CN115000411A - Alkaline battery cathode material for marine environment and battery using same - Google Patents
Alkaline battery cathode material for marine environment and battery using same Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M6/04—Cells with aqueous electrolyte
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0014—Alkaline electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses an alkaline battery cathode material for a marine environment and a battery using the same, and belongs to the technical field of battery energy materials. The cathode material is prepared from the following raw materials in parts by weight: 70-105 parts of zinc powder, 20-40 parts of composite conductive emulsion, 50-80 parts of electrolyte and 6-10 parts of nano additive. Firstly, the invention introduces the formula of the composite conductive emulsion to improve the conductivity; and then, the nano additive is introduced, so that the internal resistance of the battery can be greatly reduced, and the high-power discharge performance and the long-term storage performance of the battery are improved. The battery prepared by the cathode material is suitable for various complex special environments, and has stable performance, simple raw materials, low cost and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of battery energy materials, and particularly relates to an alkaline battery cathode material for a marine environment and a battery using the same.
Background
With the continuous development of science and technology, people can not leave the support of energy sources for clothes and clothes. The size of the articles is as small as that of articles such as mobile phones, tablet computers and smart homes, and the size of the articles is as large as that of electric vehicles and smart power grids, which become essential parts in life. However, the traditional energy reserves are limited, and the exploitation cost is higher and higher. The use of clean energy such as solar energy, wind energy and geothermal energy has the problems of strong dependence on the environment at that time, difficult transportation and the like. The battery is mainly applied to three fields, namely the traffic power field, the energy storage power field and the communication field, as an energy storage and conversion device. The battery is mature in the common life field of people, and the technology is mature.
And for special environmental fields, such as high-salt and high-corrosion marine environments, different environments place more rigorous requirements on the electrical performance, corrosion resistance and 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 such sensors,
the alkaline energy storage system belongs to a water-phase electrolyte system, so that the system has extremely high safety and does not have the risk of combustion and explosion. The aqueous electrolyte also provides excellent ion transmission rate for the battery, so that the alkaline battery has good rate performance. The alkaline battery has the advantages of low price of electrode materials, no potential harm to the environment and simple manufacturing process. In addition, the alkaline battery has simple structure, low requirement on the production process, no complicated later maintenance and long service life, and is very suitable for large-scale energy storage.
However, the current alkaline battery cannot completely meet the use requirement of a severe marine environment, and when a marine ship is soaked in a high-humidity and high-salt environment for a long time, various small sensors in the ship need to supply electric energy of the battery, so that the stability of the performance of the battery is crucial. And whether the performance of the battery or the battery pack is determined by the electrode material or not. The positive electrode material of the alkaline battery is generally nickel oxide or hydroxide, and the production process is relatively mature. The problems with alkaline battery negative electrode materials are greater than with positive electrode materials. Therefore, how to improve the performance of the negative electrode material is the key point for realizing the improvement of the performance of the alkaline battery.
Disclosure of Invention
The invention provides a novel electrode material for an alkaline battery and a battery prepared from the material, aiming at the technical problems of the current alkaline battery cathode material, and the novel electrode material is suitable for special environments such as ocean high salt and the like, has stable electrical property and high safety, and has wide application potential.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the alkaline battery cathode material for the marine environment is prepared from the following raw materials in parts by weight: 70-105 parts of zinc powder, 20-40 parts of composite conductive emulsion, 50-80 parts of electrolyte and 6-10 parts of nano additive.
Furthermore, the zinc powder is lead-free and mercury-free zinc powder, and the average particle size is 10-100 mu m.
Further, the electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
Further, the composite conductive emulsion is prepared by mixing the following raw materials in parts by weight: 30-40 parts of conductive graphite, 8-18 parts of water-soluble resin emulsion, 3-6 parts of conductive carbon black, 2-4 parts of conductive polymer auxiliary agent, 2-4 parts of dispersing auxiliary agent and 28-55 parts of deionized water.
The specific preparation method of the composite conductive emulsion comprises the following steps: preparing a conductive polymer auxiliary agent and a dispersing auxiliary agent into an aqueous solution through deionized water; and then sequentially adding the conductive graphite, the water-soluble resin emulsion and the conductive carbon black into a stirring container, stirring and mixing for 10-20min, then adding the prepared aqueous solution, stirring and dispersing for 15-25min, then performing ball milling for 20-30min, and then performing ultrasonic oscillation on the ball-milled slurry for 20-30min to obtain the composite conductive emulsion.
