CN111816847A - Lead paste for preparing positive plate and preparation method thereof - Google Patents

Lead paste for preparing positive plate and preparation method thereof Download PDF

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Publication number
CN111816847A
CN111816847A CN202010649960.6A CN202010649960A CN111816847A CN 111816847 A CN111816847 A CN 111816847A CN 202010649960 A CN202010649960 A CN 202010649960A CN 111816847 A CN111816847 A CN 111816847A
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hollow glass
lead
glass microspheres
pbo
stirring
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CN111816847B (en
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高士元
蔡伟波
高芳开
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Zhaoqing Leoch Battery Technology Co Ltd
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Zhaoqing Leoch Battery Technology Co Ltd
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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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • H01M4/20—Processes of manufacture of pasted electrodes
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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 lead paste for preparing a positive plate and a preparation method thereof, wherein the lead paste comprises the following components: hollow glass microspheres, deionized water, PbO and sulfuric acid; the mass ratio of the hollow glass microspheres to the lead of the PbO is 0.05-0.2; the mass ratio of the sulfuric acid to the lead in the PbO is 0.06-0.16; the apparent density of the lead plaster is 3-6 g/cm3. The invention relates to hollow glass microspheres and a positive active substance PbO2Compounding, preparing lead plaster with special structure type, and exerting the hollow glass microsphere and PbO2Synergistic effect of (1), increase of PbO2Contact area with electrolyteThe reaction contact surface is increased, and the reversibility and reaction kinetics of charge and discharge are improved, so that the capacitance and the service life are improved; meanwhile, the stability of the electrode structure is improved, so that the electrode adapts to large strain without causing volume expansion, the failure of the electrode is avoided, and the service life of the battery is greatly ensured.

Description

Lead paste for preparing positive plate and preparation method thereof
Technical Field
The invention relates to the technical field of lead paste of a positive plate, in particular to lead paste for preparing the positive plate and a preparation method thereof.
Background
The traditional lead-acid battery has been successfully applied to systems such as communication and electric vehicles by virtue of the advantages of low cost, mature technology and the like, and is an energy storage battery which accords with the industrial layout and manufacturing level in China. However, lead-acid batteries also have the problems of insufficient specific mass energy, insufficient cycle life, and the like, and therefore, improvement research on the performance improvement of lead-acid batteries is continuously carried out at present.
Positive active material porous PbO of traditional lead-acid battery2Is a polymorphic compound, and has the core problem that the active substance PbO2Poor conductivity and lead paste falling off due to softening. Active material PbO during charging2The amorphous state is metastable state, the amorphous state is gradually crystallized along with the circulation, namely, the crystallinity is increased, the number of hydrate is reduced, the amorphous state is increased, PbO2The electrical contact between the particles deteriorates, eventually leading to the active substance PbO2Softening and dropping off. While in charging, due to PbSO4Is itself non-electroactive and has poor conductivity, and only by shear stress can redox substances be used as PbSO4The abnormal substances of the membrane are drawn into the membrane, and the charge transfer in the electrode is carried out by the diffusion of ions or electroactive particles and the transfer of the charges in adjacent redox centers, so that the charges need to pass through PbSO4The film is then transferred to the internal active material PbO2. Because of the surface PbSO4The layer hinders the occurrence of the body reaction of the lead-acid battery, and a bias voltage applied to the positive electrode causes a hydrogen-oxidation reaction (HOR) to occur, which causes a change in the concentration of the electrolyte, and a vicious circle further causes a reduction in the performance of the battery and a reduction in the life of the battery. Meanwhile, the positive electrode has failure modes such as poor conductivity, water loss, acid stratification and the like caused by softening of active substances. Therefore, lead paste softening can prevent electrolyte from being applied to PbO2The effective infiltration of the surface leads to low utilization ratio of the specific surface area of the active substance, thereby hindering the electron transfer between the electrolyte and the electrode and playing a role in inhibiting the charge transmission in the electrochemical reaction process. Traditional leadThe defects of small specific energy, short cycle service life and the like of the acid battery cannot meet the requirements of the modern society on long-life and high-capacity batteries, the electrochemical property of the electrode material has important influence on the performance of the lead-acid battery, and the electrode material and PbO have important influence on the performance of the lead-acid battery2The positive electrode materials with the same position have few types in practical application and the research is slow. Therefore, the improvement of the conventional chemical power source is an important subject to be overcome urgently. The hollow glass microsphere is a novel material which has wide application and excellent performance and is developed in recent years. The hollow glass microsphere is a hollow sphere which is made of inorganic materials, mainly contains borosilicate, has the granularity of 10-250 mu m, the density of 0.1-0.7 g/ml and the wall thickness of 1-2 mu m. The hollow glass microsphere has the advantages of light weight, large volume, low heat conductivity coefficient, high compressive strength, good dispersibility, good fluidity and good stability. In addition, the composite material also has the excellent performances of self-lubrication, light weight, no toxicity, non-combustibility, good chemical stability, high dispersion and the like, and has lipophobic and hydrophilic performances after special treatment.
