CN111224097A - Lead paste, battery plate and preparation method and application thereof - Google Patents
Lead paste, battery plate and preparation method and application thereof Download PDFInfo
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- CN111224097A CN111224097A CN202010049733.XA CN202010049733A CN111224097A CN 111224097 A CN111224097 A CN 111224097A CN 202010049733 A CN202010049733 A CN 202010049733A CN 111224097 A CN111224097 A CN 111224097A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a lead plaster, a battery plate, a preparation method and an application thereof, wherein the raw material of the lead plaster comprises a lignin-based compound/conductive polymer composite material; wherein the lignin-based compound is at least one selected from lignin and lignosulfonate. The lead paste is used for lead-acid batteries or lead-carbon battery electrode plates, has good conductivity and capacitance, improves the sulfation problem of electrodes, effectively reduces the polarization of the electrodes, and improves the charge-discharge cycle life and the specific capacity of the lead-acid batteries.
Description
Technical Field
The application relates to lead paste, a battery plate, a preparation method and application thereof, and belongs to the field of lead-acid batteries or lead-carbon battery additives.
Background
Lead-acid batteries are widely used in the fields of automobile starting, communication base stations, industry and the like due to the advantages of high safety, low price, high recyclability and the like, and are batteries with the highest market share. However, when the lead-acid battery works in a high-rate charge state, compact lead sulfate crystals can be formed on the surface of an electrode of the lead-acid battery, so that the electrode is sulfated, the utilization rate of the electrode is low, and the charge-discharge cycle life is short. In order to improve electrode sulfation, research on adding a novel expanding agent such as lignin and lignosulfonate to replace the existing humic acid and the like and reduce the compactness of lead sulfate crystals. However, lignin, lignosulfonate, etc. are easily adsorbed on the surface of lead to hinder the charging thereof, and cannot effectively prolong the charge-discharge cycle life of the lead-acid battery.
Disclosure of Invention
According to one aspect of the present application, there is provided a lead paste including a raw material including a lignin-based compound/conductive polymer composite, which has excellent charge and discharge properties for a lead-acid battery.
According to the application, the conductive polymer is used for modifying lignin-based compounds such as lignin and lignosulfonate, so that the conductive polymer not only plays a role of an expanding agent, but also has good conductivity and capacitance, the sulfation problem of an electrode is improved, the polarization of the electrode is effectively reduced, and the charge-discharge cycle life and the specific capacity of a lead-acid battery are improved.
Compared with a graphene/conductive polymer composite material with a two-dimensional sheet structure, the lignin-based compound/conductive polymer composite material can form a three-dimensional structure composite, so that the conductivity of an electrode can be improved, and the diffusion of electrolyte in the electrode is facilitated, so that the polarization phenomenon of a battery is reduced, and the cycle life of the battery is prolonged.
The lead plaster is characterized in that the raw material of the lead plaster comprises a lignin-based compound/conductive polymer composite material;
wherein the lignin-based compound is at least one selected from lignin and lignosulfonate.
Optionally, the raw material of the lead paste further comprises lead powder;
wherein the mass of the lignin-based compound/conductive polymer composite material in the raw material of the lead plaster is 0.05-0.5% of the mass of the lead powder.
Optionally, the mass of the lignin-based compound/conductive polymer composite material in the raw material of the lead plaster is 0.12-0.3% of the mass of the lead powder.
Optionally, the upper limit of the mass of the lignin-based compound/conductive polymer composite material in the raw material of the lead paste to the mass of the lead powder is selected from 0.1%, 0.15%, 0.2%, 0.25% or 0.3%; the lower limit is selected from 0.05%, 0.1%, 0.12%, 0.15%, 0.2% or 0.25%.
