CN110611090A - Preparation method of positive active material of lead-acid storage battery - Google Patents
Preparation method of positive active material of lead-acid storage battery Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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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
- 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
- H01M4/626—Metals
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- 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
- H01M2004/028—Positive electrodes
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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 a preparation method of a positive active material of a lead-acid storage battery, belonging to the technical field of production and manufacturing of lead-acid storage batteries. The preparation method of the invention comprises the steps of firstly synthesizing nano lead oxide, wherein the nano lead oxide is doped with antimony in the synthesis process; and then preparing lead paste of the positive electrode of the lead-acid storage battery by adopting the antimony-doped nano lead oxide, namely the positive electrode active material of the lead-acid storage battery. The lead-acid storage battery positive active material can improve the utilization rate of the positive active material, thereby improving the gravimetric specific energy of the battery, simultaneously keeping the stable structure of the positive electrode in the circulating process and prolonging the deep circulating service life of the battery.
Description
Technical Field
The invention relates to the technical field of production and manufacturing of lead-acid storage batteries, in particular to a preparation method of a positive active material of a lead-acid storage battery.
Background
For a long time, the emission of automobile exhaust causes serious electrical pollution, and the living condition of human beings is obviously worsened. In order to protect the environment and save energy, the development of the electric vehicle is imperative, and many acquaintances at home and abroad predict that the century will be an era that the electric vehicle replaces a fuel vehicle. Lead-acid batteries are the ideal choice for power sources for electric vehicles in recent and transitional periods due to their excellent cost performance.
The concept of lead-acid batteries was generated by prandtl research and invention in 1860, and lead-acid batteries have evolved into a wide range of commercial products over the course of more than a century. Although lead-acid batteries containing lead and lead sulfate components have many disadvantages, they have advantages of low manufacturing cost, simple design, high reliability, relative safety, etc., compared to other chemical power sources such as lithium batteries. The lead-acid storage battery is widely applied to occasions such as automobile starting, traction power of forklifts, ships and the like, power of electric bicycles, power of electric tools, fixed energy storage, illumination and the like due to relatively good specific power characteristics. However, the application of lead-acid batteries to new energy automobile power sources is limited due to the higher specific energy and longer deep discharge cycle life required for batteries for power applications, and further improvements and improvements in gravimetric energy and cycle life are also required for electric bicycles and tools.
The lead-acid storage battery mainly comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive active material of the lead-acid storage battery is lead dioxide, the negative active material of the lead-acid storage battery is lead, and the electrolyte is sulfuric acid aqueous solution. The electrode reactions follow the bipolar sulfation theory proposed by glasiton and terapp. The current failure modes of the lead-acid storage battery mainly comprise early capacity loss of a positive electrode, softening and falling of a positive electrode active substance, sulfation of a negative electrode, water loss thermal runaway of the battery and the like. The early capacity loss and the softening and falling of the active substance of the positive electrode are root causes influencing the service life of the battery, particularly the deep cycle service life for power, and the performance of the active substance of the positive electrode can directly influence the specific capacity characteristic of the battery, so that the problem of the active substance of the positive electrode is solved, and the active substance plays a vital role in prolonging the service life of the battery, developing the lead-acid battery industry and fully utilizing social resources.
The traditional lead-acid accumulator is prepared by ball milling method, which contains about 70% lead oxide, the ball contains about 30% metal lead, then it is mixed with sulfuric acid and water to make lead paste, and then it is coated on the grid, and solidified and dried to make the raw plate, then the battery is assembled, and converted into lead dioxide active material by formation process. Because the lead oxide particles prepared by the ball milling method are large, the prepared polar plate has low electrochemical activity, the inside of the ball is difficult to participate in charge-discharge reaction, and the utilization rate of active substances is low. Meanwhile, the consistency of the lead oxide particles prepared by the ball milling method is poor, so that the consistency of the battery is poor. Since the positive electrode plate undergoes volume expansion and contraction during charge and discharge, large particles also tend to cause softening and shedding of the active material during cycling. In addition, the positive electrode active material is likely to undergo a significant early decay phenomenon (PCL2) during cyclic charge and discharge, mainly due to deterioration in conductivity between the active materials as the cycle progresses.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a positive active material of a lead-acid storage battery. The lead-acid storage battery positive active material prepared by the invention can improve the utilization rate of the positive active material, thereby improving the gravimetric specific energy of the battery, simultaneously keeping the positive structure stable in the circulating process and prolonging the deep circulating service life of the battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a positive active material of a lead-acid storage battery comprises the steps of firstly synthesizing nano lead oxide, wherein the nano lead oxide is doped with antimony in the synthesis process; and then preparing lead paste of the positive electrode of the lead-acid storage battery by adopting the antimony-doped nano lead oxide, namely the positive electrode active material of the lead-acid storage battery.
