CN113690432A - Graphene quantum dot/PbOx composite material and preparation method and application thereof - Google Patents
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- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
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Abstract
The invention discloses a graphene quantum dot/PbOxA composite material, a preparation method and an application thereof, a carbon source and PbO are mixedxUniformly mixing, reacting at 45-80 ℃ for at least 30min, and continuously heating for reaction or continuously reacting by microwave treatment to obtain the graphene quantum dots/PbOxA composite material. According to the graphene quantum dot/PbOx composite material disclosed by the invention, GQDs are generated in situ, are uniformly and discontinuously distributed, so that the capacity is effectively reduced due to self-discharge of the battery and local electrochemical reaction escape during high-rate operation of the battery, and meanwhile, the reaction sites of the battery are fixed and uniform. GQDs have large specific surface area and excellent conductivity, which can increase the contact area of electrode materials and electrolyte and improve the electronic conductivity of the materials, thereby improving the active sites of the reaction, namelyThe method is favorable for improving the reaction kinetics characteristic, so that the electrochemical performance of the material in the lead-acid battery is improved.
Description
Technical Field
The invention belongs to the field of nano composite materials, relates to application of lead-acid battery materials, and particularly relates to graphene quantum dots/PbOxA composite material and a preparation method and application thereof.
Background
The global fossil energy is gradually exhausted, the environmental pollution caused by the application of the fossil energy in aspects of power, electric power and the like is increasingly serious, and the global energy and environmental problems are very severe. People must solve the contradiction between economic growth and resource environment and ensure the sustainable development of human society and economy, so people need to search renewable clean energy. The lead-acid battery is the oldest secondary battery, is invented by the French plena in 1859, has application development history of nearly 150 years, has great progress in the aspects of product types, product electrical performance, cycle life and the like, is particularly superior to a lithium battery in use safety and high and low temperature environments, and a lead-acid battery recovery system is established and operated well, so that lead pollution caused by the lead-acid battery is effectively avoided. Therefore, lead-acid batteries are widely used in various economic fields such as transportation (various motor vehicles), communication, electric power, military, navigation and aviation, and are used as starting lead-acid batteries, power lead-acid batteries, fixed valve-regulated sealed lead-acid batteries, mining lamps or street lamps, communication base station lead-acid batteries, and the like.
The cycle life of a lead-acid storage battery is usually short, and the lead-acid storage battery is generally used for about 300 times, and the maximum is 600 times in practical application, so that the lead-acid storage battery is more limited to be used as a start-stop battery (storage battery) in the field of automobiles. This short life is due to excessive sulfation of the electrode material during use (PbSO)4The size is increased, the activity is reduced), the capacity is obviously reduced, and the service life of the lead-acid storage battery is 1-1.5 years.
The preparation method of the graphene quantum dot comprises a top-down approach (top-down approach) and a bottom-up approach (bottom-up approach), wherein the common point is that the preparation of the graphene quantum dot is completed by performing dialysis on a semi-permeable membrane for a long time (24-48 h) to remove soluble impurities (molecules or ions and the like), the former usually utilizes macromolecules (such as graphite powder, large graphene sheets, carbon nano tubes, carbon fibers, biomass, part of carbon-containing polymers and the like) to be cut to prepare the graphene quantum dot, and the latter utilizes micromolecule carbon sources (such as citric acid and derivatives thereof, carbohydrates, aromatic ring organic matters and the like) to be condensed, dehydrated and subjected to radical removal to generate the graphene quantum dot. No matter hydrothermal or solvent heating or reflux is adopted, graphene quantum dots with uniformly distributed sizes can be obtained only in a dilute dispersion liquid due to the existence of a temperature gradient, a large amount of side reactions and reaction unevenness caused by the temperature gradient exist in the melting of a concentrated solution or a pure carbon source, and in addition, agglomeration is caused, so that the size distribution is very wide, and even a large amount of amorphous carbon precipitates are generated due to too fast reaction. In comparison, hydrothermal method, solvent thermal method or reflux method usually takes a lot of time (6 h or more) to prepare graphene quantum dots, and various costs (labor, small batch, environmental waste liquid, etc.) are very high due to complicated separation, cleaning and dialysis, so that the industrial scale is more difficult to form. Therefore, at present, the application of single graphene quantum dots is mostly limited to various probe fields with high requirements on purity. For the practical application of standard industries (including batteries), an innovative preparation method of the graphene quantum dots with low cost, simple process and high product application performance is urgently needed.
