CN115117360B - Mercury-free active negative electrode material and preparation method thereof - Google Patents
Mercury-free active negative electrode material and preparation method thereof Download PDFInfo
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention discloses a mercury-free active negative electrode material and a preparation method thereof, and belongs to the technical field of battery energy materials. The cathode material is prepared from the following raw materials: 70-80 parts of zinc active composite material, 5-8 parts of acetylene black, 1-3 parts of carboxymethyl cellulose solution, 1-3 parts of sodium dodecyl benzene sulfonate, 0.3-0.6 part of PTFE aqueous solution and 0.5-1 part of inorganic additive. According to the invention, by synthesizing the short rod-shaped uniform and regular zinc cathode material and uniformly loading cerium and graphene oxide, the hydrogen evolution overpotential of the material is greatly improved, the occurrence of hydrogen evolution reaction can be reduced, the corrosion inhibition effect is obvious, and the structural stability and the capacity performance of the zinc electrode are greatly improved. Meanwhile, the composite material of the graphene oxide and the graphene oxide material can greatly improve the conductivity of the electrode, reduce electrochemical polarization and improve the rate capability and cycle performance of the battery.
Description
Technical Field
The invention belongs to the technical field of battery energy materials, and particularly relates to a mercury-free active negative electrode material and a preparation method thereof.
Background
The power supply is the core power of the marine vessel and is an important guarantee for carrying out deep sea scientific investigation, detection operation and deep sea resource development. And for special environmental fields, such as marine environments with high salt content, high corrosion content and the like, and different environments, more severe requirements are provided for the electrical property, the corrosion resistance and the safety performance of the battery. Such as various ocean detection sensors, need to work for a long time on the deep and open sea bottom, serving ocean development and national defense requirements. The effective and stable supply of power is an important guarantee for the long-term operation of the sensor.
Secondary alkaline batteries have attracted attention because of their advantages of high energy density, low cost, absolute safety, no environmental pollution, etc. The secondary zinc-based alkaline battery is characterized in that zinc or zinc oxide is used as a negative electrode, and manganese dioxide, nickel hydroxide and the like are used as positive electrode materials; the battery system takes sodium hydroxide or potassium hydroxide solution as electrolyte and zinc oxide as electrolyte additive. The anode and cathode materials have the advantage of low price; and the water-based system is used, so that the method has the advantages of safety and environmental protection.
However, because zinc is thermodynamically unstable in alkaline solution and can react with alkaline solution to release hydrogen, the capacity of the battery is reduced in the storage and use processes, and the released hydrogen can also cause the battery to deform, leak electrolyte and even explode, so that the traditional alkaline battery adopts a zinc powder amalgamation method to form an amalgamation film to uniformly and flatly cover the surface of zinc powder, change the surface condition of zinc particles and activate the zinc battery, thereby improving the electrical property of the battery, reducing the corrosion speed of zinc and reducing the leakage rate of the battery. However, it is known that mercury is a toxic heavy metal element, and is prohibited from being used in many products including batteries for the purpose of protecting marine environments.
In order to replace the effect of mercury on the battery negative electrode, the skilled person has developed various additives, which are commonly used as components of the negative electrode material, including indium oxide, indium hydroxide, and mixtures of the two, or various organic chemicals. Meanwhile, the zinc powder is also improved, and rare earth elements and various trace metals such as indium, bismuth, lead, calcium and the like which can improve the hydrogen evolution potential of the zinc are added, so that the self-corrosion speed of the zinc powder in alkaline solution is reduced. However, the method can reduce the charge and discharge performance of the battery more or less, and the power supply stability of the battery is influenced macroscopically. Therefore, it is an urgent technical problem to develop a mercury-free cathode material and provide stable power supply performance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a mercury-free active negative electrode material and a preparation method thereof, so that the charge-discharge performance and the power supply stability of a battery are greatly improved under the condition of no mercury addition.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 70-80 parts of zinc active composite material, 5-8 parts of acetylene black, 1-3 parts of carboxymethyl cellulose solution, 1-3 parts of sodium dodecyl benzene sulfonate, 0.3-0.6 part of PTFE aqueous solution and 0.5-1 part of inorganic additive.