Further, the preparation method of the positive active material of the lead-acid storage battery comprises the following steps:
(1) adding polyvinylpyrrolidone and sodium antimonate into a lead nitrate solution containing 0.02mol/L, performing ultrasonic treatment for 20-30min, and slowly adding sufficient sodium hydroxide solution to obtain a mixture I; the addition amount of the polyvinylpyrrolidone is 8-15 g/L; the addition amount of the sodium antimonate is 0.5-10 g/L;
(2) performing ultrasonic treatment on the mixture I for 20-30min, filtering, and washing with distilled water and ethanol to obtain a precipitate I; then adding 10g of the precipitate I into 50-60ml of ethanol, carrying out ultrasonic treatment for 30-40min, and carrying out ultrasonic filtration to obtain a precipitate II; dehydrating the precipitate II at the temperature of 300-320 ℃ for 3-4h to obtain antimony doped nano lead oxide particles;
(3) carrying out ultrasonic treatment on the antimony-doped nano lead oxide particles in ethanol for 20-30min to obtain a mixture II, filtering the mixture II and drying at the temperature of 105-110 ℃ to obtain powdery antimony-doped nano lead oxide;
(4) adding powdery antimony doped nano lead oxide into colloidal graphite, mixing and stirring uniformly, adding deionized water, mixing and stirring uniformly, then slowly adding a sulfuric acid aqueous solution, mixing and stirring uniformly to obtain the lead-acid storage battery positive electrode active material.
In the technical scheme, preferably, in the step (1), the addition amount of the polyvinylpyrrolidone is 10 g/L; the addition amount of the sodium antimonate is 2 g/L.
In the above technical solution, preferably, in the step (1), the concentration of the sodium hydroxide solution is 2mol/L, and the addition amount is 10 to 20 mL.
Preferably, in the step (1), the step (2) and the step (3), the ultrasonic conditions are 240W, 40KHz and 60 ℃.
In the above technical solution, preferably, in the step (4), the addition amounts of the respective substances are as follows: 1000g of powdery antimony doped nano lead oxide, 3g of colloidal graphite, 105g of deionized water and 1.4g/cm380g of aqueous sulfuric acid solution.
Compared with the prior art, the invention has the following beneficial effects:
(1) the lead-acid storage battery positive lead plaster is prepared by adopting the antimony doped nano lead oxide, the electrochemical activity of a positive active substance is improved by utilizing the small-size effect and the surface effect of a nano material, the utilization rate of the active substance is improved, and the weight of the battery is improvedSpecific energy. The nanometer lead oxide adopted by the invention is doped with a certain amount of antimony element, the surface catalysis of antimony ions is utilized to accelerate the electrochemical reaction speed of the lead dioxide, and the conductivity of metal antimony is utilized to increase the electronic conductivity among nanometer materials. The existence of antimony ions enables the positive active substance to have higher proton conductivity and electron conductivity, and the analysis reason is probably that the antimony ions are metal ions and are easy to combine with protons, which is equivalent to the jump of the protons among water molecules, so that the electrochemical reaction of the positive active substance can be carried out at a higher speed, and the active electrochemical activity of the positive electrode is improved. Simultaneous PbO2The particles are composed of highly crystalline inner portions (crystalline regions) and amorphous, hydrated surfaces (amorphous regions); the presence of antimony ions aids in the formation of a hydrated surface layer and is also one of the beneficial factors in improving electrochemical activity and deep cycle life.
(2) The invention solves the problem of reduced deep cycle life after the utilization rate of the active substance of the positive electrode is improved by double means of nano-crystallization and antimony doping, stabilizes the small-particle nano lead oxide by the 'bridge' generated by antimony ions, improves the electrode performance by the surface catalysis of the antimony ions, realizes double improvement of the utilization rate of the active substance and the deep cycle service life of the battery, and improves the performance of the positive electrode by double means of antimony doping and nano-crystallization. On one hand, the electrochemical activity is improved through nanocrystallization, on the other hand, a stable structure of the positive active material is formed through an antimony doping means, the two materials supplement each other and cooperate with each other, and the deep cycle service life of the electrode is prolonged.
