CN111430717A - Positive plate of lead-acid storage battery, preparation method of positive plate and storage battery - Google Patents
Positive plate of lead-acid storage battery, preparation method of positive plate and storage battery Download PDFInfo
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- CN111430717A CN111430717A CN202010250070.8A CN202010250070A CN111430717A CN 111430717 A CN111430717 A CN 111430717A CN 202010250070 A CN202010250070 A CN 202010250070A CN 111430717 A CN111430717 A CN 111430717A
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M4/14—Electrodes for 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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- 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
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Abstract
The invention discloses a positive plate of a lead-acid storage battery, a preparation method of the positive plate and the storage battery, belongs to the technical field of lead-acid storage batteries, and solves the problems that positive lead plaster is easy to soften, fall off or increase cost and the like in the prior art. A positive plate of a lead-acid storage battery comprises a grid and positive lead plaster coated on the grid; a protective layer is arranged outside the positive lead plaster and is used for slowing down the softening and expansion of the lead plaster; the protective layer composition comprises polytetrafluoroethylene. The invention can obviously improve the charge-discharge performance of the lead-acid battery and prolong the cycle life of the lead-acid battery.
Description
Technical Field
The invention belongs to the technical field of lead-acid storage batteries, and particularly relates to a positive plate of a lead-acid storage battery, a preparation method of the positive plate and the storage battery.
Background
The lead-acid storage battery is one of the secondary batteries with larger consumption in the current market due to high output power, safe and reliable use and low price of raw materials. When the battery is charged, the anode is converted into lead dioxide, the concentration of sulfuric acid in the electrolyte is increased, and energy is stored; when the battery discharges, the positive active substance is converted into lead sulfate, the concentration of the sulfuric acid in the electrolyte is reduced, and the storage and release of the capacity are realized in the repeated process of the charging and discharging of the battery.
However, lead sulfate generated during discharge increases in volume, and repeated cycles lead to softening and falling of the positive electrode lead paste.
Aiming at the problem of softening and shedding of positive lead paste, the conventional practice in the industry is to add 4BS (tetrabasic lead sulfate) and form more α -PbO in the formation stage2However, the addition of 4BS requires high-temperature curing, which leads to an increase in cost and difficulty in battery formation.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a positive plate of a lead-acid storage battery, a preparation method thereof and a storage battery, which are used for solving the problems of easy softening, falling off or cost increase of a positive lead paste in the prior art. The invention can obviously improve the charge-discharge performance of the lead-acid battery and prolong the cycle life of the lead-acid battery.
The purpose of the invention is mainly realized by the following technical scheme:
the invention discloses a positive plate of a lead-acid storage battery, which comprises a grid and positive lead plaster coated on the grid; a protective layer is arranged outside the positive lead plaster and is used for slowing down the softening and expansion of the lead plaster; the protective layer composition comprises polytetrafluoroethylene.
Furthermore, the protective layer component also comprises graphite, and the graphite is oxidized to form micropores during formation and circulation of the battery.
The invention also discloses a preparation method of the positive plate of the lead-acid storage battery, which comprises the following steps:
step 11, uniformly mixing raw materials of graphite, polytetrafluoroethylene emulsion and lead oxide;
step 12, adding a proper amount of dispersing agent to completely soak the raw materials, stirring to obtain a pasty mixture, and rolling into slices;
step 13, preparing positive lead plaster and coating the positive lead plaster on a grid to obtain an initial polar plate;
and step 14, attaching the sheets serving as protective layers to two sides of the initial pole plate, and performing acid spraying and compression roller curing to obtain the positive plate of the lead-acid storage battery.
Further, in the step 11, the raw material components by mass percentage are 0.01-10% of graphite, 0.01-10% of polytetrafluoroethylene emulsion and 80-99.98% of lead oxide.
Further, in step 12, the dispersant is water or alcohol, and the raw materials are added with the dispersant and then heated while stirring until a pasty mixture is obtained.
Further, in step 12, the pasty mixture is rolled into a sheet of 0.01 to 0.3 mm.