Further, the mass concentration of the carboxymethyl cellulose solution is 2-3.5%.
Further, the mass concentration of the PTFE aqueous solution is 50-60%.
Further, the preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate, 3g of cerium nitrate and 3g of graphene oxide in 200ml of deionized water, adding 1-4g of terephthalic acid and 0.5-1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 10-20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating, setting the reaction temperature to be 100-180 ℃, reacting for 30-60min, and centrifugally filtering and drying after the reaction is finished to obtain a solid mixture;
(3) And then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 480-500 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation, calcination and activation for 2-4h, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
Furthermore, the graphene oxide is graphene oxide GO prepared by using natural graphite as a raw material by a Hummers method.
Further, the inorganic additive is indium oxide or indium hydroxide.
A preparation method of a mercury-free active negative electrode material comprises the following steps:
(1) Preparing a zinc active composite material: dispersing 10g of zinc nitrate and 3g of cerium nitrate into 200ml of deionized water, adding 1-4g of terephthalic acid and 0.5-1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 10-20min; adjusting the pH value of the mixed solution to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating, setting the reaction temperature to be 100-180 ℃, reacting for 30-60min, and centrifugally filtering and drying after the reaction is finished to obtain a solid mixture; then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 480-500 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation, calcining and activating for 2-4h, and cooling to room temperature along with the furnace to obtain a target product zinc active composite material;
(2) Weighing the raw materials in parts by weight, placing the raw materials in a container, uniformly mixing to prepare a negative electrode slurry, namely a negative electrode material, subsequently coating the negative electrode slurry on two sides of a copper strip through a slurry drawing die, drying, rolling and cutting to prepare a negative electrode plate, and then using the negative electrode plate.
Each of the raw materials of the present invention is commercially available.
The zinc-nickel secondary battery consists of a nickel positive electrode, a zinc negative electrode and electrolyte, wherein the positive electrode is Ni (OH) 2 NiOOH, znO/Zn as negative electrode, and KOH solution as electrolyte. Ni (OH) during charging 2 Losing electrons and converting the electrons into NiOOH, converting ZnO into electrons and converting the electrons into Zn, and when discharging, on the contrary, the electrolyte KOH aqueous solution plays a role in providing ion migration charges in the charge-discharge reaction of the zinc-nickel battery.
The inherent defects of the cathode material of the zinc-nickel secondary battery are always the technical barriers which prevent the zinc-nickel secondary battery from being commercialized to a high degree. For example, zinc oxide has high solubility in alkaline solution, zinc electrode is easy to deform during circulation and dendrite is easy to form during zinc deposition. Among these defects, the dissolution of zinc in alkaline solution is the most important factor affecting the cycle performance of zinc-nickel batteries. In order to inhibit the dissolution of zinc oxide in alkali liquor, improve the cycle performance of the battery and enable the zinc-nickel battery to be better commercially applied, many scholars at home and abroad carry out a lot of research. Most of the studies so far have been mainly directed to a negative electrode additive or an electrolyte additive, which reduces the solubility of zinc oxide in an alkaline solution, increases the reversibility of the reaction, reduces polarization, and the like, by the characteristics of the additive. Although the performance of the zinc-nickel battery can be improved to a certain extent by using the traditional method for physically mixing the additive and the active substance, the method has limitations, including low utilization rate of the additive, poor improvement of the cycle performance, addition of toxic and harmful corrosion-inhibiting metal elements such as mercury and the like. Therefore, the problem can be fundamentally solved only by modifying from the perspective of the core active material zinc.
The particle shape of the traditional zinc oxide is mainly hexagonal prism, and researches show that different electrochemical properties can be obtained by changing the crystal form of the zinc oxide. Compared with the traditional zinc oxide, the rodlike nano zinc oxide and the spherical nano zinc oxide can improve the electrochemical performance of the zinc-nickel battery.