Drawings
FIG. 1 is a comparative graph of different multiplying power discharge capacities of the positive electrodes of a test battery, a comparison battery 1, a comparison battery 2 and a comparison battery 3; notation in the figure: 1-control cell 1; 2-control cell 2; 3-control cell 3; 4-test cell;
fig. 2 is a graph comparing the positive 100% DOD cycle life of test cell, control cell 1, control cell 2, and control cell 3, labeled: 1-control cell 1; 2-control cell 2; 3-control cell 3; 4-test cell.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
A preparation method of a positive active material of a lead-acid storage battery comprises the following steps:
(1) adding polyvinylpyrrolidone and sodium antimonate into a lead nitrate solution containing 0.02mol/L, performing ultrasonic treatment (240W, 40KHz, 60 ℃) for 30min, and then slowly adding 15mL of a 2mol/L sodium hydroxide solution (similar to a titration method) to obtain a mixture I; the addition amount of the polyvinylpyrrolidone is 10 g/L; the addition amount of the sodium antimonate is 2 g/L; in this step, antimony doped nano lead hydroxide is formed in the following reaction:
Pb(NO3)2(aq)+2NaOH(aq)→Pb(OH)2+2NaNO3(aq)
(2) performing ultrasonic treatment (240W, 40KHz, 60 ℃) on the mixture I for 30min, filtering the separated lead hydroxide, and washing the lead hydroxide with distilled water and ethanol for three times to obtain a precipitate I; then adding 10g of the precipitate I into 50ml of ethanol, carrying out ultrasonic treatment (240W, 40KHz, 60 ℃) for 30min, and carrying out ultrasonic filtration to obtain a precipitate II; dehydrating the precipitate II at 320 ℃ for 3h, and forming the antimony-doped nano lead oxide in a dehydration stage to obtain antimony-doped nano lead oxide particles; the dehydration stage takes place as follows:
Pb(OH)2(s)→PbO(s)+H2O(g)
(3) carrying out ultrasonic treatment (240W, 40KHz, 60 ℃) on the antimony-doped nano lead oxide particles in ethanol for 30min to obtain a mixture II, filtering the mixture II, and drying at 110 ℃ to obtain powdery antimony-doped nano lead oxide;
(4) adding 1000g of powdery antimony-doped nano lead oxide into 3g of colloidal graphite, mixing and stirring for 15min, adding 105g of deionized water, mixing and stirring for 5min, and slowly adding 80g of lead oxide with the concentration of 1.4g/cm3The sulfuric acid aqueous solution is mixed and stirred for 10min to obtain the positive active material of the lead-acid storage battery.
Example 2
A preparation method of a positive active material of a lead-acid storage battery comprises the following steps:
(1) adding polyvinylpyrrolidone and sodium antimonate into a lead nitrate solution containing 0.02mol/L, performing ultrasonic treatment (240W, 40KHz, 60 ℃) for 25min, and then slowly adding 20mL of a 2mol/L sodium hydroxide solution to obtain a mixture I; the addition amount of the polyvinylpyrrolidone is 15 g/L; the addition amount of the sodium antimonate is 10 g/L;
(2) performing ultrasonic treatment (240W, 40KHz, 60 ℃) on the mixture I for 25min, filtering, and washing with distilled water and ethanol to obtain a precipitate I; then adding 10g of the precipitate I into 60ml of ethanol, performing ultrasonic treatment (240W, 40KHz, 60 ℃) for 40min, and performing ultrasonic filtration to obtain a precipitate II; dehydrating the precipitate II at 310 ℃ for 3.5h to obtain antimony-doped nano lead oxide particles;
(3) carrying out ultrasonic treatment (240W, 40KHz, 60 ℃) on the antimony-doped nano lead oxide particles in ethanol for 25min to obtain a mixture II, filtering the mixture II, and drying at 110 ℃ to obtain powdery antimony-doped nano lead oxide;
(4) adding 1000g of powdery antimony-doped nano lead oxide into 3g of colloidal graphite, uniformly mixing and stirring, adding 105g of deionized water, uniformly mixing and stirring, and slowly adding 80g of lead oxide with the concentration of 1.4g/cm3The sulfuric acid aqueous solution is mixed and stirred evenly to obtain the positive active material of the lead-acid storage battery.
