CN103606656B - A kind of preparation method of the lead oxide/graphene nanocomposite material for plumbous charcoal superbattery - Google Patents
A kind of preparation method of the lead oxide/graphene nanocomposite material for plumbous charcoal superbattery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/56—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead
- H01M4/57—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of lead of "grey lead", i.e. powders containing lead and lead oxide
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- 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 preparation method that the invention discloses a kind of PbO/ graphene nanocomposite material for plumbous charcoal superbattery, prepares graphene sol first with native graphite, adds certain surfactant in described graphene sol；Solubility lead salt is dissolved in deionized water, is configured to the leaded solion that solubility is 0.5～5mol/L；The described leaded solion of 1L is slowly added in described graphene sol, forms stable colloidal sol；In described colloidal sol, under agitation drip aqueous slkali；Filter solid reaction product, in air atmosphere, calcining solid reactant, obtain PbO/ graphene nanocomposite material.Adopt PbO/ graphene nanocomposite material prepared by this law, not only avoid the reunion of Graphene, achieve the homogeneous dispersion of Graphene and PbO, and with Hydrocerussitum (Ceruse) is capable of homogeneous mixing, used as the efficient additive of plumbous charcoal superbattery lead negative, it is remarkably improved charge acceptance and the HRPSoC cycle life of battery.
Description
Technical field
The present invention relates to technical field of chemical power, the preparation method particularly relating to a kind of lead oxide/graphene nanocomposite material for plumbous charcoal superbattery.
Background technology
At present, plumbous charcoal superbattery is by the one in composite power source integrated to lead-acid accumulator and ultracapacitor, it is by adding a certain amount of Carbon Materials (usual Carbon Materials is added in negative plate) with high specific capacitance in the pole plate of lead-acid accumulator, the Carbon Materials added can store in moment or discharge a large amount of electric charge, and anticathode plate plays the effect of certain buffer current.Therefore, plumbous charcoal superbattery has the high rate during charging-discharging of excellence, adds Carbon Materials simultaneously and can effectively suppress negative pole sulfation, improve the cycle life of battery under HRPSoC in negative pole.
In prior art, the charcoal additive in plumbous charcoal superbattery mainly has the materials such as activated carbon, graphite, white carbon black, and wherein the specific surface area of activated carbon is big, and electric capacity activity is high but electric conductivity is poor, and impurity content is high, and overpotential of hydrogen evolution is low；The electric conductivity of graphite is better, but almost without capacitance characteristic, it is impossible to the instantaneous large-current passed through in buffering negative plate；The excellent electric conductivity of white carbon black, but electric capacity activity is low, easily reunites, and when content is more than 1%, water suction is serious, it is difficult to realize closing cream.Graphene is a kind of special Carbon Materials, is with sp by carbon atom2The hexangle type of hybrid orbital composition is the flat film of honeycomb lattice.Due to the feature of monoatomic layer crystal structure, Graphene has special power electro-optic-thermal characteristic, and under room temperature, its electron mobility is more than 15000cm2/ Vs, and resistivity about 10-6Ω cm, lower than copper or silver, for the material that resistivity is minimum in the world at present, Graphene, as the quasi-two-dimensional material of thickness only one of which carbon atom, also has significantly high specific surface area and high electric capacity activity.Therefore, using the Graphene cathode additive agent as plumbous charcoal superbattery, it is possible to improve the electrical conductivity of negative pole, cushion instantaneous large-current, suppress the sulfation on negative plate surface, improve the cycle life under battery compartment state-of-charge high current charge-discharge (HRPSoC) operating mode.
But in prior art, the addition manner of plumbous charcoal superbattery Carbon Materials mainly carries out mechanical mixture with Hydrocerussitum (Ceruse), owing to Hydrocerussitum (Ceruse) density is far longer than the density of Carbon Materials, therefore both Homogeneous phase mixing would become hard to realize, and by the mode of mechanical mixture, plumbous active substance is less with effective contact interface of Carbon Materials, high conductance and the bulky capacitor advantage of charcoal can not be given full play to, Graphene solid is in the process being dry mixed with plumbous negative material, easily cause the reunion of Graphene, and not easily mix homogeneously, thus affecting the performance of Graphene advantage.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of lead oxide/graphene nanocomposite material for plumbous charcoal superbattery, adopt lead oxide PbO/ graphene nanocomposite material prepared by this law, not only avoid the reunion of Graphene, achieve the homogeneous dispersion of Graphene and PbO, and with Hydrocerussitum (Ceruse) is capable of homogeneous mixing, used as the efficient additive of plumbous charcoal superbattery lead negative, it is remarkably improved charge acceptance and the HRPSoC cycle life of battery.