Optionally, the lignosulfonate comprises at least one of ammonium lignosulfonate, potassium lignosulfonate, sodium lignosulfonate;
the conductive polymer is at least one selected from polypyrrole, polyaniline, polythiophene, polyacetylene, polyphenylene ethylene, polydiyne, polypyrrole derivatives, polyaniline derivatives, polythiophene derivatives, polyacetylene derivatives, polyphenylene ethylene derivatives and polydiyne derivatives.
As a specific embodiment thereof, the conductive polymer comprises one or more of polyacetylene, polyaniline, polypyrrole, polythiophene, and the like, and derivatives thereof;
the lignosulfonate comprises one or more of ammonium lignosulfonate, potassium lignosulfonate, and sodium lignosulfonate.
Alternatively, the method for preparing the lignin-based compound/conductive polymer composite material comprises:
the lignin-based compound/conductive polymer composite material is prepared from raw materials containing a conductive polymer monomer, a lignin-based compound and an oxidant.
Alternatively, the reaction is carried out under stirring conditions.
Optionally, the oxidizing agent comprises at least one of iron trichloride, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, potassium permanganate, iron sulfate, potassium dichromate, iron p-toluenesulfonate, copper chloride, manganese dioxide.
Optionally, the mass ratio of the conductive polymer monomer to the lignin-based compound is 5: 1-1: 5;
the molar ratio of the conductive polymer monomer to the oxidant is 0.3: 1-1: 1;
the preparation conditions comprise:
the reaction temperature is-5-10 ℃;
the reaction time is 6-48 h.
Optionally, the upper limit of the mass ratio of the conductive polymer monomer to the lignin-based compound is selected from 5:1, 4:1, 3:1, 2:1, 1:2, 1:3 or 1: 4; the lower limit is selected from 4:1, 3:1, 2:1, 1:2, 1:3, 1:4 or 1: 5.
Optionally, the upper limit of the molar ratio of the conductive polymer monomer to the oxidizing agent is selected from 0.3:1, 0.5:1, 0.7:1, 0.9:1, or 1: 1; the lower limit is selected from 0.35:1, 0.55:1, 0.75:1, 0.95:1 or 1: 1.
Optionally, the upper temperature limit of the reaction is selected from-1 ℃, 0 ℃, 5 ℃ or 10 ℃; the lower limit is selected from-1 deg.C, -5 deg.C, 0 deg.C or 5 deg.C.
Optionally, the upper time limit of the reaction is selected from 12h, 24h or 48 h; the lower limit is selected from 6h, 12h or 24 h.
Optionally, the temperature of the reaction is 0-5 ℃.
Optionally, the mass ratio of the conductive polymer monomer to the lignin-based compound is 3: 1-1: 3.
Optionally, the mass ratio of the conductive polymer monomer to the lignin-based compound is 2: 1-1: 2.
Alternatively, the raw material containing the conductive polymer monomer, the lignin-based compound, and the oxidizing agent is obtained in a manner including:
mixing the solution A containing the conductive polymer monomer with the solution B containing the oxidant to obtain a solution containing the conductive polymer monomer, the lignin-based compound and the oxidant;
wherein the solution A and/or the solution B contain lignin-based compounds.
As a specific embodiment, the solution a contains a conductive polymer monomer and a lignin-based compound, and the solution B contains an oxidizing agent;
or the solution A contains a conductive polymer monomer, and the solution B contains an oxidant and a lignin-based compound;
or the solution A contains a conductive polymer monomer and a lignin-based compound, and the solution B contains an oxidant and a lignin-based compound;
optionally, the solution A and the solution B contain acid, and the molar concentration of the acid is 0.8-1.2 mol/L.
As a specific embodiment thereof, the method for preparing the lignin-based compound/conductive polymer comprises:
s1) preparing a solution A containing a conductive polymer monomer;
s2) preparing a solution B containing an oxidant; at least one of solution A or solution B contains a lignin-based compound;
s3) mixing and reacting the solution B with the solution A to prepare a suspension C containing the lignin-based compound/conductive polymer composite material;
s4) carrying out suction filtration, washing and drying on the suspension C to obtain the lignin-based compound/conductive polymer composite material.
