CN113683082A - Graphene quantum dot composite material and application thereof - Google Patents

Graphene quantum dot composite material and application thereof Download PDF

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CN113683082A
CN113683082A CN202110927160.0A CN202110927160A CN113683082A CN 113683082 A CN113683082 A CN 113683082A CN 202110927160 A CN202110927160 A CN 202110927160A CN 113683082 A CN113683082 A CN 113683082A
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carbon source
composite material
graphene quantum
quantum dot
dot composite
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CN113683082B (en
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何可立
铁绍龙
何幸华
吴嘉豪
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Zhaoqing Zhongteneng Technology Investment Co ltd
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Abstract

The invention discloses a graphene quantum dot composite material and application thereof, wherein the composite material is prepared by uniformly mixing a carbon source and solid carrier particles, and reacting at 45-80 ℃ for at least 30 min; and then heating to 180-220 ℃ for continuous reaction, or carrying out microwave treatment for continuous reaction. The graphene quantum dot composite material is a nano composite material synthesized in situ, the size distribution of quantum dots is uniform, the uniformity is better, and the performance is more stable and controllable. The GQDs in the graphene quantum dot composite material has 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, so that the active sites of the reaction can be improved, the reaction kinetics can be improved, the electrochemical performance of the material in a lead-acid battery can be improved, and the long service life of a secondary battery of the lead-acid battery can be realized.

Description

Graphene quantum dot composite material and application thereof
Technical Field
The invention relates to a novel functional material, in particular to a graphene quantum dot composite material and application thereof.
Background
With the deep development of economy, society and science and technology, the requirements of people on the environment are improved, the environmental pollution brought by the application of various fields to the aspects of power, electric power and the like is increasingly emphasized, clean energy enters various scenes in need, the contradiction between economic growth and resource environment is better solved, and the method makes positive contribution to the sustainable development of human society and economy. The lead-acid battery which is applied and developed in the past 150 years is invented by the prankian in 1859, various technologies are injected so far, such as coating plates for replacing lead plates, gel for replacing flowing dilute sulfuric acid and the like, so that the product type, the product electrical property, the cycle life, the convenience, the environmental protection safety and the like of the lead-acid battery are greatly improved and developed, the lead-acid battery is particularly superior to a lithium battery in high and low temperature environments, a global lead-acid battery recovery system is established and well operated, and lead pollution caused by the lead-acid battery is effectively avoided, therefore, the lead-acid battery is used as a starting lead-acid battery, a power lead-acid battery, a fixed valve-controlled sealed lead-acid battery, a mine lamp or street lamp lead-acid battery, a communication base station lead-acid battery, an extreme scene application and the like, and the lead-acid battery is still applied in various fields including traffic (various motor vehicles), communication, electric power and the like, The method is widely applied to various economic fields of military, navigation and aviation.
The lead-acid storage battery is low in price, but the cycle life of the lead-acid storage battery is short, and the lead-acid storage battery is generally charged and discharged for about 300-500 times in a circulating manner in practical application. This is due to excessive sulfation of the electrode material during use or charge-discharge cycles (PbSO)4Size increase and reduced activity) results in a significant reduction in capacity and cycle performance, resulting in a lead acid battery having a useful life of 1-1.5 years. In order to prolong the service life of lead-acid batteries, researchers at home and abroad adopt various methods, such as adding various additives into electrode materials, such as titanium dioxide, white carbon black, various activated carbons, acetylene black, graphene, bismuth oxide, sulfate and the like, or changing the structure into a lead-carbon battery structure or compounding the lead-acid battery structure and the sulfate. These additives contribute more or less well to the dynamic life of the battery, but still bring other negative effects, such as still severe sulfation, aggravation of partial self-discharge, significant decrease of absolute capacity of (lead-carbon battery), high cost, etc., for example, the effect of improving cycle life and rate stability of graphene as reported in the literature, but the comprehensive cost performance is too low compared with the expensive cost of graphene. Therefore, how to overcome the short service life of the lead-acid battery at an acceptable cost, especially the serious performance degradation caused by the sulfation of the electrode material, is one of the key problems worthy of solution.
