CN110707302B - Preparation method and application of sisal fiber carbon/lead composite material - Google Patents
Preparation method and application of sisal fiber carbon/lead composite material Download PDFInfo
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- CN110707302B CN110707302B CN201910974917.4A CN201910974917A CN110707302B CN 110707302 B CN110707302 B CN 110707302B CN 201910974917 A CN201910974917 A CN 201910974917A CN 110707302 B CN110707302 B CN 110707302B
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- 244000198134 Agave sisalana Species 0.000 title claims abstract description 133
- 239000000835 fiber Substances 0.000 title claims abstract description 133
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000010406 cathode material Substances 0.000 claims abstract description 4
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- 239000002253 acid Substances 0.000 claims description 12
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- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
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- 239000013543 active substance Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000002427 irreversible effect Effects 0.000 abstract description 4
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- 238000005470 impregnation Methods 0.000 abstract description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 description 22
- 239000002028 Biomass Substances 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 4
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000002142 lead-calcium alloy Substances 0.000 description 2
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
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- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
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- -1 polytetrafluoroethylene Polymers 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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Images
Classifications
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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
- H01M4/362—Composites
-
- 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
-
- 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
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 sisal fiber carbon/lead composite material. Pretreating sisal fibers by using 5% of sodium hydroxide and 5% of phosphoric acid solution; fully soaking the pretreated sisal fibers in a lead chloride solution by magnetic stirring in a constant-temperature oil bath at the temperature of 80 ℃; dry lead chloride impregnated sisal fibers in N2Calcining in the atmosphere, controlling the temperature at 600 ℃, and keeping the temperature for 3 h to obtain the sisal fiber carbon/lead composite material. The sisal fiber carbon/lead composite material is applied to a lead-carbon battery cathode material. The invention has the advantages that: the solution impregnation method can ensure that the active substance lead is more uniformly distributed on the carbon material, has better interface compatibility, more effectively improves the utilization rate of the active substance lead, and ensures that the carbon material and Pb/PbSO are mixed4The working potential is more matched, so that the irreversible sulfation phenomenon of the negative electrode of the lead-carbon battery in the HRPSoC state is inhibited, and the service life of the battery is prolonged.
Description
Technical Field
The invention belongs to the technical field of lead-carbon battery cathode materials, and particularly relates to a preparation method and application of a sisal fiber carbon/lead composite material.
Background
With the increasing demand for energy, the development and application research of advanced energy storage devices has become a hot spot. At present, electrochemical energy storage is mainly divided into lead-acid storage batteries, lithium ion batteries, sodium-sulfur batteries, flow batteries and the like. At present, the development of mobile equipment and hybrid energy vehicles has higher and higher requirements on electrochemical energy storage devices, and lead-acid storage batteries are the most common chemical batteries, have the advantages of high cost performance, safety, reliability, low cost and the like, account for more than 60% of chemical power supplies no matter the output value or the sales volume, and can be said that the lead-acid storage batteries still have an irreplaceable position in the storage battery market. However, lead-acid batteries also face some problems, such as severe irreversible sulfation of the negative electrode when the batteries are operated under a high rate partial state of charge (HRPSoC), resulting in too short service life and poor dynamic charging capability, and the braking energy recovery of the batteries is lost during the operation of the hybrid energy vehicle.
In order to make up the defects of the lead-acid storage battery in the aspects of hybrid electric vehicles, electric vehicles and energy storage, a proper amount of carbon material is added into the negative electrode of the lead-acid storage battery, and the lead-carbon battery is produced accordingly. The lead-carbon battery not only reserves the advantages of safety, reliability, high recovery rate and low price of the lead-acid storage battery, but also has the dual functions of the lead-acid storage battery and the super capacitor, and has excellent cycle service life and higher power density in the HRPSoC state, thereby having wide market prospect. However, the development of lead-carbon batteries has some problems, for example, in most cases, one simply mixes the carbon material with the active material, hydrogen evolution inhibitor, binder, etc. in the negative electrode material, mechanically stirs the mixture in a certain amount of water and sulfuric acid solution, then obtains a lead paste, coats the lead paste on a lead-calcium alloy grid, and then obtains a negative electrode plate through acid leaching, curing, drying, formation, etc. However, since the carbon additive has a small density, and has a certain difference from the density of the negative electrode material additive, especially a large difference from the density of lead powder, simple mechanical mixing causes interfacial incompatibility between the carbon material in the lead paste and the negative electrode active material, which increases interfacial ohmic resistance, which may cause interruption of the battery in the HRPSoC state for a long time, and ultimately affect the conductivity of the negative electrode active material.