Further, the conductive graphite is micropowder graphite having an average particle diameter of less than 30 μm.
Further, the water-soluble resin emulsion is a mixed emulsion of equal amounts of epoxy resin and phenolic resin.
Further, the conductive carbon black is polymer graft modified conductive carbon black; the preparation method of the polymer graft modified conductive carbon black comprises the following steps: adding excessive 10 wt% KOH solution into conductive carbon black, fully reacting, adding beta-propiolactone with the mass of 3-5% of the solution, reacting for 5-6h at 65-75 ℃, standing after the reaction is finished, removing the upper-layer alkali liquor, washing with water for several times to remove residual alkali and salt, and finally dehydrating to obtain the polymer graft modified conductive carbon black.
Furthermore, the conductive polymer additive is at least one of polyacetylene, polypyrrole, polythiophene, polytereene, polyaniline and polyphenylene sulfide.
Furthermore, the dispersing auxiliary agent is at least one of ammonia water, sodium sulfonate and sodium hexametaphosphate.
Further, the preparation method of the nano additive comprises the following steps: dissolving 0.5g of zinc nitrate hexahydrate and 0.4g of polyvinylpyrrolidone in 60mL of ethanol, then dropwise adding 50mL of ethanol solution in which 1.2g of trimesic acid is dissolved, stirring for 10-20min, standing and aging the suspension for 24h, centrifuging and cleaning the precipitate, and drying; then placing the precipitate in nitrogen atmosphere at 2-3 deg.C/min -1 The temperature is raised to 300 ℃ at the temperature raising rate, and the temperature is naturally lowered when the temperature is kept for 2 hours, so that the nano additive is obtained.
The cathode material of the invention is further upgraded and optimized in the prior art, and the preparation method refers to the prior art to carry out vacuum stirring, namely: preparing the composite conductive emulsion, adding the electrolyte, uniformly stirring, adding zinc powder and a nano additive, and stirring in vacuum to form the negative electrode zinc paste material containing the composite conductive emulsion.
The negative electrode material of the battery adopts the negative electrode material.
Preparing a battery: and injecting the negative electrode zinc paste material into the diaphragm paper, assembling a negative electrode end, a sealing ring and a negative current collector copper needle into a sealing body, inserting the sealing body into the negative electrode zinc paste, and sealing the positive electrode steel shell and the sealing body to obtain the battery.
At present, the alkaline battery technology is mature, and all performances are stable in daily life environment. Under extreme environmental conditions, such as marine environment, plateau environment and the like, the current alkaline manganese battery has the problems of low discharge current density, accelerated zinc polarization of a negative electrode and the like when discharging, and the battery performance is influenced. Therefore, how to optimize the performance of the battery and greatly improve the corrosion resistance and the power supply stability of the battery so as to quickly adapt to the use requirements of various extreme environmental temperatures and humidity is a problem which needs to be solved urgently.
In the existing research on improving the performance of the negative electrode of the alkaline manganese battery, people mostly perform more research on the appearance and granularity of zinc powder, and pay attention to research and improvement on the appearance, bulk density, particle size and alloying elements of the zinc powder, but the research on the appearance and granularity of the zinc powder is a bottleneck at present, so that the performance of the alkaline manganese battery must be further improved through other approaches.
Advantageous effects
(1) Firstly, a compound conductive emulsion formula is introduced, conductive graphite, water-soluble resin emulsion and conductive carbon black are used as main materials, wherein the conductive graphite has excellent conductivity, the adhesive force of the neutral water resin to a positive electrode ring of an alkaline battery is excellent, the alkali corrosion resistance is good, the conductive carbon black has lower resistivity, the conductive graphite, the water-soluble resin emulsion and the conductive carbon black can be uniformly dispersed through a nano additive and a dispersing auxiliary agent, and the conductivity can be further improved through a conductive polymer auxiliary agent;
(2) secondly, introducing a nano additive which is cubic and has a large specific surface area, uniformly dispersing the nano additive in the calamine cream containing the composite conductive emulsion, and mutually matching the raw materials, so that the internal resistance of the battery can be greatly reduced, and the high-power discharge performance and the long-term storage performance of the battery can be improved; meanwhile, the cubic nano material can play a supporting role, so that the shape of the zinc paste is stable and is not easy to change, and the power supply stability is improved;
(3) the negative electrode material disclosed by the invention is used for preparing the battery, so that the internal resistance of the battery can be greatly reduced, the high-power discharge performance, the long-term storage performance and the corrosion resistance of the battery are improved, the battery is suitable for various complex special environments, and the performance of the battery is stable; and the raw materials are simple, the cost is low, and the application prospect is wide.