Graphene Quantum Dots (GQDs) are a new carbonaceous fluorescent material with the graphene sheet layer size within 100nm and the number of sheet layers below 10. Generally, the graphene quantum dots include a general term of a large class of carbonaceous fluorescent materials and derivatives thereof with similar structure and the same performance of graphene quantum dots, graphene oxide quantum dots and partially reduced graphene oxide quantum dots.
The preparation of the graphene quantum dots has two methods from top to bottom and from bottom to top.
Top-down synthesis
The top-down method refers to etching large-sized substances into nano-sized graphene quantum dots by a physical or chemical method, and has preparation paths such as a solvothermal method, electrochemistry, chemical stripping and the like.
The solvothermal method is one of a plurality of methods for preparing the graphene quantum dots, and the process can be divided into three steps: firstly, reducing graphene oxide into graphene nanosheets at high temperature in a vacuum state; oxidizing and cutting the graphene nanosheets in concentrated sulfuric acid and concentrated nitric acid; and finally, reducing the oxidized graphene nanosheets in a solvothermal environment to form graphene quantum dots.
The process of the process for preparing the graphene quantum dots by the electrochemical method can be summarized into three stages: the first stage is an induction period in which graphite is peeled off to form graphene, and the color of the electrolyte begins to change from colorless to yellow to dark brown; the second stage is that the graphite of the anode undergoes significant expansion; the third stage is when the graphite flakes have exfoliated from the anode, forming a black solution with the electrolyte. In the second and third stages, sediment was found at the bottom of the beaker. In the electrochemical reaction, water interacts with anions in the ionic liquid, so that the shape and size distribution of the product can be adjusted by changing the ratio of water to ionic liquid. The electrolyte with high ion concentration has larger size than the quantum dots prepared by the electrolyte with low ion concentration.
The chemical stripping carbon fiber method is to strip a carbon source layer by layer through chemical reaction to obtain graphene quantum dots. Peng et al use resin-based carbon fibers as a carbon source and exfoliate graphite stacked in the fibers by acid treatment. The graphene quantum dots can be obtained only in one step, but the particle sizes of the graphene quantum dots are not uniform.
Bottom-up synthesis
The measure from bottom to top is that a small structural unit is used as a precursor to prepare the graphene quantum dots through a series of interaction forces, and preparation paths such as a solution chemical method, an ultrasonic method and a microwave method are mainly adopted.
The solution chemical method is mainly used for preparing the graphene quantum dots by a solution phase chemical method of aryl oxidation condensation. The synthesis process comprises the steps of gradually condensing micromolecule (3-iodine-4-bromoaniline or other benzene derivatives) polymers to prepare a polyphenylenedendritic precursor, preparing graphene base through oxidation reaction, and finally etching to prepare the graphene quantum dot.
The microwave method uses saccharides (e.g., glucose, fructose, etc.) as a carbon source because the saccharides can form C = C after dehydration and thus can constitute a basic skeleton unit of the graphene quantum dot. The hydrogen and oxygen elements in the hydroxyl and carboxyl can be dehydrated and removed in a hydrothermal environment, and the residual functional groups are still bonded on the surface of the graphene quantum dot and exist as a 'passivation layer', so that the graphene quantum dot has good water solubility and fluorescence properties.
The existing graphene quantum dot synthesis process is generally complex in operation, needs strong acid, strong oxidant and the like, is relatively complex and consumes long time. After the synthesis, complex purification treatment is required, so that the cost is high, and the application range is severely limited.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides a graphene quantum dot composite material and application thereof.
The technical scheme adopted by the invention is as follows:
in a first aspect of the present invention, there is provided:
a graphene quantum dot composite material is prepared by the following steps:
uniformly mixing a carbon source and solid carrier particles, and reacting at 45-80 ℃ for at least 30 min; the solid carrier particles are selected from additives acceptable for lead-acid batteries;
heating to 180-220 ℃ for continuous reaction, or carrying out microwave treatment for continuous reaction to obtain the graphene quantum dot composite material.