Optionally, the solution A in the step S1) contains acid, and the molar concentration is 0.8-1.2 mol/L; preferably, the acid is hydrochloric acid.
Optionally, in the step S2), the solution B contains an acid, and the molar concentration is 0.8-1.2 mol/L; preferably, the acid is hydrochloric acid.
Optionally, grinding is performed after the drying in step S4).
Optionally, the lead paste further comprises sulfuric acid, barium sulfate, polyester short fibers, a carbon material and water.
Optionally, the raw materials of the lead paste comprise the following components in parts by weight:
100 parts of lead powder;
4.0-10 parts of sulfuric acid;
0.5-2.0 parts of barium sulfate;
0.05-0.5 part of lignin-based compound/conductive polymer composite material;
0.05-0.3 part of polyester staple fiber;
0.01-0.5 parts of carbon material;
9-16 parts of water.
Optionally, the carbon material is conductive carbon black, activated carbon, carbon nanotubes, graphene, expanded graphite.
Optionally, the concentration of the sulfuric acid is 1-3 g/mol.
Optionally, the concentration of sulfuric acid is 1.45 g/mol.
In another aspect of the present application, there is provided a method for preparing the lead paste, including: and uniformly mixing the raw materials to prepare the lead plaster.
As a specific embodiment, the method for preparing the lead paste comprises the following steps: mixing and stirring lead powder, a lignin-based compound/conductive polymer composite material (preferably sodium lignosulfonate/polyaniline composite powder), sulfuric acid, barium sulfate, polyester short fibers, a carbon material and water uniformly to prepare the lead plaster.
As a specific embodiment, the method for preparing the lead paste comprises the following steps: mixing and stirring lead powder, a lignin-based compound/conductive polymer composite material (preferably sodium lignosulfonate/polyaniline suspension C), sulfuric acid, barium sulfate, polyester short fibers, a carbon material and water uniformly to prepare the lead plaster.
In yet another aspect of the present application, a battery plate is provided, wherein the battery plate comprises lead paste;
the lead plaster is at least one selected from the lead plaster of any one of the above and the lead plaster obtained by the preparation method.
Optionally, the battery plate is a battery negative plate.
Optionally, the preparation method of the battery plate comprises the following steps:
and coating the lead plaster on a grid, and curing to obtain the battery plate.
Optionally, the grid comprises a lead tin calcium grid.
Optionally, the curing conditions include: curing for 12-48 h at 40-100 ℃ and 20-80% humidity.
Optionally, the curing conditions include: curing at 65 ℃ and 40% humidity for 24 h.
In yet another aspect of the present application, a battery is provided, comprising a battery plate;
the battery polar plate is selected from at least one of the battery polar plate and the battery polar plate obtained by the preparation method.
Optionally, the battery is a lead-acid battery or a lead-carbon battery.
Optionally, the lead-acid or lead-carbon battery comprises a negative battery plate;
the battery negative plate is obtained by coating the lead plaster on a lead-tin-calcium grid and curing.
Optionally, the method of making the battery (preferably a lead-acid battery) comprises: assembling a lead-acid battery core according to the arrangement sequence of the positive plate, the glass fiber, the negative plate, the glass fiber and the positive plate, injecting sulfuric acid electrolyte, and sealing a battery shell to prepare the battery (the lead-acid battery).
According to the invention, the sodium lignosulfonate/polyaniline compound is added to the negative electrode of the lead-acid battery and the like, so that the effect of the expanding agent is exerted, the good conductivity and capacitance are realized, and the polarization phenomenon of the lead-acid battery and the like in the charging and discharging processes is reduced.
The beneficial effects that this application can produce include:
the lead plaster provided by the application is used for applying the negative plate of the battery to a lead-acid battery or a lead-carbon battery, has good conductivity and capacitance, improves the sulfation problem of the electrode, effectively reduces the polarization of the electrode, and improves the charge-discharge cycle life and the specific capacity of the lead-acid battery.
