CN111146419A - Method for manufacturing long-life lead-acid battery cathode by using trace graphene oxide sheets - Google Patents
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Abstract
The invention discloses a method for manufacturing a long-life lead-acid battery cathode by using trace graphene oxide sheets, which prepares graphene oxide sheet dispersion liquid by a modified Hummer' method and is used as a lead-acid battery cathode plate additive. On the basis of the traditional formula, the trace graphene oxide sheets are added into the lead plaster in a liquid form, so that the growth of a large-size and porous lead rod in the formation process can be induced. The lead rod is of a one-dimensional structure and has good conductivity, and the lead rod is in a three-dimensional porous network formed by mutual crosslinking in the lead paste, so that the diffusion of sulfuric acid is facilitated, the generation of electrochemical reaction is accelerated, the mutual conversion between lead and lead sulfate is promoted, and the service life of the battery is prolonged. The obtained lead-acid battery has good cycle performance under the high-rate partial charge state, but does not affect the hydrogen evolution of the battery, and is particularly suitable for the field of power batteries.
Description
Technical Field
The invention relates to a preparation method of a lead-acid battery cathode, in particular to a high-rate partial charge state long-life lead-acid battery constructed by graphene oxide serving as a cathode additive, which is applied to the technical field of electrochemical energy storage of lead-acid batteries.
Background
Currently, although a variety of novel batteries appear in the market, lead-acid storage batteries still occupy a large market due to the advantages of high safety, low price, strong recycling capability and the like, and are widely applied to the field of hybrid electric vehicles at present. In a hybrid vehicle, severe sulfation of the negative battery plates occurs when the lead-acid battery is operated at a high rate partial state of charge. The carbon-based material has large specific surface area and good conductivity, can provide double-layer capacitance, and is widely applied to the field of electrochemistry. Researches show that the addition of the carbon material into the negative plate of the lead-acid battery can effectively inhibit the sulfation of the negative plate, and improve the charge receiving capacity and cycle life of the battery.
The graphene has the characteristics of high specific surface area, excellent electronic conductivity, high chemical stability, good flexibility and the like, and can form a continuous conductive network when added into a negative active material. However, graphene and other carbon materials have the following disadvantages: the price is high, which is not beneficial to large-scale industrialization. Promoting the hydrogen evolution of the polar plate, destroying the internal structure of the lead plaster and causing the water loss of the battery. The defects limit the application of the graphene material in the lead-acid storage battery, and become a technical problem to be solved urgently. The application discloses a method for constructing a long-life lead-acid battery by utilizing trace graphene oxide sheets.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a method for manufacturing a long-life lead-acid battery cathode by using trace graphene oxide sheets. On the basis of the traditional formula, the performance of the battery assembled by the negative plate added with the trace graphene oxide sheets is improved by 1.4 times compared with the battery assembled by the traditional formula. Under the high-rate partial charge state, the method effectively relieves the sulfation of the negative plate, and provides a new possibility for the preparation method of the lead-acid battery.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method for manufacturing a long-life lead-acid battery cathode by using trace graphene oxide sheets comprises the following steps:
a. preparing a graphene oxide sheet dispersion stock solution by using a modified Hummer' method;
b. preparing lead plaster:
uniformly mixing carbon black, lignin and barium sulfate to obtain mixed powder;
then adding lead powder into the mixed powder, and stirring and mixing to obtain a raw material mixture;
dropwise adding the stock solution of the graphene oxide sheet dispersion liquid prepared in the step a into deionized water to obtain a uniform graphene oxide sheet dispersion liquid; then, adding the graphene oxide sheet dispersion liquid into the raw material mixture at one time, uniformly stirring, dropwise adding dilute sulfuric acid with the mass percentage concentration not higher than 70%, and carrying out acid mixing to obtain acid lead paste for later use;
c. preparing a lead-acid battery cathode:
and c, coating the lead plaster prepared in the step b on a negative plate grid of the lead-acid battery, and controlling the curing temperature to be 50-70 ℃ and the humidity to be 50-95% so as to prepare the negative plate of the lead-acid battery.
As a preferable technical solution of the present invention, in the step a, the solid content of graphene oxide sheets dispersed in water in the prepared stock solution of graphene oxide sheet dispersion liquid is not higher than 5 mg/mL.