Due to the high specific pore volume, the large specific surface area, the adsorption capacity, the low resistivity, the high electron mobility, the chemical inertness and the like of the hollow glass microspheres, the hollow glass microspheres have potential application values in various fields such as adsorption, chemical sensors, catalyst carriers, energy storage, novel functional composite materials and the like. In view of the good adsorbability and the electron storage/release capacity of the hollow glass microspheres, the material can effectively improve adsorption and chemical reaction in the mesoporous, promote the charge transfer efficiency of the key element step of catalytic reaction, and further obviously strengthen the corresponding chemical reaction process.
Disclosure of Invention
The invention aims to provide a lead paste for preparing a positive plate and a preparation method thereof2Compounding, preparing lead plaster with special structure type, and exerting the hollow glass microsphere and PbO2Synergistic effect of (1), increase of PbO2The contact area with the electrolyte is increased, the reaction contact surface is increased, and the reversibility and reaction kinetics of charge and discharge are improved, so that the capacitance and the service life are improved; simultaneously, the stability of the electrode structure is improved, and the electrode is adaptive to large strain without leadingThe volume expansion of the battery is realized, the failure of the electrode is avoided, and the service life of the battery is greatly ensured.
The technical scheme provided by the invention is as follows:
a lead paste for preparing a positive electrode plate, comprising: hollow glass microspheres, deionized water, PbO and sulfuric acid; the mass ratio of the hollow glass microspheres to the lead of the PbO is 0.05-0.2; the mass ratio of the sulfuric acid to the lead in the PbO is 0.06-0.16; the apparent density of the lead plaster is 3-6 g/cm3。
Preferably, the adhesive also comprises an adhesive, wherein the adhesive is short fiber with the length of 1-5 mm.
Preferably, the hollow glass microspheres are passivated hollow glass microspheres.
Preferably, the diameter of the hollow glass microsphere is 20-50 μm.
The invention also provides a preparation method of the lead paste for preparing the positive plate, which comprises the following steps:
s2, preparing a hollow glass microsphere dispersion liquid: mixing and stirring deionized water and hollow glass microspheres to obtain a hollow glass microsphere dispersion liquid;
s3, preparing the hollow glass microsphere/Pb composite material: mixing and stirring the hollow glass microsphere dispersion liquid and lead powder to obtain the hollow glass microsphere/Pb composite material; wherein the mass ratio of the hollow glass microspheres to the lead powder is 0.05-0.2;
s4, preparing a hollow glass microsphere/PbO composite material lead paste: mixing the hollow glass microsphere/Pb composite material and sulfuric acid, and stirring at 40-70 ℃ to form the lead plaster; wherein the mass ratio of the sulfuric acid to the lead powder is 0.06-0.16, and the apparent density of the lead plaster is 3-6 g/cm3。
Preferably, step S3 specifically includes: preparing a hollow glass microsphere/Pb composite material: mixing and stirring the hollow glass microsphere dispersion liquid, the lead powder and the bonding material to obtain the hollow glass microsphere/Pb composite material; the mass ratio of the hollow glass microspheres to the lead powder is 0.05-0.2, and the bonding material is short fiber with the length of 1-5 mm.