Therefore, zinc nitrate and cerium nitrate are used as raw materials to synthesize cerium-element-loaded zinc oxide in a rod-like shape, and on one hand, the rare earth element cerium has a good hydrogen evolution overpotential and can effectively inhibit hydrogen evolution; on the other hand, the zinc oxide in the shape of a regular hexagonal prism mainly has a cone structure caused by the outward growth of a vertical substrate of a crystal, and particles with tapered ends can be converted into a needle form, namely zinc dendrites, in the circulation process.
Meanwhile, the graphene oxide is also assisted in the invention, so that the graphene oxide can play a role of a lubricant in the active zinc material with a regular rod-like structure, the anti-seismic performance of the battery can be improved, the contact resistance between the zinc materials can be reduced, and the discharge performance of the battery can be improved. The two are mutually matched and cooperate to jointly realize the stable improvement of the battery performance.
The invention also adds carboxymethyl cellulose solution, sodium dodecyl benzene sulfonate, PTFE aqueous solution and other organic additives. The organic additive can be adsorbed on the surface of the zinc material to form a hydration protective film, so that the occurrence of two-pole reaction in zinc corrosion conjugation reaction is hindered, and the function of the zinc material is promoted to be exerted. And the inorganic additive indium oxide or indium hydroxide can further help the active zinc material to improve the hydrogen evolution overpotential and inhibit hydrogen evolution.
Advantageous effects
According to the invention, by synthesizing the short rod-shaped uniform and regular zinc cathode material and uniformly loading cerium and graphene oxide, the hydrogen evolution overpotential of the material is greatly improved, the occurrence of hydrogen evolution reaction can be reduced, the corrosion inhibition effect is obvious, and the structural stability and the capacity performance of the zinc electrode are greatly improved. Meanwhile, the composite material of the graphene oxide and the graphene oxide material can greatly improve the conductivity of the electrode, reduce electrochemical polarization and improve the rate capability and cycle performance of the battery. The zinc-nickel secondary battery prepared by the novel cathode material has the advantages of high specific energy, high specific power and long cycle life.
Drawings
FIG. 1 is a micro-topography of a zinc active composite obtained in example 3 of the present invention;
fig. 2 is a graph showing cyclic voltammetry tests of electrochemical performance using the negative electrode materials of example 3 and comparative examples 1 to 3 of the present invention.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
The mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 70 parts of zinc active composite material, 8 parts of acetylene black, 3 parts of carboxymethyl cellulose solution, 1 part of sodium dodecyl benzene sulfonate, 0.3 part of PTFE aqueous solution and 0.5 part of inorganic additive.
The mass concentration of the carboxymethyl cellulose solution is 2%.
The mass concentration of the PTFE aqueous solution is 50%.
The preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate, 3g of cerium nitrate and 3g of graphene oxide in 200ml of deionized water, adding 1g of terephthalic acid and 0.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 10min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to 100 ℃, reacting for 30min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) And transferring the solid mixture into a muffle furnace, carrying out temperature programming to 480 ℃ at the speed of 3 ℃/min, carrying out heat preservation, calcining and activating for 2 hours, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
The graphene oxide is graphene oxide GO prepared by adopting a Hummers method and taking natural graphite as a raw material.
The inorganic additive is indium oxide.
A preparation method of a mercury-free active negative electrode material comprises the following steps:
(1) Preparing a zinc active composite material: dispersing 10g of zinc nitrate and 3g of cerium nitrate in 3g of graphene oxide in 200ml of deionized water, adding 1g of terephthalic acid and 0.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 10min; adjusting the pH value of the mixed solution to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating, setting the reaction temperature to be 100 ℃, reacting for 30min, and centrifugally filtering and drying after the reaction is finished to obtain a solid mixture; then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 480 ℃ at the speed of 3 ℃/min, carrying out heat preservation, calcining and activating for 2 hours, and cooling to room temperature along with the furnace to obtain a target product, namely the zinc active composite material;
(2) Weighing the raw materials in parts by weight, placing the raw materials in a container, uniformly mixing to prepare a negative electrode slurry, namely a negative electrode material, subsequently coating the negative electrode slurry on two sides of a copper strip through a slurry drawing die, drying, rolling and cutting to prepare a negative electrode plate, and then using the negative electrode plate.