In the step b, the mass ratios of the carbon black, the barium sulfate and the lignin to the prepared lead oxide are calculated according to the mass ratios of the carbon black, the barium sulfate and the lignin to the prepared lead oxide respectively: 0.2%, 0.8%, 0.2%.
As a preferable technical scheme of the present invention, in the step b, the mass ratio of the deionized water in the graphene oxide sheet dispersion liquid to the prepared lead oxide is not higher than 12%, and the density of the dilute sulfuric acid is not more than 1.4g/cm-3The mass ratio of the dilute sulfuric acid to the prepared lead oxide is not more than 4.8%.
In a preferred embodiment of the present invention, in the step b, the addition amount of the graphene oxide sheets in the acidic lead paste is not more than 2 ppm.
In the step c, the lead paste is coated on the grid and cured by a step-by-step curing process, wherein the curing time is at least 96 hours.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method for constructing the long-life lead-acid battery by using the trace graphene oxide sheets is simple to operate, low in cost, free of special equipment and convenient to produce; the graphene oxide sheet is adopted, so that the growth of a large-size and porous lead rod in the formation process can be induced, the conductivity is improved, the porosity of the polar plate is increased, the diffusion of sulfuric acid is facilitated, and the electrochemical reaction is promoted. The additive is used for a negative plate additive of a lead-acid battery, and the obtained lead-acid battery has good cycle performance and is particularly suitable for the field of power batteries;
2. the method is simple and easy to implement, high in yield, good in repeatability and suitable for popularization and use.
Drawings
Fig. 1 is a TEM image of a graphene oxide sheet prepared by a method according to an embodiment of the present invention.
Fig. 2 is an SEM image of the negative plate prepared by the method of the embodiment of the present invention after formation.
Fig. 3 is a CV test chart of the negative plate produced by the method of the embodiment of the present invention and the negative plate produced by the comparative example.
Fig. 4 is a cycle test chart of a negative plate manufactured by one method of the embodiment of the present invention and a negative plate manufactured by a comparative example after assembled into a battery in a high-rate partial state of charge.
Fig. 5 is an SEM image of negative plates fabricated by the comparative example method after failure at high-rate partial state of charge.
Fig. 6 is an SEM image of a negative plate fabricated by a method according to an embodiment of the present invention after assembling into a battery, and after failure at a high-rate partial state of charge.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, a method for manufacturing a long-life lead-acid battery negative electrode by using a trace amount of graphene oxide sheets includes the following steps:
a. preparing a graphene oxide sheet dispersion solution stock solution by using a modified Hummer' method, wherein the solid content of graphene oxide sheets dispersed in water in the prepared graphene oxide sheet dispersion solution stock solution is 5 mg/mL; the prepared graphene oxide sheet is shown in figure 1;
b. preparing lead plaster:
calculating according to the mass ratio of the carbon black, the barium sulfate and the lignin to the prepared lead oxide respectively, and uniformly mixing 0.2% of the carbon black, 0.2% of Norway lignin and 0.8% of barium sulfate to obtain mixed powder;
then adding lead powder into the mixed powder, and stirring and mixing to obtain a raw material mixture;
dropwise adding the stock solution of the graphene oxide sheet dispersion liquid prepared in the step a into deionized water to obtain a uniform graphene oxide sheet dispersion liquid, and controlling the mass ratio of the deionized water in the graphene oxide sheet dispersion liquid to the prepared lead oxide to be 12%; then, adding the graphene oxide sheet dispersion liquid into the raw material mixture at one time, uniformly stirring, dropwise adding dilute sulfuric acid, and carrying out acid mixing to obtain acid lead paste for later use; the density of the dilute sulfuric acid is1.4g/cm-3The mass ratio of the dilute sulfuric acid to the prepared lead oxide is 4.8 percent; in the obtained acid lead paste, the addition amount of the graphene oxide sheets is 2 ppm;
c. preparing a lead-acid battery cathode:
and c, coating the lead plaster prepared in the step b on a negative plate grid of the lead-acid battery, and controlling the curing temperature to be 50-70 ℃, the humidity to be 50-95% and the curing time to be 96h, so as to prepare the negative plate of the lead-acid battery. Fig. 2 is an SEM image of the negative plate obtained by adding 2ppm graphene oxide sheets in the present example.
