CN114477174B - Composite carbon material, preparation thereof and application thereof in lead-carbon battery - Google Patents
Composite carbon material, preparation thereof and application thereof in lead-carbon battery Download PDFInfo
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- CN114477174B CN114477174B CN202011259150.6A CN202011259150A CN114477174B CN 114477174 B CN114477174 B CN 114477174B CN 202011259150 A CN202011259150 A CN 202011259150A CN 114477174 B CN114477174 B CN 114477174B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 14
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 239000011505 plaster Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- -1 polypropylene Polymers 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 27
- 229920001940 conductive polymer Polymers 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000019635 sulfation Effects 0.000 abstract 1
- 238000005670 sulfation reaction Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000007772 electrode material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
-
- 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
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lead-carbon battery, in particular to a composite carbon material and preparation thereof as well as application thereof in the lead-carbon battery, which are characterized in that an ethanol aqueous solution, a conductive polymer material, an oxidant and an active carbon material are added into a hydrothermal reaction vessel to form a mixed solution, the mixed solution is subjected to hydrothermal reaction, and a solid product is dried and then is dispersed in a polyvinylpyrrolidone (PVP) aqueous solution again, and is dried; at N 2 Sintering in atmosphere environment to obtain sintered product CO 2 And (5) activating in an atmosphere environment to obtain the composite carbon material. The invention reduces the peak current density of hydrogen gas precipitation in the charging process of the lead-carbon battery, reduces the sulfation of the battery and prolongs the cycle life of the battery.
Description
Technical Field
The invention relates to the field of lead-carbon batteries, in particular to the field of energy storage batteries and power-on and power-off batteries.
Background
Lead-carbon batteries are increasingly receiving attention from businesses and researchers as an upgrade product for lead-acid batteries due to their excellent cycling stability and low development costs. The most direct problem caused by the introduction of carbon materials in the lead-carbon battery is that a large amount of hydrogen is separated out from a negative electrode at the end of battery charging, so that electrolyte is dried up, even hydrogen is gathered, and the battery explodes.
Disclosure of Invention
In order to solve the problems, the invention provides a composite carbon material, a preparation method thereof and application thereof in lead-carbon batteries.
A process for preparing composite carbon material includes such steps as adding aqueous solution of alcohol, pyrrole, oxidant and water to hydrothermal reactor with specific surface area of 300-2000m 2 Forming a mixed solution by the active carbon material of/g, fully stirring to uniformly disperse the carbon material, and catalyzing the polymerization of pyrrole by utilizing the strong oxidizing property of the strong oxidizing agent such as ammonium persulfate; the volume ratio of water to ethanol is 0.5-1.5:1, wherein the mass of the active carbon accounts for 1-10% of the total mass of the mixed solution; the strong oxidant accounts for 0.25-0.5wt% of the total mass of the mixed solution, and the pyrrole accounts for 0.8-2wt% of the total mass of the mixed solution;
the strong oxidant comprises at least one or more than two of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide and potassium permanganate;
2) Carrying out a hydrothermal reaction on the mixed solution obtained in the step 1), wherein the hydrothermal reaction time is 8-24 hours, and the hydrothermal reaction temperature is 140-240 ℃;
3) The solid product prepared in the step 2) is dried and then dispersed in polyvinylpyrrolidone (PVP) aqueous solution with the mass concentration of 1-10%, wherein the mass of the dried solid product is 2-20% of that of the polyvinylpyrrolidone solution; drying the solid product after fully stirring;
4) Transferring the dried product of step 3) to N 2 Sintering at 600-1200deg.C for 1-10 hr, preferably 750-850deg.C for 4-6 hr, and transferring the sintered product to CO 2 Activating for 1-10 hours at 600-1200 deg.C, preferably 750-850 deg.C for 4-6 hours in atmosphere environment to obtain the composite carbon material.