As a renewable resource, biomass has low price, abundant reserves and environmental friendliness, and has attracted extensive attention to the preparation of carbon materials by using biomass as a carbon source. The biomass carbon material contains rich active functional groups, has a large specific surface area and a controllable pore structure, and is often applied to the fields of adsorbents, catalyst carriers, electrochemical detection, new energy and the like. The biomass carbon material treated at high temperature has a highly graphitized structure, and the structure endows the biomass carbon material with the characteristics of excellent conductivity, stable electrochemical performance and the like, so the biomass carbon material is widely applied to electrode materials, and has positive significance for widening the application range of the biomass carbon material and fully utilizing waste biomass.
The biomass sisal fiber is used as a carbon source to obtain the composite material combining the negative active substance and the carbon material so as to increase the phase interface compatibility of the material, and the composite material is applied to the negative material of the lead-carbon battery, so that the ohmic resistance of a polar plate can be reduced, and the electrochemical performance of the lead-carbon battery is improved.
Disclosure of Invention
The invention aims to increase the phase interface compatibility of a biomass carbon material and a negative electrode active material lead, and provides a preparation method and application of a sisal fiber carbon/lead composite material.
The preparation method of the sisal fiber carbon/lead composite material comprises the following specific steps:
(1) weighing 30 g of sisal fibers, adding the sisal fibers into a NaOH aqueous solution with the mass percent of 5%, magnetically stirring at 60 ℃, soaking for 24 hours, and removing small molecular substances adsorbed on the surfaces of the sisal fibers to obtain the sisal fibers soaked by alkali.
(2) Fishing out the alkali-dipped sisal fibers obtained in the step (1), and adding H with the mass percent of 5%3PO4And (3) soaking in the aqueous solution for 24 hours at 60 ℃ under magnetic stirring to obtain alkali and acid pretreated sisal fibers.
(3) Fishing out the pretreated sisal fibers obtained in the step (2), repeatedly washing the sisal fibers with distilled water until the washing liquid is neutral, drying the sisal fibers in a vacuum freeze drying box for 72 hours, grinding the dried sisal fibers in a sealed grinder, and grinding the ground sisal fibers into powder of 200-300 meshes to obtain sisal fiber powder.
(4) 21.1149 g of lead chloride is weighed and put into a 1000 ml big beaker, 750 ml of distilled water is added, and the mixture is magnetically stirred in a constant temperature water bath kettle at 100 ℃ until the lead chloride is completely dissolved, so that a lead chloride solution is obtained.
(5) And (3) weighing 15 g of sisal fiber powder prepared in the step (3), adding the sisal fiber powder into the lead chloride solution prepared in the step (4), magnetically stirring in a constant-temperature oil bath kettle at the temperature of 80 ℃, soaking for 24 hours, and then transferring the sisal fiber powder into a vacuum drying oven for drying for 12 hours to obtain the sisal fiber powder containing lead chloride.
(6) Weighing 8.10 g of the sisal fiber powder containing lead chloride prepared in the step (5), putting the sisal fiber powder into an alumina crucible, covering the alumina crucible with a cover, and putting the sisal fiber powder into N2In a vacuum tube furnace under atmosphere protection, N2Controlling the flow rate to be 100 mL/min, heating to 600 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 3 h to obtain the sisal fiber carbon/lead composite material.
The sisal fiber carbon/lead composite material is applied to a lead-carbon battery cathode material.
The invention has the advantages that: the solution dipping method can ensure that the active substance lead is more uniformly distributed on the carbon material, has better interface compatibility, more effectively improves the utilization rate of the active substance lead, and ensures that the carbon material and Pb/PbSO are mixed4The working potential is more matched, so that the irreversible sulfation phenomenon of the negative electrode of the lead-carbon battery in the HRPSoC state is inhibited, and the service life of the battery is prolonged.
Performing characterization analysis on the sisal fiber carbon/lead composite material by using a Scanning Electron Microscope (SEM), an X-ray diffraction spectrometer (EDS), an X-ray diffraction spectrometer (XRD) and a specific surface adsorption instrument (BET); testing the electrochemical performance of the anode material containing the sisal fiber carbon/lead composite material by using an electrochemical measurement technology; and assembling the anode material containing the sisal fiber carbon/lead composite material into a simulated lead-carbon battery, and carrying out first charge-discharge and cycle life test analysis.
Drawings
Fig. 1 is a scanning electron microscope image of a sisal fiber-based carbon material (fig. 1 (a)) and a sisal fiber carbon/lead composite material (fig. 1 (b)) in an embodiment of the present invention.