Example 3
A preparation method of a positive active material of a lead-acid storage battery comprises the following steps:
(1) adding polyvinylpyrrolidone and sodium antimonate into a lead nitrate solution containing 0.02mol/L, performing ultrasonic treatment (240W, 40KHz, 60 ℃) for 20min, and then slowly adding 10mL of a 2mol/L sodium hydroxide solution to obtain a mixture I; the addition amount of the polyvinylpyrrolidone is 8 g/L; the addition amount of the sodium antimonate is 0.5 g/L;
(2) performing ultrasonic treatment (240W, 40KHz, 60 ℃) on the mixture I for 20min, filtering, and washing with distilled water and ethanol to obtain a precipitate I; then adding 10g of the precipitate I into 55ml of ethanol, carrying out ultrasonic treatment (240W, 40KHz, 60 ℃) for 35min, and carrying out ultrasonic filtration to obtain a precipitate II; dehydrating the precipitate II at 300 ℃ for 4h to obtain antimony-doped nano lead oxide particles;
(3) carrying out ultrasonic treatment on the antimony-doped nano lead oxide particles in ethanol for 20min to obtain a mixture II, filtering the mixture II and drying at 105 ℃ to obtain powdery antimony-doped nano lead oxide;
(4) adding 1000g of powdery antimony-doped nano lead oxide into 3g of colloidal graphite, uniformly mixing and stirring, adding 105g of deionized water, uniformly mixing and stirring, and slowly adding 80g of lead oxide with the concentration of 1.4g/cm3The sulfuric acid aqueous solution is mixed and stirred evenly to obtain the positive active material of the lead-acid storage battery.
Preparing a battery:
s1, taking the positive active material of the lead-acid storage battery prepared in the embodiment 1, and manually coating and filling the positive active material on a prepared positive grid according to the required weight;
s2, curing and drying the polar plate: curing at 50 ℃ for 24h in a high-temperature high-humidity box under the condition of 95% water vapor, and drying at 70 ℃ for 24h in a ventilation drying box;
s3, battery assembling and formation: the semi-finished battery is assembled by a normally produced negative plate and an AGM diaphragm, the battery formation is the same as the conventional normal production process, and the battery is made into a 12V12Ah battery and then used as a test battery for experiments.
As a control, the inventors also made the following tests:
comparative battery 1: preparing lead oxide particles by adopting a ball milling method, specifically according to the production of the current lead-acid storage battery by adopting an Ishijin lead powder machine, firstly extruding and cutting lead ingots into small lead blocks, colliding the lead blocks in a rotary cylinder and reacting with oxygen to generate lead oxide particles, wherein unreacted metal lead is in the particles, the surface of the metal lead is lead oxide, and the oxidation degree of the metal lead oxide particles is 73-78%, so that ball-milled lead powder is obtained; adding 1000g of ball-milling lead powder prepared by the method into 3g of colloidal graphite, mixing and stirring uniformly, adding 105g of deionized water, mixing and stirring uniformly, and then slowly adding 80g of deionized water with the concentration of 1.4g/cm3The sulfuric acid aqueous solution is mixed and stirred evenly to obtain the positive active material of the lead-acid storage battery; and preparing according to the steps of S1-S4.
Comparative battery 2: preparing ball-milling lead powder according to the method of a reference battery 1, and mixing 98% of ball-milling lead powder and 2% of antimony oxideUniformly mixing the powder serving as ball-milling lead powder and antimony anode active substance, taking the ball-milling lead powder and antimony anode active substance, adding 1000g of the ball-milling lead powder and antimony anode active substance into 3g of colloidal graphite, uniformly mixing and stirring, adding 105g of deionized water, uniformly mixing and stirring, and slowly adding 80g of the mixture with the concentration of 1.4g/cm3The sulfuric acid aqueous solution is mixed and stirred uniformly to obtain the positive active material of the lead-acid storage battery; and preparing according to steps S1-S4.
Comparative battery 3: the method for preparing the nano lead oxide is different from the method in the embodiment 1 in that sodium antimonate is not added in the preparation process, and the prepared nano lead oxide is pure nano lead oxide without doping antimony; adding 1000g of pure nano lead oxide into 3g of colloidal graphite, uniformly mixing and stirring, adding 105g of deionized water, uniformly mixing and stirring, and slowly adding 80g of deionized water with the concentration of 1.4g/cm3The sulfuric acid aqueous solution is mixed and stirred uniformly to obtain the positive active material of the lead-acid storage battery; and preparing according to the steps of S1-S4.
Effect verification:
1. table 1 shows the current discharge time data for each set of experimental cells.