Drawings
FIG. 1 is a cycle life curve of a lead acid battery in an example of the present application.
Fig. 2 is a test curve of the capacity of a lead-acid battery in the example of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
According to one embodiment of the present application, the lignin/conductive polymer composite comprises a conductive polymer and lignin and/or lignosulfonate; the conductive polymer comprises one or more of polyacetylene, polyaniline, polypyrrole, polythiophene and the like and derivatives thereof; the lignosulfonate comprises one or more of ammonium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate; the mass ratio of the conductive polymer monomer to the lignin and/or the lignosulfonate is 5: 1-1: 5, preferably 3: 1-1: 3, and preferably 2: 1-1: 2.
As a specific embodiment, the preparation method of the lignin/conductive polymer composite material comprises the following steps:
1) preparing a solution A containing a conductive polymer monomer;
2) preparing a solution B containing an oxidant; at least one of solution A or solution B contains a lignin-based compound;
3) and mixing and reacting the solution B with the solution A to prepare a suspension C containing the lignin/conductive polymer composite material.
The reaction time is preferably 6-48 h.
Preferably, mixing the solution B with the solution A, and reacting at the temperature of-5-10 ℃;
preferably while stirring the reaction;
the molar mass ratio of the conductive polymer monomer to the oxidant is 0.3: 1-1: 1;
the conductive polymer material is selected from one or more of polypyrrole, polyaniline, polythiophene, polyacetylene, polyphenylene ethylene, polydiyne and derivatives thereof, and the lignosulfonate comprises one or more of ammonium lignosulfonate, potassium lignosulfonate and sodium lignosulfonate;
the oxidant comprises at least one of ferric trichloride, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, potassium permanganate, ferric sulfate, potassium dichromate, iron p-toluenesulfonate, copper chloride and manganese dioxide.
As a specific embodiment, the preparation method of the lignin/conductive polymer composite material comprises the following steps:
3) and carrying out suction filtration, washing and drying on the suspension C to prepare the lignin/conductive polymer composite powder.
Preferably dried and then ground.
In a specific embodiment, the negative plate of the lead-acid battery comprises a lignin/conductive polymer composite material, wherein the mass of the lignin/conductive polymer composite material is 0.05-0.5%, preferably 0.12-0.3% of that of the lead powder.
As a specific embodiment, the method for preparing the negative plate of the lead-acid battery,
the following formulations were used as references:
100 parts of lead powder;
4.0-10 parts of sulfuric acid;
0.5-2.0 parts of barium sulfate;
0.05-0.5 part of lignin-based compound/conductive polymer composite material;
0.05-0.3 part of polyester staple fiber;
0.01-0.5 parts of carbon material;
9-16 parts of water.
Optionally, the carbon material is conductive carbon black, activated carbon, carbon nanotubes, graphene, expanded graphite.
As a specific embodiment, the lead-acid battery is assembled by: the preparation of the lead-acid battery comprises the steps of assembling a lead-acid battery core according to the arrangement sequence of a positive plate, glass fibers, a negative plate, the glass fibers and the positive plate, injecting sulfuric acid electrolyte, and sealing a battery shell to prepare the lead-acid battery.
Example 1
(1) Preparing sodium lignosulfonate/polyaniline composite powder:
adding 1.86g of aniline and 0.93g of sodium lignin sulfonate into 50ml of 1 mol/hydrochloric acid solution, and stirring for 30min at 5 ℃ in ice bath to prepare solution A; 4.56g of ammonium persulfate is added into 50ml of 1mol/L hydrochloric acid solution to prepare solution B; adding the solution B into the solution A, and magnetically stirring for 24 hours at the temperature of 5 ℃ in an ice bath to prepare a lignin/sodium sulfonate polyaniline suspension C; and (3) carrying out suction filtration on the suspension C, washing the suspension C with alcohol and deionized water, placing the suction-filtered substance in a vacuum oven at 60 ℃ for drying for 24 hours, taking out and grinding to obtain the sodium lignosulfonate/polyaniline composite powder.