Fig. 2 is an X-ray energy spectrum of a sisal fiber-based carbon material (fig. 2 (a)) and a sisal fiber carbon/lead composite material (fig. 2 (b)) according to an embodiment of the present invention.
FIG. 3 is an X-ray powder diffraction pattern of a sisal fiber-based carbon material and a sisal fiber carbon/lead composite material according to embodiments of the present disclosure.
Fig. 4 is an adsorption and desorption curve of the sisal fiber-based carbon material in the embodiment of the invention.
FIG. 5 is a graph showing the distribution of the pore diameters of sisal fiber-based carbon material according to an embodiment of the present invention.
Fig. 6 is an adsorption and desorption curve of sisal fiber carbon/lead composite material in the embodiment of the invention.
FIG. 7 is a graph showing the pore size distribution of a sisal fiber carbon/lead composite material according to an embodiment of the present invention.
Fig. 8 is a cyclic voltammogram of a sisal fiber-based carbon material and a negative electrode material comprising a sisal fiber carbon/lead composite material according to an embodiment of the present disclosure.
Fig. 9 is an electrochemical ac impedance spectrum of a sisal fiber-based carbon material and a negative electrode material comprising a sisal fiber carbon/lead composite material according to an embodiment of the present invention.
Fig. 10 is a first charge-discharge curve diagram of a sisal fiber-based carbon material and a negative electrode material comprising a sisal fiber carbon/lead composite material according to an embodiment of the present invention.
Fig. 11 is a graph of cycle life for a sisal fiber-based carbon material and a negative electrode material comprising a sisal fiber carbon/lead composite in accordance with an embodiment of the present invention.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which do not limit the scope of the invention.
Example (b):
(1) preparing 5% NaOH aqueous solution by mass, weighing 30 g of sisal fibers, soaking the sisal fibers into the prepared NaOH aqueous solution at 60 ℃, magnetically stirring, soaking for 24 hours, and removing pectin, wax and other micromolecular substances adsorbed on the surfaces of the sisal fibers to obtain the alkali-soaked sisal fibers.
(2) Fishing out the sisal fibers soaked in the alkali in the step (1), and using 5% of H in percentage by mass3PO4Soaking the aqueous solution at 60 deg.C under magnetic stirringAnd obtaining the sisal fibers pretreated by alkali and acid 24 hours.
(3) Fishing out the sisal fibers pretreated in the step (2), repeatedly washing the sisal fibers with distilled water until the washing liquid is neutral, drying the sisal fibers in a vacuum freeze drying box for 72 hours, grinding the dried sisal fibers in a sealed grinding machine, and grinding into powder of 200 meshes and 300 meshes to obtain sisal fiber powder.
(4) 21.1149 g of lead chloride is weighed and put into a 1000 ml big beaker, 750 ml of distilled water is added, and the mixture is magnetically stirred in a constant temperature water bath kettle at 100 ℃ until the lead chloride is completely dissolved, so that a lead chloride solution is obtained.
(5) Weighing 15 g of sisal fiber powder obtained in the step (3), adding the sisal fiber powder into the lead chloride solution prepared in the step (4), magnetically stirring in a constant-temperature oil bath at 80 ℃, soaking for 24 h, and then transferring the sisal fiber powder into a vacuum drying oven for drying for 12 h to obtain the sisal fiber powder containing lead chloride.
(6) Weighing 8.10 g of the sisal fiber powder containing lead chloride dried in the step (5), placing the sisal fiber powder into an alumina crucible, covering the alumina crucible with a cover, placing the sisal fiber powder into a vacuum tube furnace, and performing vacuum distillation on the obtained product in a N-shaped furnace2Heating under atmosphere protection, N2Controlling the flow rate at 100 mL/min, heating at 5 ℃/min, keeping the temperature at 600 ℃ for 3 h to obtain the sisal fiber carbon/lead composite material.
The sisal fiber carbon/lead composite material prepared in the embodiment is characterized and analyzed by using SEM, EDS, XRD and BET, and the results are shown in fig. 1, fig. 2, fig. 3, and fig. 4 to 7.