In some examples, the solid support is selected from Na2SO4、TiO2、BaSO4、SiO2Activated carbon, PbSO4、NiSO4、Bi2O3NiO, glass fiber, talcum powder and CaSiO3At least one of (1).
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 is selected from a sulfur and/or nitrogen containing carbon source, or a carbon source containing carboxyl groups above C6.
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 containing carboxyl groups above C6 is selected from citric acid and derivatives thereof, salicylic acid and derivatives thereof, benzoic acid and derivatives thereof.
In some examples, the carbon source includes at least one sulfur and/or nitrogen containing carbon source and one carbon source containing carboxyl groups and above C6.
In some examples, the molar ratio of the sulfur and/or nitrogen-containing carbon source to the carboxyl-containing carbon source above C6 is (2-3): 1.
in some examples, the sulfur and/or nitrogen containing carbon source is thiourea and the carboxyl containing carbon source above C6 is citric acid.
In some examples, the carbon source is dissolved in a solvent and then mixed with the solid support particles.
In some examples, the carbon source is used in an amount of 0.001 to 0.1 by mass of the solid support.
In some examples, the reaction time of 180 to 220 ℃ is not less than 60 min, preferably 120 to 240 min.
In some examples, the microwave treatment is performed for 5-20 min; the preferable microwave power is 600-800W/g carbon source.
In a second aspect of the present invention, there is provided:
use of a graphene quantum dot composite material as described in the first aspect of the invention in the preparation of a lead-acid battery additive.
In a third aspect of the present invention, there is provided:
an electrode material for a lead-acid battery, which is mixed with the graphene quantum dot composite material according to the first aspect of the present invention.
The electrode material is a positive electrode material or a negative electrode material.
In a fourth aspect of the present invention, there is provided:
a lead-acid battery is provided, wherein the graphene quantum dot composite material according to the first aspect of the invention is mixed in an electrode material of the lead-acid battery.
The invention has the beneficial effects that:
in some embodiments of the present invention, the graphene quantum dot composite material is a nanocomposite synthesized in situ, and the size distribution of the quantum dots is uniform, the uniformity is better, and the performance is more stable and controllable. The GQDs in the graphene quantum dot composite material has 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, so that the active sites of the reaction can be improved, the reaction kinetics can be improved, the electrochemical performance of the material in a lead-acid battery can be improved, and the long service life of a secondary battery of the lead-acid battery can be realized.
According to some examples of the invention, the synthesis process of the graphene quantum dots is simple, strong acid, strong oxidant and the like are not needed, the solvents used in the synthesis process can be completely and simply recycled for secondary use, the complex purification operation is omitted, the synthesis cost of the graphene quantum dot composite material is low, the synthesis process is green and environment-friendly, and the industrial production is easy to realize.
According to some embodiments of the present invention, the synthesis time of the graphene quantum dot composite material can be shortened to be within 1 h.
In some examples of the invention, the graphene quantum dot composite material can be simply and conveniently added into the lead-acid battery, the service life of the lead-acid battery is obviously prolonged, the cycle life of the obtained lead-acid battery exceeds 2000 times under a 1C-Rate Partial State of Charge (HRPSoC), and the maximum value reaches 12000 times. Compared with the addition of graphene powder, the cost of the graphene quantum dot composite material added with the embodiments of the invention can be reduced to one thousandth or less.
In some embodiments of the present invention, the graphene quantum dots contain S, and are firmly bonded to Pb in the matrix of the lead-acid electrode material during use, the reaction sites of the battery are fixed and uniform, and part of the sulfur is converted into nano-PbSO4In the battery reaction, the PbSO is refined as seed crystal4And (4) acting. The performance of the lead-acid battery can be further improved.
Drawings
FIG. 1 is SiO as prepared in example 12TEM image of/graphene quantum dot composite.