The active material refers to: one or more of carbon materials such as carbon nanotube, graphene, activated carbon, porous carbon, etc.
The composite carbon material prepared by the preparation method.
The application of the composite carbon material in the lead-carbon battery electrode.
The lead-carbon battery electrode comprises the following materials in parts by weight: 500-800 parts of lead powder, 1-20 parts of the composite carbon material, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m.
The preparation process of the lead-carbon battery electrode comprises the following steps: (1) According to parts by weight, premixing 500-800 parts of lead powder, 1-20 parts of the composite carbon material, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m by a high-speed stirrer, adding 1-100 parts of deionized water into the premixed powder while stirring, and continuously stirring for 1-60min to obtain lead plaster; (2) Scraping the lead plaster on a metal lead grid, and drying to obtain a lead-carbon battery cathode; the curing temperature is 30-50 ℃, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120 ℃ and the drying time is 10-30 hours.
The size of the metal lead plate grid is 0.5-1000mm long and 0.2-80mm wide and 0.5-4mm thick.
The lead-carbon battery electrode is a negative electrode of the lead-carbon battery.
The invention has the beneficial effects that:
by means of in-situ synthesis of the conductive polymer on the surface of the carbon material, the conductivity of the composite material is ensured, and meanwhile, hydrogen evolution active sites on the surface of the carbon material are covered, so that the peak current of hydrogen evolution in the charging process of the lead-carbon battery is reduced, and the rate of gas generated in the charging process of the battery is reduced.
Drawings
FIG. 1 is a graph of LSV test results for the three electrode system of examples 1-7.
Detailed Description
The present invention is described in detail below with reference to examples.
Unless otherwise specified, the starting materials in the examples were purchased commercially and used without treatment; the instrument and equipment are recommended to use parameters by manufacturers.
In the examples, the cycle life of the lead-carbon battery was tested using a blue charge-discharge tester and a new-wire charge-discharge tester.
Example 1 step 1: the composite carbon material is prepared by the following method:
1): 1. 1.952g of pyrrole was dissolved in 200ml of a blend of ultrapure water and ethanol, wherein the volume ratio of alcohol to water was 1:1 to form a solution a. 2. Solution B was prepared by dissolving 0.64g of ammonium persulfate in 40ml of water, and the production of polypyrrole was catalyzed by the strong oxidizing property of a strong oxidizing agent such as ammonium persulfate. 3. 10g of a solution A having a specific surface area of 1300m was added 2 The activated carbon material per gram forms a mixed liquor C. 4. Mixing the solution B and the solution C and fully stirring to uniformly disperse the carbon material;
2) Transferring the mixed solution obtained in the step 1) into a hydrothermal kettle with the volume of 500ml, preserving heat for 12 hours at 180 ℃, taking 10g of dried product after preserving heat, and dispersing the product into 250ml of polyvinylpyrrolidone (PVP) aqueous solution with the mass concentration of 5%. Stirring for 30 min, and drying the mixed solution;
3) Transferring 10g of the dried product of step 2) to N 2 Sintering at 800 deg.c in atmosphere for 5 hr, transferring the sintered product to CO 2 Activated for 5 hours at 800 ℃ in an atmosphere. Obtaining the composite carbon material.
