CN113140732A - Lead-acid storage battery and paste acid as well as preparation method and application thereof - Google Patents

Lead-acid storage battery and paste acid as well as preparation method and application thereof Download PDF

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Publication number
CN113140732A
CN113140732A CN202110395721.7A CN202110395721A CN113140732A CN 113140732 A CN113140732 A CN 113140732A CN 202110395721 A CN202110395721 A CN 202110395721A CN 113140732 A CN113140732 A CN 113140732A
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acid
lead
polytetrafluoroethylene
paste
storage battery
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CN113140732B (en
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李伟伟
刘孝伟
张�雄
吴永新
代少振
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Chaowei Power Group Co Ltd
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Chaowei Power Group 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
    • H01M4/62—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
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 relates to the technical field of lead-acid storage batteries, and discloses a lead-acid storage battery and paste acid, and a preparation method and application thereof. The paste acid comprises polytetrafluoroethylene, sulfuric acid and water, wherein the mass fraction of the polytetrafluoroethylene in the paste acid is 0.1-2 wt%. The preparation method of the paste acid comprises the following steps: adding the polytetrafluoroethylene emulsion into the sulfuric acid solution under stirring, and uniformly dispersing to obtain the lead-acid storage battery and the paste acid. According to the invention, the polytetrafluoroethylene is added into the diachylon acid and then used for preparing the lead plaster, so that the dispersion uniformity of the polytetrafluoroethylene in the lead plaster can be improved, and the positive and negative performance improvement effect of the polytetrafluoroethylene is improved. The diachylic acid of the invention is used in the preparation of negative lead pasteAnd the molecular weight of the polytetrafluoroethylene is controlled to be 2 x 104‑5×104Within the range, the oxygen recombination efficiency in the negative electrode can be improved, and the water loss phenomenon of the lead-acid storage battery is reduced.

Description

Lead-acid storage battery and paste acid as well as preparation method and application thereof
Technical Field
The invention relates to the technical field of lead-acid storage batteries, in particular to a lead-acid storage battery paste acid, a preparation method and an application thereof.
Background
Lead powder, deionized water, paste acid, additives and the like are mixed in paste mixing equipment according to certain process requirements and carry out related chemical reaction, so that the lead paste meeting the related technical requirements and the coating requirements is generated. The paste-mixing acid used in the paste-mixing process is a dilute sulfuric acid solution with a relative density of 1.0-1.4, and the preparation method comprises the steps of slowly adding concentrated sulfuric acid with a given proportion into deionized water and continuously stirring to prepare the dilute sulfuric acid solution with a corresponding concentration. The current research on the kojic acid mainly focuses on the influence of sulfuric acid solutions with different relative densities on the lead paste and the performance of the final battery, and few reports on the kojic acid additive exist.
The polytetrafluoroethylene emulsion is a common additive in the lead plaster and is used for reducing the softening and falling-off of positive and negative active substances caused by volume expansion and shrinkage in the charge and discharge processes, but the polytetrafluoroethylene emulsion is separately added in the paste mixing process in the prior art, for example, the polytetrafluoroethylene emulsion is added after the polytetrafluoroethylene emulsion is mixed with lead powder and the like in the patent document with the publication number of CN104377359B, and the paste acid is added after the polytetrafluoroethylene emulsion is added and kneaded in the patent document with the publication number of CN110783566A, so that the problem of uneven dispersion of the polytetrafluoroethylene in the lead plaster is easily caused, and the improvement of the positive and negative performances of the polytetrafluoroethylene emulsion is influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lead-acid storage battery, paste acid, a preparation method and application thereof. According to the invention, the polytetrafluoroethylene is added into the diachylon acid, so that the dispersion uniformity of the polytetrafluoroethylene in the diachylon acid can be improved, and the positive and negative performance improvement effect of the polytetrafluoroethylene is improved.
The specific technical scheme of the invention is as follows:
a lead-acid battery and paste acid comprising the following components: polytetrafluoroethylene, sulfuric acid, water; the mass fraction of the polytetrafluoroethylene in the paste acid is 0.1-2 wt%.
