CN114477174A - Composite carbon material, preparation thereof and application of composite carbon material in lead-carbon battery - Google Patents
Composite carbon material, preparation thereof and application of composite carbon material in lead-carbon battery Download PDFInfo
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- CN114477174A CN114477174A CN202011259150.6A CN202011259150A CN114477174A CN 114477174 A CN114477174 A CN 114477174A CN 202011259150 A CN202011259150 A CN 202011259150A CN 114477174 A CN114477174 A CN 114477174A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000001723 curing Methods 0.000 claims description 9
- 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
- 239000011505 plaster Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 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
- 239000011149 active material Substances 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
- 239000011812 mixed powder Substances 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
- 238000007790 scraping Methods 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
- 229920001940 conductive polymer Polymers 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 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 28
- 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
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture 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
- 239000000178 monomer Substances 0.000 description 2
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration 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
- 238000004146 energy storage Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910000371 mercury(I) sulfate Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
Abstract
The invention relates to a lead-carbon battery, in particular to a composite carbon material and a preparation method and application thereof in the lead-carbon battery.A hydrothermal reaction vessel is added with an ethanol aqueous solution, a conductive polymer material, an oxidant and an activated carbon material to form a mixed solution, the hydrothermal reaction is carried out, a solid product is dried and then dispersed in a polyvinylpyrrolidone (PVP) aqueous solution again, and the solid product is dried; in N2Sintering in atmosphere environment, and mixing the sintered product CO2And (5) activating in an atmosphere environment to obtain the composite carbon material. The method reduces the peak current density of hydrogen gas precipitation in the charging process of the lead-carbon battery, lightens 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 start-stop batteries.
Background
The lead carbon battery is gradually paid more attention by enterprises and researchers as an upgraded product of the lead acid battery due to its excellent cycle stability and low development cost. The most direct problem brought by the introduction of the carbon material in the lead-carbon battery is that hydrogen is greatly separated out from the negative electrode at the last stage of battery charging, so that the electrolyte is dried, even the hydrogen is accumulated, so that the battery explodes and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a composite carbon material, a preparation method thereof and application of the composite carbon material in a lead-carbon battery.
A preparation method of a composite carbon material, 1) adding ethanol aqueous solution, pyrrole, oxidant and 2000m of specific surface into a hydrothermal reaction vessel2The activated carbon material per gram forms a mixed solution, the mixed solution is fully stirred to enable the carbon material to be uniformly dispersed, and the strong oxidizing property of strong oxidizing agents such as ammonium persulfate is utilized to catalyze the 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 to 0.5 weight percent of the total mass of the mixed solution, and the pyrrole accounts for 0.8 to 2 weight percent of the total mass of the mixed solution;
the strong oxidant comprises at least one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide and potassium permanganate;
2) carrying out 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) drying the solid product prepared in the step 2), and dispersing the dried solid product into a 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; fully stirring and drying the solid product;
4) transferring the dried product of step 3) to N2Sintering at 600-1200 deg.C for 1-10 hr, preferably at 750-850 deg.C for 4-6 hr in atmosphere, and transferring the sintered product to CO2Activating for 1-10 hours at the temperature of 600-1200 ℃ in an atmosphere environment, preferably for 4-6 hours at the temperature of 750-850 ℃ to obtain the composite carbon material.
The active material is: one or more of carbon materials such as carbon nanotubes, graphene, activated carbon, porous carbon and the like.
The composite carbon material prepared by the preparation method.
The composite carbon material is applied to the lead-carbon battery electrode.
The lead-carbon battery electrode comprises the following materials in parts by weight: 800 parts of 500-one 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 the weight parts, pre-mixing 800 parts of 500-one 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 by using a high-speed mixer, adding 1-100 parts of deionized water into the pre-mixed powder while stirring, and continuously stirring for 1-60min to obtain lead plaster; (2) coating the lead paste on a metal lead grid in a scraping manner, and drying, curing and drying to obtain a lead-carbon battery cathode; curing temperature is 30-50 ℃, humidity is 70-95%, and curing time is 10-30 hours; the drying temperature is 60-120 deg.C, and the drying time is 10-30 hr.
