CN111129478A - Preparation method of corrosion-resistant magnesium alloy cathode material for seawater battery - Google Patents
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- H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
- H01M6/34—Immersion cells, e.g. sea-water cells
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Abstract
The invention relates to a preparation method of an anti-corrosion magnesium alloy cathode material for a seawater battery, belonging to the technical field of new energy materials. According to the technical scheme, the composite sol of boric acid and silicic acid is prepared, fully coated on the surface of the magnesium alloy material, the matching performance with the metal magnesium alloy material is excellent, the magnesium alloy material is prevented from being corroded by seawater by coating the boron silicate gel film on the magnesium alloy material, the magnesium powder is added into the gel material, so that a composite gel coating formed by the gel material has an excellent pore structure, the utilization rate of a magnesium alloy anode is improved, the specific capacity of a battery is improved, and the surface of the coating is densely filled with a carbonization phenomenon when the effective micro-nano structure composite dicalcium phosphate coating is soaked in seawater, so that the seawater corrosion resistance of the anode material in the using process is further improved.
Description
Technical Field
The invention relates to a preparation method of an anti-corrosion magnesium alloy cathode material for a seawater battery, belonging to the technical field of new energy materials.
Background
The seawater battery is a battery which takes seawater as electrolyte and is characterized by not needing to carry the electrolyte. Generally, seawater is used as a chemical power source of an electrolyte in a marine environment, the electrolyte is an important component of a battery, and the electrolyte mainly has the function of ensuring the directional movement of ions in electrode reaction to form stable and continuous current. The seawater battery is an important power source of underwater instruments such as military equipment and commercial equipment. The deep sea environment condition is complex, and the conventional power supply is difficult to meet the long-term power supply requirement of small-power electronic instruments (such as a submarine seismic monitor, a marine monitoring system, underwater acoustic communication equipment, a submarine navigator and the like) working under the sea in the aspects of service life and safety. Therefore, the development of the renewable distributed marine power supply-seawater dissolved oxygen battery is widely regarded. In seawater oxygen-dissolved batteries, one of the key points for material application is the use of anode materials that increase the discharge voltage and battery capacity. The magnesium alloy is an important anode material applied to a seawater activated battery, can provide a very negative standard electrode potential of-2.37V, has high faradaic capacity and proper corrosion rate, and has electrochemical equivalent which is only lower than that of metallic lithium and aluminum. Magnesium has a faradaic capacity of 2205mAh/g, which is significantly higher than that of metallic zinc, and has a lower specific weight than aluminum, which is about 25% of that of zinc, so magnesium has a potentially high energy density and can be applied to light batteries. The magnesium alloy anode battery uses seawater as an electrolyte, so that the magnesium alloy anode battery has greater practicability and better cost advantage than other lithium ion batteries or alkaline batteries. However, the magnesium alloy serving as the anode of the seawater battery has the defects of large self-corrosion rate, low utilization rate and the like due to the side reaction of hydrogen evolution, and the search for the magnesium alloy anode material with high anode utilization rate is a hotspot and difficult problem of international magnesium seawater battery research.
According to the constitution of the magnesium seawater battery, the most outstanding characteristic is that the battery does not need to carry electrolyte and can be used when needed
When necessary, the electrolyte is formed by utilizing natural seawater, and based on such a structural characteristic, the magnesium seawater battery has
The following outstanding advantages are achieved:
(1) the electrolyte and a special storage and control device are not required to be carried, so that the related structure is simplified, the weight of the battery is reduced, and the unit energy density of the battery is directly improved.
The electrolyte is flowing seawater, so that the polarization of reactants on the electrode is eliminated to a certain extent, the stability of the discharge performance of the electrode is facilitated, and the efficiency of the electrode is improved.
The problem that the discharge performance of the magnesium seawater battery is not obvious along with the change of the depth of the seawater due to the fact that the magnesium seawater battery is an open system is avoided, and the magnesium seawater battery is suitable for being used in seawater with different depths.
By changing electrode materials, different types of batteries can be developed, the application range is wide, and the cost performance is high.
The whole battery is an open system relative to seawater, is balanced with seawater external pressure, does not need the protection of a pressure-resistant container, can bring out the heat released by electrode reaction due to seawater flow, controls the temperature of the battery system, and can improve the safety. Therefore, compared with a conventional power supply, the seawater battery is more suitable for supplying power to underwater equipment.