The invention also discloses a preparation method of the other lead-acid storage battery positive plate, which comprises the following steps:
step 21, uniformly mixing raw materials of graphite and polytetrafluoroethylene emulsion;
step 22, adding a proper amount of dispersant and stirring to obtain a mixture in a solution state;
step 23, preparing positive lead plaster and coating the positive lead plaster on a grid to obtain an initial polar plate;
and 24, taking the mixture in the solution state as acid spraying liquid to spray acid on the initial polar plate, forming protective layers on two sides of the initial polar plate, and then carrying out compression roller curing to obtain the positive plate of the lead-acid storage battery.
Further, in step 21, the raw material components comprise, by mass, 10% -50% of graphite and 50% -90% of polytetrafluoroethylene emulsion.
Further, in step 22, the dispersant is a dilute acid solution, and the mass ratio of the raw material to the dilute acid solution is 1: (100-500).
The invention also discloses a lead-acid storage battery, and the positive plate of the lead-acid storage battery is adopted.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) the protective layer is arranged outside the positive lead plaster and is used for slowing down the softening and expansion of the lead plaster; the protective layer composition includes graphite and Polytetrafluoroethylene (PTFE). During formation charging, part of graphite is oxidized to form micropores, so that electrolyte can enter the micropores, the charge and discharge performance of the battery can be obviously improved, the charge and discharge speed is increased, and the charge and discharge time is shortened.
PTFE has good cohesiveness, can make firm the connecting on positive pole lead plaster of protective layer, prevents that positive pole lead plaster inflation from droing, simultaneously because graphite oxidation forms the micropore, can form intensive network structure on positive pole lead plaster surface, not only can strengthen the conducting capacity, can effectually slow down softening and the inflation of surface lead plaster simultaneously, improves the life cycle of battery from this.
2) The protective layer composition of the present invention may also include lead oxide to facilitate the formation of α -PbO during charging2Further prevent the softening and dropping of the positive electrode lead paste.
3) The lead-acid storage battery is prepared by adopting the positive plate of the lead-acid storage battery. The cycle life of the lead-acid battery is prolonged when the lead-acid battery is fully charged and fully put down. Compared with the prior lead-acid battery, the manufacturing cost is not increased, and the cycle performance of the battery is improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 is a schematic view of a positive plate of a lead acid battery;
FIG. 2 is a scanning electron microscope image of the surface of the positive plate of the lead-acid storage battery in example 3;
FIG. 3 is a cycle life curve for example 3 and comparative example 1.
Wherein
1-grid and positive lead plaster; 2-a first protective layer; 3-a second protective layer.
Detailed Description
A lead-acid battery positive plate, a method of making the same, and a battery are described in further detail below with reference to specific examples, which are provided for purposes of comparison and explanation only, and the invention is not limited to these examples.
A positive plate of a lead-acid storage battery comprises a plate grid and positive lead plaster 1, wherein the positive lead plaster is coated on the plate grid; the protective layer comprises a first protective layer 2 and a second protective layer 3 which are rolled or sprayed and are respectively adhered to two sides of the positive lead paste.
In a preferred embodiment of the invention, the protective layer composition comprises graphite and Polytetrafluoroethylene (PTFE).
During formation and later-period circulation, graphite is oxidized to form micropores, so that the electrolyte can enter the micropores, the charge and discharge performance of the battery can be obviously improved, the charge and discharge speed is improved, and the charge and discharge time is shortened.
PTFE has good cohesiveness, can make firm the connecting on anodal lead plaster of protective layer, prevents that anodal lead plaster inflation from droing, simultaneously because graphite oxidation forms the micropore, can make the protective layer form intensive network structure, not only can strengthen the conducting capacity, can effectually slow down softening and the inflation of surface lead plaster simultaneously, improves the cycle life of battery from this. If directly add PTFE to anodal lead plaster, can cause the lead plaster to scribble the board difficulty, and PTFE nonconducting, directly add in the lead plaster can cause the positive plate resistance to increase, electric conductive property weakens.
Specifically, the raw material components of the protective layer comprise, by mass, 10% -50% of graphite and 50% -90% of polytetrafluoroethylene emulsion. The graphite is one of flake graphite, crystalline flake graphite, colloidal graphite and the like, and the solid content (mass) of the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 10-70%.