Preferably, step S2 is preceded by the steps of:
s11, passivating and modifying the surface of the hollow glass microsphere: mixing the hollow glass microspheres with H2O2Mixing the solution and stirring at 35-45 ℃; then cooling to room temperature for suction filtration; and finally, drying to constant weight to obtain the passivated hollow glass microspheres.
Preferably, said H2O2The mass ratio of the solution to the hollow glass microspheres is 40-120, and H is2O2Is occupied by H2O2The mass fraction of the solution is 8-12%, and the drying temperature is 55-60 ℃.
Preferably, step S2 is preceded by the steps of:
s12, passivating and modifying the surface of the hollow glass microsphere: mixing the hollow glass microspheres and a strong acid solution and stirring at 60-90 ℃; then cooling to room temperature for suction filtration; and finally, drying to constant weight to obtain the passivated hollow glass microspheres.
Preferably, in step S2: the mass ratio of the deionized water to the hollow glass microspheres is 1500-4500, the stirring time is not less than 20min, and the stirring temperature is room temperature.
The lead paste for preparing the positive plate and the preparation method thereof provided by the invention can bring at least one of the following beneficial effects:
1. hollow glass microsphere for improving active substance PbO2Porosity and conductivity. The hollow glass microspheres have larger specific surface area and pore volume, and the structural characteristics are favorable for adsorbing and fixing electrolyte molecules, are favorable for the transmission and adsorption of electrolyte ions, and improve the specific surface utilization rate, thereby improving the electrochemical capacitance performance of the electrode and enhancing the electrochemical characteristics of the electrode.
2. The hollow glass microspheres reinforce the active substance PbO2Internal proton H + conduction. The vector charge transfer effect of the hollow glass microspheres is strengthened in processes of charge transmission in the electrodes, inter-phase crossing of electrolyte and the surfaces of the hollow glass microspheres and the like in the HER process, the active center density in the electrocatalysis process is improved, and the electrochemical performance is reducedDegree of polarization of the chemical process.
3. The hollow glass microsphere has the characteristics of excellent thermal stability, high-speed electron mobility which is not influenced by temperature, small thermal expansion coefficient, mechanochemical stability and the like, and shows great advantages as a thermoelectric material. The invention effectively combines the hollow glass microspheres and the PbO2The advantages of the two are combined, so that the high-temperature accelerated cycle performance of the electrode is improved.
4. The hollow glass microspheres can effectively improve the adsorption and chemical reaction in the mesoporous, promote the charge transfer efficiency of the key element step of catalytic reaction, further improve the cycle life of the battery and prolong the service life of the battery.
5. The hollow glass microspheres enhance electron e-conduction. The lead paste generates electrons through two ways: charging process, active material PbO2Electrochemical oxidation of surfaces (PbSO)4+2H2O→PbO2+3H++HSO4 -+2e-) generates electrons; hollow glass microspheres as PbO2The charge transport layer and the electrochemical reaction interface generate anode reaction on the surface of the hollow glass microsphere to generate electrons. The electrons generated by the two ways are converged, so that the electron concentration in the electrode is greatly improved, the charge transfer efficiency of the step of catalyzing reaction key elements can be effectively promoted, and the reaction rate is greatly improved. The charge transfer efficiency of the key element step of the catalytic reaction is promoted, and the reaction kinetics is promoted.
6. The hollow glass microspheres as charge conduction carriers have good electron transmission channels, strengthen the electrochemical reaction on the surface of the electrode and the charge transfer of the two-phase interface of the electrolyte/the surface of the electrode, enhance the capacity of conducting electrons, accelerate the charge-discharge rate, reduce the diffusion resistance between the electrode and the electrolyte, increase the storage capacity of charges, and improve the charge state of a part of the battery, thereby improving the electric capacity of the electrode.