The inventor finds that the mechanical strength of the positive electrode can be improved by adding polytetrafluoroethylene into the positive electrode lead plaster, and the mechanical strength of the positive electrode can be improved by adding the polytetrafluoroethylene into the negative electrode, so that oxygen recombination can be promoted, and the water loss phenomenon of the battery can be reduced. According to the invention, the polytetrafluoroethylene is added into the diachylon acid, and after the diachylon acid is added in the lead plaster preparation process, the polytetrafluoroethylene can be uniformly mixed with the positive and negative electrode active substances and the additive along with the sulfuric acid solution, so that the polytetrafluoroethylene can be more uniformly dispersed in the lead plaster, and the improvement effect on positive and negative polarity performance of the polytetrafluoroethylene can be exerted to a greater extent.
Preferably, the mass fraction of the sulfuric acid in the paste acid is 10 to 30 wt%.
Preferably, the polytetrafluoroethylene is modified polytetrafluoroethylene; the preparation method of the modified polytetrafluoroethylene emulsion comprises the following steps: (a) preparation of the polycarboxy oligourethane: under the protection of inert gas, adding 1, 4-butyl diisocyanate and tartaric acid into N, N-dimethylformamide according to the molar ratio of 1:0.8-1.2, reacting at 60-70 ℃ for 0.5-1.5h, and removing the solvent to obtain polycarboxy oligourethane;
in the step (a), the reaction between isocyanate and hydroxyl group causes the polymerization between butyl 1, 4-diisocyanate and tartaric acid, thereby producing an oligourethane having a large number of carboxyl groups (the carboxyl group is derived from tartaric acid).
(b) Preparation of a polytetrafluoroethylene-aminohexene emulsion: uniformly mixing an emulsifier, a stabilizer, an initiator and water, replacing air in a reaction container with inert gas, introducing tetrafluoroethylene, reacting at 70-80 ℃ under 1.0-1.5MPa for 0.5-1h, adding 5-hexene-1-amine, wherein the molar ratio of the tetrafluoroethylene to the 5-hexene-1-amine is 20-30:1, and continuously reacting at 70-80 ℃ under 1.0-1.5MPa for 0.5-1h to obtain a polytetrafluoroethylene-amino hexene emulsion;
in step (b), amino groups are introduced into the side chains of polytetrafluoroethylene by copolymerization of tetrafluoroethylene with 5-hexene-1-amine. Furthermore, the tetrafluoroethylene is prepolymerized, and then the 5-hexene-1-amine is added for further polymerization, so that the amino groups are uniformly distributed in the polytetrafluoroethylene-amino hexene, and the mechanical strength of the electrode is improved after the polycarboxyl polyurethane oligomer is grafted.
(c) Preparing modified polytetrafluoroethylene emulsion: adding polycarboxyl polyurethane oligomer into the polytetrafluoroethylene-amino hexene emulsion, fully mixing, and stirring to react for 0.5-1h at the temperature of 40-50 ℃ to obtain the polytetrafluoroethylene-amino hexene emulsion;
in the step (c), the polycarboxy polyurethane oligomer is grafted to a side chain of the polytetrafluoroethylene-amino hexene through the reaction of an isocyanate end group and an amino group in the polytetrafluoroethylene-amino hexene, so that the position of the side chain of the modified polytetrafluoroethylene, which is close to the tail end, has more carboxyl groups.
Polytetrafluoroethylene has poor adhesiveness and poor bonding strength with positive and negative active materials, so that the improvement effect on the mechanical strength of the electrode is limited. Aiming at the problem, the invention modifies the polytetrafluoroethylene, introduces polyurethane with more carboxyl on the side chain of the polytetrafluoroethylene, and can improve the bonding strength between the polytetrafluoroethylene and the positive and negative active substances through the complexation of the carboxyl and the-NHCOO-group (generated by the reaction of isocyanate and hydroxyl in the step (a)) and lead, thereby improving the mechanical strength of the electrode. In addition, in the invention, the polycarboxy polyurethane oligomer exists at the side chain of the modified polytetrafluoroethylene close to the tail end, so that the hydrophobicity of the main chain is not influenced, and the polytetrafluoroethylene is favorable for forming an oxygen recombination channel in the negative electrode so as to improve the oxygen recombination efficiency.
Further, in the step (b), the mass volume ratio of the tetrafluoroethylene to the water is 1g:2-4 mL; in the step (c), the mass volume ratio of the polycarboxy polyurethane oligomer to the polytetrafluoroethylene-amino hexene emulsion is 1g:3-6 mL.
Further, in the step (b), the initiator is ammonium persulfate; the mass volume ratio of the initiator to the water is 1g: 100-150L.