FIG. 1 is a scanning electron micrograph. As seen from FIG. 1 (a), the sisal fiber carbon material has a dense and abundant pore structure and is arranged in a tube bundle shape in a relatively ordered manner; by impregnating PbCl2The sisal fiber is sintered at 600 ℃ to obtain the Pb/sisal fiber-based carbon composite material, the pore channel structure of the sisal fiber is relatively well reserved, white particles are loaded on the surfaces of the sisal fiber and the pipe wall, white small particles are loaded on the surfaces of the sisal fiber and the pipe wall, the white small particles are lead (figure 1 (b)), the sisal fiber carbon/lead composite material prepared by the method has a relatively large specific surface area,the lead-carbon battery negative electrode material has the characteristics of high specific surface area, can provide electric double layer capacitance during high-power charging and discharging and pulse discharging, weakens the damage of current to a negative electrode, simultaneously can enable the interior of the negative electrode material to have a porous structure, is beneficial to rapid migration of electrolyte ions under high-power charging and discharging, and in addition, Pb and a carbon material are compounded in a built-in structure, and the synergistic effect can enhance the electrochemical performance of the lead-carbon battery.
FIG. 2 is an X-ray energy spectrum. As can be seen by comparing fig. 2 (a) and fig. 2 (b), the characteristic peak of carbon atom and the characteristic peak of lead atom can be clearly seen, which proves that the sisal fiber carbon/lead composite material is successfully prepared by the solution impregnation method.
FIG. 3 is an X-ray powder diffraction pattern. By comparison with the standard card for Pb, it can be seen from FIG. 2 that the sisal fiber carbon/lead composite material is 31 at 2 Ɵ0、360、520、620、650Characteristic peaks of Pb with different crystal forms appear, which shows that Pb is generated after the heat treatment at the temperature of 600 ℃, and the generation is consistent with the SEM analysis result.
As can be seen from FIGS. 4 to 7, the diameters of the apertures of the sisal fiber-based carbon material are mainly distributed in the range of 15.0 to 18.9, and the specific surface area is 314.26 m2The prepared sisal fiber carbon/lead composite material has the pore diameters mainly distributed between 2.4-2.7 nm, 7.4-8.9 nm and 22.0-32.4 nm, wherein the pore diameters are the most between 22.0-32.4 nm, and the specific surface area is 97.58 m2And/g, due to the composite lead, the pore channel of the carbon material is partially blocked, but the prepared sisal fiber carbon/lead composite material still well keeps the pore structure of the sisal fiber carbon material, and the prepared composite material is used as a negative electrode material of the lead-carbon battery, and the pore structure is favorable for the transmission of electrolyte ions, so that the performance of the lead-carbon battery is improved.
In this example, electrochemical performance tests were also performed on the negative electrode material containing sisal fiber carbon/lead composite material, and the negative electrode plate of the lead-carbon battery was prepared by the following steps:
1 g of sisal fiber carbon/lead composite material, 3 g of lead oxide, 0.15 g of acetylene black, 0.8 g of barium sulfate, 0.1 g of humic acid, 1 g of barium stearate, 0.1 g of calcium sulfate, sodium stearateg of gallium oxide, 0.1 g of indium oxide and 0.1 g of bismuth oxide were mixed, first dry-mixed for 30 min in a planetary ball mill, and then 5 mL of a mixture having a density of 1.28 g/cm was added3Mechanically stirring the sulfuric acid solution, 3 mL of polytetrafluoroethylene emulsion and 25 mL of distilled water for 24 h to generate a paste substance, uniformly coating the paste substance on a lead-calcium alloy negative plate grid, and then drying the negative plate grid in a 60 ℃ drying oven for 12 h to obtain the sisal fiber carbon/lead composite material negative material.
A three-electrode system is adopted, the prepared negative electrode plate is used as a working electrode, a calomel electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, sulfuric acid is used as electrolyte, and electrochemical tests are carried out on the negative electrode material containing the sisal fiber carbon/lead composite material and the sisal fiber base carbon material, and the electrochemical tests are shown in attached figures 5 and 6.
FIG. 8 is a cyclic voltammogram. The capacity density of the negative electrode material of the lead-carbon battery is calculated according to a capacity density calculation formula, and the analysis of figure 8 shows that the area of the sisal fiber carbon/lead composite material is obviously larger than that of the sisal fiber carbon material, and the capacity densities of the sisal fiber carbon/lead composite material and the sisal fiber carbon material are 41.036F ∙ g respectively-1And 6.084F ∙ g-1The result shows that the capacity density of the anode material containing the sisal fiber carbon/lead composite material is higher, and the energy storage efficiency is better.
FIG. 9 is an electrochemical AC impedance spectrum. An appropriate electrochemical model is established through Z-View software, and electrochemical alternating current impedance spectrum fitting is respectively carried out on the negative plates added with the sisal fiber carbon material and the sisal fiber carbon/lead composite material, as can be seen from figure 9, the negative electrode material Rs added with the sisal fiber carbon material is 0.448, and the negative electrode material Rs added with the Pb/sisal fiber base carbon material is 0.298, so that the in-situ generated sisal fiber carbon/lead composite material has good compatibility, and the interface compatibility of physically ground lead powder and the sisal fiber carbon material is relatively poor.