Drawings
FIG. 1 is an electron microscope image of the micro-morphology of the nano-additive 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 alkaline battery cathode material for the marine environment is prepared from the following raw materials in parts by weight: 70 parts of zinc powder, 20 parts of composite conductive emulsion, 50 parts of electrolyte and 6 parts of nano additive.
The zinc powder is lead-free and mercury-free zinc powder, and the average particle size is 10-100 mu m.
The electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
The composite conductive emulsion is prepared by mixing the following raw materials in parts by weight: 30 parts of conductive graphite, 8 parts of water-soluble resin emulsion, 3 parts of conductive carbon black, 2 parts of conductive polymer additive, 2 parts of dispersing additive and 28 parts of deionized water.
The specific preparation method of the composite conductive emulsion comprises the following steps: preparing a conductive polymer auxiliary agent and a dispersing auxiliary agent into an aqueous solution through deionized water; and then sequentially adding the conductive graphite, the water-soluble resin emulsion and the conductive carbon black into a stirring container, stirring and mixing for 10min, then adding the prepared aqueous solution, stirring and dispersing for 15min, then carrying out ball milling for 20min, and then carrying out ultrasonic oscillation on the ball-milled slurry for 20min to obtain the composite conductive emulsion.
The conductive graphite is micro-powder graphite with the average grain diameter of less than 30 mu m.
The water-soluble resin emulsion is a mixed emulsion of epoxy resin and phenolic resin with equal amount.
The conductive carbon black is polymer graft modified conductive carbon black; the preparation method of the polymer graft modified conductive carbon black comprises the following steps: adding excessive 10 wt% KOH solution into conductive carbon black, fully reacting, adding beta-propiolactone with the mass of 3% of the solution, reacting for 5 hours at 65 ℃, standing after the reaction is finished, removing the upper-layer alkali liquor, washing with water for several times to remove the residual alkali and salt, and finally dehydrating to obtain the polymer graft modified conductive carbon black.
The conductive polymer additive is polyacetylene.
The dispersing auxiliary agent is ammonia water.
The preparation method of the nano additive comprises the following steps: dissolving 0.5g of zinc nitrate hexahydrate and 0.4g of polyvinylpyrrolidone in 60mL of ethanol, then dropwise adding 50mL of ethanol solution in which 1.2g of trimesic acid is dissolved, stirring for 10min, standing and aging the suspension for 24h, centrifuging and cleaning the precipitate, and drying; then placing the precipitate in nitrogen atmosphere at 2-3 deg.C/min -1 The temperature is raised to 300 ℃ at the heating rate, and the nano additive is obtained after natural cooling when the temperature is kept for 2 hours.
Example 2
The alkaline battery cathode material for the marine environment is prepared from the following raw materials in parts by weight: 90 parts of zinc powder, 30 parts of composite conductive emulsion, 65 parts of electrolyte and 8 parts of nano additive.
The zinc powder is lead-free and mercury-free zinc powder, and the average particle size is 10-100 mu m.
The electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
The composite conductive milk is prepared by mixing the following raw materials in parts by weight: 30 parts of conductive graphite, 13 parts of water-soluble resin emulsion, 5 parts of conductive carbon black, 3 parts of conductive polymer additive, 3 parts of dispersing additive and 35 parts of deionized water.
The specific preparation method of the composite conductive emulsion comprises the following steps: preparing a conductive polymer auxiliary agent and a dispersing auxiliary agent into an aqueous solution through deionized water; and then sequentially adding the conductive graphite, the water-soluble resin emulsion and the conductive carbon black into a stirring container, stirring and mixing for 20min, then adding the prepared aqueous solution, stirring and dispersing for 25min, then carrying out ball milling for 30min, and then carrying out ultrasonic oscillation on the ball-milled slurry for 30min to obtain the composite conductive emulsion.
The conductive graphite is micropowder graphite with the average grain diameter of less than 30 mu m.
The water-soluble resin emulsion is a mixed emulsion of epoxy resin and phenolic resin with equal amount.
The conductive carbon black is polymer graft modified conductive carbon black; the preparation method of the polymer graft modified conductive carbon black comprises the following steps: adding excessive 10 wt% KOH solution into conductive carbon black, after full reaction, adding beta-propiolactone with the mass of 5% of the solution, reacting for 6h at 75 ℃, standing after the reaction is finished, removing the upper-layer alkali liquor, then washing with water for several times to remove residual alkali and salt, and finally dehydrating to obtain the polymer graft modified conductive carbon black.