Further, in step (b), the emulsifier is ammonium perfluorooctanoate; the mass volume ratio of the emulsifier to the water is 1g: 4-5L.
Further, in the step (b), the stabilizer is paraffin wax; the mass volume ratio of the stabilizer to water is 1kg: 20-30L.
A preparation method of the cream acid comprises the following steps: adding the polytetrafluoroethylene emulsion into the sulfuric acid solution under stirring, and uniformly dispersing to obtain the lead-acid storage battery and the paste acid.
Preferably, the relative density of the sulfuric acid solution is 1.1-1.2; the solid content of the polytetrafluoroethylene emulsion is 10-65 wt%; the mass ratio of the sulfuric acid solution to the polytetrafluoroethylene emulsion is 15-35: 1.
A method for preparing lead-acid storage battery positive electrode lead paste comprises the following steps: and (3) uniformly mixing the lead powder and the positive lead plaster additive, adding water and the diacidic acid, and uniformly mixing to obtain the positive lead plaster of the lead-acid storage battery.
As the chemical reaction in the paste mixing process is generally exothermic reaction, the temperature of the lead paste can reach 60-80 ℃, the polytetrafluoroethylene can generate crosslinking reaction under the temperature and the complex chemical reaction condition in the paste mixing process, and meanwhile, the polytetrafluoroethylene molecular chains can also form physical crosslinking. Through such chemical and physical crosslinking, polytetrafluoroethylene can form a crosslinked skeleton in the lead paste, thereby playing a role in enhancing mechanical strength by adhesion in the positive electrode.
A method for preparing lead-acid storage battery negative electrode lead paste comprises the following steps: and uniformly mixing the lead powder and the negative lead plaster additive, adding water and the diacidic acid, and uniformly mixing to obtain the negative lead plaster of the lead-acid storage battery.
After the polytetrafluoroethylene forms a cross-linked network in the negative electrode, because the polytetrafluoroethylene has strong hydrophobicity and poor wettability of electrolyte, the polytetrafluoroethylene can play a role of an oxygen composite channel in the electrode, so that oxygen and hydrogen can be diffused along the polytetrafluoroethylene cross-linked network, the compounding of the oxygen and the hydrogen is promoted, and the water loss phenomenon of the lead-acid storage battery is effectively reduced.
Preferably, the molecular weight of the polytetrafluoroethylene in the kneading acid is 2X 104-5×104。
The molecular weight of polytetrafluoroethylene can influence the effect of improving the oxygen recombination efficiency in the negative electrode, and the specific mechanism is as follows: if the molecular weight of the polytetrafluoroethylene is too large, the fluidity of the polytetrafluoroethylene along with a sulfuric acid solution is poor, and the polytetrafluoroethylene is difficult to uniformly disperse into the lead paste in the paste mixing processThe uniformity of the distribution of the cross-linked network in the negative electrode is influenced, and the oxygen recombination efficiency is further influenced; if the molecular weight of the polytetrafluoroethylene is too low, it is difficult to form cross-linking after being dispersed in the lead paste, which is not favorable for forming interconnected oxygen recombination channels and also affects the oxygen recombination efficiency. The invention controls the molecular weight of the polytetrafluoroethylene to be 2 x 104-5×104Within the range, the negative electrode has higher oxygen recombination efficiency, and further reduces the water loss phenomenon of the lead-acid storage battery.
Preferably, the mass ratio of the lead powder to the diacidic acid is 7-10: 1.
Preferably, the mass ratio of the lead powder to the water is 8-12: 1.
Preferably, the negative electrode lead paste additive comprises one or more of barium sulfate, lignin and carbon black.
A lead-acid storage battery is prepared from the positive lead plaster prepared by the method and/or the negative lead plaster prepared by the method.
An electric vehicle comprises the lead-acid storage battery.