FIG. 2 is SiO as prepared in example 12Raman spectrogram of GQDs in the graphene quantum dot composite material.
FIG. 3 shows examples 1, 2 and 3, each using SiO2Graphene quantum dot composite material and TiO used for same2And the comparison graph of the 1C rate HRPSoC cycle curves of the lead-acid battery made of the/graphene quantum dot composite material and the lead-acid battery made of the comparative example (blank: without adding the A/graphene quantum dot composite material).
FIG. 4 is a fluorescence spectrum measured by 365nm ultraviolet light excitation after the graphene quantum dot composite material aqueous solution prepared in example 3 is diluted by 100 times
FIG. 5 is Na prepared in example 32SO4Raman spectrogram of GQDs in the graphene quantum dot composite material.
FIG. 6 is a graph of the rate cycle curves of lead-acid batteries corresponding to examples 4-6, respectively corresponding to the addition of Na2SO4/GQDs、BaSO4And the multiplying power cycle curve of the lead-acid battery made of the electrode materials of the/GQDs and the active carbon/GQD.
FIG. 7 is a lead-acid battery rate cycle curve corresponding to examples 7-10, which corresponds to the addition of PbSO4/ GQDs、NiSO4/GQDs、Bi2O3The multiplying power cycle curve of lead-acid battery made of electrode material of/GQDs, NiO/GQDs.
FIG. 8 is a graph showing the rate cycle curves of lead-acid batteries according to examples 11 to 13, which correspond to the respective examplesAdding glass fiber/GQDs, talcum powder/GQDs, CaSiO3GQDs (0.1% of SiO prepared in example 1 was also added to the electrolyte)2Graphene quantum dot composite) into the negative electrode material.
Fig. 9 and 10 are HRPSoC curves for different lead acid batteries.
Fig. 11 is a 1C cycle curve for different lead acid batteries.
Detailed Description
A graphene quantum dot composite material is prepared by the following steps:
uniformly mixing a carbon source and solid carrier particles, and reacting at 45-80 ℃ for at least 30 min; the solid carrier particles are selected from additives acceptable for lead-acid batteries;
heating to 180-220 ℃ for continuous reaction, or carrying out microwave treatment for continuous reaction to obtain the graphene quantum dot composite material.
The solid carrier has no special requirements, and is acceptable for lead-acid batteries. In some examples, the solid support is selected from Na2SO4、TiO2、BaSO4、SiO2Activated carbon, PbSO4、NiSO4、Bi2O3NiO, glass fiber, talcum powder and CaSiO3At least one of (1). The specific type of the solid carrier can be selected correspondingly according to the specific performance of the lead-acid battery.
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 is selected from a sulfur and/or nitrogen containing carbon source, or a carbon source containing carboxyl groups above C6.
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 containing carboxyl groups above C6 is selected from citric acid and derivatives thereof, salicylic acid and derivatives thereof, benzoic acid and derivatives thereof.
The carbon sources are wide in source, and have a surface chemical adsorption effect with a solid carrier in solid-solid mixing or a solvent, graphene quantum dots are dehydrated and subjected to radical removal on the surface of the solid carrier in situ to form a uniform dispersion system in the subsequent heating process, and the agglomeration of GQDs is effectively prevented.
In some examples, the carbon source includes at least one sulfur and/or nitrogen containing carbon source and one carbon source containing carboxyl groups and above C6.
In some examples, the molar ratio of the sulfur and/or nitrogen-containing carbon source to the carboxyl-containing carbon source above C6 is (2-3): 1.
in some examples, the sulfur and/or nitrogen containing carbon source is thiourea and the carboxyl containing carbon source above C6 is citric acid.
In some examples, the carbon source is dissolved in a solvent and then mixed with the solid support particles.
In some examples, the carbon source is used in an amount of 0.001 to 0.1 by mass of the solid support.
In some examples, the reaction time of 180 to 220 ℃ is not less than 60 min, preferably 120 to 240 min.