Experimental test analysis:
the negative plate of the lead-acid battery prepared by the embodiment is used as a working electrode, the positive counter electrode of a commercial lead-acid battery and the mercury/mercurous sulfate electrode are used as reference electrodes to form a three-electrode system, and the prepared negative electrode of the lead-acid battery is subjected to electrochemical representation. The potential window for the cyclic voltammetry test is 0 to-1.5V. The cell was assembled from negative and commercial positive plates and tested by simulating the high rate partial state of charge.
Comparative example:
in this embodiment, a method for manufacturing a negative electrode of a lead-acid battery includes the following steps:
(1) preparing lead plaster:
calculating according to the mass ratio of the carbon black, the barium sulfate and the lignin to the prepared lead oxide respectively, and uniformly mixing 0.2% of the carbon black, 0.2% of Norway lignin and 0.8% of barium sulfate to obtain mixed powder;
then adding lead powder into the mixed powder, and stirring and mixing to obtain a raw material mixture; adding deionized water into the mixed lead powder at one time, and controlling the mass ratio of the deionized water to the prepared lead oxide to be 12%; stirring uniformly; finally, dropwise adding dilute sulfuric acid, and uniformly mixing for later use; the density of the dilute sulfuric acid is 1.4g/cm-3The mass ratio of the dilute sulfuric acid to the prepared lead oxide is 4.8 percent;
(2) preparing a lead-acid battery cathode:
and (2) coating the lead plaster prepared in the step (1) on a negative plate grid of the lead-acid battery, and controlling the curing temperature to be 50-70 ℃, the humidity to be 50-95% and the curing time to be 96h, so as to prepare the negative plate of the lead-acid battery.
Experimental test analysis:
the negative plate of the lead-acid battery prepared by the comparative example is used as a working electrode, the positive plate of the commercial lead-acid battery is used as a counter electrode, and the mercury/mercurous sulfate electrode is used as a reference electrode to form a three-electrode system, so that the prepared negative electrode of the lead-acid battery is subjected to electrochemical representation. The potential window for cyclic voltammetry was 0 to-1.5V. The assembled batteries of negative and commercial positive plates (one negative and two positive) were tested by simulating a high rate partial state of charge.
Referring to fig. 3 and 4, fig. 3 is a CV test chart of the negative plate manufactured by the method of the embodiment of the present invention and the negative plate manufactured by the comparative example. Fig. 4 is a cycle test chart of a negative plate manufactured by one method of the embodiment of the present invention and a negative plate manufactured by a comparative example after assembled into a battery in a high-rate partial state of charge. According to the method provided by the embodiment of the invention, on the basis of a formula of a comparative example, the performance of the battery assembled by the negative plate added with the trace graphene oxide sheets is improved by 1.4 times compared with the battery assembled by a traditional formula. Moreover, the battery assembled by the formulation of the lead paste of the comparative example failed after two cycles, while the battery assembled by the negative plate added with a trace amount of graphene oxide sheets still reached 6301 cycles in the fourth cycle. Under the high-rate partial charge state, the sulfation of the negative plate is effectively relieved, and a new possibility is provided for the preparation method of the lead-acid battery. See fig. 5 as well as fig. 6. Fig. 5 is an SEM image of negative plates fabricated by the comparative example method after failure at high-rate partial state of charge. Fig. 6 is an SEM image of a negative plate fabricated by a method according to an embodiment of the present invention after assembling into a battery, and after failure at a high-rate partial state of charge. The method provided by the embodiment of the invention utilizes the trace graphene oxide sheets to construct the long-life lead-acid battery, solves the problem of low cycle life of the lead-acid battery in a high-rate partial charge state, and can greatly improve the cycle performance of the lead-acid battery by adding the trace graphene oxide sheets in a liquid form on the basis of the traditional lead plaster formula without influencing the hydrogen evolution of the battery. The method is simple to operate, low in cost, mature in process and good in application prospect.