Compared with the prior art, the invention has the following advantages:
(1) by adding the polytetrafluoroethylene into the diachylon, the dispersity of the polytetrafluoroethylene in the diachylon can be improved, so that the improvement effect of the polytetrafluoroethylene on the mechanical property of the positive electrode and the oxygen recombination efficiency of the negative electrode is improved;
(2) the diachylon acid is used for preparing the negative lead plaster, and the molecular weight of polytetrafluoroethylene in the diachylon acid is controlled within a certain range, so that the oxygen recombination efficiency in the negative electrode can be improved, and the water loss phenomenon of a lead-acid storage battery is reduced;
(3) by modifying the polytetrafluoroethylene and introducing the polycarboxylic polyurethane at the tail end of the side chain, the bonding strength between the polytetrafluoroethylene and the positive and negative active substances can be improved, and the mechanical property of the electrode is improved.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
Lead-acid storage battery and paste acidThe composition comprises the following components: polytetrafluoroethylene, sulfuric acid and water. The molecular weight of the polytetrafluoroethylene is 2 multiplied by 104-5×104The mass fraction of the acid in the paste acid is 0.1-2 wt%. The mass fraction of the sulfuric acid in the paste acid is 10-30 wt%.
A preparation method of the cream acid comprises the following steps: adding polytetrafluoroethylene emulsion with the solid content of 10-65wt% into sulfuric acid solution with the relative density of 1.1-1.2 under stirring, wherein the mass ratio of the sulfuric acid solution to the polytetrafluoroethylene emulsion is 15-35:1, and uniformly dispersing to obtain the lead-acid storage battery and the paste acid.
A method for preparing lead-acid storage battery positive electrode lead paste comprises the following steps: and (3) uniformly mixing the lead powder and the positive lead plaster additive, adding water and the diacidic acid, and uniformly mixing to obtain the positive lead plaster of the lead-acid storage battery.
A method for preparing lead-acid storage battery negative electrode lead paste comprises the following steps: and uniformly mixing lead powder and a negative pole lead plaster additive, adding water and the diachylon acid, wherein the mass ratio of the lead powder to the diachylon acid is 7-10:1, and the mass ratio of the lead powder to the water is 8-12:1, and uniformly mixing to obtain the negative pole lead plaster of the lead-acid storage battery.
Optionally, the polytetrafluoroethylene is a modified polytetrafluoroethylene; the preparation method of the modified polytetrafluoroethylene emulsion comprises the following steps:
(a) preparation of the polycarboxy oligourethane: under the protection of inert gas, adding 1, 4-butyl diisocyanate and tartaric acid into N, N-dimethylformamide according to the molar ratio of 1:0.8-1.2, reacting at 60-70 ℃ for 0.5-1.5h, and removing the solvent to obtain polycarboxy oligourethane;
(b) preparation of a polytetrafluoroethylene-aminohexene emulsion: uniformly mixing an emulsifier, a stabilizer, an initiator and water, replacing air in a reaction container with inert gas, introducing tetrafluoroethylene, wherein the mass volume ratio of the tetrafluoroethylene to the water is 1g:2-4mL, reacting for 0.5-1h at 70-80 ℃ and 1.0-1.5MPa, adding 5-hexene-1-amine, wherein the molar ratio of the tetrafluoroethylene to the 5-hexene-1-amine is 20-30:1, and continuously reacting for 0.5-1h at 70-80 ℃ and 1.0-1.5MPa to obtain a polytetrafluoroethylene-amino hexene emulsion;
(c) preparing modified polytetrafluoroethylene emulsion: adding the polycarboxy polyurethane oligomer into the polytetrafluoroethylene-amino hexene emulsion according to the mass volume ratio of 1g:3-6mL, fully mixing, and stirring and reacting for 0.5-1h at the temperature of 40-50 ℃ to obtain the polytetrafluoroethylene-amino hexene emulsion.
Example 1
A lead-acid battery and paste acid are prepared by the following steps:
(1) slowly adding concentrated sulfuric acid into deionized water, and continuously stirring to uniformly mix the concentrated sulfuric acid and the deionized water to prepare a sulfuric acid solution with the relative density of 1.15;
(2) adding polytetrafluoroethylene emulsion with the solid content of 32 wt% into sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the polytetrafluoroethylene emulsion is 15:1, and the number average molecular weight of polytetrafluoroethylene is 2.07 x 104And dispersing uniformly to obtain the lead-acid storage battery and the paste acid.
The method for preparing the lead-acid storage battery anode by adopting the diacidic acid of the embodiment comprises the following specific steps:
(I) preparing positive lead paste: adding lead powder, red lead, tetrabasic lead sulfate, anisotropic graphite and short fibers into a paste mixer, stirring for 5min, adding water, stirring for 10min, slowly adding paste acid into the paste mixer within 15min, stirring for 20min, and discharging paste to obtain positive lead paste; the mass ratio of the lead powder to the red lead to the tetrabasic lead sulfate to the anisotropic graphite to the short fibers to the water to the paste acid is 100:3:0.2:0.1:0.1:9: 10;
(II) preparing a positive electrode: and coating the positive lead plaster, and curing to obtain the positive electrode of the lead-acid storage battery.