Example 2
The mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 74 parts of zinc active composite material, 6 parts of acetylene black, 2 parts of carboxymethyl cellulose solution, 2 parts of sodium dodecyl benzene sulfonate, 0.4 part of PTFE aqueous solution and 0.8 part of inorganic additive.
The mass concentration of the carboxymethyl cellulose solution is 3%.
The mass concentration of the PTFE aqueous solution is 50%.
The preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate, 3g of cerium nitrate and 3g of graphene oxide in 200ml of deionized water, adding 2g of terephthalic acid and 1g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to 180 ℃, reacting for 60min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) And transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcining and activating for 4h, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
The graphene oxide is graphene oxide GO prepared by adopting a Hummers method and taking natural graphite as a raw material.
The inorganic additive is indium hydroxide.
A preparation method of a mercury-free active negative electrode material comprises the following steps:
(1) Preparing a zinc active composite material: dispersing 10g of zinc nitrate and 3g of cerium nitrate in 3g of graphene oxide in 200ml of deionized water, adding 2g of terephthalic acid and 1g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min; adjusting the pH value of the mixed solution to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating, setting the reaction temperature to be 180 ℃, reacting for 60min, and centrifugally filtering and drying after the reaction is finished to obtain a solid mixture; then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, and cooling to room temperature along with the furnace to obtain a target product, namely the zinc active composite material;
(2) Weighing the raw materials in parts by weight, placing the raw materials in a container, uniformly mixing to prepare a negative electrode slurry, namely a negative electrode material, subsequently coating the negative electrode slurry on two sides of a copper strip through a slurry drawing die, drying, rolling and cutting to prepare a negative electrode plate, and then using the negative electrode plate.
Example 3
The mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 80 parts of zinc active composite material, 5 parts of acetylene black, 1 part of carboxymethyl cellulose solution, 3 parts of sodium dodecyl benzene sulfonate, 0.6 part of PTFE aqueous solution and 1 part of inorganic additive.
The mass concentration of the carboxymethyl cellulose solution is 3.5%.
The mass concentration of the PTFE aqueous solution is 60%.
The preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate, 3g of cerium nitrate and 3g of graphene oxide in 200ml of deionized water, adding 4g of terephthalic acid and 1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to 180 ℃, reacting for 60min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) And transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcining and activating for 4h, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
The graphene oxide is graphene oxide GO prepared by adopting a Hummers method and taking natural graphite as a raw material.
The inorganic additive is indium oxide.
A preparation method of a mercury-free active negative electrode material comprises the following steps:
(1) Preparing a zinc active composite material: dispersing 10g of zinc nitrate and 3g of cerium nitrate in 3g of graphene oxide in 200ml of deionized water, adding 4g of terephthalic acid and 1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min; adjusting the pH value of the mixed solution to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating, setting the reaction temperature to be 180 ℃, reacting for 60min, and centrifugally filtering and drying after the reaction is finished to obtain a solid mixture; then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcination and activation for 4h, and cooling to room temperature along with the furnace to obtain a target product, namely the zinc active composite material;
(2) Weighing the raw materials in parts by weight, placing the raw materials in a container, uniformly mixing to prepare a negative electrode slurry, namely a negative electrode material, subsequently coating the negative electrode slurry on two sides of a copper strip through a slurry drawing die, drying, rolling and cutting to prepare a negative electrode plate, and then using the negative electrode plate.
Comparative example 1
The mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 80 parts of zinc active composite material, 5 parts of acetylene black, 1 part of carboxymethyl cellulose solution, 3 parts of sodium dodecyl benzene sulfonate, 0.6 part of PTFE aqueous solution and 1 part of inorganic additive.
The mass concentration of the carboxymethyl cellulose solution is 3.5%.
The mass concentration of the PTFE aqueous solution is 60%.
The preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate and 3g of graphene oxide in 200ml of deionized water, adding 4g of terephthalic acid and 1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to 180 ℃, reacting for 60min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) And transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcining and activating for 4 hours, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
In the comparative example, the raw materials and the preparation method are the same as those in example 3 except that cerium nitrate is not added to the zinc composite material for modification.