The corrosion resistance of magnesium alloy is controlled by the corrosion reaction of single component phase in magnesium alloy, and if the magnesium alloy contains components which can easily react with the external environment, the corrosion resistance is relatively poor. The corrosion of magnesium alloy is mostly started from a base phase, and the magnesium alloy base phase has some physical and chemical properties and crystal structures similar to those of pure magnesium, and the corrosion mechanism of the magnesium alloy base phase is similar to that of the pure magnesium, so that the research on the corrosion reaction of the pure magnesium is important, and the magnesium alloy is greatly helpful for understanding the corrosion reaction of other various magnesium alloys.
In the aqueous solution, magnesium and water can generate electrochemical reaction to dissolve magnesium in the aqueous solution, and hydrogen and magnesium hydroxide can be generated by the reaction, so that the corrosion of the magnesium alloy is not controlled by the concentration of oxygen, but the corrosion of the magnesium alloy in the air is greatly influenced by the presence of the oxygen. In aqueous solution, the corrosion of magnesium generally comprises the micro-galvanic corrosion of magnesium alloy between a cathode and an anode, which is widely applied to seawater batteries due to the excellent conductivity, processability and electrochemical equivalent second to lithium and aluminum, but due to the high activity, the self-corrosion is serious, and the use efficiency of the magnesium alloy as the anode material of the seawater battery is severely limited. The magnesium alloy is subjected to surface treatment to make the surface of the magnesium alloy hydrophobic, so that the problems of overhigh activity, serious self-corrosion and low current efficiency can be solved. Therefore, how to prepare the magnesium alloy composite material with excellent seawater corrosion resistance and improved use conductivity of the anode material is the key of the research on the existing seawater battery material.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: aiming at the problems that the activity is higher and the self-corrosion is serious in the process of preparing the seawater battery by using the magnesium alloy material, and the use efficiency of the magnesium alloy material as the anode material of the seawater battery is seriously restricted, the preparation method of the corrosion-resistant magnesium alloy anode material for the seawater battery is provided.
In order to solve the technical problems, the invention adopts the technical scheme that:
(1) according to the mass ratio of 1:5, stirring, mixing and drying the white carbon black and the shell powder, collecting dried particles, placing the dried particles into a nylon tank, ball-milling, collecting mixed ball grinding materials, placing the mixed ball grinding materials into a tubular atmosphere furnace, heating, keeping warm, calcining, standing, cooling to room temperature, grinding, crushing and sieving to obtain sieved particles; taking magnesium strips, crushing, grinding, sieving, collecting magnesium powder, stirring and mixing the magnesium powder and acetic acid according to the mass ratio of 1:15, filtering, collecting filter cakes, washing, drying and collecting the treated magnesium powder;
(2) stirring and mixing ethyl orthosilicate and absolute ethyl alcohol according to a mass ratio of 1:5 to obtain a mixed solution, then dropwise adding hydrochloric acid with the mass fraction of 0.5% into the mixed solution, stirring and mixing, standing to obtain a matrix sol solution, adding formaldehyde into the treated magnesium powder according to a mass ratio of 1:15, stirring and mixing to obtain coated magnesium powder according to a mass ratio of 1:5, stirring and mixing the matrix sol solution and the coated magnesium powder, placing the mixture into a mortar, grinding and dispersing the mixture, placing the mixture into a reaction kettle, introducing nitrogen to remove air, performing temperature programming and heat preservation reaction after the introduction is finished, standing and cooling to room temperature to obtain modified particles;
(3) adding graphite oxide into deionized water according to the mass ratio of 1:15, stirring, mixing and ultrasonically oscillating, collecting ultrasonic oscillation liquid, respectively weighing 45-50 parts of ultrasonic oscillation liquid, 1-2 parts of glutathione and 3-5 parts of 10% ammonia water by mass fraction, placing the ultrasonic oscillation liquid, the 1-2 parts of glutathione and the 3-5 parts of 10% ammonia water in parts by weight into a triangular flask, stirring, mixing, carrying out heat preservation in a water bath, standing, cooling to room temperature and collecting to obtain mixed gel liquid;
(4) and (2) placing the mixed gel liquid in a water bath, removing impurities, collecting modified gel liquid, stirring and mixing the sieved particles, the modified particles and the modified gel liquid according to the mass ratio of 1:5:10, spraying the surface of the magnesium alloy by adopting an atmospheric plasma spraying process, and standing for 25-30 min to obtain the corrosion-resistant magnesium alloy cathode material for the seawater battery.
