CN112864391B - Preparation method and application of lead/reduced graphene oxide nanocomposite - Google Patents
Preparation method and application of lead/reduced graphene oxide nanocomposite Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method and application of a lead/reduced graphene oxide nanocomposite. The lead/reduced graphene oxide nanocomposite prepared by the method is added into a negative plate of a commercial lead-acid battery as an additive, so that the layering phenomenon of the plate in the use process of the battery can be avoided, and meanwhile, the utilization rate of active substances of the battery and the cycle life under a high-rate partial charge state (HRPSoC) are improved.
Description
Technical Field
The invention belongs to the technical field of lead-acid batteries, and particularly relates to a preparation method and application of a lead/reduced graphene oxide nanocomposite.
Background
The lead-acid battery is a secondary battery with the largest market share and the widest application range in chemical batteries, and particularly in the application fields of starting, large-scale energy storage and the like, the lead-acid battery is difficult to replace by other novel batteries for a long time. The lead-acid battery has the advantages of low price, mature technology, excellent high and low temperature performance, stability, reliability, high safety, good resource recycling property and the like, and has obvious market competitive advantage.
The lead-acid battery has the following disadvantages: low energy density and short cycle life. Lead sulfate that lead acid battery's negative plate formed at the discharge in-process, the battery is put the back, and the lead sulfate of small granule can turn into large granule lead sulfate, and large granule lead sulfate can not turn into lead in the charging process because the solubility is little, and there is irreversibility, called the sulfate phenomenon in charge-discharge in-process in the battery negative plate promptly, and leads to the battery performance deterioration and final inefficacy. This is the main reason for the short cycle life of lead acid batteries. At present, a certain amount of carbon materials (mainly comprising activated carbon, graphite, carbon black and the like, and the added amount is less than 2 wt%) with high specific capacitance are added into a negative plate of a lead-acid battery to relieve the problem, because the carbon materials form a conductive network between active matters of the plate, the conductive performance of the plate is increased, the added carbon materials can instantly store or release a large amount of charges, play a role in buffering current for the negative plate, and can effectively inhibit sulfation of the negative plate and prolong the cycle life of the battery under a high-rate partial charge state (HRPSoC). However, the hydrogen evolution overpotential of the negative electrode added with the carbon material is lowered. At present, the adding mode is mainly mechanical mixing with micron-sized lead powder and the like, and the micron-sized lead powder is far higher than the carbon material in density, so that the mixing of the micron-sized lead powder and the carbon material is difficult to realize uniformly, and the lamination phenomenon of a polar plate of a battery in the using process is caused. These undesirable phenomena can cause the battery to fail.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a lead/reduced graphene oxide nanocomposite.
Another object of the present invention is to provide an application of the above lead/reduced graphene oxide nanocomposite.
The technical scheme of the invention is as follows:
a preparation method of a lead/reduced graphene oxide nanocomposite comprises the following steps:
(1) adding Pb (CH)3COO)2·3H2Uniformly mixing O, vitamin C, polyvinylpyrrolidone, graphene oxide solution and water to obtain a reaction material, wherein the Pb (CH) is contained in 1L of the reaction material3COO)2·3H2The mass of the O, the vitamin C, the polyvinylpyrrolidone and the graphene oxide in the graphene oxide solution is 12-13g, 0.6-0.8g and 1.3-1.6g in sequence;
(2) carrying out hydrothermal reaction on the material obtained in the step (1), and then carrying out solid-liquid separation, washing and vacuum drying;
(3) and (3) pyrolyzing the material obtained in the step (2) in a nitrogen atmosphere to obtain the lead/reduced graphene oxide nanocomposite.
In a preferred embodiment of the present invention, in 1L of the reaction mass, the Pb (CH)3COO) 2·3H2The mass of the O, the vitamin C, the polyvinylpyrrolidone and the graphene oxide in the graphene oxide solution is 12.5g, 0.75g and 1.5g in sequence.
In a preferred embodiment of the present invention, the hydrothermal reaction is carried out at a temperature of 175 ℃ and 185 ℃ for a time of 11-13 h.
In a preferred embodiment of the present invention, the pyrolysis temperature is 590-610 ℃ and the time is 2-4 h.
The other technical scheme of the invention is as follows:
the lead/reduced graphene oxide nanocomposite prepared by the preparation method is applied to preparation of a negative electrode of a lead-acid battery.
The invention adopts another technical scheme as follows:
a lead-acid battery negative plate comprises the lead/reduced graphene oxide nanocomposite prepared by the preparation method.
In a preferred embodiment of the invention, the raw materials further comprise micron-sized lead powder with the oxidation degree of 74-76wt%, short fibers, carbon black, barium sulfate, humic acid, concentrated sulfuric acid with the mass concentration of 98wt% and water.