The anode material containing the sisal fiber carbon/lead composite material is assembled into a simulated lead-carbon battery, after the battery is subjected to a formation process, a new power BTS high-precision battery testing system (CT-48-5V 20A) is utilized, after the battery is fully charged, a first charge-discharge curve test is carried out simultaneously with a contrast sample material physically ground by the sisal fiber-based carbon material and lead powder under the condition of constant current of 3.5C, and the result is shown in figure 7 and figure 8.
Fig. 10 is a graph showing a first charge and discharge curve. By comparing the charge-discharge curves of the physical grinding comparison sample material and the negative electrode material containing the sisal fiber/lead composite material, the battery discharge platform with the sisal fiber carbon/lead composite material added in the negative electrode material is longer than that of the physical grinding comparison sample material, and the final specific capacities are 146.9 mAh/g and 120.6 mAh/g respectively. In comparison, the specific capacity of a simulated lead-carbon battery assembled by the anode material containing the sisal fiber carbon/lead composite material is improved by 21.8%.
FIG. 11 is a graph of cycle life. The figure shows that after the negative electrode materials prepared by the two methods are cycled for 200 circles, the capacity retention rate shows a certain difference, the specific capacity of the negative electrode material containing the sisal fiber carbon/lead composite material is 70.83% of the initial specific capacity, and the specific capacity retention rate of the material of the control sample added with the physical grinding method is 61.70%. Therefore, the simulated lead-carbon battery assembled by the negative electrode material containing the sisal fiber carbon/lead composite material has better performance in the aspect of cycle performance. The solution dipping method is adopted to ensure that the active substance lead is more uniformly distributed on the carbon material, has better interface compatibility, more effectively improves the utilization rate of the active substance lead and ensures that the carbon material and Pb/PbSO are mixed4The working potential is more matched, so that the irreversible sulfation phenomenon of the negative electrode of the lead-carbon battery in the HRPSoC state is inhibited, and the service life of the battery is prolonged.
Claims (2)
1. A preparation method of a sisal fiber carbon/lead composite material is characterized by comprising the following specific steps:
(1) weighing 30 g of sisal fibers, adding the sisal fibers into a NaOH aqueous solution with the mass percent of 5%, magnetically stirring at 60 ℃, soaking for 24 hours, and removing small molecular substances adsorbed on the surfaces of the sisal fibers to obtain alkali-soaked sisal fibers;
(2) fishing out the alkali-dipped sisal fibers obtained in the step (1), and adding H with the mass percent of 5%3PO4Magnetically stirring in water solution at 60 deg.C, and soaking for 24 hr to obtain alkali and acid pretreated sisal fiber;
(3) fishing out the pretreated sisal fibers obtained in the step (2), repeatedly washing the sisal fibers with distilled water until the washing liquid is neutral, drying the sisal fibers in a vacuum freeze drying box for 72 hours, grinding the dried sisal fibers in a sealed grinder, and grinding the ground sisal fibers into powder of 200-300 meshes to obtain sisal fiber powder;
(4) weighing 21.1149 g of lead chloride, putting the lead chloride into a 1000 ml big beaker, adding 750 ml of distilled water, and magnetically stirring the mixture in a constant-temperature water bath kettle at 100 ℃ until the lead chloride is completely dissolved to obtain a lead chloride solution;
(5) weighing 15 g of sisal fiber powder prepared in the step (3), adding the sisal fiber powder into the lead chloride solution prepared in the step (4), carrying out magnetic stirring in a constant-temperature oil bath kettle at the temperature of 80 ℃, soaking for 24 hours, and then transferring the sisal fiber powder into a vacuum drying oven for drying for 12 hours to obtain sisal fiber powder containing lead chloride;
(6) weighing 8.10 g of the sisal fiber powder containing lead chloride prepared in the step (5), putting the sisal fiber powder into an alumina crucible, covering the alumina crucible with a cover, and putting the sisal fiber powder into N2In a vacuum tube furnace under atmosphere protection, N2Controlling the flow rate to be 100 mL/min, heating to 600 ℃ at the heating rate of 5 ℃/min, and preserving the temperature for 3 h to obtain the sisal fiber carbon/lead composite material.
2. Use of the sisal fiber carbon/lead composite material prepared by the preparation method according to claim 1, wherein: the sisal fiber carbon/lead composite material is applied to a lead-carbon battery cathode material.
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