Step 2: the lead-carbon battery electrode is prepared by the following steps:
1) Premixing 10g of lead powder, 0.15g of the composite carbon material prepared in the step 1, 0.14g of barium sulfate and 0.005g of polypropylene short fiber with the length of 5mm and the diameter of 0.5-1.5 mu m by a high-speed stirrer, adding 1.4g of deionized water into the premixed powder while stirring, and continuously stirring for 10min to obtain lead plaster;
2) And (3) scraping the lead plaster prepared in the step 0.21g 1) into one blank of a hollowed-out metal lead grid, wherein the size of the grid is 105mm long, 14mm wide and 2mm thick, the grid comprises 15 hollow blanks which are arranged longitudinally, the inner diameter of each blank is 12mm long, 6mm wide and 2mm thick, and drying the blank to obtain the lead-carbon battery cathode. Curing temperature is 40 ℃, humidity is 80 percent, and curing time is 20 hours; the drying temperature is 80 ℃ and the drying time is 24 hours;
3)the same process as in steps 1) and 2) is used,is different from the positive electrode in the preparation processWithout adding Any carbon material [ ]I.e. without adding composite carbon material) Preparing positive electrode of lead-carbon battery, the paste coating quantity of the positive electrode is 0.36gThe method comprises the steps of carrying out a first treatment on the surface of the And carrying out a three-electrode system LSV test on the prepared negative electrode, the positive electrode and the commercial mercury-mercurous sulfate reference electrode, wherein the prepared positive electrode is used as a counter electrode of the three-electrode system, the prepared negative electrode is used as a working electrode of the three-electrode system, the sulfuric acid electrolyte adopted in the three-electrode system is 70g of sulfuric acid electrolyte with the density of 1.275g/ml, the test range is (-1) V to (-1.6) V, and the test result is shown in figure 1. The prepared electrode material has a hydrogen evolution current of 18.5519mA under the condition that the electrode potential is-1.6V. The three-electrode system is fixed by using a soft rubber plug, the three-electrode system is respectively and fully sealed by using a laboratory special commercial paraffin mold, then an air duct is inserted into the rubber plug of the working electrode, the air duct integrally penetrates through the rubber plug, one end of the air duct, which is positioned in the working electrode cavity, penetrates through the rubber plug for 5mm in length and is positioned on the liquid levelIn the equipment for testing the gas volume by introducing a drainage method into one end of the gas guide pipe, which is positioned outside the working electrode cavity, various connecting parts between the inner surface and the outer surface of a rubber plug penetrated by the gas guide pipe and a commercial drainage method testing gas volume device are firmly sealed by commercial AB glue, the purpose is to ensure that the gas generated by the working electrode end is completely introduced into the commercial drainage method gas volume measuring device, the device is used for collecting the gas volume generated by the working electrode end and calculating the gas generation rate, a battery system is placed in a constant temperature environment at 25 ℃ in the testing process, constant 2.4V voltage is applied to the two ends of the battery for 48 hours, and the gas generation rate of the lead-carbon battery of the formula carbon material is 0.29 ml/(wh.h).
Example 2 [ pyrrole and ammonium persulfate are at upper limit ]
The procedure was as in example 1, except that the lead-carbon battery was changed to 4.392g of pyrrole and to 1.175g of ammonium persulfate by the requirements of example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 106.6285mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.27 ml/(wh.h).
Example 3
The procedure was as in example 1, except that the lead-carbon battery was changed to 2.245g in the amount of pyrrole added according to the requirements of example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 26.94419mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.28 ml/(wh.h).
Example 4
The procedure was as in example 1 except that the lead-carbon battery was changed to 1.1g in the amount of ammonium persulfate added as required in example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 37.26935mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.22 ml/(wh.h).
Example 5
The procedure was as in example 1 except that the lead-carbon battery was changed to 0.86g in the amount of ammonium persulfate added as required in example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 27.26935mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.21 ml/(wh.h).
Example 6
The procedure was as in example 1, except that the lead-carbon battery was modified as required in example 1, and the product obtained by the hydrothermal reaction was dried and then redispersed in 250ml of a 2% by mass aqueous polyvinylpyrrolidone (PVP) solution. The prepared electrode material has a hydrogen evolution current of 56.12762mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.24 ml/(wh.h).
Example 7
The procedure was as in example 1, except that the lead-carbon battery was modified as required in example 1, and the product obtained by the hydrothermal reaction was dried and then redispersed in 250ml of a 20% by mass aqueous polyvinylpyrrolidone (PVP) solution. The prepared electrode material has a hydrogen evolution current of 72.85048mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.23 ml/(wh.h).