The temperature is increased to 1400-1500 ℃ at a speed of 5 ℃/min, and the heat preservation calcination is carried out for 3-4 h.
The particle size of the sieved particles is 150 meshes.
The dropwise adding amount of the hydrochloric acid with the mass fraction of 0.5 percent is 1/2 of the mass of the tetraethoxysilane.
The nitrogen gas introduction rate is 25-30 mL/min.
The temperature programming and heat preservation reaction is carried out at the temperature of 5 ℃/min to 200-250 ℃ for 1-2 h.
The magnesium alloy can be preferably magnesium alloy AZ31 or magnesium alloy AZ 61.
The spraying treatment is carried out under the condition that the current is controlled to be 650A, the spraying distance is 100-120 mm, and the argon plasma flow is 45-50 slm p.
The impurity removal treatment is a heat preservation reaction at 90-95 ℃ for 10-12 h.
Compared with other methods, the method has the beneficial technical effects that:
(1) according to the technical scheme, white carbon black and shell powder are mixed to prepare the composite dicalcium silicate, a dicalcium silicate solution is soaked by seawater to generate hydrated calcium silicate gel C-S-H and Ca (OH)2, wherein Ca (OH)2 and carbon dioxide in the air are dissolved in water to form CO 32-and HCO 3-which react to form calcium carbonate, the product at the initial stage of soaking is calcite, vaterite is arranged at the later stage of soaking, the surface of a coating generates a carbonization phenomenon when a dicalcium silicate coating is soaked by seawater, the product calcium carbonate is in a whisker-shaped aragonite structure due to the crystal form control function of Mg2+, C-S-H gel formed by hydration fills pores and microcracks in the coating, the coating structure tends to be densified, and the corrosion resistance of the material is effectively improved;
(2) the technical scheme of the invention adopts double hydrolysis of ethyl orthosilicate and tributyl borate to prepare the composite sol of boric acid and silicic acid, which has high purity and high uniformity, the uniformity of the composite sol can reach the level of molecules or atoms, so that the composite sol can be fully coated on the surface of a magnesium alloy material, has lower dielectric property and excellent matching property with the metal magnesium alloy material, and can be prevented from being corroded by seawater by coating the magnesium alloy material with a borosilicate gel film, and the composite film prepared by the technical scheme of the invention can be stored in the atmosphere for a longer time when not used, can prevent anode corrosion, can overcome the problems of overhigh discharge activity, overhigh dissolution speed, high hydrogen evolution speed and low anode utilization rate caused by serious self corrosion in the discharge process, and magnesium powder is added into the gel material, the composite gel coating formed by the composite gel coating has an excellent pore structure, the micro-nano pores can contain oxygen in seawater electrolyte, a layer of air cushion is formed on the surface, the contact between a matrix and water is reduced, the utilization rate of a magnesium alloy anode is improved, and therefore the specific capacity of the battery is improved.
Detailed Description
Stirring and mixing white carbon black and shell powder according to a mass ratio of 1:5, placing the mixture in an oven, drying the mixture for 3-5 hours at 100-110 ℃, collecting dried particles, placing the dried particles in a nylon tank, carrying out ball milling for 10-12 hours, collecting mixed ball milled materials, placing the mixed ball milled materials in a tubular atmosphere furnace, heating the mixture to 1400-1500 ℃ at a speed of 5 ℃/min, carrying out heat preservation and calcination for 3-4 hours, standing and cooling the mixture to room temperature, grinding and crushing the mixture, and sieving the mixture with a 150-mesh sieve to obtain sieved particles; taking magnesium strips, crushing and grinding, sieving with a 200-mesh sieve, collecting magnesium powder, stirring and mixing the magnesium powder and acetic acid with the mass fraction of 1% for 25-30 min according to the mass ratio of 1:15, filtering, collecting filter cakes, washing with deionized water for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, vacuum drying for 2-3 h, and collecting the treated magnesium powder; stirring and mixing tetraethoxysilane and absolute ethyl alcohol according to a mass ratio of 1:5 to obtain a mixed solution, then dropwise adding hydrochloric acid with the mass fraction of 0.5% into the mixed solution, controlling the dropwise adding amount of the hydrochloric acid to be 1/2 of the mass of the tetraethoxysilane, stirring and mixing after the dropwise adding is finished, standing for 20-30 min, and stirring and mixing to obtain a matrix sol solution; adding formaldehyde into the treated magnesium powder according to the mass ratio of 1:15, stirring and mixing to obtain coated magnesium powder, stirring and mixing the matrix sol solution and the coated magnesium powder according to the mass ratio of 1:5, placing the mixture