In some examples, the microwave treatment is performed for 5-20 min; the preferable microwave power is 600-800W/g carbon source.
The principle of the invention is as follows: by utilizing the surface chemical adsorption effect of small molecular organic matters (such as amino and carboxyl contained in thiourea and citric acid in example 1) and the solid carrier in solid-solid mixture or a solvent, graphene quantum dots are dehydrated and subjected to radical removal on the surface of the solid carrier in situ to form a uniform dispersion system in the subsequent heating process, and the agglomeration of GQDs is effectively prevented.
The invention applies the graphene quantum dot composite material to the lead-acid battery as one of the components in the electrode material, because the graphene quantum dot/solid carrier composite material with uniformly distributed graphene quantum dots is used (which is attributed to the fact that the solid carrier plays a role in-situ catalysis on subsequent dehydration and radical removal reactions among carbon source functional groups in subsequent heating), the dispersion performance is good, the electrochemical performance is greatly improved when the composite material is used in scenes such as batteries, and is attributed to the fact that GQDs generated in situ and a matrix have electrostatic adsorption, the solid carrier prevents the GQDs from mutually agglomerating, the size of the composite material is less than 10nm, the specific surface area is large, the conductivity is good, more reaction active sites can be provided, the composite material plays roles in heterogeneous crystal nucleus and electron transfer when the composite material is used in charge and discharge scenes of the lead-acid battery, such as the formation of refined lead sulfate is accelerated during discharge, the polarization and the generation of crystal nucleus are reduced, and it is favorable to the transmission of electron, thus improve the dynamic characteristic of discharge/charge reaction, and improve the rate performance, improve the stability and slow down the rate of capacity decay. All of these excellent properties, addition of GQDs alone (which tend to agglomerate due to sizes less than 5 nm), are difficult to achieve.
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
For convenience of description, the parameters of lead-acid battery fabrication, formation and testing in the following examples are briefly summarized as follows:
(1) Assembling the whole battery: the prepared solid carrier/graphene quantum dot composite material is added into a negative electrode material PbO according to a certain proportion, the blank case corresponds to an untreated PbO negative electrode material and paste, the formula and the process are similar to those reported in the published lead-acid battery manufacturing literature, for example, the negative electrode material is mixed and pasted with an expanding agent, polytetrafluoroethylene emulsion, sodium sulfate and deionized water according to the general mass ratio of the positive electrode material to the negative electrode material of the lead-acid battery, and then a plate, a baking plate and the like are coated, sulfuric acid (1.25-1.3M) is used as an electrolyte solution, and the lead-acid full battery is assembled.
(2) Formation: the formation is carried out by adopting a four-charge three-discharge mode commonly used by lead-acid batteries.
(3) And (3) charge and discharge test: carrying out a rate cycle test on a lead-acid battery prepared by adding the solid carrier/graphene quantum dot composite material of each embodiment and a lead-acid battery prepared by adding the negative electrode material PbO of the blank case at HRPSoC under 1C, wherein the test parameters are as follows: cut-off voltage is 1.75-2.2V; the charge and discharge were carried out at a constant current, and the discharge was terminated when the capacity had decayed to 80% or less of the initial capacity.
Example 1
Graphene quantum dot/SiO of the embodiment2The preparation method of the composite material comprises the following specific preparation steps:
under the condition of stirring, thiourea and citric acid with the molar ratio of 3:1 are added into the white carbon black SiO2In the xylene dispersion, the mass of thiourea and citric acid is SiO21% of the mass; stirring for 30min, reacting at 80 ℃ for 1h, then refluxing and heating at 180 ℃ for 1h, cooling, centrifuging and drying to obtain graphene quantum dots/SiO2Composite materials, i.e. GQDs/SiO2The lead-acid battery additive can be directly used as a lead-acid battery additive, and the addition amount of the lead-acid battery additive is 1 percent of the mass of the negative electrode material.