(2) Preparing a negative plate of the lead-acid battery:
mixing and stirring lead powder, carbon black, sodium lignosulfonate/polyaniline composite powder, barium sulfate and polyester short fibers for 30min, adding water and stirring for 30min, adding sulfuric acid and stirring for 30min to prepare negative lead paste of the lead-acid battery; the mass fraction of each substance is as follows: 100 parts of lead powder, 0.25 part of carbon black, 0.15 part of sodium lignosulfonate/polyaniline composite powder, 1 part of barium sulfate, 0.1 part of polyester short fiber, 11.46 parts of water and 8.93 parts of sulfuric acid (1.45 ml/g). And coating the lead plaster on a lead-tin-calcium (Pb-Ca-Sn) grid, and curing for 24 hours in an environment with the temperature of 65 ℃ and the humidity of 40% to prepare the negative plate of the lead-acid battery.
(3) Preparing a positive plate of a lead-acid battery:
mixing and stirring lead powder, tin sulfate, antimony oxide, lead tetroxide and polyester fiber for 30min, adding water and stirring for 30min, adding sulfuric acid and stirring for 30min, and preparing positive lead plaster of a lead-acid battery; wherein 100 parts of lead powder, 0.15 part of tin sulfate, 0.15 part of antimony oxide, 5 parts of lead tetroxide, 0.12 part of polyester fiber, 11.5 parts of water and 9.5 parts of sulfuric acid (1.45 ml/g). And coating the lead plaster on a lead-tin-calcium grid, and curing the wet plate to obtain the positive plate of the lead-acid battery.
(4) Preparing a lead-acid battery:
and (2) assembling the positive plate, the glass fiber, the negative plate, the glass fiber and the positive plate into a lead-acid battery core in sequence, injecting sulfuric acid electrolyte (the concentration is 1.265g/ml), and sealing a battery shell to prepare the lead-acid battery.
Example 2: the amount of sodium lignosulfonate/polyaniline composite powder added in step (2) is 0.25 parts, and the rest is the same as that in example 1.
Examples 3 to 5: replacing sodium lignosulfonate with lignin, ammonium lignosulfonate and potassium lignosulfonate in the embodiment 1 respectively to obtain lignin/polyaniline composite powder, ammonium lignosulfonate/polyaniline composite powder and potassium lignosulfonate/polyaniline composite powder; the lead acid battery was then assembled as in example 1; the parameters of examples 3 to 5 were the same as those of example 1 except that the starting materials were different from those of example 1.
Examples 6 to 12: the mass ratios of the conductive polymer monomer to the sodium lignin sulfonate in examples 6 to 12 were 5:1, 4:1, 3:1, 2:1, 1:2, 1:3 and 1:5, respectively, and the others were the same as in example 1.
Examples 13 to 17: the mass of the lignin/conductive polymer composite materials in examples 13 to 17 was 0.05%, 0.1%, 0.2%, 0.3% and 0.5% of the mass of the lead powder, respectively, and the rest was the same as in example 1.
Examples 18 to 21:
the reaction times of the solution A and the solution B in examples 18 to 21 were respectively replaced by 6h, 12h, 16h and 48h, and the rest was the same as in example 1.
Examples 22 to 24:
the reaction temperatures of solution A and solution B in examples 22 to 24 were changed to-5 deg.C, 5 deg.C and 10 deg.C, respectively, and the other steps were the same as in example 1.
Example 25:
example 25 the oxidant was replaced with potassium permanganate and the molar ratio of conductive polymer monomer to the oxidant was replaced with 0.33:1, all other things being equal to example 1.