In order to prolong the service life of lead-acid batteries, researchers have adopted various methods, such as a lead-carbon battery structure, addition of graphene, and the like. The former contributes well to the dynamic life, for example, in CN201410154850.7, the graphene-coated lead composite material is formed by coating lead powder with graphene and other additives, and compared with a comparative example, the cycle life of the obtained lead-acid battery is improved from 300 times to 420-485 times; CN,201510253410.1 added to the negative electrode material using colloidal graphite in combination with nano-sized graphene, the cycling durability increased from 531 to 896 times. However, the size of the graphene is 30-300 nm, the electron mobility in the coverage area of the graphene is high, so that the self-discharge is accelerated, and the electrons are rapidly transferred by the graphene in the electrochemical conversion process, so that the absolute capacity is remarkably reduced at a high multiplying power; theoretically, the graphene with the quantum size of less than 10nm is expected to improve the effects of cycle life and rate stability, but the cost of the common few-layer graphene is high due to the high cost of the preparation method and the difficulty in preparing the quantum size, so that the cost performance brought by the use of the graphene is low. How to solve the problem that the lead-acid battery has short service life, the problem that the performance is seriously degraded due to the sulfation of an electrode material is solved, the problem that the cost performance is low by adding few layers of graphene is one of the key directions worth of further research.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a preparation method and application of a low-cost graphene quantum dot/PbOx composite material.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
graphene quantum dot/PbOxA composite material, the method of making comprising:
mixing a carbon source with PbOxUniformly mixing, and reacting at 45-80 ℃ for at least 30min, wherein x = 0-2 and is not 0;
heating to 180-220 ℃ for continuous reaction, or carrying out microwave treatment for continuous reaction to obtain the graphene quantum dots/PbOxA composite material.
In some examples, the carbon source is added in an amount of 0.001 to 0.1 times the mass of the lead oxide.
In some examples, the carbon source is added in an amount of 0.005 to 0.01 times the mass of the lead oxide.
In some examples, the carbon source is selected from carbon sources having a molecular weight of no greater than 1000.
In some examples, the carbon source comprises at least one sulfur and/or nitrogen containing carbon source.
In some examples, the sulfur-containing carbon source is selected from the group consisting of thioaromatic alcohols or acids, thiophene derivatives, thioamides, thioureas.
In some examples, the nitrogen-containing carbon source is selected from the group consisting of pyridine, bipyridine derivatives, para-aniline, quinine, and derivatives thereof.
In some examples, the carbon source further comprises at least one C6-C12 oxygen-containing organic substance.
In some examples, the oxygen-containing organic is selected from the group consisting of citric acid, ammonium citrate, citrate esters, glucose, gluconate esters, aminogluconic acid, salicylic acid, and derivatives thereof.
In some examples, the carbon source comprises citric acid and at least one sulfur and/or nitrogen containing carbon source.
In some examples, the molar ratio of the sulfur and/or nitrogen containing carbon source (total molar amount) to citric acid is (2-3): 1.
in some examples, the reaction system is a solid-solid dispersion or a solid-liquid dispersion.
In a second aspect of the present invention, there is provided:
graphene quantum dot/PbOxThe composite material is applied to preparation of a positive electrode material or a negative electrode material of a lead-acid battery, and the graphene quantum dot/PbOxThe composite material is as described in the first aspect of the invention.
In a third aspect of the present invention, there is provided:
a lead-acid battery, wherein the electrode material of the lead-acid battery contains the graphene quantum dot/PbO of the first aspect of the inventionxA composite material.
The invention has the beneficial effects that:
according to the graphene quantum dot/PbOx composite material disclosed by the invention, GQDs are generated in situ, are uniformly and discontinuously distributed, so that the capacity is effectively reduced due to self-discharge of the battery and local electrochemical reaction escape during high-rate operation of the battery, and meanwhile, the reaction sites of the battery are fixed and uniform. The GQDs have larger specific surface area and excellent conductivity, so that the contact area of an electrode material and electrolyte can be increased, and the electronic conductivity of the material can be improved, thereby improving the active sites of the reaction, being beneficial to improving the reaction kinetics, and improving the electrochemical performance of the material in a lead-acid battery. PbOx can well promote the generation of graphene quantum dots.