In FIG. 3, the SiO used in example 1 is shown2The lead-acid battery made of the graphene quantum dot composite material has a corresponding 1C multiplying power HRPSoC cycle curve diagram. As can be seen in fig. 3, the lifetime reached 6000 times or more, which was 10 times or more that of comparative example PbO (500 times) (see fig. 11).
Example 2
Graphene quantum dot/TiO used in this example2The preparation method of the composite material comprises the following specific preparation steps:
adding benzothiazole and benzoic acid in a molar ratio of 2:1 to the TiO under stirring2In the solid powder, the p-benzothiazole and the citric acid are TiO in mass20.5% of the mass. Grinding for 30min, reacting at 60 ℃ for 1h, heating at 200 ℃ for 1h, and cooling to obtain graphene quantum dots/TiO2Composite materials, i.e. GQDs/TiO2And the lead-acid battery electrode material can be used as an additive of a lead-acid battery electrode material. The addition amount is 0.5 percent of the mass percent of the negative electrode material.
Application example 2 graphene quantum dots/TiO is given in FIG. 42The 1C multiplying power HRPSoC cycle curve diagram of the lead-acid battery made of the composite material and the additive amount of which is 0.5 percent of the mass percent of the negative electrode material. As can be seen from fig. 4, the lifetime reached more than 5000 times, which is 10 times that of comparative example PbO.
Example 3
Na used in this example2SO4The preparation method of the graphene quantum dot composite material comprises the following specific preparation steps:
adding 5g of thiosalicylic acid and (citric acid + aniline, molar ratio 1: 1) with a total mass of 3:1 to Na under stirring2SO4In the solid powder, the mass of the thiosalicylic acid and the (citric acid + aniline, mol ratio is 1: 1) is Na2SO410% by mass. Grinding for 30min, placing into 800W microwave oven, heating at low fire for 4min, heating at medium fire for 5min, and cooling to obtain graphene quantum dot/Na2SO4Composite materials, i.e. GQDs/Na2SO4The lead-acid battery cathode material additive can be used as a lead-acid battery cathode material additive, and the addition proportion is 0.55%.
Fig. 5 is a fluorescence spectrum measured by 365nm ultraviolet light excitation after the graphene quantum dot composite material aqueous solution prepared in example 3 is diluted by 100 times.
FIG. 6 is Na prepared in example 32SO4Raman spectrogram of the/graphene quantum dot composite material.
Fig. 7 shows a 1C rate HRPSoC cycle curve diagram of a lead-acid battery prepared by adding 0.55 mass% of the graphene quantum dot composite material to the negative electrode material PbO in example 3. As can be seen in fig. 7, the lifetime reached 4000 times, 8 times that of comparative example PbO.
Example 4
BaSO used in this example4The preparation method of the/GQDs composite material comprises the following specific preparation steps:
adding p-thiophene and ethyl citrate with the molar ratio of 3:1 into BaSO under the stirring condition4In the solid powder, the mass of thiourea and citric acid ethyl ester is Na2SO45% by mass. Grinding for 30min, placing into 80 deg.C oven, heating and reacting for 1h, then heating and reacting for 1h in 200 deg.C oven, cooling to obtain BaSO4the/GQDs composite material can be used as an additive of lead-acid battery electrode materials. 0.55 percent of the additive is added into the negative electrode material PbO.
The addition example of BaSO of 4 is given in FIG. 84HRPSoC cycle curve diagram of 1C multiplying power of lead-acid batteries made of/GQDs composite materials. As can be seen in fig. 8, the lifetime reached 3000 times, 6 times that of comparative example PbO.
Examples 5 to 12charcoal/GQD, PbSO4/GQDs、NiSO4/GQDs、Bi2O3GQDs, NiO/GQDs, glass fibers/GQDs, talc/GQDs, CaSiO3GQDs (example 12 electrolyte with 0.1% of SiO prepared in example 12Graphene quantum dot composite) nanocomposite was prepared in the same manner as in example 1. And the additives are respectively added into the negative electrode material, and the addition amounts are respectively 0.2%, 10%, 0.1%, 0.3%, 0.25%, 5%, 3% and 1%. The HRPSoC performances of the obtained batteries are respectively summarized in FIGS. 9 and 10, and the results show that the battery performance performances of the batteries are remarkably superior to those of the comparative example.