In another preferred embodiment of the present invention, the protective layer composition further comprises lead oxide, havingα -PbO is generated during charging2Further prevent the softening and dropping of the positive electrode lead paste. The raw material components by mass percentage are 0.01-10% of graphite, 0.01-10% of polytetrafluoroethylene emulsion and 80-99.98% of lead oxide. The graphite is one of flake graphite, crystalline flake graphite, colloidal graphite and the like, and the solid content (mass) of the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 10-70%.
The thickness of the protective layer is 0.01-0.3 mm.
The grid is a rectangular plate uniformly provided with grids, when the battery specification is 2V20Ah, the size of the grid is 66 × 138mm, and the thickness of the coated positive electrode lead paste is 2.5 mm.
The invention discloses a preparation method of a positive plate of a lead-acid storage battery, which comprises the following steps:
step 11, uniformly mixing raw materials of graphite, polytetrafluoroethylene emulsion and lead oxide;
step 12, adding a proper amount of dispersing agent to completely soak the raw materials, stirring to obtain a pasty mixture, and rolling into slices;
step 13, preparing positive lead plaster and coating the positive lead plaster on a grid to obtain an initial polar plate;
and step 14, attaching the sheets serving as protective layers to two sides of the initial pole plate, and performing acid spraying and compression roller curing to obtain the positive plate of the lead-acid storage battery. During the curing process, the dispersant is dried and evaporated to form micropores on the protective layer.
In the step 11, the raw material components by mass percentage are 0.01-10% of graphite, 0.01-10% of polytetrafluoroethylene emulsion and 80-99.98% of lead oxide. Preferably, the graphite is one of flake graphite, crystalline flake graphite, colloidal graphite and the like, and the solid content (mass) of the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 10-70%.
In step 12, the dispersant is water or alcohol, and the raw materials are added with the dispersant and then heated while stirring until a pasty mixture is obtained. And rolling the pasty mixture into a sheet with the thickness of 0.01-0.3 mm. The heating temperature is 40-60 ℃, so that redundant dispersing agent is evaporated, the viscosity of polytetrafluoroethylene is increased, and the mixture can be rolled into a sheet.
In step 14, the sheets are laminated to both sides of the starting plate.
The invention also discloses a preparation method of the other lead-acid storage battery positive plate, which comprises the following steps:
step 21, uniformly mixing raw materials of graphite and polytetrafluoroethylene;
step 22, adding a proper amount of dispersant and stirring to obtain a mixture in a solution state;
step 23, preparing positive lead plaster and coating the positive lead plaster on a grid to obtain an initial polar plate;
and 24, taking the mixture in the solution state as acid spraying liquid to spray acid on the initial polar plate, forming protective layers on two sides of the initial polar plate, and then carrying out compression roller curing to obtain the positive plate of the lead-acid storage battery.
In step 21, the raw material components comprise, by mass, 10% -50% of graphite and 50% -90% of polytetrafluoroethylene emulsion.
In step 22, the dispersant is a dilute acid solution, and the mass ratio of the raw material to the dilute acid solution is 1: (100-500).
In step 24, the acid leaching process comprises: and (3) putting the initial polar plate prepared in the step (23) into the solution prepared in the step (2) for soaking for 1-2 s, taking out, and forming protective layers on two sides of the initial polar plate.
A lead-acid storage battery adopts the positive plate of the lead-acid storage battery, a finished battery is assembled according to a normal production process, and the negative plate adopts a normal production pole plate. And forming by adopting a normal internal formation process for production to obtain the finished battery. The cycle life of the lead-acid battery is prolonged when the lead-acid battery is fully charged and fully put down. Compared with the prior lead-acid battery, the manufacturing cost is not increased, and the cycle performance of the battery is improved.
Example 1
The embodiment provides a preparation method of a positive plate of a lead-acid storage battery, which comprises the following steps:
step 11, uniformly mixing 1g of graphite, 1g of polytetrafluoroethylene emulsion and 20g of lead oxide; the graphite is flake graphite, and the solid content (mass) of the polytetrafluoroethylene in the polytetrafluoroethylene milk is 55%.