Example two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
in the embodiment, when the lead plaster is prepared in the step b, the lead plaster is coated on a grid and cured by adopting a step-by-step curing process, so that uniform curing of a negative plate of the lead-acid battery is better realized, and the high-quality negative plate of the lead-acid battery is obtained. A total of two cell comparisons were made, so that only the processes of example one and comparative example were used, and all processes were cured in the same manner
According to the method for constructing the long-life lead-acid battery by using the trace graphene oxide sheets, the appropriate amount of carbon material is added into the negative plate, so that the sulfation of the negative plate can be effectively inhibited, the cycle life of the battery in a high-rate partial charge state is prolonged, and the hydrogen evolution is not influenced. The graphene serving as a carbon material has excellent performance and can improve the circulating capacity of the lead-acid battery in a high-rate partial charge state. The following problems may occur due to graphene and other carbon materials:
(1) the price is high, which is not beneficial to large-scale industrialization.
(2) The carbon material promotes the pole plate to generate hydrogen, destroys the internal structure of the lead plaster and causes water loss of the battery. The traditional paste mixing method is to physically mix graphene and other expanding agents with lead powder, and then add water and dilute sulfuric acid for blending. On the basis of the traditional formula, trace graphene oxide sheets are dispersed in a proper amount of water, and then graphene oxide sheet dispersion liquid and dilute sulfuric acid are added into a mixture to prepare the lead plaster. The method adopts trace graphene oxide sheets, and can induce the growth of the porous lead rod in the formation process. This is due to:
(1) the lead rod is of a one-dimensional structure and has good conductivity;
(2) the large-size lead rods are mutually crosslinked to form a three-dimensional porous network, so that the diffusion of sulfuric acid is facilitated, and the mutual conversion of lead and lead sulfate is promoted;
(3) the porous structure on the lead rod is beneficial to storing electrolyte and accelerating the electrochemical reaction of lead and lead sulfate.
Meanwhile, it was found that in the CV test, although the redox peaks of lead and lead sulfate were greatly increased after the addition of the graphene oxide sheet, the current generated by hydrogen evolution at a voltage of-1.5V was hardly changed. The method of the invention can improve the performance of the lead-acid battery, but does not affect the hydrogen evolution. Experiments show that the first cycle time of a battery assembled by a traditional lead paste formula is 21307 circles, and the cycle performance of the battery assembled by adding 2ppm of graphene oxide sheets is improved by 1.4 times after 29971 circles. And the battery assembled by the traditional lead plaster formula fails after 2 cycles, and the fourth cycle of the battery added with 2ppm graphene oxide sheets can still reach 6301 circles.
According to the embodiment of the invention, the graphene oxide sheet dispersion liquid is prepared by a modified Hummer' method and is used as an additive of a negative plate of a lead-acid battery. On the basis of the traditional formula, the trace graphene oxide sheets are added into the lead plaster in a liquid form, so that the growth of a large-size and porous lead rod in the formation process can be induced. The lead rod is of a one-dimensional structure and has good conductivity, and the lead rod is in a three-dimensional porous network formed by mutual crosslinking in the lead paste, so that the diffusion of sulfuric acid is facilitated, the generation of electrochemical reaction is accelerated, the mutual conversion between lead and lead sulfate is promoted, and the service life of the battery is prolonged. The method for constructing the long-life lead-acid battery by using the trace graphene oxide sheets is simple to operate, low in cost, free of special equipment and convenient to produce. The graphene oxide sheet can induce the growth of a large-size porous lead rod in the formation process, improve the conductivity, increase the porosity of the polar plate, facilitate the diffusion of sulfuric acid and promote the generation of electrochemical reaction. The lead-acid battery negative plate additive is used for the lead-acid battery negative plate additive, and the obtained lead-acid battery has good cycle performance and charge receiving capacity, and is particularly suitable for the field of power batteries.
While the embodiments of the present invention have been described with reference to the accompanying drawings, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principles of the present invention should be equivalent substitutions, so long as the objects of the present invention are met, and the present invention is within the scope of protection of the present invention as long as the technical principles and inventive concepts of the method for manufacturing a long-life lead-acid battery negative electrode using a trace amount of graphene oxide sheets are not departed from the present invention.