7. Hollow glass microsphere for inhibiting positive active material PbO in charging and discharging process2The volume is changed, so that the effective contact area of the electrode surface and the electrolyte is increased, the specific surface area and the electric double layer capacitance required by the reaction are provided, and the efficiency of the electrolyte penetrating into the electrode is promoted.
8. Stabilizing the active substance. The larger specific surface area of the hollow glass microspheres is beneficial to the contact and diffusion of electrolyte, and is beneficial to oxygen separated out from the positive electrode in the electrocatalysis process to rapidly leave the surface of the electrode, so that the stability of the electrode is improved.
9. The hollow glass microspheres are subjected to surface passivation modification treatment to remove surface grease, so that the hollow glass microspheres become hydrophilic and have certain chemical activity, and are easier to disperse in deionized water, and uniform hollow glass microsphere dispersion liquid is obtained; the traditional lead plaster preparation method of the lead plaster additive modified electrode is that carbon materials and lead powder are mixed and stirred, water and sulfuric acid are added to prepare the lead plaster, so that the additive is unevenly dispersed, and the local energy density of a polar plate is low. Compared with the hollow glass microspheres passivated by concentrated acid at high temperature (60-90 ℃), the concentrated acid volatilizes at high temperature to cause concentration change, the process is not easy to control, and environmental pollution and human health are caused. And H2O2The passivation temperature (35-45 ℃) is milder, H2O2The concentration is stable and the process is easy to control and realize, and the method does not cause environmental pollution and influence human health, and is more environment-friendly and healthy.
10. The addition of the bonding material can form a network structure in the lead plaster, and the strength of the positive plate polar plate provided with the lead plaster is greatly improved through the bridging, flocculation and other effects of the bonding material, so that the anti-falling performance of the positive plate is improved, and the service life of the battery is prolonged.
Drawings
The above characteristics, technical features, advantages and implementation modes of the lead paste for manufacturing the positive plate and the method for manufacturing the same will be further described in a clearly understandable manner by referring to the accompanying drawings.
FIG. 1 is an elemental distribution diagram of the present lead paste;
fig. 2 is a graph showing the distribution of elements of the present lead paste applied to a positive plate (before testing);
fig. 3 is an elemental distribution plot of a positive plate (after testing) provided with the present lead paste.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will be made with reference to the accompanying drawings. It is obvious that the drawings in the following description are only some examples of the invention, and that for a person skilled in the art, other drawings and embodiments can be derived from them without inventive effort.
For the sake of simplicity, the drawings only schematically show the parts relevant to the present invention, and they do not represent the actual structure as a product.
In one embodiment of the present invention, a lead paste for preparing a positive electrode plate includes: hollow glass microspheres, deionized water, PbO and sulfuric acid; the mass ratio of the hollow glass microspheres to the lead of the PbO is 0.05-0.2; the mass ratio of the sulfuric acid to the lead of the PbO is 0.06-0.16; the apparent density of the lead plaster is 3-6 g/cm3。
It is worth to say that the lead paste is spread on a substrate after being solidified at high temperature to form the hollow glass microsphere/PbO of the lead-acid battery2The PbO in the lead paste is changed into PbO in the process of high-temperature curing of the composite positive plate2. The hollow glass microspheres and PbO in the lead paste2The following synergistic effects are achieved: 1) the large specific surface area of the hollow glass microspheres is utilized to accelerate gas separated out in the electrocatalysis process to rapidly leave the surface of the electrode, so that the stability of the electrode is ensured; 2) the hollow glass microsphere has a large amount of edge surface defects and is used as a dopant for changing PbO2The energy band structure of the electrodes enables the electrodes to show different semiconductor characteristics; 3) the reaction active center is provided by the hollow glass microspheres: multi-layer structure hollowThe glass microspheres are more contact reaction sites on the contact interface of the electrode and the electrolyte, and the hollow glass microsphere particles form a uniform mass transfer network structure in the electrode, so that the electrochemical reaction is promoted to be