Comparative example 1
(1) Mixing and stirring 81.7% of lead powder, 0.15% of sodium lignosulfonate, 4% of sulfuric acid, 1% of barium sulfate, 0.1% of polyester short fiber, 0.05% of carbon material and 13% of water uniformly to prepare lead-acid battery negative lead paste; and (3) coating the lead plaster on a lead-tin-calcium grid, keeping the temperature at 65 ℃ and the humidity at 40%, and curing for 24h to obtain the negative plate of the lead-acid battery. The positive electrode plate was prepared according to the conventional method (same as example 1).
(2) Assembling a lead-acid battery core according to the arrangement sequence of the positive plate, the glass fiber, the negative plate, the glass fiber and the positive plate, injecting sulfuric acid electrolyte, and sealing a battery shell to prepare the lead-acid battery.
Example 26 electrochemical Performance test
Electrochemical Performance test in examples 1-25 and comparative example 1
Electrochemical performance tests were performed on the lead-acid batteries prepared in examples 1 to 25 and comparative example 1, and the performance is shown in table 1. The test method comprises the following steps: the cycle life of the battery is tested by adopting a battery test system (model: CT-4008-5V6A) of Shenzhen New Wille electronics Limited. And setting the 1C current as a cycle life test current by taking the theoretical capacity of the battery as a basis. (Charge and discharge 60s is one cycle, and the cycle cut-off voltage of the unit cell is 1.75V)
TABLE 1
| Examples | Charging and discharging cycle life (second time) | Capacity (mAh) |
| Example 1 | 5209 | 1106 |
| Example 2 | 3208 | 920 |
| Example 3 | 1815 | 891 |
| Example 4 | 5011 | 1002 |
| Example 5 | 4907 | 1033 |
| Example 6 | 4934 | 997 |
| Example 7 | 3904 | 965 |
| Example 8 | 5209 | 1106 |
| Example 9 | 3208 | 920 |
| Example 10 | 1815 | 891 |
| Example 11 | 1423 | 754 |
| Example 12 | 1019 | 687 |
| Example 13 | 2927 | 901 |
| Example 14 | 4054 | 1056 |
| Example 15 | 4028 | 1044 |
| Example 16 | 3577 | 937 |
| Example 17 | 3061 | 899 |
| Example 18 | 1908 | 731 |
| Example 19 | 2539 | 796 |
| Example 20 | 3614 | 877 |
| Example 21 | 4788 | 1099 |
| Example 22 | 5001 | 1041 |
| Example 23 | 5209 | 1106 |
| Example 24 | 4166 | 954 |
| Example 25 | 5155 | 1001 |
| Comparative example 1 | 712 | 624 |
As can be seen from the data in table 1, the lead paste of the lead-acid battery containing the sodium lignosulfonate/conductive polymer composite prepared in the embodiments 1 to 25 of the present invention has significantly higher charge-discharge cycle life and capacity than the lead-acid battery prepared by the conventional method in the comparative example 1. The lignosulfonate/conductive polymer composite material and the negative plate prepared by the invention are beneficial to improving the charge-discharge cycle life and capacity of the lead-acid battery.
Fig. 1 is a cycle life curve of a lead-acid battery in a high-rate state of charge, and a 1C current is set as a cycle life test current based on a theoretical capacity of the battery. (the charge and discharge 60s is one cycle, and the cycle cut-off voltage of the unit cell is 1.75V). It can be seen from the figure that the charge voltage of comparative example 1 rapidly increased in the late stage of the cycle test, which is mainly due to the low conductivity of sodium lignosulfonate, resulting in severe polarization of the battery. Examples 1 to 3 the charging voltage remained stable throughout the cycle test, mainly due to the high conductivity of the conductive polymer, which increased the conductivity of the negative plate, decreased the polarization of the battery, accelerated the rate of conversion of lead sulfate to lead, and extended the cycle life of the battery.