The method for preparing the negative electrode of the lead-acid storage battery by adopting the diacidic acid of the embodiment comprises the following specific steps:
(I) preparing negative lead plaster: adding lead powder, barium sulfate, lignin and carbon black into a paste mixer, stirring for 5min, adding water, stirring for 10min, slowly adding paste acid into the paste mixer within 15min, stirring for 20min, and discharging paste to obtain negative lead paste; the mass ratio of the lead powder to the barium sulfate to the lignin to the carbon black to the water to the paste acid is 100:1:0.1:0.3:9: 10;
(II) preparing a negative electrode: and coating the negative lead plaster, and curing to obtain the negative electrode of the lead-acid storage battery.
Example 2
A lead-acid battery and paste acid are prepared by the following steps:
(1) slowly adding concentrated sulfuric acid into deionized water, and continuously stirring to uniformly mix the concentrated sulfuric acid and the deionized water to prepare a sulfuric acid solution with the relative density of 1.15;
(2) adding polytetrafluoroethylene emulsion with the solid content of 26 wt% into sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the polytetrafluoroethylene emulsion is 25:1, and the number average molecular weight of polytetrafluoroethylene is 3.35 multiplied by 104And dispersing uniformly to obtain the lead-acid storage battery and the paste acid.
The steps of preparing the positive electrode and the negative electrode of the lead-acid storage battery by adopting the diacidic acid of the embodiment are the same as those of the embodiment 1.
Example 3
A lead-acid battery and paste acid are prepared by the following steps:
(1) slowly adding concentrated sulfuric acid into deionized water, and continuously stirring to uniformly mix the concentrated sulfuric acid and the deionized water to prepare a sulfuric acid solution with the relative density of 1.1;
(2) adding polytetrafluoroethylene emulsion with the solid content of 18 wt% into sulfuric acid solution under stirring, wherein the mass ratio of the sulfuric acid solution to the polytetrafluoroethylene emulsion is 35:1, and the number average molecular weight of polytetrafluoroethylene is 4.74 multiplied by 104And dispersing uniformly to obtain the lead-acid storage battery and the paste acid.
The steps of preparing the positive electrode and the negative electrode of the lead-acid storage battery by adopting the diacidic acid of the embodiment are the same as those of the embodiment 1.
Example 4
The difference between this example and example 1 is that, in step (2), the polytetrafluoroethylene is modified polytetrafluoroethylene, and the modified polytetrafluoroethylene emulsion is prepared by the following method:
(a) preparation of the polycarboxy oligourethane: under the protection of nitrogen, adding 1, 4-butyl diisocyanate and tartaric acid into N, N-dimethylformamide according to the molar ratio of 1:1, wherein the mass volume ratio of the 1, 4-butyl diisocyanate to the N, N-dimethylformamide is 1g:5mL, reacting for 0.5-1.5h at the temperature of 60-70 ℃, and performing rotary evaporation under reduced pressure to remove the solvent to obtain polycarboxy polyurethane oligomer;
(b) preparation of a polytetrafluoroethylene-aminohexene emulsion: uniformly mixing ammonium perfluorooctanoate, paraffin, ammonium persulfate and water according to the mass-volume ratio of 35g:6kg:1g:150L, replacing air in a reaction container with inert gas, introducing tetrafluoroethylene, wherein the mass-volume ratio of the tetrafluoroethylene to the water is 1g:2.1mL, reacting for 0.5h at 75 ℃ and 1.3MPa, adding 5-hexene-1-amine, wherein the molar ratio of the tetrafluoroethylene to the 5-hexene-1-amine is 25:1, and continuously reacting for 1h at 75 ℃ and 1.3MPa to obtain polytetrafluoroethylene-aminohexene emulsion;
(c) preparing modified polytetrafluoroethylene emulsion: adding the polycarboxy polyurethane oligomer into the polytetrafluoroethylene-amino hexene emulsion according to the mass volume ratio of 1g:3mL, fully mixing, and stirring and reacting for 1h at 45 ℃ to obtain the polytetrafluoroethylene-amino hexene emulsion.