uniformly carried out on the surface and inside of the electrode, and the volume expansion phenomenon of a buffer polar plate in the charging and discharging process is avoided; 4) hollow glass microsphere and positive electrode PbO2The energy band bending and the electrochemical active surface area of the electrode electrolyte and the electrode surface are improved compositely, the impedance of the electrode process is reduced, the accumulation of charges on the electrode surface is reduced, the interphase transfer of electrons from the electrolyte to the electrode surface and the transmission in the electrode are accelerated, the polarization degree of the electrode is reduced, and the electrode process is strengthened; 5) the hollow glass microspheres are used as heterogeneous materials to improve the dispersion of active substances, improve the utilization rate of the active substances, inhibit the volume change in the charging and discharging processes, and delay the softening failure of the anode material due to the dual structural characteristics; 6) by pairing PbO2The electronic structure of the electrode is adjusted, the binding energy of reactants on the surface of the catalyst is optimized to form the dual-functional composite anode, the hollow glass microspheres are used as an intermediate and a storage base for electron transfer, the interface electronic state between a carrier and an active site is regulated and controlled, and the transfer of electrons to an active center is strengthened, so that the whole catalytic process is promoted. The following preparation method can be referred to for the preparation of the lead paste.
In another embodiment of the invention, in addition to the above embodiment, the adhesive further comprises a binder, wherein the binder is short fibers with the length of 1-5 mm. Preferably, the binder is a staple fiber having a length of 2 mm. It is worth mentioning that the binder is preferably made of aramid fibers or a material having similar properties to aramid fibers.
In another embodiment of the present invention, based on any of the above embodiments, the hollow glass microspheres are passivated hollow glass microspheres. It is worth noting that the hollow glass microspheres are prepared by a strong oxidizing agent (e.g., H)2O2Etc.) or strong acid (e.g., concentrated nitric acid, etc.), the specific passivation process may be referred to the following preparation method.
In another embodiment of the invention, based on any one of the above embodiments, the diameter of the hollow glass microsphere is 20-50 μm. Preferably, the diameter of the hollow glass microsphere is 25-40 μm. Preferably, the diameter of the hollow glass microsphere is 30-35 μm.
In another embodiment of the present invention, based on any one of the above embodiments, the mass ratio of the hollow glass microspheres to the lead (i.e., lead powder) is 0.1 to 0.11; the mass ratio of the sulfuric acid to the lead is 0.1-0.12; the apparent density of the lead plaster is 4.25-4.3 g/cm3. Preferably, the sulfuric acid has a sulfuric acid density of 1.325 ± 0.01 g/ml.
In another embodiment of the present invention, a method for preparing a lead paste for a positive electrode plate includes the steps of:
s2, preparing a hollow glass microsphere dispersion liquid: mixing and stirring deionized water and hollow glass microspheres to obtain a hollow glass microsphere dispersion liquid;
s3, preparing the hollow glass microsphere/Pb composite material: mixing and stirring the hollow glass microsphere dispersion liquid and lead powder to obtain the hollow glass microsphere/Pb composite material; wherein the mass ratio of the hollow glass microspheres to the lead powder is 0.05-0.2;
s4, preparing a hollow glass microsphere/PbO composite material lead paste: mixing the hollow glass microsphere/Pb composite material and sulfuric acid, and stirring at 40-70 ℃ to form the lead plaster; wherein the mass ratio of the sulfuric acid to the lead powder is 0.06-0.16, and the apparent density of the lead plaster is 3-6 g/cm3。
In this embodiment, the traditional lead plaster preparation method of the electrode modified by the lead plaster additive is to mix and stir the carbon material and the lead powder, and then add water and sulfuric acid to prepare the lead plaster, which may cause uneven dispersion of the additive and lower local energy density of the electrode plate. The mixing technology can realize the uniform mixing of the hollow glass microspheres and the lead powder, can ensure the stability of the lead plaster coating paste and the combining capacity of the polar plate and the lead plaster, and is beneficial to forming a hollow glass microsphere conductive network structure in the lead plaster, thereby improving the conduction and the conductivity of protons H & lt + & gt in the positive plate. It should be noted that deionized water may exist as water molecules and/or as bound water in the lead paste due to temperature and stirring during the whole preparation process, but all should fall within the scope of the present invention.