The GQDs prepared from the graphene quantum dot/PbOx composite material of some examples of the invention contain S or N, can generate chemical adsorption with a matrix, and is firmer in combination and more stable in performance.
In the graphene quantum dot/PbOx composite material of some embodiments of the present invention, part of the sulfur is converted into nano PbSO in the subsequent heat treatment or electrochemical process4In the battery reaction, the PbSO is refined as seed crystal4And (4) grain action.
The graphene quantum dot/PbOx composite material of some examples of the invention has the advantages of easily available raw materials, low price, simple preparation method, easy industrial production and continuous production, and is environment-friendly because the solvent can be recycled in the reaction.
Drawings
Fig. 1 is an SEM image of the graphene quantum dot/PbO composite material prepared in example 1.
Fig. 2 is a TEM image of the graphene quantum dot/PbO composite prepared in example 1.
Fig. 3 is an SEM image of blank PbO.
Fig. 4 is a graph comparing the rate cycle curves of the graphene quantum dot/PbO composite material prepared in example 1 and the lead-acid battery manufactured in comparative example PbO.
Fig. 5 is a fluorescence spectrum obtained by dissolving the graphene quantum dot/PbO composite material prepared in example 1 in 2M acetic acid solution, diluting the solution by 100 times, and exciting the solution with 365nm ultraviolet light.
FIG. 6 is a Raman spectrum of example 4.
Fig. 7 is a representation of a lead-acid soft package battery prepared as a negative electrode material in example 2 as a start-stop battery.
Fig. 8 is a graph comparing deep discharge performance of lead-acid soft package batteries prepared from blank PbO materials in example 2.
Detailed Description
The principle of some examples of the invention is: the chemical adsorption of sulfur and/or nitrogen coordination atoms in a small molecular carbon source and PbOx in solid-solid mixture or a solvent is utilized, graphene quantum dots are dehydrated on the surface of PbOx in the subsequent heating process, and are subjected to in-situ radical removal to generate graphene quantum dots, and the quantum dots are tightly combined with a PbOx matrix due to chemical adsorption.
The method is unique and simple in design, and the graphene quantum dots can be obtained by one-step continuous reaction and are uniformly distributed on the surface of the parent PbOx material to form the graphene quantum dot/PbOx composite material. This is due to the in situ catalysis of PbOx in the heating for the subsequent dehydration, degrouping reaction. The synthesized composite material has good dispersion performance and greatly improved electrochemical performance, which is attributed to the fact that the GQDs generated in situ are firmly combined with the matrix PbOx, the size is less than 10nm, the specific surface area is large, the conductivity is good, more reaction active sites can be provided, the formation of refined lead sulfate is accelerated by the action of heterogeneous crystal nuclei, the polarization is reduced, and the composite material is favorable for the transmission of electrons, so that the dynamic characteristic of discharge/charge reaction is improved.
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The preparation method of the graphene quantum dot/PbO composite material of the embodiment includes the following specific preparation steps:
under the condition of stirring, adding thioacetamide and citric acid with the molar ratio of 3:1 into the aqueous dispersion of PbO, wherein the sum of the mass of the thioacetamide and the citric acid is five thousandth of the mass of the PbO;
stirring for 30min, reacting at constant temperature of 45 ℃ for 1h, then refluxing and heating at 180 ℃ for 1h, cooling, and centrifugally drying to obtain the graphene quantum dot/PbOx composite material, namely GQDs/PbO.
GQDs/PbO can be used as the negative electrode material of lead-acid batteries.
Example 2
The preparation method of the graphene quantum dot/Pb composite material provided by the embodiment comprises the following specific preparation steps:
under the condition of stirring, adding thiosalicylic acid and ethyl citrate with the molar ratio of 2:1 into the ethanol dispersion liquid of Pb powder, wherein the mass of the thiosalicylic acid and the ethyl citrate is one thousandth of that of Pb. Stirring for 30min, reacting at a constant temperature of 60 ℃ for 1h, then refluxing and heating at 200 ℃ for 1h, cooling, and centrifugally drying to obtain the graphene quantum dot/Pb composite material, namely GQDs/Pb. The material can be used as the negative electrode material of the lead-acid battery.