Fig. 2 is a test curve of the capacity of the lead-acid battery, and the 0.1C current is set as the test current of the capacitor based on the theoretical capacity of the battery. The discharge plateaus of examples 1 to 3 in the figure are all longer than those of comparative examples, mainly because the conductivity of the conductive polymer is high, the conductivity of the negative plate is improved, lead sulfate of the negative plate can be completely converted into lead again after the lead sulfate is charged and discharged for the first time, and the capacity is improved during discharging.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A lead paste, characterized in that the raw material of the lead paste comprises a lignin-based compound/conductive polymer composite;
wherein the lignin-based compound is at least one selected from lignin and lignosulfonate.
2. The lead paste as defined in claim 1, wherein the raw material of the lead paste further comprises lead powder;
wherein the mass of the lignin-based compound/conductive polymer composite material in the raw material of the lead plaster is 0.05-0.5% of the mass of the lead powder;
preferably, the mass of the lignin-based compound/conductive polymer composite material in the raw material of the lead plaster is 0.12-0.3% of the mass of the lead powder.
3. The lead paste of claim 1, wherein the lignosulfonate comprises at least one of ammonium lignosulfonate, potassium lignosulfonate, sodium lignosulfonate;
the conductive polymer is at least one selected from polypyrrole, polyaniline, polythiophene, polyacetylene, polyphenylene ethylene, polydiyne, polypyrrole derivatives, polyaniline derivatives, polythiophene derivatives, polyacetylene derivatives, polyphenylene ethylene derivatives and polydiyne derivatives.
4. The lead paste as claimed in claim 1, wherein the preparation method of the lignin-based compound/conductive polymer composite material comprises:
preparing a lignin-based compound/conductive polymer composite material from raw materials containing a conductive polymer monomer, a lignin-based compound and an oxidant;
the oxidant contains at least one of ferric trichloride, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, potassium permanganate, ferric sulfate, potassium dichromate, iron p-toluenesulfonate, copper chloride and manganese dioxide.
5. The lead paste as claimed in claim 4, wherein the mass ratio of the conductive polymer monomer to the lignin-based compound is 5:1 to 1: 5;
the molar ratio of the conductive polymer monomer to the oxidant is 0.3: 1-1: 1;
the preparation conditions comprise: the reaction temperature is-5-10 ℃; the reaction time is 6-48 h;
preferably, the mass ratio of the conductive polymer monomer to the lignin-based compound is 3: 1-1: 3;
further preferably, the mass ratio of the conductive polymer monomer to the lignin-based compound is 2: 1-1: 2;
preferably, the raw material containing the conductive polymer monomer, the lignin-based compound and the oxidizing agent is obtained by a method comprising:
mixing the solution A containing the conductive polymer monomer with the solution B containing the oxidant to obtain a solution containing the conductive polymer monomer, the lignin-based compound and the oxidant;
wherein the solution A and/or the solution B contain lignin-based compounds.
6. The lead paste according to claim 1 or 2, further comprising sulfuric acid, barium sulfate, polyester staple fibers, carbon material and water;
preferably, the raw materials of the lead paste comprise the following components in parts by weight:
100 parts of lead powder;
4.0-10 parts of sulfuric acid;
0.5-2.0 parts of barium sulfate;
0.05-0.5 part of lignin-based compound/conductive polymer composite material;
0.05-0.3 part of polyester staple fiber;
0.01-0.5 parts of carbon material;
9-16 parts of water.
7. The method for preparing a lead paste according to any one of claims 1 to 6, characterized in that it comprises: and uniformly mixing the raw materials to obtain the lead plaster.
8. A battery plate, wherein the battery plate comprises lead paste;
at least one lead paste selected from the lead paste according to any one of claims 1 to 6 and the lead paste obtained by the preparation method according to claim 7;
preferably, the battery plate is a battery negative plate.
9. The method of making a battery plate of claim 8, comprising:
and coating the lead plaster on a grid, and curing to obtain the battery plate.