In another embodiment of the present invention, on the basis of the above embodiment, the step S3 specifically includes: preparing a hollow glass microsphere/Pb composite material: mixing and stirring the hollow glass microsphere dispersion liquid, the lead powder and the bonding material to obtain the hollow glass microsphere/Pb composite material; the mass ratio of the hollow glass microspheres to the lead powder is 0.05-0.2, and the bonding material is short fiber with the length of 1-5 mm. Preferably, the binder is a staple fiber having a length of 2 mm. It is worth mentioning that the binder is preferably made of aramid fibers or a material having similar properties as aramid fibers. Preferably, the stirring time in step S3 is not less than 5 min. Preferably, the stirring time in step S3 is 5min to 10 min. In practical applications, the amount of the binder added may be set according to the strength requirements of the electrode, but the electrochemical properties of the electrode are not affected as much as possible. The lead powder and the bonding material can be mixed together and added into the hollow glass microsphere dispersion liquid, or the bonding material is added in the mixing process of the lead powder and the hollow glass microsphere dispersion liquid, and the setting is specifically carried out according to the actual requirement.
In another embodiment of the present invention, a method for preparing a lead paste for a positive electrode plate, on the basis of any one of the above embodiments, the step S2 is preceded by the steps of:
s11, passivating and modifying the surface of the hollow glass microsphere: mixing the hollow glass microspheres with H2O2Mixing the solution and stirring at 35-45 ℃; then cooling to room temperature for suction filtration; and finally, drying to constant weight to obtain the passivated hollow glass microspheres.
Preferably, in step S11: said H2O2The mass ratio of the solution to the hollow glass microspheres is 40-120, and H is2O2Is occupied by H2O2The mass fraction of the solution is 8-12%, and the drying temperature is 55-60 ℃. Preferably, step S11, the following steps: said H2O2The mass ratio of the solution to the hollow glass microspheres is 50-100, and H2O2Is occupied by H2O2The mass fraction of the solution is 10%, and the drying temperature is 55-60 ℃. Preferably, the stirring time in step S11 is not less than 1.5 h. Preferably, the stirring time in step S11 is 1.5 to 6 hours. Preferably, the stirring time in step S11 is 2 to 4 hours.
In another embodiment of the present invention, unlike the above embodiments, a method for preparing a lead paste for a positive electrode plate includes, before step S2, the steps of:
s12, passivating and modifying the surface of the hollow glass microsphere: mixing the hollow glass microspheres and a strong acid solution and stirring at 60-90 ℃; then cooling to room temperature for suction filtration; and finally, drying to constant weight to obtain the passivated hollow glass microspheres.
In this embodiment, the strong acid may be nitric acid, hydrogen fluoride, or concentrated hydrochloric acid, or a mixture of two or more of the foregoing strong acids. Preferably, in step S12: the stirring temperature is 80 ℃, and the drying temperature is higher than 90 ℃.
In another embodiment of the present invention, a method for preparing a lead paste for a positive electrode plate, on the basis of any one of the above embodiments, in step S2: the mass ratio of the deionized water to the hollow glass microspheres is 1500-4500, the stirring time is not less than 20min, and the stirring temperature is room temperature. Preferably, in step S2: the mass ratio of the deionized water to the hollow glass microspheres is 2000-3500, and the stirring time is not 30-60 min. Preferably, the diameter of the hollow glass microsphere is 20-50 μm. Preferably, the diameter of the hollow glass microsphere is 25-40 μm. Preferably, the diameter of the hollow glass microsphere is 30-35 μm. Preferably, the mass ratio of the hollow glass microspheres to the lead powder is 0.1-0.11; the mass ratio of the sulfuric acid to the lead powder is 0.1-0.12; the apparent density of the lead plaster is 4.25-4.3 g/cm3. Preferably, the sulfuric acid has a sulfuric acid density of 1.325 ± 0.01 g/ml. Preferably, in step S4: the stirring time is not less than 15 min. Preferably, in step S4: stirring time is 20min to 25 min. It is to be noted that the room temperature referred to in the present invention is 25. + -. 5 ℃. The value range of the invention includes the end value, for example, the stirring time is 20 min-25 min, and the stirring time can be 20min, 25min or more than 20min and less than 25 min.