The size of the metal lead slab lattice is 0.5-1000mm long, 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 guaranteed, 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 showing the results of the LSV test for the three-electrode system of examples 1-7.
Detailed Description
The present invention will be described in detail with reference to examples.
Unless otherwise specified, the raw materials in the examples were purchased commercially and used without treatment; the used instruments and equipment adopt the use parameters recommended by manufacturers.
In the examples, the cycle life of the lead-carbon battery was measured using a blue-ray charge-discharge instrument and a novyi charge-discharge tester.
Example 1, step 1: the composite carbon material is prepared by the following method:
1): 1. 1.952g 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 a solution B, and the generation of polypyrrole was catalyzed by the strong oxidizing property of a strong oxidizing agent such as ammonium persulfate. 3. 10g of solution A having a specific surface area of 1300m were added2The activated carbon material/g forms a mixed liquid 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 ℃, and dispersing 10g of dried product into 250ml of polyvinylpyrrolidone (PVP) aqueous solution with the mass concentration of 5% again after heat preservation is finished. Fully stirring for 30 minutes and then drying the mixed solution;
3) transferring 10g of the oven-dried product of step 2) to N2Sintering at 800 deg.C for 5 hr in atmosphere, and transferring sintered product to CO2Activating at 800 deg.C for 5 hr in atmosphere. And 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 fibers with the length of 5mm and the diameter of 0.5-1.5 mu m by using 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) blade-coating the lead plaster prepared in the step (0.21 g1) into a blank of a hollow metal lead grid, wherein the size of the grid is 105mm long, 14mm wide and 2mm thick, the grid comprises 15 same longitudinally-arranged hollow blanks, and the inner diameter of each blank is 12mm long, 6mm wide and 2mm thick, and drying, curing and drying to obtain the negative electrode of the lead-carbon battery. The curing temperature is 40 ℃, the humidity is 80 percent, and the curing time is 20 hours; the drying temperature is 80 ℃, and the drying time is 24 hours;
3)the same process as 1) and 2) of step 2 is adopted,the difference is in the preparation process of the anodeWithout adding Any carbon material (CI.e. without adding composite carbon material) System for makingThe paste amount of the anode of the lead-carbon battery is 0.36g(ii) a The prepared cathode, the prepared anode and the commercial mercury-mercurous sulfate reference electrode are used for carrying out LSV test of a three-electrode system, the prepared anode is used as a counter electrode of the three-electrode system, the prepared cathode is used as a working electrode of the three-electrode system, 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 hydrogen evolution current of the prepared electrode material is 18.5519mA under the condition that the electrode potential is-1.6V. The three-electrode system is fixed by a soft rubber plug, the three-electrode system is respectively and independently and fully sealed by a special commercial stone wax mold in a laboratory, then a gas guide pipe is inserted into the rubber plug of a working electrode, the gas guide pipe integrally penetrates through the rubber plug, the length of the end, positioned in a working electrode cavity, of the gas guide pipe penetrating through the rubber plug is 5mm, the gas guide pipe is positioned above the liquid level, one end, positioned outside the working electrode cavity, of the gas guide pipe is introduced into equipment for testing the gas volume by a drainage method, various connecting parts between the inner surface and the outer surface of the rubber plug, through which the gas guide pipe penetrates, of the gas guide pipe and a commercial drainage method testing gas volume device are firmly sealed by commercial AB glue, the aim 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 utilized to collect the gas volume generated by the working electrode end, the gas generation rate is calculated, and the battery system is placed in a constant temperature environment of 25 ℃ in the testing process, the constant voltage of 2.4V is applied to the two ends of the battery for 48 hours, and the gas production rate of the lead-carbon battery of the formula carbon material is calculated to be 0.29ml/(wh h).