into a mortar, grinding and dispersing the mixture, placing the mixture into a reaction kettle, introducing nitrogen to remove air, controlling the nitrogen introduction rate to be 25-30 mL/min, heating to 200-250 ℃ at the speed of 5 ℃/min after the introduction is finished, carrying out heat preservation reaction for 1-2 h, standing and cooling to room temperature to obtain modified particles; adding graphite oxide into deionized water according to a mass ratio of 1:15, stirring, mixing, placing at 2500-3000W for 6-8 h of ultrasonic oscillation, collecting ultrasonic oscillation liquid, weighing 45-50 parts of ultrasonic oscillation liquid, 1-2 parts of glutathione and 3-5 parts of 10% ammonia water by mass fraction respectively according to parts by weight, placing in a triangular flask, stirring, mixing, placing in a heat preservation water bath at 85-95 ℃ for 10-12 h, standing, cooling to room temperature, collecting to obtain mixed gel liquid, placing the mixed gel liquid in a water bath, performing heat preservation reaction at 90-95 ℃ for 10-12 h, removing impurities, and collecting to obtain modified gel liquid; stirring and mixing the sieved particles, the modified particles and the modified gel liquid according to the mass ratio of 1:5:10, spraying the surface of the AZ31 magnesium alloy by adopting an atmospheric plasma spraying process, controlling the current to be 650A and the spraying distance to be 100-120 mm, spraying under the argon plasma flow of 45-50 slm p, and standing for 25-30 min to obtain the corrosion-resistant magnesium alloy anode material for the seawater battery.
Example 1
Stirring and mixing white carbon black and shell powder according to a mass ratio of 1:5, placing the mixture into an oven, drying the mixture at 100 ℃ for 3 hours, collecting dried particles, placing the dried particles into a nylon tank, carrying out ball milling for 10 hours, collecting mixed ball milling materials, placing the mixed ball milling materials into a tubular atmosphere furnace, heating the mixed ball milling materials to 1400 ℃ at a speed of 5 ℃/min, carrying out heat preservation and calcination for 3 hours, standing and cooling the mixture to room temperature, carrying out grinding and crushing, and sieving the mixture through a 150-mesh sieve to obtain sieved particles; taking magnesium strips, crushing and grinding, sieving by using a 200-mesh sieve, collecting magnesium powder, stirring and mixing the magnesium powder and acetic acid with the mass fraction of 1% for 25min according to the mass ratio of 1:15, filtering and collecting filter cakes, washing the filter cakes with deionized water for 3 times, washing the filter cakes with absolute ethyl alcohol for 3 times, drying the filter cakes in vacuum for 2 hours, and collecting the treated magnesium powder; stirring and mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1:5 to obtain a mixed solution, then dropwise adding hydrochloric acid with the mass fraction of 0.5% into the mixed solution, controlling the dropwise adding amount of the hydrochloric acid to be 1/2 of the mass of the tetraethoxysilane, stirring and mixing after the dropwise adding is finished, standing for 20min, and stirring and mixing to obtain a matrix sol solution; adding formaldehyde into the treated magnesium powder according to the mass ratio of 1:15, stirring and mixing to obtain coated magnesium powder, stirring and mixing the matrix sol solution and the coated magnesium powder according to the mass ratio of 1:5, placing the mixture into a mortar, grinding and dispersing the mixture, placing the mixture into a reaction kettle, introducing nitrogen to remove air, controlling the nitrogen introduction rate to be 25mL/min, after the introduction is finished, heating to 200 ℃ according to the speed of 5 ℃/min, carrying out heat preservation reaction for 1h, standing and cooling to room temperature to obtain modified particles; adding graphite oxide into deionized water according to the mass ratio of 1:15, stirring, mixing, placing at 2500W for 6 hours of ultrasonic oscillation, collecting ultrasonic oscillation liquid, weighing 45 parts of ultrasonic oscillation liquid, 1 part of glutathione and 3 parts of 10% ammonia water by mass fraction respectively according to the parts by weight, placing in a triangular flask, stirring, mixing, placing in a heat-preservation water bath at 85 ℃ for 10 hours, standing, cooling to room temperature, collecting to obtain mixed gel liquid, placing the mixed gel liquid in a water bath, reacting at 90 ℃ for 10 hours in a heat preservation manner, removing impurities, treating, and collecting to obtain modified gel liquid; stirring and mixing the sieved particles, the modified particles and the modified gel liquid according to the mass ratio of 1:5:10, spraying the surface of the AZ31 magnesium alloy by adopting an atmospheric plasma spraying process, controlling the current to be 650A and the spraying distance to be 100mm, spraying under the argon plasma flow of 45slm p, and standing for 25min to obtain the corrosion-resistant magnesium alloy anode material for the seawater battery.