Example 3
The preparation method of the graphene quantum dot/PbO composite material of the embodiment includes the following specific preparation steps:
under the condition of stirring, thiophene and glucose with the molar ratio of 3:1 are added into the solid powder of PbO, and the mass of the thiophene and the glucose is ten thousandth of that of the PbO. And grinding and stirring for 30min, reacting at the constant temperature of 50 ℃ for 1h, heating at the temperature of 220 ℃ for 1h, and cooling to obtain the graphene quantum dot/PbO composite material, namely GQDs/PbO. The material can be used as the negative electrode material of the lead-acid battery.
Example 4
The preparation method of the graphene quantum dot/PbO composite material of the embodiment includes the following specific preparation steps:
adding benzothiazole and ethyl gluconate with the molar ratio of 2:1 into the solid powder of PbO under the condition of stirring, wherein the mass of the benzothiazole and the ethyl gluconate is 10 percent of that of the PbO. Grinding and stirring for 30min, heating at 50 ℃ for reacting for 1h at constant temperature, heating in a household 800W microwave for 5 min, and cooling to obtain the graphene quantum dot/PbO composite material, namely GQDs/PbO. The material can be used as the negative electrode material of the lead-acid battery.
Example 5
Graphene quantum dot/PbO of the embodiment2The preparation method of the composite material comprises the following specific preparation steps:
adding glucose and ammonium citrate in a molar ratio of 2:1 to PbO under stirring2In the solid powder, the mass of the glucose and the ammonium citrate is PbO23% by mass. Grinding and stirring for 30min, reacting at the constant temperature of 75 ℃ for 1h, heating at the temperature of 200 ℃ for 1h, and cooling to obtain the graphene quantum dot/PbO2Composite materials, i.e. GQDs/PbO2. The lead-acid battery anode material can be used as the lead-acid battery anode material.
Example 6
The preparation method of the graphene quantum dot/PbO composite material of the embodiment includes the following specific preparation steps:
under the condition of stirring, thiourea and salicylic acid with the molar ratio of 3:1 are added into the aqueous dispersion of PbO, and the mass of the thiourea and the salicylic acid is two thousandth of that of the PbO. Stirring for 30min, putting into a reaction kettle with a polytetrafluoroethylene lining, reacting at the constant temperature of 80 ℃ for 1h and at the constant temperature of 180 ℃ for 1h, cooling, and centrifugally drying to obtain the graphene quantum dot/PbO composite material, namely GQDs/PbO. The material can be used as the negative electrode material of the lead-acid battery.
Example 7
The preparation method of the graphene quantum dot/PbO composite material of the embodiment includes the following specific preparation steps:
under the condition of stirring, thiourea and propyl citrate with the molar ratio of 2.5:1 are added into the ethanol dispersion liquid of PbO, and the mass of the thiourea and the propyl citrate is eight thousandth of that of the PbO. Stirring for 30min, putting into a reaction kettle with a polytetrafluoroethylene lining, reacting at a constant temperature of 60 ℃ for 1h and at a constant temperature of 190 ℃ for 1h, cooling, and centrifugally drying to obtain the graphene quantum dot/PbO composite material, namely GQDs/PbO. The material can be used as the negative electrode material of the lead-acid battery.
Example 8
The preparation method of the graphene quantum dot/Pb composite material provided by the embodiment comprises the following specific preparation steps:
under the condition of stirring, adding thiophene and ammonium gluconate with the molar ratio of 3:1 into butanol dispersion liquid of Pb powder, wherein the mass of the thiophene and the ammonium gluconate is six thousandth of that of the Pb powder. Stirring for 30min, placing into a reaction kettle with a polytetrafluoroethylene lining, reacting at a constant temperature of 60 ℃ for 1h and at a constant temperature of 180 ℃ for 1h, cooling, and centrifugally drying to obtain the graphene quantum dot/Pb composite material, namely GQDs/Pb. The material can be used as the negative electrode material of the lead-acid battery.
Comparative example
PbO in example 1 and PbO in example 52The obtained product is a commercial battery grade commodity and is respectively used as a blank anode and cathode material contrast.
And (3) testing physical and chemical properties:
(1) assembling the whole battery: adding BaSO into the graphene quantum dot/PbOx composite material and the corresponding negative or positive electrode material prepared in each embodiment4Preparing positive electrode slurry and negative electrode slurry from acetylene black and PVDF, coating on lead net, treating by corresponding process, and injecting H2SO4And (5) assembling the electrolyte solution into a full cell. It is not specified that when the graphene quantum dot/PbOx (x =0, 1) composite material is the negative electrode material, blank PbO is adopted2As a positive electrode material; when graphene quantum dots/PbO2When the composite material is a positive electrode material, blank PbO is adopted as a negative electrode material.