Example 2 [ pyrrole and ammonium persulfate at the upper Limit ]
The process is the same as that of example 1, except that the lead-carbon battery is prepared by changing the addition amount of pyrrole to 4.392g and the mass of ammonium persulfate to 1.175g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 106.6285mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.27ml/(wh h).
Example 3
The process was the same as example 1, except that the amount of pyrrole added was changed to 2.245g in the lead-carbon battery according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 26.94419mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.28ml/(wh h).
Example 4
The process is the same as example 1, except that in the lead-carbon battery, the amount of ammonium persulfate added is changed to 1.1g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 37.26935mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.22ml/(wh h).
Example 5
The process is the same as that of example 1, except that in the lead-carbon battery, the amount of ammonium persulfate added is changed to 0.86g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 27.26935mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.21ml/(wh h).
Example 6
The process is the same as example 1, except that the lead-carbon battery is prepared by drying the product obtained by hydrothermal reaction according to the requirements of example 1 without changing other conditions, and dispersing the dried product in 250ml of 2% polyvinyl pyrrolidone (PVP) aqueous solution. The hydrogen evolution current of the prepared electrode material is 56.12762mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.24ml/(wh h).
Example 7
The process is the same as example 1, except that the lead-carbon battery is prepared by drying the product obtained by hydrothermal reaction according to the requirements of example 1 without changing other conditions, and dispersing the dried product in 250ml of 20% polyvinyl pyrrolidone (PVP) aqueous solution. The hydrogen evolution current of the prepared electrode material is 72.85048mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.23ml/(wh h).
Comparative example 1
The process is the same as example 1, and is different from the process in that the lead-carbon battery is prepared according to the requirements of example 1, other conditions are not changed, the material preparation of the step 1 is not carried out, and 0.15g of commercial activated carbon is directly added in the preparation process of the negative electrode of the step 2 to be used as a lead-carbon battery additive material to replace a composite carbon material. The hydrogen evolution current of the prepared electrode material is 110.9738mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.34ml/(wh h).
Comparative example 2:
the process is the same as example 1, except that the amount of pyrrole added is changed to 0.9g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 120.7834mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.36ml/(wh h). The amount of the conductive polymer synthesized in situ on the surface of the carbon material is reduced due to the excessively small addition amount of the conductive polymer material, and the coverage 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 process is the same as example 1, except that the amount of pyrrole added is changed to 8.0g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 130.5868mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.35ml/(wh h). Because the conductive polymer material pyrrole is added in too much amount and can not be completely polymerized, a large amount of monomer is remained in the electrode material and can not 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 can be further increased.
Comparative example 4:
the process is the same as example 1, except that in the lead-carbon battery, the amount of ammonium persulfate added is changed to 0.30g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 130.4377mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.34ml/(wh h). The amount of the conductive polymer synthesized in situ on the surface of the carbon material is reduced due to the excessively small amount of the oxidizing agent, and the hydrogen evolution-inhibiting effect is poor because the amount of the hydrogen evolution-active sites on the surface of the carbon material is not sufficiently covered.
Comparative example 5:
the process is the same as that of example 1, except that in the lead-carbon battery, the amount of ammonium persulfate added is changed to 3.0g according to the requirements of example 1 without changing other conditions. The hydrogen evolution current of the prepared electrode material is 130.2195mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery with the formula carbon material is 0.31ml/(wh h). Because the addition amount of the oxidant is too much, the polymerization reaction of the monomer is too violent, the polymerization of the conductive polymer layer is not uniform, the agglomeration 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 procedure was the same as in example 1, except that step 1 "step 1: the composite carbon material is prepared by the following method: 1. 1.952g 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 a solution B. 3. To the solution A was added 10g of a solution having a specific surface area of 1300m2The activated carbon material/g forms a mixed liquor C. 4. Mixing the solution B and the solution C and fully stirring to uniformly disperse the carbon material; step 1 of "changing to": the composite carbon material is prepared by the following method: 1. 1.952g polypyrrole was dissolved in 200ml of a blend of ultrapure water and ethanol in a volume ratio of alcohol to water of 1: 1 to form a solution a. 2. 10g of solution A having a specific surface area of 1300m were added2Mixing 40ml water with each g of activated carbon material to form mixed liquid B. 3. Fully stirring the solution B to uniformly disperse the carbon material; ". The hydrogen evolution current of the prepared electrode material is 152.8350mA under the condition that the electrode potential is-1.6V. The gas production rate of the lead-carbon battery of the formula carbon material is 0.33ml/(wh h). The conductive polymer directly introduced to the surface of the activated carbon cannot be fully and accurately covered on the hydrogen evolution active site on the surface of the carbon material, so that the effect of inhibiting hydrogen evolution cannot be achieved.