Example 2
Stirring and mixing white carbon black and shell powder according to a mass ratio of 1:5, placing the mixture into an oven, drying the mixture at 105 ℃ for 4 hours, collecting dried particles, placing the dried particles into a nylon tank, carrying out ball milling for 11 hours, collecting mixed ball milling materials, placing the mixed ball milling materials into a tubular atmosphere furnace, heating the mixed ball milling materials to 1450 ℃ at a speed of 5 ℃/min, carrying out heat preservation and calcination for 3 hours, standing and cooling the mixture to room temperature, carrying out grinding and crushing, and sieving the mixture through a 150-mesh sieve to obtain sieved particles; taking magnesium strips, crushing and grinding, sieving by using a 200-mesh sieve, collecting magnesium powder, stirring and mixing the magnesium powder and acetic acid with the mass fraction of 1% for 28min according to the mass ratio of 1:15, filtering and collecting filter cakes, washing the filter cakes with deionized water for 4 times, washing the filter cakes with absolute ethyl alcohol for 4 times, drying the filter cakes in vacuum for 2 hours, and collecting the treated magnesium powder; stirring and mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1:5 to obtain a mixed solution, then dropwise adding hydrochloric acid with the mass fraction of 0.5% into the mixed solution, controlling the dropwise adding amount of the hydrochloric acid to be 1/2 of the mass of the tetraethoxysilane, stirring and mixing after the dropwise adding is finished, standing for 25min, and stirring and mixing to obtain a matrix sol solution; adding formaldehyde into the treated magnesium powder according to the mass ratio of 1:15, stirring and mixing to obtain coated magnesium powder, stirring and mixing the matrix sol solution and the coated magnesium powder according to the mass ratio of 1:5, placing the mixture into a mortar, grinding and dispersing the mixture, placing the mixture into a reaction kettle, introducing nitrogen to remove air, controlling the nitrogen introduction rate to be 27mL/min, after the introduction is finished, heating to 225 ℃ according to the speed of 5 ℃/min, carrying out heat preservation reaction for 1h, standing and cooling to room temperature to obtain modified particles; adding graphite oxide into deionized water according to the mass ratio of 1:15, stirring, mixing, placing at 2750W for ultrasonic oscillation for 7h, collecting ultrasonic oscillation liquid, weighing 47 parts of ultrasonic oscillation liquid, 1 part of glutathione and 4 parts of ammonia water with the mass fraction of 10% respectively according to the parts by weight, placing in a triangular flask, stirring, mixing, placing in a heat-preservation water bath at 90 ℃ for 11h, standing, cooling to room temperature, collecting to obtain mixed gel liquid, placing the mixed gel liquid in a water bath, performing heat-preservation reaction at 92 ℃ for 11h, removing impurities, and collecting to obtain modified gel liquid; stirring and mixing the sieved particles, the modified particles and the modified gel liquid according to the mass ratio of 1:5:10, spraying the surface of the AZ31 magnesium alloy by adopting an atmospheric plasma spraying process, controlling the current to be 650A and the spraying distance to be 110mm, spraying at the argon plasma flow rate of 47slm p, and standing for 27min to prepare the corrosion-resistant magnesium alloy anode material for the seawater battery.