10. A battery comprising a battery plate;
the battery plate is selected from at least one of the battery plate of claim 8 and the battery plate obtained by the preparation method of claim 9;
preferably, the battery is one of a lead-acid battery, a lead-carbon battery and a lead-carbon battery.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114639802A (en) * | 2022-03-02 | 2022-06-17 | 中国科学院福建物质结构研究所 | Barium sulfate-conductive polymer composite material and preparation method and application thereof |
| CN114784245A (en) * | 2022-04-21 | 2022-07-22 | 山东合泰新能源有限公司 | Zinc electrode containing organic expanding agent and preparation method thereof |
| CN115188961A (en) * | 2022-07-07 | 2022-10-14 | 中国科学院福建物质结构研究所 | Lead-carbon battery negative lead paste, preparation method, battery pole plate, preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199244A (en) * | 2013-04-25 | 2013-07-10 | 浙江天能电池江苏新能源有限公司 | Negative plate ead paste of lead-acid battery and preparation method of negative lead paste |
| CN103408932A (en) * | 2013-07-15 | 2013-11-27 | 长春市三化实业有限责任公司 | Water-soluble conductive polyaniline nano-fiber/lignin composite material and preparation method thereof |
| CN105098159A (en) * | 2015-08-26 | 2015-11-25 | 深圳市燕峰科技有限公司 | Cathode material, anode, battery and preparation method of cathode material |
| CN105140474A (en) * | 2015-07-28 | 2015-12-09 | 安徽超威电源有限公司 | Anode lead paste for power lead-acid storage battery and preparation method of anode lead paste |
| CN106450293A (en) * | 2016-11-09 | 2017-02-22 | 骆驼集团蓄电池研究院有限公司 | Battery cathode diachylon formulation high in utilization rate of active substance and preparation method of battery cathode diachylon formulation |
| US20180183060A1 (en) * | 2015-10-21 | 2018-06-28 | Imerys Graphite & Carbon Switzerland Ltd. | Carbonaceous composite materials with snowball-like morphology |
-
2020
- 2020-01-16 CN CN202010049733.XA patent/CN111224097B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103199244A (en) * | 2013-04-25 | 2013-07-10 | 浙江天能电池江苏新能源有限公司 | Negative plate ead paste of lead-acid battery and preparation method of negative lead paste |
| CN103408932A (en) * | 2013-07-15 | 2013-11-27 | 长春市三化实业有限责任公司 | Water-soluble conductive polyaniline nano-fiber/lignin composite material and preparation method thereof |
| CN105140474A (en) * | 2015-07-28 | 2015-12-09 | 安徽超威电源有限公司 | Anode lead paste for power lead-acid storage battery and preparation method of anode lead paste |
| CN105098159A (en) * | 2015-08-26 | 2015-11-25 | 深圳市燕峰科技有限公司 | Cathode material, anode, battery and preparation method of cathode material |
| US20180183060A1 (en) * | 2015-10-21 | 2018-06-28 | Imerys Graphite & Carbon Switzerland Ltd. | Carbonaceous composite materials with snowball-like morphology |
| CN106450293A (en) * | 2016-11-09 | 2017-02-22 | 骆驼集团蓄电池研究院有限公司 | Battery cathode diachylon formulation high in utilization rate of active substance and preparation method of battery cathode diachylon formulation |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114639802A (en) * | 2022-03-02 | 2022-06-17 | 中国科学院福建物质结构研究所 | Barium sulfate-conductive polymer composite material and preparation method and application thereof |
| CN114639802B (en) * | 2022-03-02 | 2023-09-29 | 中国科学院福建物质结构研究所 | Barium sulfate-conductive polymer composite material and preparation method and application thereof |
| CN114784245A (en) * | 2022-04-21 | 2022-07-22 | 山东合泰新能源有限公司 | Zinc electrode containing organic expanding agent and preparation method thereof |
| CN115188961A (en) * | 2022-07-07 | 2022-10-14 | 中国科学院福建物质结构研究所 | Lead-carbon battery negative lead paste, preparation method, battery pole plate, preparation method and application |
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