Comparative example
Negative electrode PbO and positive electrode PbO2Commercial battery grade commercial products used in example 1 were used as blank negative electrode positive electrode material controls, respectively. The lead-acid battery is manufactured by the same process and is tested in the same way.
Fig. 11 (blank) shows a charge-discharge curve cycle number of about 500 for 1C charge mode operation (HRPSoC), and for comparison, the cell performance with PbO/GQDs added is also shown in fig. 11.
From fig. 3 to 11 and the detection data, it can be seen that the a/graphene quantum dot composite material obtained by the preparation method of the invention is used for a lead-acid battery, can obtain a stable and long-life rate cycle performance, and is significantly superior to that of a blank or a comparative example. This is related to the close loading of GQDs on the A surface (which is beneficial to the uniform dispersion of GQDs in the electrode material or electrolyte), the discontinuous distribution of GQDs and the excellent conductivity. In contrast, the comparative example resulted in sulfation, PbSO, during battery operation4The size is increased, the effective contact area of the active substance and the electrolyte is greatly reduced, the polarization of the material is obvious, the material utilization rate is low, and 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 (10)

1. A graphene quantum dot composite material is prepared by the following steps:
uniformly mixing a carbon source and solid carrier particles, and reacting at 45-80 ℃ for at least 30 min; the solid carrier particles are selected from additives acceptable for lead-acid batteries; preferably, the solid support is selected from Na2SO4、TiO2、BaSO4、SiO2Activated carbon, PbSO4、NiSO4、Bi2O3NiO, glass fiber, talcum powder and CaSiO3At least one of;
heating to 180-220 ℃ for continuous reaction, or carrying out microwave treatment for continuous reaction to obtain the graphene quantum dot composite material.
2. The graphene quantum dot composite material of claim 1, wherein: the carbon source is selected from carbon sources with molecular weight not more than 1000.
3. The graphene quantum dot composite material of claim 2, wherein: the carbon source is selected from a carbon source containing sulfur and/or nitrogen, or a carbon source containing carboxyl above C6;
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;
preferably, the carbon source containing a carboxyl group having at least C6 is selected from citric acid and derivatives thereof, salicylic acid and derivatives thereof, and benzoic acid and derivatives thereof.
4. The graphene quantum dot composite material of claim 3, wherein: the carbon source comprises at least one carbon source containing sulfur and/or nitrogen and a carbon source containing carboxyl with the carbon number of above C6; further, the molar ratio of the carbon source containing sulfur and/or nitrogen to the carbon source containing carboxyl above C6 is (2-3): 1; in particular, the carbon source containing sulfur and/or nitrogen is thiourea, and the carbon source containing a carboxyl group of at least C6 is citric acid.
5. The graphene quantum dot composite material of claim 1, wherein: and after the carbon source is dissolved in the solvent, uniformly mixing the carbon source with the solid carrier particles.
6. The graphene quantum dot composite material according to any one of claims 1 to 5, wherein: the using amount of the carbon source is 0.001-0.1 of the mass of the solid carrier.
7. The graphene quantum dot composite material according to any one of claims 1 to 5, wherein:
the reaction time at 180-220 ℃ is not shorter than 60 min, preferably 120-240 min;
the microwave treatment time is 5-20 min; the preferable microwave power is 600-800W/g carbon source.
8. The application of the graphene quantum dot composite material in the preparation of the lead-acid battery additive is characterized in that: the graphene quantum dot composite material is as defined in any one of claims 1 to 7.
9. An electrode material for a lead-acid battery, characterized in that: the graphene quantum dot composite material mixed with any one of claims 1 to 7, wherein the electrode material is a positive electrode material or a negative electrode material.
10. A lead-acid battery characterized by: the graphene quantum dot composite material according to any one of claims 1 to 7 is mixed in an electrode material.
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