Except for the above differences, the preparation processes of this example and the paste acid, the positive electrode and the negative electrode were the same as those of example 1.
Comparative example 1
This comparative example is different from example 1 in that step (2) is not performed, and the sulfuric acid solution obtained in step (1) is used as a kneading acid.
The method for preparing the lead-acid storage battery positive electrode by adopting the diacidic acid of the comparative example comprises the following specific steps:
(I) preparing positive lead paste: adding lead powder, red lead, tetrabasic lead sulfate, anisotropic graphite and short fiber into a paste mixer, and dry-stirring for 5 min; adding water and polytetrafluoroethylene emulsion with the solid content of 32 wt% (wherein, the molecular weight of polytetrafluoroethylene is 2.07 x 10)4) Stirring for 10 min; slowly adding paste mixing acid into the paste mixing machine within 15min, and stirring for 20 min; discharging paste to obtain positive lead paste; the mass ratio of the lead powder to the red lead to the tetrabasic lead sulfate to the anisotropic graphite to the short fibers to the water to the polytetrafluoroethylene emulsion to the paste acid is 100:3:0.2:0.1:0.1:9:0.6: 9.4;
(II) preparing a positive electrode: and coating the positive lead plaster, and curing to obtain the positive electrode of the lead-acid storage battery.
The method for preparing the negative electrode of the lead-acid storage battery by adopting the diacidic acid of the comparative example comprises the following specific steps:
(I) preparing negative lead plaster: adding lead powder, barium sulfate, lignin and carbon black into a paste mixer, and dry-stirring for 5 min; adding water and polytetrafluoroethylene emulsion with the solid content of 32 wt% (wherein, the molecular weight of polytetrafluoroethylene is 2.07 x 10)4) Stirring for 10 min; slowly adding the paste mixing acid into a paste mixing machine within 15min, stirring for 20min, and discharging paste to obtain negative lead paste; the mass ratio of the lead powder, the barium sulfate, the lignin, the carbon black, the water, the polytetrafluoroethylene emulsion and the paste acid is 100:1:0.1:0.3:9:0.6: 9.4;
(II) preparing a negative electrode: and coating the negative lead plaster, and curing to obtain the negative electrode of the lead-acid storage battery.
Comparative example 2
This comparative example differs from example 1 in that in step (2), the polytetrafluoroethylene has a number average molecular weight of 0.83X 104The remaining preparation processes of the paste acid, the positive electrode and the negative electrode were the same as in example 1.
Comparative example 3
This comparative example differs from example 3 in that in step (2), the polytetrafluoroethylene has a number average molecular weight of 6.14X 104The remaining preparation processes of the paste acid, the positive electrode and the negative electrode were the same as in example 3.
Comparative example 4
The comparative example is different from comparative example 1 in that polytetrafluoroethylene emulsion is not added in the process of preparing the positive electrode and the negative electrode, and the rest of the preparation processes of the paste acid, the positive electrode and the negative electrode are the same as comparative example 1.
Test example 1
The positive electrodes of examples 1 to 4 and comparative example 1 were freely dropped parallel to the bottom surface at a height of 1.5m from the ground, and the mass loss rates at 1, 3, and 5 repeated drops were measured and recorded in table 1.
The positive electrodes of examples 1 to 4 and comparative example 1 were prepared into a valve-regulated lead-acid battery, respectively, according to a conventional method, and the negative electrode of comparative example 1 was used as the negative electrode. The cycle life of the valve-regulated lead-acid battery was tested according to GB/T22199.1-2017 valve-regulated lead-acid battery for moped, and is recorded in Table 1.
TABLE 1
Figure BDA0003018528160000071
Analyzing the data of table 1, the following conclusions can be drawn:
(1) compared with the method that the polytetrafluoroethylene emulsion is added into the diacritic after being blended with the lead powder and the lead plaster additive (comparative example 1), the method that the polytetrafluoroethylene emulsion is added into the diacritic (example 1) can improve the mechanical strength of the positive electrode and the cycle life of the battery. The reason is that: by adding the polytetrafluoroethylene into the diachylon acid and adding the diachylon acid in the lead plaster preparation process, the polytetrafluoroethylene can be uniformly mixed with the positive and negative electrode active substances and the additive along with a sulfuric acid solution, and the polytetrafluoroethylene can be dispersed in the lead plaster more uniformly by the mode, so that the improvement of the mechanical strength of the positive electrode is facilitated, the softening and falling of the positive electrode active substances in the circulation process are reduced, and the circulation life of the battery is prolonged.