Comparative example 2
The mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 80 parts of zinc active composite material, 5 parts of acetylene black, 1 part of carboxymethyl cellulose solution, 3 parts of sodium dodecyl benzene sulfonate, 0.6 part of PTFE aqueous solution and 1 part of inorganic additive.
The mass concentration of the carboxymethyl cellulose solution is 3.5%.
The mass concentration of the PTFE aqueous solution is 60%.
The preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate and 3g of cerium nitrate in 200ml of deionized water, adding 4g of terephthalic acid and 1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to 180 ℃, reacting for 60min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) And transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcining and activating for 4 hours, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
The comparative example is the same as example 3 except that graphene oxide is not used in the zinc active negative electrode material for modification, and the other raw materials and the preparation method are the same.
Comparative example 3
The mercury-free active negative electrode material is prepared from the following raw materials in parts by weight: 80 parts of zinc active composite material, 5 parts of acetylene black, 1 part of carboxymethyl cellulose solution, 3 parts of sodium dodecyl benzene sulfonate, 0.6 part of PTFE aqueous solution and 1 part of inorganic additive.
The mass concentration of the carboxymethyl cellulose solution is 3.5%.
The mass concentration of the PTFE aqueous solution is 60%.
The preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate into 200ml of deionized water, adding 4g of terephthalic acid and 1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to 180 ℃, reacting for 60min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) And transferring the solid mixture into a muffle furnace, carrying out temperature programming to 500 ℃ at the speed of 5 ℃/min, carrying out heat preservation, calcining and activating for 4h, and cooling to room temperature along with the furnace to obtain the target product zinc active composite material.
The comparative example is the same as example 3 except that the zinc active negative electrode material is modified by neither cerium nitrate nor graphene oxide.
Performance test
Experimental materials: negative electrode materials obtained in examples 1 to 3 and comparative examples 1 to 3.
And (3) manufacturing a negative electrode: and coating the copper strip on two sides of the copper strip through a slurry drawing die, and drying, rolling and cutting the copper strip to obtain a negative plate for use.
The test method comprises the following steps:
the manufactured cathode and the sintered nickel hydroxide electrode are used as the anode and put into an organic glass container to form a semi-sealed simulation battery. 6MKOH +15g/LLIOH solution is used as electrolyte, and a polypropylene film is used as a diaphragm.
A constant current charge and discharge test was performed on the analog battery using a blue CT2001A battery test system (Wuhan LAND electronics co. Cyclic voltammetry tests and Tafel corrosion analysis were performed using a Chi660C electrochemical workstation (Shanghai Chenhua Instruments co., china).
And (3) testing the battery performance: after the battery is activated by 0.2C, the battery is charged for 6h by 0.2C, then the battery is placed for 30min, and then the battery is discharged to the voltage of 1.4 and 1.2V by 0.2C and 5C respectively, and the capacity performance of the negative electrode material is measured. And (3) testing the cycle performance of the battery: the cells were subjected to 1C charge and discharge tests at ambient temperature of 25C, respectively, with the capacity fade terminating at 80% of the maximum capacity.
And analyzing the micro morphology of the zinc active composite material by a scanning electron microscope, and treating a sample by adopting metal spraying.
The specific test results are shown in table 1:
TABLE 1 Battery Performance test results
As can be seen from data in the table, the battery obtained by the negative electrode material provided by the embodiment of the invention has high battery capacity and long cycle life, and completely meets the requirements of high energy and long endurance of marine electrical appliances. It can also be seen from the cyclic voltammetry curve (fig. 2) that the potential difference between the cathode peak and the anode peak is small, and the reversibility of the electrode is large when the difference between the peak potentials of the cathode and the anode is small, so that the cathode material in the embodiment of the invention has good electrochemical activity and strong reversibility in the aspect of cyclic reversibility of the electrode material. Meanwhile, the battery provided by the embodiment of the invention has a higher corrosion potential and a lower corrosion current density. I.e. has a better resistance to corrosion. In the electrochemical corrosion principle, the corrosion potential Ecorr plays a crucial role in electrode corrosion, the more negative the corrosion potential Ecorr is, the greater the corrosion degree is, and another parameter Jcorr represents the corrosion rate, the greater the corrosion rate is, and conversely, the smaller the Jcorr value is, the better corrosion resistance is.