(2) Formation: setting parameters according to a general lead-acid battery formation method for formation.
(3) And (3) charge and discharge test: the lead-acid batteries manufactured in the examples were charged and discharged at different rates. The 1C cycle number is defined as the number of charge and discharge cycles that are terminated when the specific capacity decays to less than the initial 80%.
Fig. 1 is an SEM image of the graphene quantum dot/PbO composite material (not sprayed with gold, placed on the surface of a single crystal silicon wafer) prepared in example 1. As can be seen from FIG. 1, the composite material obtained by the method of the present invention shows uniform GQDs nanoparticles supported on the surface of flaky PbO, with a size of about 5 nm.
Fig. 2 is a TEM image of a graphene quantum dot/PbO composite prepared from the nickel mesh prepared in example 1. As can be seen from FIG. 2, in the material obtained by the method of the present invention, the GQDs nanoparticles are uniform nanoparticles with a size of about 5nm, are uniformly loaded on the surface of the sheet-like PbO, and are discontinuously distributed.
Fig. 3 is an SEM image of comparative example PbO. As can be seen from fig. 3, the comparative example material was flaky particles having non-uniform sizes.
Fig. 4 (a, B) is a comparison graph of rate cycle charge and discharge curves of the lead-acid battery using the graphene quantum dot/PbO composite material prepared in example 1 as a negative electrode and a blank comparative example at 1C. As can be seen from fig. 4A and table 1, when the lead-acid battery using the graphene quantum dot/PbO composite material obtained in example 1 as the negative electrode works at 1C, the rate stability is better than that of the comparative example (blank example), the first discharge capacity is 53 mAh/g, the first coulombic efficiency is 76%, the cycle number is 4500, while the blank example first discharge capacity is 45 mAh/g, the first coulombic efficiency is 70%, and the cycle number is only 500. More importantly, fig. 4B shows that the capacity loss is significantly lower than the blank case at high magnification 2C cycles; when the high multiplying power 2C is recovered to the low multiplying power 0.3C, the battery corresponding to the invention recovers well, but the blank case is poor. Therefore, the lead-acid battery made of the graphene quantum dot/PbO composite material prepared by the invention has stable performance of rate cycle performance and long 1C rate cycle life, namely, the electrochemical performance is more excellent.
Fig. 5 is a fluorescence spectrum obtained by dissolving the graphene quantum dot/PbO composite material prepared in example 1 in 2M acetic acid solution, diluting the solution by 100 times, and exciting the solution with 365nm ultraviolet light. It can be seen from FIG. 5 that the luminescence peak is at 445 nm.
FIG. 6 is a Raman spectrum of example 4, and D, G peak is evident from FIG. 6At 1320 and 1582 cm respectively-1The graphene has obvious characteristics.
Fig. 7 is a representation of a lead-acid soft package battery prepared as a negative electrode material in example 2 as a start-stop battery, and the test method refers to a partial charge rate test (JB/T12666-. One cycle unit was set to 3600 cycles (industry level), and the batteries were left to stand for 48h after each unit was finished. If the discharge voltage during the cycle is less than 1.2V, the test is terminated. The results show that PbO @ GQDs can complete 9 units of cycles of over 30000 times under the condition. The results are well above the industry standard.
Fig. 8 shows a comparison graph of deep discharge performance of lead-acid pouch batteries prepared from the blank PbO material in example 2. Deep discharging, namely comparing the service lives of the batteries by using accelerated charging and discharging, discharging the formed 2V battery to 1.73V at 0.35C, then carrying out constant-current constant-voltage charging, setting the charging current to be 0.5C and the constant-voltage current to be 2.4V, setting the cut-off current to be 0.02C and the cut-off time to be 280 min, standing for 10 min after the charging is finished, then carrying out 0.33C discharging, setting the cut-off voltage to be 1.733V, and then standing for 10 min. As shown in FIG. 8, when the negative electrode of PbO @ GQDs in example 2 is used, the discharge specific capacity is significantly higher than that of the battery in the blank group, the average discharge capacity within 200 cycles is 52.7mAh/g, the highest specific capacity reaches 63mAh/g, the average discharge specific capacity of the blank group is 40.3mAh/g, and the capacity of the negative electrode of PbO @ GQDs is improved by 30.2% compared with that of the blank group, so that the difference is consistent with the discharge performance of the first cycle after formation. More importantly, in the 200 cycles, the capacity retention rate of PbO @ GQDs is about 90%, PbO is 70.0%, and the cycle life of the battery is longer while the PbO @ GQDs as the negative electrode has higher specific discharge capacity.