Illustratively, the preparation method of the lead paste for preparing the positive plate specifically comprises the following steps:
s11: adding 50g of hollow glass microspheres with the diameter of 20-50 mu m into 2000ml of 10% H2O2Stirring the solution for 2 hours at the reaction temperature of 40 ℃; and then cooling to room temperature, removing the supernatant solution, centrifuging the suspension for 3 times to form a hollow glass sphere mixture, repeatedly washing the hollow glass sphere mixture by using deionized water, performing suction filtration until the hollow glass sphere mixture is neutral, and finally drying the neutral hollow glass sphere mixture in a drying box at 60 ℃ to constant weight to form the passivated hollow glass microspheres.
S2: and (4) adding the passivated hollow glass microspheres obtained by the treatment in the step S11 into 100kg of deionized water, and stirring for 30min at the room temperature of 25 ℃ to obtain a uniform hollow glass microsphere dispersion liquid.
S3: adding the hollow glass microsphere dispersion liquid prepared in the step S2 into a paste mixer, mixing and stirring the hollow glass microsphere dispersion liquid and 1000g of lead powder for 8min at room temperature, and adding a bonding substance into the mixing and stirring process of the hollow glass microsphere dispersion liquid and the lead powder to form a hollow glass microsphere/Pb composite material in order to uniformly mix the hollow glass microsphere and the lead powder and ensure the stability of the lead paste coating of the hollow glass microsphere/PbO composite material and the bonding capability of a polar plate and the lead paste;
s4, adding 10kg of sulfuric acid with the density of 1.325g/ml into the hollow glass microsphere/Pb composite material mixed in the step S3, stirring for 20min, controlling the reaction temperature at 65 ℃, and obtaining the lead plaster with the density of 4.28 g/cm3In this step lead will be oxidized to form PbO.
To further demonstrate that the lead paste is suitable for use in electrodes, applicants prepared the lead paste prepared according to the above steps and cured at high temperature to make hollow glass microspheres/PbO2The positive plate was compounded and characterized by EDS mapping (JSM-7500F)The elemental distribution of the lead paste before application to the positive plate (as shown in fig. 1) and the elemental distribution of the positive plate (as shown in fig. 2). As can be seen from fig. 1, the distribution of O and Pb elements in the above lead paste is wide and substantially uniform, indicating that O and Pb elements combine together to form a large amount of PbO. The Pb element exists mostly in the form of PbO. As can be seen from FIG. 2, it can be seen that the O element and the Pb element are combined together, and that the Pb element is mostly PbO2Exist in the form of (1). The distribution area of the O element is more favorable because of PbO2The plate physically adsorbs O2 in the air due to the porous structure. Meanwhile, the applicant conducted the hollow glass microsphere/PbO2After the composite positive plate is subjected to external formation, no hollow glass microsphere material is separated out on the surface, and no expansion deformation phenomenon of a grid occurs.
To further demonstrate that the present lead pastes are suitable for use in lead acid batteries, applicants have incorporated the above hollow glass microspheres/PbO2And assembling the energy storage battery on the composite positive plate, and detecting the charge acceptance and the cycle life so as to research the electrochemical characteristics of the composite electrode. The primary basis for the test is YDT 799-. The test results are shown as: the charge acceptance capacity Ica of the energy storage battery is more than or equal to 3, and the cycle life 50 percent DOD is more than 600 times.