Further preferably, the short fiber, the carbon black, the barium sulfate, the humic acid, the concentrated sulfuric acid with the mass concentration of 98wt%, the water and the lead/reduced graphene oxide nanocomposite material are sequentially in an amount of 0.05-0.07wt%, 0.3-0.5wt%, 0.7-0.9wt%, 0.5-0.7wt%, 11-13wt%, 12.5-13.5wt% and 0.5-2.0wt% of the micron-sized lead powder.
Still more preferably, the preparation method comprises: mechanically mixing the lead/reduced graphene oxide nano composite material, micron-sized lead powder, short fibers, carbon black, barium sulfate, humic acid, concentrated sulfuric acid with the mass concentration of 98wt% and water, mixing paste and curing.
The invention also provides another technical scheme as follows:
a lead-acid battery is provided with the negative plate of the lead-acid battery.
The invention has the beneficial effects that:
1. the method adopts hydrothermal and pyrolysis to prepare the lead/reduced graphene oxide nanocomposite, and has the advantages of simple process, few synthesis steps, greenness and high efficiency.
2. The lead/reduced graphene oxide nano composite material prepared by the invention is used as a negative electrode additive, and is mixed with commercial micron-sized lead powder to prepare a negative plate through the traditional paste mixing, curing and other processes.
3. According to the invention, lead is formed on the surface of the graphene sheet layer in situ, graphene has a current buffering effect on the electrode plate, and a graphene conductive network structure is formed between the graphene and the electrode plate, so that the conductivity of the material is greatly improved, the conversion efficiency of lead sulfate and lead can be improved, and the occurrence of large-particle lead sulfate can be well inhibited.
4. In the charging process, the hydrogen evolution overpotential of the lead/reduced graphene oxide nano composite material prepared by the invention is larger than that of a carbon material, and the hydrogen evolution degree of a battery in the charging process can be reduced, so that the performance of the graphene can be ensured to be exerted, the dryness of an electrolyte is inhibited, and the service life of the battery is prolonged.
5. The specific capacity and the cycle performance of the battery are obviously improved by using the lead/reduced graphene oxide nanocomposite material as a novel negative plate of the additive.
Drawings
Fig. 1 is a scanning electron micrograph of a lead/reduced graphene oxide nanocomposite (Pb-rGO) prepared in example 1 of the present invention.
FIG. 2 shows XRD (right) and Raman spectra (left) of GO, rGO and Pb-rGO composites of example 1 of the present invention.
FIG. 3 shows the scan rate of 1mV s in example 2 of the present invention-1Polarization curves for negative plates containing different levels of Pb-rGO.
Fig. 4 is a lead acid battery assembled from negative plates containing different contents of Pb-rGO in example 3 of the present invention: (a)0.05C (C)20) Discharge of electricityInitial discharge capacity map of (d); (b) HRPSoC cycle life plot at 1C discharge rate (left).
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Graphene Oxide (GO) is prepared by improved Hummers, and a GO aqueous solution of 2mg/mL is prepared.
(2) 12.5g of Pb (CH)3COO)2·3H2Dissolving 0 (lead acetate), 12.5g of vitamin C and 0.75g of polyvinylpyrrolidone (PVP) in deionized water, adding the GO aqueous solution (containing 1.5g of graphene oxide) prepared in the step (1) after completely dissolving, adding deionized water to a constant volume of 1L, and stirring uniformly to obtain a reaction material.
(3) And transferring the reaction materials into a reaction kettle, carrying out hydrothermal reaction for 12 hours at 180 ℃, carrying out centrifugal separation to obtain a lead compound/rGO, washing a separated substance, and carrying out vacuum drying.
(4) And (3) pyrolyzing the material obtained in the step (3) for 3 hours at 600 ℃ under the nitrogen condition to obtain the lead/reduced graphene oxide nanocomposite (marked as Pb-rGO).
For comparison, the above procedure was repeated without the addition of Pb (CH)3COO)2·3H2And O, obtaining reduced graphene oxide (marked as rGO).
The structure of Pb-rGO was characterized using Scanning Electron Microscopy (SEM), energy spectroscopy, X-ray diffraction (XRD) and Raman spectroscopy, with the following results:
the SEM test results show that: as shown in fig. 1, in the Pb-rGO prepared in this embodiment, lead is in a nano-scale spherical structure, and the diameter of the nanoparticles is about 200-300nm, and the nanoparticles are relatively uniformly distributed between two-dimensional graphene sheets, so that stacking of the graphene sheets is effectively inhibited. These lead nanosphere shaped particles were coated with large particle size rGO sheets to form an effective three dimensional channel. The unique three-dimensional structure inevitably improves the dynamic rate of the lead redox reaction, forms an effective path for electrolyte ion diffusion, increases the active sites of the Faraday redox reaction, and can obviously improve the specific capacity of the electrode material and the electrochemical reaction rate in the charging and discharging process. Energy spectrum analysis shows that the Pb-rGO has the following mass content: 70.13 wt% of carbon C, 7.27 wt% of oxygen O and 22.58 wt% of lead Pb.