Step 12, adding 50ml of alcohol, completely soaking the raw materials, and then heating while stirring; heating to 45 deg.C, stirring to paste, and rolling the paste mixture into 0.2mm thick sheet.
And step 13, preparing positive lead plaster according to a normal production process and coating the positive lead plaster on a grid to obtain an initial plate.
And step 14, attaching the sheets serving as protective layers to two sides of the initial pole plate, and performing acid spraying and compression roller curing according to a normal production process to obtain the positive plate of the lead-acid storage battery.
And assembling a finished battery, namely assembling the finished battery according to a normal production process, wherein the negative plate adopts a normal polar plate for production. And forming by adopting a normal internal formation process for production to obtain the finished battery.
Example 2
The embodiment provides a preparation method of a positive plate of a lead-acid storage battery, which comprises the following steps:
step 11, uniformly mixing 0.5g of graphite, 1g of polytetrafluoroethylene emulsion and 15g of lead oxide; the graphite is crystalline flake graphite, and the solid content (mass) of the polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 50%.
Step 12, adding 30ml of alcohol, completely soaking the raw materials, and then heating while stirring; heating to 40 deg.C, stirring to paste, and rolling the paste mixture into 0.05mm thick sheet.
And step 13, preparing positive lead plaster according to a normal production process and coating the positive lead plaster on a grid to obtain an initial plate.
And step 14, attaching the sheets serving as protective layers to two sides of the initial pole plate, and performing acid spraying and compression roller curing according to a normal production process to obtain the positive plate of the lead-acid storage battery.
And assembling a finished battery, namely assembling the finished battery according to a normal production process, wherein the negative plate adopts a normal polar plate for production. And forming by adopting a normal internal formation process for production to obtain the finished battery.
Example 3
The embodiment provides another preparation method of a positive plate of a lead-acid storage battery, which comprises the following steps:
and step 21, uniformly mixing 0.5g of graphite and 4.5g of polytetrafluoroethylene emulsion, wherein the graphite is flake graphite, and the solid content (mass) of polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 55%.
Step 22, adding 595g of dilute sulfuric acid solution, wherein the concentration of the dilute sulfuric acid is 1-1.1g/cm3. The mixture after addition of dilute sulfuric acid is in solution.
And 23, preparing positive lead plaster according to a normal production process and coating the positive lead plaster on a grid to obtain an initial plate.
Step 24, putting the initial polar plate prepared in the step 23 into the solution prepared in the step 22 for soaking for 1s, and taking out; and then, carrying out compression roller curing to obtain the positive plate of the lead-acid storage battery.
And assembling a finished battery, namely assembling the finished battery according to a normal production process, wherein the negative plate adopts a normal polar plate for production. And forming by adopting a normal internal formation process for production to obtain the finished battery.
FIG. 2 is a scanning electron microscope image of the surface of the positive plate of the lead-acid storage battery in example 3. As can be seen from the figure, the surface of the positive plate of the lead-acid storage battery is of a compact network structure, so that the lead paste of the positive plate is effectively prevented from softening and falling, meanwhile, the lead paste of the positive plate is beneficial to entering of electrolyte, and the conductivity of the battery is improved.
Example 4
The embodiment provides another preparation method of a positive plate of a lead-acid storage battery, which comprises the following steps:
step 21, uniformly mixing 1.5g of graphite and 3.5g of polytetrafluoroethylene emulsion, wherein the graphite is colloidal graphite, and the solid content (mass) of polytetrafluoroethylene in the polytetrafluoroethylene emulsion is 60%.
Step 22, adding 1000g of dilute sulfuric acid solution, wherein the concentration of the dilute sulfuric acid is 1-1.1g/cm3. The mixture after addition of dilute sulfuric acid is in solution.
And 23, preparing positive lead plaster according to a normal production process and coating the positive lead plaster on a grid to obtain an initial plate.
Step 24, putting the initial polar plate prepared in the step 23 into the solution prepared in the step 22 for soaking for 2s, and taking out; and then, carrying out compression roller curing to obtain the positive plate of the lead-acid storage battery.
And assembling a finished battery, namely assembling the finished battery according to a normal production process, wherein the negative plate adopts a normal polar plate for production. And forming by adopting a normal internal formation process for production to obtain the finished battery.