At the same time, applicants also characterized the hollow glass microspheres/PbO after cycle life testing by EDS mapping (JSM-7500F)2The element distribution of the composite positive plate (as shown in fig. 3). As can be seen from FIG. 3, it can be seen that the distribution of O and Pb elements is wide and substantially uniform, indicating that O and Pb elements combine together to form a large amount of PbO2. The distribution area of Pb element can be covered with O, S element, which shows that S, Pb element is combined together to form a small amount of PbSO4The Pb element is mostly PbO2Exist in the form of (1).
It should be noted that the above embodiments can be freely combined as necessary. The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A lead paste for producing a positive electrode plate, comprising:
hollow glass microspheres, deionized water, PbO and sulfuric acid;
the mass ratio of the hollow glass microspheres to the lead of the PbO is 0.05-0.2;
the mass ratio of the sulfuric acid to the lead of the PbO is 0.06-0.16;
the apparent density of the lead plaster is 3-6 g/cm3。
2. The lead paste as claimed in claim 1, further comprising a binder, wherein the binder is short fibers having a length of 1 to 5 mm.
3. The lead paste of claim 1, wherein the hollow glass microspheres are passivated hollow glass microspheres.
4. The lead paste as claimed in any one of claims 1 to 4, wherein the diameter of the hollow glass microspheres is 20 to 50 μm.
5. A method for preparing a lead paste for preparing a positive plate is characterized by comprising the following steps:
s2, preparing a hollow glass microsphere dispersion liquid: mixing and stirring deionized water and hollow glass microspheres to obtain a hollow glass microsphere dispersion liquid;
s3, preparing the hollow glass microsphere/Pb composite material: mixing and stirring the hollow glass microsphere dispersion liquid and lead powder to obtain the hollow glass microsphere/Pb composite material; wherein the mass ratio of the hollow glass microspheres to the lead powder is 0.05-0.2;
s4, preparing a hollow glass microsphere/PbO composite material lead paste: mixing the hollow glass microsphere/Pb composite material and sulfuric acid, and stirring at 40-70 ℃ to form the lead plaster; wherein the mass ratio of the sulfuric acid to the lead powder is 0.06-0.16, and the lead plasterApparent density of 3-6 g/cm3。
6. The method according to claim 5, wherein step S3 specifically includes:
preparing a hollow glass microsphere/Pb composite material: mixing and stirring the hollow glass microsphere dispersion liquid, the lead powder and the bonding material to obtain the hollow glass microsphere/Pb composite material; the mass ratio of the hollow glass microspheres to the lead powder is 0.05-0.2, and the bonding material is short fiber with the length of 1-5 mm.
7. The method of claim 5, wherein step S2 is preceded by the steps of:
s11, passivating and modifying the surface of the hollow glass microsphere: mixing the hollow glass microspheres with H2O2Mixing the solution and stirring at 35-45 ℃; then cooling to room temperature for suction filtration; and finally, drying to constant weight to obtain the passivated hollow glass microspheres.
8. The method of claim 7, wherein the H is2O2The mass ratio of the solution to the hollow glass microspheres is 40-120, and H is2O2Is occupied by H2O2The mass fraction of the solution is 8-12%, and the drying temperature is 55-60 ℃.
9. The method of claim 5, wherein step S2 is preceded by the steps of:
s12, passivating and modifying the surface of the hollow glass microsphere: mixing the hollow glass microspheres and a strong acid solution and stirring at 60-90 ℃; then cooling to room temperature for suction filtration; and finally, drying to constant weight to obtain the passivated hollow glass microspheres.
10. The production method according to any one of claims 5 to 9, wherein in step S2:
the mass ratio of the deionized water to the hollow glass microspheres is 1500-4500, the stirring time is not less than 20min, and the stirring temperature is room temperature.
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Denomination of invention: A lead paste for preparing positive electrode plates and a preparation method thereof

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Pledgee: Bank of Beijing Limited by Share Ltd. Shenzhen branch

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