Comparative example 1
The process is the same as in example 1, except that according to the requirements of example 1, other conditions are not changed, the preparation of the material in step 1 is not carried out, and 0.15g of commercial activated carbon is directly added as an additive material of the lead-carbon battery to replace a composite carbon material in the preparation process of the negative electrode in step 2. The prepared electrode material has a hydrogen evolution current of 110.9738mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.34 ml/(wh.h).
Comparative example 2:
the procedure was as in example 1, except that the lead-carbon battery was changed to 0.9g in the amount of pyrrole added according to the requirements of example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 120.7834mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.36 ml/(wh.h). Because the addition amount of the conductive polymer material is too small, the amount of in-situ synthesized conductive polymer on the surface of the carbon material is reduced, and the coverage amount of hydrogen evolution active sites on the surface of the carbon material is insufficient, so that the effect of inhibiting hydrogen evolution is poor.
Comparative example 3:
the procedure was as in example 1, except that the lead-carbon battery was changed to 8.0g in the amount of pyrrole added according to the requirements of example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 130.5868mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.35 ml/(wh.h). Because the addition amount of the conductive polymer material pyrrole is too large, the pyrrole cannot be completely polymerized, a large amount of monomer remains in the electrode material and cannot occupy hydrogen evolution active sites on the surface of the carbon material, so that the hydrogen evolution is serious, and in addition, the internal resistance of the carbon material is further increased.
Comparative example 4:
the procedure was as in example 1 except that the lead-carbon battery was changed to 0.30g in the amount of ammonium persulfate added as required in example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 130.4377mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.34 ml/(wh.h). The amount of the conductive polymer synthesized in situ on the surface of the carbon material is reduced due to the too small addition amount of the oxidant, and the coverage amount of hydrogen evolution active sites on the surface of the carbon material is insufficient, so that the effect of inhibiting hydrogen evolution is poor.
Comparative example 5:
the procedure was as in example 1 except that the lead-carbon battery was changed to 3.0g in the amount of ammonium persulfate added as required in example 1 without changing other conditions. The prepared electrode material has a hydrogen evolution current of 130.2195mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.31 ml/(wh.h). The addition amount of the oxidant is too large, so that the polymerization reaction of the monomer is too strong, the polymerization of the conductive polymer layer is uneven, the aggregation is serious, the internal resistance of the material is increased, and the effect of inhibiting hydrogen evolution cannot be achieved.
Comparative example 6 (polypyrrole)
The process is the same as that of the real processExample 1 differs therefrom in that step 1 "step 1: the composite carbon material is prepared by the following method: 1. 1.952g of pyrrole was dissolved in 200ml of a blend of ultrapure water and ethanol, wherein the volume ratio of alcohol to water was 1:1 to form a solution a. 2. 0.64g of ammonium persulfate was dissolved in 40ml of water to form solution B. 3. 10g of solution A having a specific surface area of 1300m were added to 2 The activated carbon material per gram forms a mixed liquor C. 4. Mixing the solution B and the solution C and fully stirring to uniformly disperse the carbon material; "change to" step 1: the composite carbon material is prepared by the following method: 1. 1.952g of polypyrrole was dissolved in 200ml of a blend of ultrapure water and ethanol, wherein the volume ratio of alcohol to water was 1:1 to form a solution a. 2. 10g of a solution A having a specific surface area of 1300m was added 2 The active carbon material/g was mixed with 40ml of water to form a mixture B. 3. Fully stirring the solution B to uniformly disperse the carbon material; ". The prepared electrode material has a hydrogen evolution current of 152.8350mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the carbon material of the formula is 0.33 ml/(wh.h). Because the conductive polymer directly introduced on the surface of the activated carbon can not be covered on the hydrogen evolution active site on the surface of the carbon material sufficiently and accurately, the effect of inhibiting hydrogen evolution can not be achieved.