The modification of the performances lies in the optimization of the preparation method of the zinc cathode material, the synergistic effect of the short rod-shaped structure and the cerium oxide and the graphene oxide, the deformation of the cathode is greatly reduced, zinc branches are reduced, and the hydrogen evolution reaction of the zinc branches is obviously inhibited, so that the overall performance of the cathode is improved. It can also be seen from the microscopic electron microscope image of the zinc active composite material of the invention that the zinc oxide has regular and uniform appearance and can effectively inhibit zinc dendrites. And the comparative examples 1-3 which lack the modification of cerium oxide and graphene oxide have no synergistic effect between the cerium oxide and the graphene oxide, and all performances of the comparative examples are obviously reduced.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons skilled in the art based on the above embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.
Claims (6)
1. The mercury-free active negative electrode material is characterized by being prepared from the following raw materials in parts by weight: 70-80 parts of zinc active composite material, 5-8 parts of acetylene black, 1-3 parts of carboxymethyl cellulose solution, 1-3 parts of sodium dodecyl benzene sulfonate, 0.3-0.6 part of PTFE aqueous solution and 0.5-1 part of inorganic additive;
the preparation method of the zinc active composite material comprises the following steps:
(1) Dispersing 10g of zinc nitrate, 3g of cerium nitrate and 3g of graphene oxide in 200ml of deionized water, adding 1-4g of terephthalic acid and 0.5-1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 10-20min;
(2) Adjusting the pH value of the mixed solution obtained in the step (1) to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating the mixed solution, setting the reaction temperature to be 100-180 ℃, reacting for 30-60min, and centrifugally filtering and drying the mixed solution after the reaction is finished to obtain a solid mixture;
(3) Then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 480-500 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation, calcination and activation for 2-4h, and cooling to room temperature along with the furnace to obtain a target product, namely the zinc active composite material;
the preparation method of the mercury-free active negative electrode material comprises the following specific steps: weighing the raw materials in parts by weight, placing the raw materials in a container, and uniformly mixing to prepare cathode slurry, namely the cathode material.
2. The mercury-free active negative electrode material of claim 1, wherein the carboxymethyl cellulose solution has a mass concentration of 2 to 3.5%.
3. The mercury-free active negative electrode material as claimed in claim 1, wherein the PTFE aqueous solution has a mass concentration of 50 to 60%.
4. The mercury-free active anode material as claimed in claim 1, wherein the graphene oxide is graphene oxide GO prepared by a Hummers method using natural graphite as a raw material.
5. The mercury-free active negative electrode material of claim 1, wherein the inorganic additive is indium oxide or indium hydroxide.
6. A method for preparing a negative plate using the mercury-free active negative electrode material of any one of claims 1 to 5, comprising the steps of:
(1) Preparing a zinc active composite material: dispersing 10g of zinc nitrate, 3g of cerium nitrate and 3g of graphene oxide in 200ml of deionized water, adding 1-4g of terephthalic acid and 0.5-1.5g of 1, 10-phenanthroline, and carrying out ultrasonic treatment for 10-20min; adjusting the pH value of the mixed solution to 7-9 by using sodium hydroxide, transferring the mixed solution into a reaction kettle, heating, setting the reaction temperature to be 100-180 ℃, reacting for 30-60min, and centrifugally filtering and drying after the reaction is finished to obtain a solid mixture; then transferring the solid mixture into a muffle furnace, carrying out temperature programming to 480-500 ℃ at the speed of 3-5 ℃/min, carrying out heat preservation, calcination and activation for 2-4h, and cooling to room temperature along with the furnace to obtain a target product, namely the zinc active composite material;
(2) Weighing the raw materials in parts by weight, placing the raw materials in a container, uniformly mixing to prepare a negative electrode slurry, namely a negative electrode material, subsequently coating the negative electrode slurry on two sides of a copper strip through a slurry drawing die, drying, rolling and cutting to prepare a negative electrode plate, and then using the negative electrode plate.
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