Example 3
Stirring and mixing white carbon black and shell powder according to a mass ratio of 1:5, placing the mixture into an oven, drying the mixture at 110 ℃ for 5 hours, collecting dried particles, placing the dried particles into a nylon tank, carrying out ball milling for 12 hours, collecting mixed ball milling materials, placing the mixed ball milling materials into a tubular atmosphere furnace, heating the mixed ball milling materials to 1500 ℃ at a speed of 5 ℃/min, carrying out heat preservation and calcination for 4 hours, standing and cooling the mixture to room temperature, carrying out grinding and crushing, and sieving the mixture through a 150-mesh sieve to obtain sieved particles; taking magnesium strips, crushing and grinding, sieving by using a 200-mesh sieve, collecting magnesium powder, stirring and mixing the magnesium powder and acetic acid with the mass fraction of 1% for 30min according to the mass ratio of 1:15, filtering and collecting filter cakes, washing the filter cakes with deionized water for 5 times, washing the filter cakes with absolute ethyl alcohol for 5 times, drying the filter cakes in vacuum for 3 hours, and collecting the treated magnesium powder; stirring and mixing tetraethoxysilane and absolute ethyl alcohol according to the mass ratio of 1:5 to obtain a mixed solution, then dropwise adding hydrochloric acid with the mass fraction of 0.5% into the mixed solution, controlling the dropwise adding amount of the hydrochloric acid to be 1/2 of the mass of the tetraethoxysilane, stirring and mixing after the dropwise adding is finished, standing for 30min, and stirring and mixing to obtain a matrix sol solution; adding formaldehyde into the treated magnesium powder according to the mass ratio of 1:15, stirring and mixing to obtain coated magnesium powder, stirring and mixing the matrix sol solution and the coated magnesium powder according to the mass ratio of 1:5, placing the mixture into a mortar, grinding and dispersing the mixture, placing the mixture into a reaction kettle, introducing nitrogen to remove air, controlling the nitrogen introduction rate to be 30mL/min, after the introduction is finished, heating to 250 ℃ according to the speed of 5 ℃/min, carrying out heat preservation reaction for 2h, standing and cooling to room temperature to obtain modified particles; adding graphite oxide into deionized water according to a mass ratio of 1:15, stirring, mixing, placing at 3000W for ultrasonic oscillation for 8 hours, collecting ultrasonic oscillation liquid, weighing 50 parts of ultrasonic oscillation liquid, 2 parts of glutathione and 5 parts of 10% ammonia water by mass fraction respectively according to parts by weight, placing in a triangular flask, stirring, mixing, placing in a heat-preservation water bath at 95 ℃ for 12 hours, standing, cooling to room temperature, collecting to obtain mixed gel liquid, placing the mixed gel liquid in a water bath, performing heat-preservation reaction at 95 ℃ for 12 hours, removing impurities, treating, and collecting to obtain modified gel liquid; stirring and mixing the sieved particles, the modified particles and the modified gel liquid according to the mass ratio of 1:5:10, spraying the surface of the AZ31 magnesium alloy by adopting an atmospheric plasma spraying process, controlling the current to be 650A and the spraying distance to be 120mm, spraying under the argon plasma flow of 50slm p, and standing for 30min to prepare the corrosion-resistant magnesium alloy anode material for the seawater battery.
Comparative example: unmodified, direct use magnesium alloy AZ 31.
The carbon papers prepared in the examples and the comparative examples were tested, specifically as follows:
and stirring the paste for 12h according to the mass ratio of the active substance to the catalyst to the binder of 4: 3, and coating the paste on foamed nickel to prepare the battery anode, wherein the area of the cathode is 1 x 1 cm, the discharge area ratio of the anode to the cathode material is controlled to be 4: 1, and the distance is 6 mm.
The electrochemical impedance spectroscopy test is carried out by adopting a CHI604E electrochemical workstation, a research electrode is 1 x cm magnesium alloy, a counter electrode is a platinum sheet electrode, a reference electrode is a saturated calomel electrode, electrolyte is 3.5% sodium chloride solution, the amplitude of sine wave potential is 5mV, direct current potential is open circuit potential, the test frequency range is 0.01-100 kHz, and the test is carried out at room temperature.
A CHI660 electrochemical workstation is adopted to carry out potentiodynamic polarization test, a research electrode is magnesium alloy with the thickness of 1 multiplied by 1 cm, a counter electrode is a platinum sheet electrode, a reference electrode is a saturated calomel electrode, and the electrolyte is 3.5 percent of NaCl solution.
The specific test results are shown in table 1.
Table 1 comparative table of property characterization
| Detecting items | Example 1 | Example 2 | Example 3 | Comparative example |
| The self-corrosion current density is/mA/cm2 | 0.108 | 0.106 | 0.107 | 0.162 |
| Charge transfer resistance/Ω · cm2 | 145.3 | 148.6 | 147.2 | 42.3 |
As can be seen from table 1, the magnesium alloy cathode material prepared by the present invention has excellent corrosion resistance.