The conductive polymer additive is polythiophene.
The dispersing auxiliary agent is sodium hexametaphosphate.
The preparation method of the nano additive comprises the following steps: dissolving 0.5g of zinc nitrate hexahydrate and 0.4g of polyvinylpyrrolidone in 60mL of ethanol, then dropwise adding 50mL of ethanol solution in which 1.2g of trimesic acid is dissolved, stirring for 10min, standing and aging the suspension for 24h, centrifuging and cleaning the precipitate, and drying; then placing the precipitate in nitrogen atmosphere at 2-3 deg.C/min -1 The temperature is raised to 300 ℃ at the temperature raising rate, and the temperature is naturally lowered when the temperature is kept for 2 hours, so that the nano additive is obtained.
In the present embodiment, the anode material is further upgraded and optimized from the conventional anode zinc paste material, and the preparation method is performed by vacuum stirring with reference to the prior art, that is: preparing the composite conductive emulsion, adding the electrolyte, uniformly stirring, adding zinc powder and a nano additive, and stirring in vacuum to form the negative electrode zinc paste material containing the composite conductive emulsion.
The negative electrode material of the battery adopts the negative electrode material of the embodiment.
Example 3
The alkaline battery cathode material for the marine environment is prepared from the following raw materials in parts by weight: 105 parts of zinc powder, 40 parts of composite conductive emulsion, 80 parts of electrolyte and 10 parts of nano additive.
The zinc powder is lead-free and mercury-free zinc powder, and the average particle size is 10-100 mu m.
The electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
The composite conductive milk is prepared by mixing the following raw materials in parts by weight: 40 parts of conductive graphite, 18 parts of water-soluble resin emulsion, 6 parts of conductive carbon black, 4 parts of conductive polymer additive, 4 parts of dispersing additive and 55 parts of deionized water.
The specific preparation method of the composite conductive emulsion comprises the following steps: preparing a conductive polymer auxiliary agent and a dispersing auxiliary agent into an aqueous solution through deionized water; and then sequentially adding conductive graphite, water-soluble resin emulsion and conductive carbon black into a stirring container, stirring and mixing for 20min, then adding the prepared aqueous solution, stirring and dispersing for 25min, then performing ball milling for 30min, and then performing ultrasonic oscillation on the ball-milled slurry for 30min to obtain the composite conductive emulsion.
The conductive graphite is micropowder graphite with the average grain diameter of less than 30 mu m.
The water-soluble resin emulsion is a mixed emulsion of epoxy resin and phenolic resin with equal amount.
The conductive carbon black is polymer graft modified conductive carbon black; the preparation method of the polymer graft modified conductive carbon black comprises the following steps: adding excessive 10 wt% KOH solution into conductive carbon black, after full reaction, adding beta-propiolactone with the mass of 5% of the solution, reacting for 6h at 75 ℃, standing after the reaction is finished, removing the upper-layer alkali liquor, then washing with water for several times to remove residual alkali and salt, and finally dehydrating to obtain the polymer graft modified conductive carbon black.
The conductive polymer additive is polyphenylene sulfide.
The dispersing auxiliary agent is sodium hexametaphosphate.
The preparation method of the nano additive comprises the following steps: dissolving 0.5g of zinc nitrate hexahydrate and 0.4g of polyvinylpyrrolidone in 60mL of ethanol, then dropwise adding 50mL of ethanol solution in which 1.2g of trimesic acid is dissolved, stirring for 20min, standing and aging the suspension for 24h, centrifuging and cleaning the precipitate, and drying; then placing the precipitate in nitrogen atmosphere at 2-3 deg.C/min -1 The temperature is raised to 300 ℃ at the temperature raising rate, and the temperature is naturally lowered when the temperature is kept for 2 hours, so that the nano additive is obtained.
Comparative example 1
The alkaline battery cathode material for the marine environment is prepared from the following raw materials in parts by weight: 105 parts of zinc powder, 40 parts of composite conductive emulsion, 80 parts of electrolyte and 10 parts of nano additive.
The zinc powder is lead-free and mercury-free zinc powder, and the average particle size is 10-100 mu m.
The electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
The composite conductive milk is prepared by mixing the following raw materials in parts by weight: 40 parts of conductive graphite, 18 parts of water-soluble resin emulsion, 6 parts of conductive carbon black, 4 parts of conductive polymer additive, 4 parts of dispersing additive and 55 parts of deionized water.