The characteristic peak at the rGO (002)2 theta angle is about 23.8 degrees, and the characteristic peak at the GO (001) is not 10.5 degrees. Indicating that vitamin C has reduced GO to rGO via hydrothermal reaction. The XRD pattern of Pb-rGO shows characteristic diffraction peaks for lead at 2 theta angles of about 31.3 °, 36.3 °, etc., and lead oxide at 2 theta angles of about 29.9 °, etc. The rGO in the compound has an amorphous structure, so that no characteristic peak of the rGO appears. In summary, the above results show that Pb-rGO consists of a lead phase, an rGO amorphous phase and a small amount of lead oxide phase. As shown in fig. 2 (right). The Raman spectrum is an effective method for representing ordered and disordered crystal structures of the graphene oxide and the reduced graphene oxide. FIG. 2 (left) shows Raman spectra of GO, rGO and Pb-rGO. All have a typical graphene D-band (about 1345 cm)-1) And G belt (about 1587 cm)-1) The respiration vibration of the carbon atom on the aromatic ring and the in-plane stretching vibration of the carbon atom on the ring and the chain are related to each other. The D peak mainly represents defects and amorphous structures located at the carbon material edges. In general, the intensity ratio (I) of the D peak and the G peakD/IG) Which roughly reflects the defects and the degree of disorder of the material. As can be seen from FIG. 2, I for rGO and Pb-rGOD/IGThe value is far larger than that of GO, which shows that after hydrothermal reaction, the oxygen-containing functional groups on the surface of GO are reduced, and GO is reduced. In addition, the Pb-rGO is respectively at 138 and 270cm-1Peaks appear nearby, which are vibrational peaks of rGO interlayer anions. Further illustrating that lead has been successfully incorporated into rGO.
Example 2
And (3) carrying out traditional mechanical mixing, paste mixing and curing on micron-sized lead powder with the oxidation degree of 75 wt%, short fibers, carbon black, barium sulfate, humic acid, concentrated sulfuric acid with the mass concentration of 98wt%, water and Pb-rGO or rGO prepared in example 1 to obtain the negative plate. The quantities of short fibers, carbon black, barium sulfate, humic acid, concentrated sulfuric acid with mass concentration of 98wt% and water are 0.06 wt%, 0.4 wt%, 0.8 wt%, 0.6 wt%, 12 wt% and 12.5-13.5wt% of the micron-sized lead powder in sequence, the quantities of Pb-rGO prepared in example 1 are 0.5wt%, 1.0 wt% and 2.0wt% of the micron-sized lead powder respectively, and the quantities of rGO prepared in example 1 are 1.0 wt% of the micron-sized lead powder and correspond to 0.5wt%, 1.0 wt%, 2.0wt% Pb/rGO and rGO1.0 wt% of the negative plate respectively.
In a 5.3mol/L sulfuric acid aqueous solution system, a platinum sheet (3 cm. times.3 cm) was used as an auxiliary electrode, and Hg/Hg was added2SO4As a reference electrode, a negative plate containing rGO or Pb-rGO in the present example was added as a working electrode. At a potential of-1.35V (vs. Hg/Hg)2SO4) The current densities of the blank negative plate electrode and the negative plate electrode added with Pb-rGO of 0.5wt%, 1.0 wt%, 2.0wt% and rGO of 1.0 wt% are respectively 8, 22, 36, 43 and 55mA/cm2。
The cathode polarization curve of the Pb-rGO prepared in example 1 in the electrolyte is researched by an electrochemical testing system, and the result is shown in fig. 3, and compared with a blank negative plate (without adding rGO and Pb-rGO), the current density of the hydrogen evolution reaction is larger along with the increase of the adding amount of the Pb-rGO. And the same addition amount, the maximum current density of hydrogen evolution reaction caused by the addition of the rGO, and the fact that the hydrogen evolution overpotential of the Pb-rGO prepared in the example 1 is higher than that of the corresponding rGO is proved, so that the hydrogen evolution side reaction of a negative plate of the battery during charging is effectively prevented, and the cycle life of the battery is prolonged.