Table 1 experimental battery different current discharge time data table
Correspondingly, as shown in fig. 1, the discharge capacities of the positive electrodes of the test battery, the comparison battery 1, the comparison battery 2 and the comparison battery 3 are compared at different multiplying powers;
2. as shown in fig. 2, the cycle life of the positive electrode of the test cell, the control cell 1, the control cell 2 and the control cell 3 is compared by 100% DOD;
in conclusion, the comparison shows that the initial capacity, the deep cycle service life and the like of the battery prepared by the positive active material of the lead-acid storage battery are greatly improved. The invention can solve the problem of reduced deep cycle life after the utilization rate of the active substance of the anode is improved by preparing the nano lead oxide and simultaneously doping the antimony. The comparison battery 2 is ball-milled lead powder and doped antimony, the comparison battery 3 is nano lead oxide and undoped antimony, the discharge capacity and the cycle life of the two are greatly reduced, and therefore, the preparation of the nano lead oxide and the doping of the antimony need to be carried out synchronously, and the two cooperate with each other to achieve a good technical effect.
Although the present invention has been described with respect to the preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A preparation method of a positive active material of a lead-acid storage battery is characterized by comprising the following steps: firstly, synthesizing nano lead oxide, wherein the nano lead oxide is doped with antimony in the synthesis process; and then preparing lead paste of the positive electrode of the lead-acid storage battery by adopting the antimony-doped nano lead oxide, namely the positive electrode active material of the lead-acid storage battery.
2. The method of claim 1, wherein the method comprises the steps of:
(1) adding polyvinylpyrrolidone and sodium antimonate into a lead nitrate solution containing 0.02mol/L, performing ultrasonic treatment for 20-30min, and slowly adding sufficient sodium hydroxide solution to obtain a mixture I; the addition amount of the polyvinylpyrrolidone is 8-15 g/L; the addition amount of the sodium antimonate is 0.5-10 g/L;
(2) performing ultrasonic treatment on the mixture I for 20-30min, filtering, and washing with distilled water and ethanol to obtain a precipitate I; then adding 10g of the precipitate I into 50-60ml of ethanol, carrying out ultrasonic treatment for 30-40min, and carrying out ultrasonic filtration to obtain a precipitate II; dehydrating the precipitate II at the temperature of 300-320 ℃ for 3-4h to obtain antimony doped nano lead oxide particles;
(3) carrying out ultrasonic treatment on the antimony-doped nano lead oxide particles in ethanol for 20-30min to obtain a mixture II, filtering the mixture II and drying at the temperature of 105-110 ℃ to obtain powdery antimony-doped nano lead oxide;
(4) adding powdery antimony doped nano lead oxide into colloidal graphite, mixing and stirring uniformly, adding deionized water, mixing and stirring uniformly, then slowly adding a sulfuric acid aqueous solution, mixing and stirring uniformly to obtain the lead-acid storage battery positive electrode active material.
3. The method of claim 2, wherein the method comprises the following steps: in the step (1), the addition amount of the polyvinylpyrrolidone is 10 g/L; the addition amount of the sodium antimonate is 2 g/L.
4. The method of claim 2, wherein the method comprises the following steps: in the step (1), the concentration of the sodium hydroxide solution is 2mol/L, and the addition amount is 10-20 mL.
5. The method of claim 2, wherein the method comprises the following steps: in the step (1), the step (2) and the step (3), the ultrasonic condition is 240W, 40KHz and 60 ℃.
6. The method of claim 2, wherein the method comprises the following steps: in the step (4), the addition amount of each substance is as follows: 1000g of powdery antimony doped nano lead oxide, 3g of colloidal graphite, 105g of deionized water and 1.4g/cm380g of aqueous sulfuric acid solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112768640A (en) * | 2020-12-30 | 2021-05-07 | 蚌埠睿德新能源科技有限公司 | Positive active material of lead-acid storage battery electrode and product thereof |
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| JPH09283137A (en) * | 1996-04-11 | 1997-10-31 | Japan Storage Battery Co Ltd | Lead-acid battery |
| CN102689923A (en) * | 2011-03-24 | 2012-09-26 | 杨春晓 | Preparation method of lead-acid battery PbO nano-powder |
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| CN112768640A (en) * | 2020-12-30 | 2021-05-07 | 蚌埠睿德新能源科技有限公司 | Positive active material of lead-acid storage battery electrode and product thereof |
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Application publication date: 20191224 |