The specific preparation method of the composite conductive emulsion comprises the following steps: preparing a conductive polymer auxiliary agent and a dispersing auxiliary agent into an aqueous solution through deionized water; and then sequentially adding conductive graphite, water-soluble resin emulsion and conductive carbon black into a stirring container, stirring and mixing for 20min, then adding the prepared aqueous solution, stirring and dispersing for 25min, then performing ball milling for 30min, and then performing ultrasonic oscillation on the ball-milled slurry for 30min to obtain the composite conductive emulsion.
The conductive graphite is micropowder graphite with the average grain diameter of less than 30 mu m.
The water-soluble resin emulsion is a mixed emulsion of epoxy resin and phenolic resin with equal amount.
The conductive carbon black is common conductive carbon black sold in the market, namely, the modification of a polymer is not carried out.
The conductive polymer additive is polyphenylene sulfide.
The dispersing auxiliary agent is sodium hexametaphosphate.
The preparation method of the nano additive comprises the following steps: dissolving 0.5g of zinc nitrate hexahydrate and 0.4g of polyvinylpyrrolidone in 60mL of ethanol, then dropwise adding 50mL of ethanol solution in which 1.2g of trimesic acid is dissolved, stirring for 20min, standing and aging the suspension for 24h, centrifuging and cleaning the precipitate, and drying; then placing the precipitate in nitrogen atmosphere at 2-3 deg.C/min -1 The temperature is raised to 300 ℃ at the heating rate, and the nano additive is obtained after natural cooling when the temperature is kept for 2 hours.
In this comparative example, the raw materials and preparation method were the same as in example 3, except that the conductive carbon black in the composite conductive emulsion was a commercially available ordinary conductive carbon black, that is, no modification of the polymer was performed.
Comparative example 2
The alkaline battery cathode material for the marine environment is prepared from the following raw materials in parts by weight: 105 parts of zinc powder, 40 parts of composite conductive emulsion and 80 parts of electrolyte.
The zinc powder is lead-free and mercury-free zinc powder, and the average particle size is 10-100 mu m.
The electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
The composite conductive emulsion is prepared by mixing the following raw materials in parts by weight: 40 parts of conductive graphite, 18 parts of water-soluble resin emulsion, 6 parts of conductive carbon black, 4 parts of conductive polymer additive, 4 parts of dispersing additive and 55 parts of deionized water.
The specific preparation method of the composite conductive emulsion comprises the following steps: preparing a conductive polymer auxiliary agent and a dispersing auxiliary agent into an aqueous solution through deionized water; and then sequentially adding the conductive graphite, the water-soluble resin emulsion and the conductive carbon black into a stirring container, stirring and mixing for 20min, then adding the prepared aqueous solution, stirring and dispersing for 25min, then carrying out ball milling for 30min, and then carrying out ultrasonic oscillation on the ball-milled slurry for 30min to obtain the composite conductive emulsion.
The conductive graphite is micropowder graphite with the average grain diameter of less than 30 mu m.
The water-soluble resin emulsion is a mixed emulsion of epoxy resin and phenolic resin with equal amount.
The conductive carbon black is polymer graft modified conductive carbon black; the preparation method of the polymer graft modified conductive carbon black comprises the following steps: adding excessive 10 wt% KOH solution into conductive carbon black, after full reaction, adding beta-propiolactone with the mass of 5% of the solution, reacting for 6h at 75 ℃, standing after the reaction is finished, removing the upper-layer alkali liquor, then washing with water for several times to remove residual alkali and salt, and finally dehydrating to obtain the polymer graft modified conductive carbon black.
The conductive polymer additive is polyphenylene sulfide.
The dispersing auxiliary agent is sodium hexametaphosphate.
In this comparative example, the raw materials and preparation method were the same as in example 3 except that no nano-additive was added.
Comparative example 3
The traditional zinc paste is used as a comparative example, namely the zinc paste is mainly prepared by mixing zinc powder and electrolyte, and components such as composite conductive emulsion, nano additive and the like are not added.
Performance testing
The cathode materials of the zinc pastes obtained in the examples 1 to 3 and the comparative examples 1 to 3 are subjected to battery preparation.
The preparation method of the battery comprises the following steps: the negative electrode zinc paste material is injected into the diaphragm paper, the negative electrode end, the sealing ring and the negative electrode current collector copper needle are assembled into a sealing body and then inserted into the negative electrode zinc paste, and the positive electrode steel shell and the sealing body are sealed to obtain the battery. The cells were assembled into LR6 cells for related performance testing.