Example 3
A lead acid battery was assembled using 5.3mol/L sulfuric acid as an electrolyte, commercial AGM as a separator, and the negative electrode plate produced in example 2 and a conventional positive electrode plate as working electrodes. The performance of the lead-acid battery is researched by adopting a Land battery testing system, as shown in fig. 4, the initial discharge specific capacities of the battery assembled by blank negative plates (without adding rGO and Pb-rGO) and negative plates with 0.5wt%, 1.0 wt%, 2.0wt% and 1.0 wt% of the rGO are 146, 158, 178, 170 and 160mA.h/g in sequence at 0.05C, and the charge-discharge cycle periods of a high-rate partial charge state (HRPSOC) at 1C are 3144, 5195, 9351, 9028 and 7032 respectively. The results show that the negative plate with 1.0 wt% of Pb-rGO prepared in example 1 has the largest specific capacity and the longest service life under HRPSoC.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (8)
1. A preparation method of a lead/reduced graphene oxide nanocomposite is characterized by comprising the following steps: the method comprises the following steps:
(1) adding Pb (CH)3COO）2·3H2Uniformly mixing O, vitamin C, polyvinylpyrrolidone, graphene oxide solution and water to obtain a reaction material, wherein the Pb (CH) is contained in 1L of the reaction material3COO）2·3H2The mass of the O, the vitamin C, the polyvinylpyrrolidone and the graphene oxide in the graphene oxide solution is 12-13g, 0.6-0.8g and 1.3-1.6g in sequence;
(2) carrying out hydrothermal reaction on the material obtained in the step (1), and then carrying out solid-liquid separation, washing and vacuum drying; the temperature of the hydrothermal reaction is 175-185 ℃, and the time is 11-13 h;
(3) pyrolyzing the material obtained in the step (2) in a nitrogen atmosphere to obtain the lead/reduced graphene oxide nanocomposite; the pyrolysis temperature is 590-610 ℃ and the time is 2-4 h.
2. The method of claim 1, wherein: in 1L of the reaction mass, the Pb (CH)3COO）2·3H2The mass of the O, the vitamin C, the polyvinylpyrrolidone and the graphene oxide in the graphene oxide solution is 12.5g, 0.75g and 1.5g in sequence.
3. The use of the lead/reduced graphene oxide nanocomposite prepared by the preparation method of claim 1 or 2 in the preparation of a negative electrode of a lead-acid battery.
4. A negative plate of a lead-acid battery is characterized in that: the raw material comprises the lead/reduced graphene oxide nanocomposite prepared by the preparation method of claim 1 or 2.
5. A negative plate for a lead-acid battery according to claim 4, characterized in that: the raw materials also comprise micron-sized lead powder with the oxidation degree of 74-76wt%, short fibers, carbon black, barium sulfate, humic acid, concentrated sulfuric acid with the mass concentration of 98wt% and water.
6. A negative plate for a lead-acid battery according to claim 5, characterized in that: the amounts of the short fibers, the carbon black, the barium sulfate, the humic acid, the concentrated sulfuric acid with the mass concentration of 98wt%, the water and the lead/reduced graphene oxide nano composite material are 0.05-0.07wt%, 0.3-0.5wt%, 0.7-0.9wt%, 0.5-0.7wt%, 11-13wt%, 12.5-13.5wt% and 0.5-2.0wt% of the micron lead powder in sequence.
7. The negative plate for a lead-acid battery of claim 6, wherein: the preparation method comprises the following steps: mechanically mixing the lead/reduced graphene oxide nano composite material, micron-sized lead powder, short fibers, carbon black, barium sulfate, humic acid, concentrated sulfuric acid with the mass concentration of 98wt% and water, mixing paste and curing.
8. A lead-acid battery characterized by: negative plate for a lead-acid battery having the negative plate for a lead-acid battery claimed in any one of claims 4 to 7.
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| CN102912174A (en) * | 2012-11-08 | 2013-02-06 | 浙江南都电源动力股份有限公司 | Lead and graphene composite material |
| CN106531972A (en) * | 2016-08-17 | 2017-03-22 | 重庆大学 | Preparation method of lead-graphene composite material for lead-carbon battery |
| CN106856235A (en) * | 2017-01-11 | 2017-06-16 | 苏州载物强劲新材料科技有限公司 | Lead carbon superbattery negative material and preparation method thereof |
| CN108123136A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Lead carbon battery composite negative pole additive and lead carbon battery cathode and preparation and application |
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| CN102912174A (en) * | 2012-11-08 | 2013-02-06 | 浙江南都电源动力股份有限公司 | Lead and graphene composite material |
| CN106531972A (en) * | 2016-08-17 | 2017-03-22 | 重庆大学 | Preparation method of lead-graphene composite material for lead-carbon battery |
| CN108123136A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Lead carbon battery composite negative pole additive and lead carbon battery cathode and preparation and application |
| CN106856235A (en) * | 2017-01-11 | 2017-06-16 | 苏州载物强劲新材料科技有限公司 | Lead carbon superbattery negative material and preparation method thereof |
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