By comparing hydrogen evolution current and gas production rate of the battery in different examples and comparative examples, the method of synthesizing the conductive polymer on the surface of the carbon material in situ ensures the conductivity of the composite material, simultaneously covers hydrogen evolution active sites on the surface of the carbon material, introduces polyvinylpyrrolidone on the surface of the composite carbon material, and performs sintering treatment, and the carbon shell layer formed by PVP covers the hydrogen evolution active sites on the surface of the internal composite carbon material more fully on the premise of not affecting the conductivity of the internal composite carbon material, thereby effectively reducing the peak current of hydrogen evolution in the battery charging process, and obviously reducing the hydrogen production in the battery charging process after the hydrogen evolution current is reduced.
Claims (8)
1. The application of the composite carbon material in the lead-carbon battery electrode is characterized in that:
the preparation method of the composite carbon material comprises the following steps:
1) In the followingAdding ethanol water solution, pyrrole, oxidant and water with specific surface area of 300-2000m into hydrothermal reaction vessel 2 The active carbon material of/g forms mixed solution, and stir fully to make the carbon material disperse evenly, utilize strong oxidizing property of strong oxidizing agent to catalyze polymerization of pyrrole; the volume ratio of water to ethanol is 0.5-1.5:1, wherein the mass of the active carbon accounts for 1-10% of the total mass of the mixed solution; the strong oxidant accounts for 0.25-0.5-wt% of the total mass of the mixed solution, and the pyrrole accounts for 0.8-2-wt% of the total mass of the mixed solution;
the strong oxidant comprises at least one of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide and potassium permanganate;
2) Carrying out a hydrothermal reaction on the mixed solution obtained in the step 1), wherein the hydrothermal reaction time is 8-24 hours, and the hydrothermal reaction temperature is 140-240 ℃;
3) The solid product prepared in the step 2) is dried and then dispersed in polyvinylpyrrolidone (PVP) aqueous solution with the mass concentration of 1-10%, wherein the mass of the dried solid product is 2-20% of that of the polyvinylpyrrolidone solution; drying the solid product after fully stirring;
4) Transferring the dried product of step 3) to N 2 Sintering at 600-1200deg.C for 1-10 hr in atmosphere, transferring the sintered product to CO 2 Activating for 1-10 hours at 600-1200 ℃ in an atmosphere environment to obtain the composite carbon material.
2. The use according to claim 1, characterized in that: the active carbon material is as follows: one or more of carbon nanotubes, graphene and activated carbon.
3. The use according to claim 1, characterized in that: transfer of the dried product from step 4) to N 2 Sintering at 750-850 deg.c in atmosphere for 4-6 hr, and transferring the sintered product to CO 2 Activating at 750-850 deg.c for 4-6 hr in atmosphere.
4. The use according to claim 2, characterized in that: the active carbon material is porous carbon.
5. The use according to claim 1, characterized in that:
the lead-carbon battery electrode comprises the following materials in parts by weight: 500-800 parts of lead powder, 1-20 parts of the composite carbon material, 6-10 parts of barium sulfate, 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m.
6. The use according to claim 1, characterized in that:
the preparation process of the lead-carbon battery electrode comprises the following steps: (1) According to parts by weight, premixing 500-800 parts of lead powder, 1-20 parts of the composite carbon material, 6-10 parts of barium sulfate and 0.1-0.5 part of polypropylene short fiber with the length of 0.1-5mm and the diameter of 100nm-5 mu m by a high-speed stirrer, adding 1-100 parts of deionized water into the premixed powder while stirring, and continuously stirring for 1-60min to obtain lead plaster; (2) Scraping the lead plaster on a metal lead grid, and drying to obtain a lead-carbon battery cathode; the curing temperature is 30-50 ℃, the humidity is 70-95%, and the curing time is 10-30 hours; the drying temperature is 60-120 ℃ and the drying time is 10-30 hours.