Battery performance testing
The discharging performance of the battery adopts a DM2000 battery intelligent automatic detection system; the internal resistance of the battery is tested by adopting DF2811 type LCR digital bridge; the gas evolution of the battery is tested after the battery is placed in a high-temperature oven at 70 ℃ for 10 days.
The performance test results are shown in table 1:
table 1 results of performance testing
From the data in table 1, we can see that the battery using the embodiment of the present invention has good discharge performance and lower internal resistance. After high-temperature storage, the increase range of the internal resistance of the battery is small, the discharge performance is basically stable, the gas evolution amount is small when the battery is used, and the safety performance is excellent. In comparative examples 1 to 3 in which the negative electrode composition was changed, the respective performances were all reduced to different degrees. The composite conductive emulsion is added, so that the electrical property of the material is improved. The addition of the nano additive can remove zinc oxide generated on the surface of the zinc powder in time due to good dispersion performance, change the surface state of the zinc powder, keep the activity of the zinc powder, ensure that the zinc powder is in good contact with electrolyte, improve the conductivity of an electrode and reduce the internal resistance of a battery. The raw materials of the invention act together to greatly improve the performance of the traditional calamine cream. Stable discharge performance and extremely high safety, and is suitable for various complex environments such as oceans, plateaus and the like.
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 of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (10)
1. The alkaline battery cathode material for the marine environment is characterized by comprising the following raw materials in parts by weight: 70-105 parts of zinc powder, 20-40 parts of composite conductive emulsion, 50-80 parts of electrolyte and 6-10 parts of nano additive.
2. The alkaline battery anode material for the marine environment as claimed in claim 1, wherein the electrolyte comprises the following components in percentage by mass: potassium hydroxide: zinc oxide: and (5) water in a ratio of 10:1: 10.
3. The alkaline battery anode material for the marine environment as claimed in claim 1, wherein the composite conductive emulsion is prepared by mixing the following raw materials in parts by weight: 30-40 parts of conductive graphite, 8-18 parts of water-soluble resin emulsion, 3-6 parts of conductive carbon black, 2-4 parts of conductive polymer additive, 2-4 parts of dispersing additive and 28-55 parts of deionized water.
4. The alkaline battery negative electrode material for the marine environment as defined in claim 3, wherein the conductive graphite is fine graphite having an average particle diameter of less than 30 μm.
5. The negative electrode material for alkaline batteries for marine environments as claimed in claim 3, wherein the water-soluble resin emulsion is a mixed emulsion of equal amounts of epoxy resin and phenolic resin.
6. The alkaline battery negative electrode material for the ocean environment according to claim 3, wherein the conductive carbon black is a polymer graft-modified conductive carbon black; the preparation method of the polymer graft modified conductive carbon black comprises the following steps: adding excessive 10 wt% KOH solution into conductive carbon black, fully reacting, adding beta-propiolactone with the mass of 3-5% of the solution, reacting for 5-6h at 65-75 ℃, standing after the reaction is finished, removing the upper-layer alkali liquor, washing with water for several times to remove residual alkali and salt, and finally dehydrating to obtain the polymer graft modified conductive carbon black.
7. The alkaline battery negative electrode material for the ocean environment according to claim 3, wherein the conductive polymer additive is at least one of polyacetylene, polypyrrole, polythiophene, poly-p-styrene, polyaniline and polyphenylene sulfide.
8. The alkaline battery negative electrode material for ocean environments of claim 3, wherein the dispersion aid is at least one of ammonia water, sodium sulfonate and sodium hexametaphosphate.
9. The alkaline battery anode material for the ocean environment according to claim 1, wherein the nano additive is prepared by the following steps: dissolving 0.5g of zinc nitrate hexahydrate and 0.4g of polyvinylpyrrolidone in 60mL of ethanol, then dropwise adding 50mL of ethanol solution in which 1.2g of trimesic acid is dissolved, stirring for 10-20min, standing and aging the suspension for 24h, centrifuging and cleaning the precipitate, and drying; then placing the precipitate in nitrogen atmosphere at 2-3 deg.C/min -1 The temperature is raised to 300 ℃ at the temperature raising rate, and the temperature is naturally lowered when the temperature is kept for 2 hours, so that the nano additive is obtained.
10. A battery, characterized in that the negative electrode material of any one of claims 1 to 9 is applied to the negative electrode material of the battery.
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