(2) In addition to example 1, when polytetrafluoroethylene is modified by the method of the present invention (example 4), the mechanical strength of the positive electrode and the cycle life of the battery can be improved. The reason is that: the invention modifies the polytetrafluoroethylene, introduces polyurethane with more carboxyl on the side chain of the polytetrafluoroethylene, and can improve the bonding strength between the polytetrafluoroethylene and the positive active substance through the complexation of the carboxyl and the-NHCOO-group and the lead, thereby better improving the mechanical strength of the positive electrode and the cycle life of the battery.
Test example 2
The negative electrodes of examples 1 to 4 and comparative examples 1 to 3 were prepared into valve-regulated lead-acid batteries, respectively, according to a conventional method, wherein the positive electrode used was the positive electrode of comparative example 1. The cycle life of the valve-regulated lead-acid battery was tested according to GB/T22199.1-2017 valve-regulated lead-acid battery for mops, and the water loss during 500 cycles was recorded in Table 2.
TABLE 2
Water loss per gram Cycle life/time
Example 1 132 630
Example 2 140 610
Example 3 156 590
Example 4 135 690
Comparative example 1 198 350
Comparative example 2 175 560
Comparative example 3 182 530
Comparative example 4 263 290
Analyzing the data of table 2, the following conclusions can be drawn:
(1) compared with the method without adding polytetrafluoroethylene (comparative example 3), the method that the polytetrafluoroethylene emulsion, the lead powder and the lead paste additive are blended and then added with the diachylon (comparative example 1) can reduce the water loss of the battery and improve the cycle life of the battery, and the polytetrafluoroethylene emulsion is added into the diachylon (example 1) to further reduce the water loss of the battery and further prolong the cycle life of the battery. The reason is that: after the polytetrafluoroethylene forms a cross-linked network in the negative electrode, because the polytetrafluoroethylene has strong hydrophobicity and poor wettability of electrolyte, the polytetrafluoroethylene can play a role of an oxygen composite channel in the electrode, so that oxygen and hydrogen can be diffused along the polytetrafluoroethylene cross-linked network, the composition of the oxygen and the hydrogen is promoted, the water loss phenomenon of the lead-acid storage battery is effectively reduced, and the cycle life is prolonged; and the polytetrafluoroethylene is mixed in the diachylon acid for adding, so that the polytetrafluoroethylene can be more uniformly dispersed in the diachylon, and the problem of water loss of the battery can be further improved.
(2) On the basis of example 1, after the polytetrafluoroethylene is modified by the method of the invention (example 4), the water loss of the battery is not obviously different, and the cycle life is obviously prolonged. The reason is that: the polycarboxy polyurethane oligomer exists at the side chain of the modified polytetrafluoroethylene close to the tail end, and the hydrophobicity of the main chain cannot be influenced, so that the polytetrafluoroethylene cannot be influenced to form an oxygen composite channel in the negative electrode; and the carboxyl and-NHCOO-group at the tail end of the modified polytetrafluoroethylene side chain are complexed with lead, so that the softening and falling of the negative active material are reduced, and the cycle life of the battery is prolonged.
(3) Example 1 and comparative example 2 each used a number average molecular weight of 2.07X 104And 0.83X 104Compared with example 1, the water loss of the battery prepared by using the negative electrode of comparative example 2 is obviously increased, and the cycle life is obviously shortened. The reason is that: when the molecule of polytetrafluoroethyleneWhen the amount is too small, it is difficult to form cross-linking after the dispersion in the lead paste, and it is not favorable for forming interconnected oxygen recombination channels, thereby affecting the oxygen recombination efficiency.
(4) Example 3 and comparative example 3 each used a number average molecular weight of 4.74X 104And 6.14X 104Compared with example 3, the water loss of the battery prepared by using the negative electrode of comparative example 3 is obviously increased, and the cycle life is obviously shortened. The reason is that: when the molecular weight of the polytetrafluoroethylene is too large, the flowability of the polytetrafluoroethylene along with a sulfuric acid solution is poor, and the polytetrafluoroethylene is difficult to uniformly disperse into a lead paste in a paste mixing process, so that the uniformity of the distribution of a cross-linked network in a negative electrode is influenced, and the oxygen recombination efficiency is further influenced.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. The lead-acid storage battery and the paste acid are characterized by comprising the following components: polytetrafluoroethylene, sulfuric acid, water; the mass fraction of the polytetrafluoroethylene in the paste acid is 0.1-2 wt%.