7. The use according to claim 1, characterized in that:
the size of the metal lead plate grid is 0.5-1000. 1000mm long, 0.2-80. 80mm wide and 0.5-4. 4mm thick.
8. Use according to any one of claims 1-7, characterized in that: the lead-carbon battery electrode is a negative electrode of the lead-carbon battery.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617228A (en) * | 1984-09-04 | 1986-10-14 | Rockwell International Corporation | Process for producing electrically conductive composites and composites produced therein |
| CN102709527A (en) * | 2012-06-21 | 2012-10-03 | 上海锦众信息科技有限公司 | Manufacturing method of super lead-acid battery negative plate |
| CN103000882A (en) * | 2012-12-28 | 2013-03-27 | 湖南丰日电源电气股份有限公司 | Lead carbon battery cathode lead plaster and preparation method thereof |
| CN104525256A (en) * | 2014-12-26 | 2015-04-22 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof |
| CN104966836A (en) * | 2015-06-23 | 2015-10-07 | 上海交通大学 | Method for improving electrochemical performance of LiFePO4 through polypyrrole/graphene |
| CN106404873A (en) * | 2016-08-30 | 2017-02-15 | 广东省汕头市质量计量监督检测所 | Electrochemical biosensor for detecting hydrogen peroxide, preparation method and application thereof |
| WO2017139938A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Preparation method for graphene/polypyrrole/sulfur composite positive electrode material |
| CN108630937A (en) * | 2018-05-10 | 2018-10-09 | 浙江工业大学 | Negative electrode lead paste and negative electrode plate of lead-carbon battery |
| CN110137452A (en) * | 2019-04-26 | 2019-08-16 | 浙江工业大学 | A kind of preparation method and application of Nanometer sized lead oxide/carbon composite |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3284860B2 (en) * | 1995-12-18 | 2002-05-20 | 松下電器産業株式会社 | Electrode for lead-acid battery and its manufacturing method |
-
2020
- 2020-11-12 CN CN202011259150.6A patent/CN114477174B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4617228A (en) * | 1984-09-04 | 1986-10-14 | Rockwell International Corporation | Process for producing electrically conductive composites and composites produced therein |
| CN102709527A (en) * | 2012-06-21 | 2012-10-03 | 上海锦众信息科技有限公司 | Manufacturing method of super lead-acid battery negative plate |
| CN103000882A (en) * | 2012-12-28 | 2013-03-27 | 湖南丰日电源电气股份有限公司 | Lead carbon battery cathode lead plaster and preparation method thereof |
| CN104525256A (en) * | 2014-12-26 | 2015-04-22 | 中国科学院上海高等研究院 | Polypyrrole activated carbon catalyst and application thereof |
| CN104966836A (en) * | 2015-06-23 | 2015-10-07 | 上海交通大学 | Method for improving electrochemical performance of LiFePO4 through polypyrrole/graphene |
| WO2017139938A1 (en) * | 2016-02-18 | 2017-08-24 | 肖丽芳 | Preparation method for graphene/polypyrrole/sulfur composite positive electrode material |
| CN106404873A (en) * | 2016-08-30 | 2017-02-15 | 广东省汕头市质量计量监督检测所 | Electrochemical biosensor for detecting hydrogen peroxide, preparation method and application thereof |
| CN108630937A (en) * | 2018-05-10 | 2018-10-09 | 浙江工业大学 | Negative electrode lead paste and negative electrode plate of lead-carbon battery |
| CN110137452A (en) * | 2019-04-26 | 2019-08-16 | 浙江工业大学 | A kind of preparation method and application of Nanometer sized lead oxide/carbon composite |
Non-Patent Citations (1)
| Title |
|---|
| 铅酸电池负极碳基复合材料的制备及其作用机理;杨欢;《工程科技II辑》(第10期);C042-80 * |
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