Alkaline flexible electrolyte film of zinc-manganese battery and preparation method thereof |
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