Claims (9)
1. A preparation method of an anti-corrosion magnesium alloy cathode material for a seawater battery is characterized by comprising the following specific preparation steps:
(1) according to the mass ratio of 1:5, stirring, mixing and drying the white carbon black and the shell powder, collecting dried particles, placing the dried particles into a nylon tank, ball-milling, collecting mixed ball grinding materials, placing the mixed ball grinding materials into a tubular atmosphere furnace, heating, keeping warm, calcining, standing, cooling to room temperature, grinding, crushing and sieving to obtain sieved particles; taking magnesium strips, crushing, grinding, sieving, collecting magnesium powder, stirring and mixing the magnesium powder and acetic acid according to the mass ratio of 1:15, filtering, collecting filter cakes, washing, drying and collecting the treated magnesium powder;
(2) stirring and mixing ethyl orthosilicate and absolute ethyl alcohol according to a mass ratio of 1:5 to obtain a mixed solution, then dropwise adding hydrochloric acid with the mass fraction of 0.5% into the mixed solution, stirring and mixing, standing to obtain a matrix sol solution, adding formaldehyde into the treated magnesium powder according to a mass ratio of 1:15, stirring and mixing to obtain coated magnesium powder according to a mass ratio of 1:5, stirring and mixing the matrix sol solution and the coated magnesium powder, placing the mixture into a mortar, grinding and dispersing the mixture, placing the mixture into a reaction kettle, introducing nitrogen to remove air, performing temperature programming and heat preservation reaction after the introduction is finished, standing and cooling to room temperature to obtain modified particles;
(3) adding graphite oxide into deionized water according to the mass ratio of 1:15, stirring, mixing and ultrasonically oscillating, collecting ultrasonic oscillation liquid, respectively weighing 45-50 parts of ultrasonic oscillation liquid, 1-2 parts of glutathione and 3-5 parts of 10% ammonia water by mass fraction, placing the ultrasonic oscillation liquid, the 1-2 parts of glutathione and the 3-5 parts of 10% ammonia water in parts by weight into a triangular flask, stirring, mixing, carrying out heat preservation in a water bath, standing, cooling to room temperature and collecting to obtain mixed gel liquid;
(4) and (2) placing the mixed gel liquid in a water bath, removing impurities, collecting modified gel liquid, stirring and mixing the sieved particles, the modified particles and the modified gel liquid according to the mass ratio of 1:5:10, spraying the surface of the magnesium alloy by adopting an atmospheric plasma spraying process, and standing for 25-30 min to obtain the corrosion-resistant magnesium alloy cathode material for the seawater battery.
2. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the temperature is increased to 1400-1500 ℃ at a speed of 5 ℃/min, and the heat preservation calcination is carried out for 3-4 h.
3. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the particle size of the sieved particles is 150 meshes.
4. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the dropwise adding amount of the hydrochloric acid with the mass fraction of 0.5 percent is 1/2 of the mass of the tetraethoxysilane.
5. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the nitrogen gas introduction rate is 25-30 mL/min.
6. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the temperature programming and heat preservation reaction is carried out at the temperature of 5 ℃/min to 200-250 ℃ for 1-2 h.
7. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the magnesium alloy can be preferably magnesium alloy AZ31 or magnesium alloy AZ 61.
8. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the spraying treatment is carried out under the condition that the current is controlled to be 650A, the spraying distance is 100-120 mm, and the argon plasma flow is 45-50 slm p.
9. The preparation method of the corrosion-resistant magnesium alloy cathode material for the seawater battery according to claim 1, wherein the corrosion-resistant magnesium alloy cathode material comprises the following steps: the impurity removal treatment is a heat preservation reaction at 90-95 ℃ for 10-12 h.
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| CN113224337A (en) * | 2021-02-26 | 2021-08-06 | 青岛华高墨烯科技股份有限公司 | Graphene/cuprous chloride-magnesium flashing battery and preparation method thereof |
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| CN113224337A (en) * | 2021-02-26 | 2021-08-06 | 青岛华高墨烯科技股份有限公司 | Graphene/cuprous chloride-magnesium flashing battery and preparation method thereof |
| CN113224337B (en) * | 2021-02-26 | 2022-07-19 | 青岛华高墨烯科技股份有限公司 | Graphene/cuprous chloride-magnesium flashing battery and preparation method thereof |
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