Comparative example 1
And preparing positive lead paste according to a normal production process, coating the positive lead paste on a grid, and carrying out acid spraying and compression roller curing according to the normal production process to obtain the positive plate of the lead-acid storage battery. And assembling a finished battery according to a normal production process, wherein the negative plate adopts a normal production plate. And forming by adopting a normal internal formation process for production to obtain the finished battery.
In comparative example 1, the positive electrode plate has no protective layer and the rest of the process conditions are the same as in example 3.
Test battery cycling test protocol:
in the environment of 25 +/-1 ℃, discharging the fully charged battery to a cell 1.75v at a current of 0.5C, then charging to a cell 2.45v at a voltage limited for 5h at a constant voltage of 0.4C, performing charge-discharge circulation by the circulation process, and recording the discharge capacity and the circulation times.
Fig. 3 is a graph of cycle life for example 3 and comparative example 1. As can be seen from fig. 3, the discharge time of example 3 is significantly better than that of the comparative example, and the cycle life is also significantly improved as compared to that of the comparative example. The charging and discharging speed of the battery is improved, the battery 1C can be charged to 85-90% after being charged for 1h, and the charging time of the comparative example 1C can be only 75% after being charged for 1 h.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The positive plate of the lead-acid storage battery is characterized by comprising a grid and positive lead paste coated on the grid; a protective layer is arranged outside the positive lead plaster and is used for slowing down softening and expansion of the lead plaster; the protective layer composition comprises polytetrafluoroethylene.
2. The positive plate of a lead-acid battery of claim 1, wherein the protective layer composition further comprises graphite that is oxidized to form micropores during battery formation and cycling.
3. The preparation method of the positive plate of the lead-acid storage battery is characterized by comprising the following steps of:
step 11, uniformly mixing raw materials of graphite, polytetrafluoroethylene emulsion and lead oxide;
step 12, adding a proper amount of dispersing agent to completely soak the raw materials, stirring to obtain a pasty mixture, and rolling into slices;
step 13, preparing positive lead plaster and coating the positive lead plaster on a grid to obtain an initial polar plate;
and step 14, attaching the sheets serving as protective layers to two sides of the initial pole plate, and performing acid spraying and compression roller curing to obtain the positive plate of the lead-acid storage battery.
4. The method for preparing the positive plate of the lead-acid storage battery according to the claim 3, wherein in the step 11, the raw material components comprise, by mass, 0.01-10% of graphite, 0.01-10% of polytetrafluoroethylene emulsion and 80-99.98% of lead oxide.
5. The method for preparing the positive plate of the lead-acid storage battery according to the claim 4, wherein in the step 12, the dispersant is water or alcohol, and after the dispersant is added into the raw materials, the raw materials are heated and stirred until the mixture is stirred into a pasty mixture.
6. The method for preparing the positive plate of the lead-acid storage battery according to claim 5, wherein in the step 12, the pasty mixture is rolled into a sheet with the thickness of 0.01-0.3 mm.
7. The preparation method of the positive plate of the lead-acid storage battery is characterized by comprising the following steps of:
step 21, uniformly mixing raw materials of graphite and polytetrafluoroethylene emulsion;
step 22, adding a proper amount of dispersant and stirring to obtain a mixture in a solution state;
step 23, preparing positive lead plaster and coating the positive lead plaster on a grid to obtain an initial polar plate;
and 24, taking the mixture in the solution state as acid spraying liquid to spray acid on the initial polar plate, forming protective layers on two sides of the initial polar plate, and then carrying out compression roller curing to obtain the positive plate of the lead-acid storage battery.
8. The method for preparing the positive plate of the lead-acid storage battery according to claim 7, wherein in the step 21, the raw material components comprise, by mass, 10% -50% of graphite and 50% -90% of polytetrafluoroethylene emulsion.
9. The method for preparing the positive plate of the lead-acid storage battery according to claim 8, wherein in the step 22, the dispersant is a dilute acid solution, and the mass ratio of the raw material to the dilute acid solution is 1: (100-500).
10. A lead-acid battery, characterized in that a positive plate of a lead-acid battery according to claims 1-9 is used.
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