In addition, the graphene quantum dot/PbOx composite materials obtained in examples 1 to 8 were assembled into a full cell; after formation, a charge-discharge test was performed at a constant current of 1C, and the performances of the batteries according to examples 1 to 8 were determined as shown in table 1.
TABLE 1 respective cell 1C performance of each example
As can be seen from fig. 1 to 3 and the above detection data, the graphene quantum dots on the surface of the graphene quantum dot/PbOx composite material for the long-life lead-acid battery anode and cathode materials obtained by the preparation method of the present invention are uniform, and the surface loading GQDs are discontinuously distributed, which is beneficial to the function of heterogeneous crystal nuclei to avoid the formation efficiency reduction caused by local short circuit. In contrast, the comparative example PbO has non-uniform particle size and obvious agglomeration, thus greatly reducing the contact area between the active material and the electrolyte, and the conductivity is inferior to GQDs, so that the polarization of the material is obvious, the utilization rate of the electrode material is low, and the reversible progress of the electrochemical reaction is not facilitated.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. Graphene quantum dot/PbOxA composite material, the method of making comprising:
mixing a carbon source with PbOxUniformly mixing, and reacting at 45-80 ℃ for at least 30min, wherein x = 0-2 and is not 0;
heating to 180-220 ℃ for continuous reaction, or carrying out microwave treatment for continuous reaction to obtain the graphene quantum dots/PbOxA composite material.
2. The graphene quantum dot/PbO according to claim 1xA composite material characterized by: the amount of the carbon source added is 0.001 to 0.1 times, preferably 0.005 to 0.01 times, the mass of the lead oxide.
3. The graphene quantum dot/PbO according to claim 1xA composite material characterized by: the carbon source is selected from the group consisting of those having a molecular weight of not more than 1000A carbon source of (2).
4. The graphene quantum dot/PbO according to claim 3xA composite material characterized by: the carbon source comprises at least one sulfur and/or nitrogen containing carbon source;
preferably, the sulfur-containing carbon source is selected from the group consisting of thioaromatic alcohols or acids, thiophene derivatives, thioamides, thioureas;
preferably, the nitrogen-containing carbon source is selected from the group consisting of pyridine, bipyridine derivatives, p-aniline, quinine, and derivatives thereof.
5. The graphene quantum dot/PbO according to claim 4xA composite material characterized by: the carbon source also comprises at least one C6-C12 oxygen-containing organic matter, preferably, the oxygen-containing organic matter is selected from citric acid, ammonium citrate, glucose, gluconate, aminogluconic acid, salicylic acid and derivatives thereof.
6. The graphene quantum dot/PbO according to claim 1xA composite material characterized by: the carbon source comprises citric acid and at least one sulphur and/or nitrogen containing carbon source; further, the molar ratio of the carbon source containing sulfur and/or nitrogen to the citric acid is (2-3): 1.
7. the graphene quantum dot/PbO according to claim 1xA composite material characterized by: the reaction system is a solid-solid dispersion system or a solid-liquid dispersion system.
8. Graphene quantum dot/PbOxThe composite material is applied to the preparation of the anode or cathode material of the lead-acid battery, and is characterized in that: the graphene quantum dot/PbOxA composite material as claimed in any one of claims 1 to 7.
9. A lead-acid battery characterized by: the electrode material contains the graphene quantum dot/PbO as defined in any one of claims 1 to 7xA composite material.
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| CN115286034A (en) * | 2022-07-07 | 2022-11-04 | 中国科学院福建物质结构研究所 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
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| CN115286034A (en) * | 2022-07-07 | 2022-11-04 | 中国科学院福建物质结构研究所 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
| CN115286034B (en) * | 2022-07-07 | 2023-11-17 | 中国科学院福建物质结构研究所 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
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