2. The kneading acid according to claim 1, wherein the mass fraction of the sulfuric acid in the kneading acid is 10 to 30 wt%.
3. The rhein acid of claim 1, wherein the polytetrafluoroethylene is a modified polytetrafluoroethylene; the preparation method of the modified polytetrafluoroethylene emulsion comprises the following steps:
(a) preparation of the polycarboxy oligourethane: under the protection of inert gas, adding 1, 4-butyl diisocyanate and tartaric acid into N, N-dimethylformamide according to the molar ratio of 1:0.8-1.2, reacting at 60-70 ℃ for 0.5-1.5h, and removing the solvent to obtain polycarboxy oligourethane;
(b) preparation of a polytetrafluoroethylene-aminohexene emulsion: uniformly mixing an emulsifier, a stabilizer, an initiator and water, replacing air in a reaction container with inert gas, introducing tetrafluoroethylene, wherein the mass volume ratio of the tetrafluoroethylene to the water is 1g:2-4mL, reacting for 0.5-1h at 70-80 ℃ and 1.0-1.5MPa, adding 5-hexene-1-amine, wherein the molar ratio of the tetrafluoroethylene to the 5-hexene-1-amine is 20-30:1, and continuously reacting for 0.5-1h at 70-80 ℃ and 1.0-1.5MPa to obtain a polytetrafluoroethylene-amino hexene emulsion;
(c) preparing modified polytetrafluoroethylene emulsion: adding the polycarboxy polyurethane oligomer into the polytetrafluoroethylene-amino hexene emulsion according to the mass volume ratio of 1g:3-6mL, fully mixing, and stirring and reacting for 0.5-1h at the temperature of 40-50 ℃ to obtain the polytetrafluoroethylene-amino hexene emulsion.
4. A process for the preparation of a gallic acid according to any one of claims 1 to 3, comprising the steps of: adding the polytetrafluoroethylene emulsion into the sulfuric acid solution under stirring, and uniformly dispersing to obtain the lead-acid storage battery and the paste acid.
5. The method according to claim 4, wherein the sulfuric acid solution has a relative density of 1.1 to 1.2; the solid content of the polytetrafluoroethylene emulsion is 10-65 wt%; the mass ratio of the sulfuric acid solution to the polytetrafluoroethylene emulsion is 15-35: 1.
6. A method for preparing lead-acid storage battery positive electrode lead paste is characterized by comprising the following steps: uniformly mixing lead powder and the positive lead plaster additive, adding water and the diachylon acid according to any one of claims 1 to 3, and uniformly mixing to obtain the positive lead plaster of the lead-acid storage battery.
7. The method for preparing the lead-acid storage battery negative electrode lead paste is characterized by comprising the following steps of: uniformly mixing lead powder and the negative lead plaster additive, adding water and the diacidic acid according to any one of claims 1 to 4, and uniformly mixing to obtain the negative lead plaster of the lead-acid storage battery.
8. The method of claim 7, wherein the molecular weight of the polytetrafluoroethylene in the kneading acid is 2 x 104-5×104。
9. A lead-acid battery, characterized in that it is made of a positive lead paste obtained by the method according to claim 6 and/or a negative lead paste obtained by the method according to claim 7 or 8.
10. An electric vehicle comprising the lead-acid storage battery of claim 9.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104377359A (en) * 2014-10-15 2015-02-25 超威电源有限公司 Deep-cycle-resistant lead-acid storage battery anode lead paste formula and preparation process thereof
CN105355912A (en) * 2015-11-23 2016-02-24 江苏海德森能源有限公司 Surface mount lead carbon battery electrode
CN109037691A (en) * 2018-07-25 2018-12-18 江苏永达电源股份有限公司 A kind of battery novel anode material additive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104377359A (en) * 2014-10-15 2015-02-25 超威电源有限公司 Deep-cycle-resistant lead-acid storage battery anode lead paste formula and preparation process thereof
CN105355912A (en) * 2015-11-23 2016-02-24 江苏海德森能源有限公司 Surface mount lead carbon battery electrode
CN109037691A (en) * 2018-07-25 2018-12-18 江苏永达电源股份有限公司 A kind of battery novel anode material additive

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