Claims (6)
1. A method for manufacturing a long-life lead-acid battery cathode by using trace graphene oxide sheets is characterized by comprising the following steps:
a. preparing a graphene oxide sheet dispersion stock solution by using a modified Hummer' method;
b. preparing lead plaster:
uniformly mixing carbon black, lignin and barium sulfate to obtain mixed powder;
then adding lead powder into the mixed powder, and stirring and mixing to obtain a raw material mixture;
dropwise adding the stock solution of the graphene oxide sheet dispersion liquid prepared in the step a into deionized water to obtain a uniform graphene oxide sheet dispersion liquid; then, adding the graphene oxide sheet dispersion liquid into the raw material mixture at one time, uniformly stirring, dropwise adding dilute sulfuric acid with the mass percentage concentration not higher than 70%, and carrying out acid mixing to obtain acid lead paste for later use;
c. preparing a lead-acid battery cathode:
and c, coating the lead plaster prepared in the step b on a negative plate grid of the lead-acid battery, and controlling the curing temperature to be 50-70 ℃ and the humidity to be 50-95% so as to prepare the negative plate of the lead-acid battery.
2. The method for manufacturing the negative electrode of the long-life lead-acid battery by using the trace graphene oxide sheet as claimed in claim 1, wherein the method comprises the following steps: in the step a, the solid content of the graphene oxide sheets dispersed in water in the stock solution of the graphene oxide sheet dispersion liquid prepared is not higher than 5 mg/mL.
3. The method for manufacturing the negative electrode of the long-life lead-acid battery by using the trace graphene oxide sheet as claimed in claim 1, wherein the method comprises the following steps: in the step b, the mass ratios of the carbon black, the barium sulfate and the lignin to the prepared lead oxide are calculated, and the mass ratios of the carbon black, the barium sulfate and the lignin to the prepared lead oxide are as follows: 0.2%, 0.8%, 0.2%.
4. The method for manufacturing the negative electrode of the long-life lead-acid battery by using the trace graphene oxide sheet as claimed in claim 1, wherein the method comprises the following steps: in the step b, the mass ratio of the deionized water in the graphene oxide sheet dispersion liquid to the prepared lead oxide is not higher than 12%, and the density of the dilute sulfuric acid is not more than 1.4g/cm-3The mass ratio of the dilute sulfuric acid to the prepared lead oxide is not more than 4.8%.
5. The method for manufacturing the negative electrode of the long-life lead-acid battery by using the trace graphene oxide sheet as claimed in claim 1, wherein the method comprises the following steps: in the step b, the addition amount of the graphene oxide sheets in the obtained acid lead paste is not more than 2 ppm.
6. The method for manufacturing the negative electrode of the long-life lead-acid battery by using the trace graphene oxide sheet as claimed in claim 1, wherein the method comprises the following steps: in the step c, the lead plaster is coated on the grid and is cured by adopting a step-by-step curing process, and the curing time is at least 96 hours.
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| WO2021129793A1 (en) * | 2019-12-26 | 2021-07-01 | 上海大学 | Method for manufacturing long-life lead-acid battery negative electrode by using trace amount of graphene oxide flakes |
| CN113161539A (en) * | 2021-02-05 | 2021-07-23 | 肇庆理士电源技术有限公司 | Trace acidized carbon nanotube negative plate and lead paste and preparation method thereof |
| CN113764660A (en) * | 2021-09-24 | 2021-12-07 | 肇庆理士电源技术有限公司 | Trace amino modified carbon nanotube negative plate, lead paste and preparation method of trace amino modified carbon nanotube negative plate |
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| CN109888409A (en) * | 2019-04-03 | 2019-06-14 | 山东星火科学技术研究院 | The high-capacity lead-acid battery and its synthesis technology of a kind of graphene as additive |
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| WO2021129793A1 (en) * | 2019-12-26 | 2021-07-01 | 上海大学 | Method for manufacturing long-life lead-acid battery negative electrode by using trace amount of graphene oxide flakes |
| CN113161539A (en) * | 2021-02-05 | 2021-07-23 | 肇庆理士电源技术有限公司 | Trace acidized carbon nanotube negative plate and lead paste and preparation method thereof |
| CN113764660A (en) * | 2021-09-24 | 2021-12-07 | 肇庆理士电源技术有限公司 | Trace amino modified carbon nanotube negative plate, lead paste and preparation method of trace amino modified carbon nanotube negative plate |
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