By comparing the hydrogen evolution current and the gas production rate of the batteries in different examples and comparative examples, the hydrogen evolution active sites on the surface of the carbon material are covered in a mode of synthesizing a conductive polymer in situ on the surface of the carbon material while the conductivity of the composite material is ensured, polyvinylpyrrolidone is introduced into the surface of the composite carbon material and is sintered, a carbon shell layer formed by PVP is utilized to more fully cover the hydrogen evolution active sites on the surface of the composite carbon material on the premise of not influencing the conductivity of the composite carbon material inside, the peak current of hydrogen evolution in the charging process of the battery is effectively reduced, and the generation amount of hydrogen in the charging process of the battery is obviously reduced after the hydrogen evolution current is reduced.
Claims (8)
1. A method for preparing a composite carbon material is characterized in that:
1) adding ethanol water solution, pyrrole, oxidant and water with the specific surface of 300-2000m into a hydrothermal reaction vessel2The activated carbon material per gram forms a mixed solution, the mixed solution is fully stirred to enable the carbon material to be uniformly dispersed, and the strong oxidizing property of strong oxidizing agents such as ammonium persulfate is utilized to catalyze the 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 to 0.5 weight percent of the total mass of the mixed solution, and the pyrrole accounts for 0.8 to 2 weight percent of the total mass of the mixed solution;
the strong oxidant comprises at least one or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide and potassium permanganate;
2) carrying out 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) drying the solid product prepared in the step 2), and dispersing the dried solid product into a 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; fully stirring and drying the solid product;
4) transferring the dried product of step 3) to N2Sintering at 600-1200 deg.C for 1-10 hr, preferably at 750-850 deg.C for 4-6 hr in atmosphere, and transferring the sintered product to CO2Activating for 1-10 hours at 600-1200 ℃ in an atmosphere environment, and preferablyActivating at 750-850 deg.c for 4-6 hr to obtain the composite carbon material.
2. The method of claim 1, wherein: the active material is: one or more of carbon materials such as carbon nanotubes, graphene, activated carbon, porous carbon and the like.
3. A composite carbon material produced by the production method according to any one of claims 1 to 2.
4. Use of the composite carbon material of claim 3 in an electrode for a lead carbon battery.
5. Use according to claim 4, characterized in that:
the lead-carbon battery electrode comprises the following materials in parts by weight: 800 parts of 500-one 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.
6. Use according to claim 4, characterized in that:
the preparation process of the lead-carbon battery electrode comprises the following steps: (1) according to the weight parts, pre-mixing 800 parts of 500-one 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 by using a high-speed mixer, adding 1-100 parts of deionized water into the pre-mixed powder while stirring, and continuously stirring for 1-60min to obtain lead plaster; (2) coating the lead paste on a metal lead grid in a scraping manner, and drying, curing and drying to obtain a lead-carbon battery cathode; curing temperature is 30-50 ℃, humidity is 70-95%, and curing time is 10-30 hours; the drying temperature is 60-120 deg.C, and the drying time is 10-30 hr.
7. Use according to claim 4, characterized in that:
the size of the metal lead slab lattice is 0.5-1000mm long, 0.2-80mm wide and 0.5-4mm thick.
8. Use according to any of claims 4 to 7, wherein: the lead-carbon battery electrode is a negative electrode of the lead-carbon battery.
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