A kind of preparation method of the lead oxide/graphene nanocomposite material for plumbous charcoal superbattery, described preparation method includes:
Utilize native graphite to prepare graphene sol, in described graphene sol, add certain surfactant；
Solubility lead salt is dissolved in deionized water, is configured to the leaded solion that solubility is 0.5～5mol/L；
The described leaded solion of 1L is slowly added in described graphene sol, ultrasonic 30～60min, and stand 1 hour, form stable colloidal sol；
In described colloidal sol, under agitation drip aqueous slkali, regulate the pH value of described colloidal sol to 8～14, at room temperature stir 1～2 hour, then stand 1～2 hour；
Filter solid reaction product, by described solid reaction product after deionized water and dehydrated alcohol alternate repetition wash, vacuum drying 12 hours at 60 DEG C；In air atmosphere, dried solid reaction product is calcined 1 hour at 150-200 DEG C, obtains PbO/ graphene nanocomposite material.
As seen from the above technical solution provided by the invention, adopt lead oxide PbO/ graphene nanocomposite material prepared by this law, not only avoid the reunion of Graphene, achieve the homogeneous dispersion of Graphene and PbO, and with Hydrocerussitum (Ceruse) is capable of homogeneous mixing, used as the efficient additive of plumbous charcoal superbattery lead negative, it is remarkably improved charge acceptance and the HRPSoC cycle life of battery.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below the accompanying drawing used required during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawings according to these accompanying drawings.
The preparation method schematic flow sheet of the PbO/ graphene nanocomposite material for plumbous charcoal superbattery that Fig. 1 provides for the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on embodiments of the invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into protection scope of the present invention.
Below in conjunction with accompanying drawing, the embodiment of the present invention is described in further detail, it is illustrated in figure 1 the preparation method schematic flow sheet of the PbO/ graphene nanocomposite material for plumbous charcoal superbattery that the embodiment of the present invention provides, in conjunction with Fig. 1, described preparation method includes:
Step 11: utilize native graphite to prepare graphene sol, adds certain surfactant in described graphene sol；
In this step, the described detailed process utilizing native graphite to prepare graphene sol is:
First native graphite Hume's method Hummers method is prepared into graphite oxide；
Graphite oxide prepared by 50g is joined in the deionized water of 5L, after sonic oscillation a period of time, obtain yellow solution；
The hydrazine hydrate of 50mL is joined in described yellow solution, is heated to 90 DEG C, and the 24h that refluxes, graphite oxide is reduced fully, obtains graphene sol.
It addition, described surfactant includes one or more of:
Cetyl trimethylammonium bromide, Tetramethylammonium hydroxide, dodecyl sodium sulfate and polyvinylpyrrolidone.
Step 12: be dissolved in deionized water by solubility lead salt, is configured to the leaded solion that solubility is 0.5～5mol/L；
In implementing process, above-mentioned solubility lead salt may include that plumbi nitras or lead acetate.
Step 13: the described leaded solion of 1L is slowly added in described graphene sol, ultrasonic 30～60min, and stand 1 hour, form stable colloidal sol；
Step 14: under agitation drip aqueous slkali in described colloidal sol, regulate the pH value of described colloidal sol to 8～14, at room temperature stir 1～2 hour, then stand 1～2 hour；
In implementing, described aqueous slkali may include that NaOH aqueous solution, KOH aqueous solution or ammonia spirit.
Step 15: filter solid reaction product, in air atmosphere, calcining solid reactant, obtain PbO/ graphene nanocomposite material.
In this step, detailed process is:
First solid reaction product is filtered, by described solid reaction product after deionized water and dehydrated alcohol alternate repetition wash, vacuum drying 12 hours at 60 DEG C；Then, in air atmosphere, dried solid reaction product is calcined 1 hour at 150-200 DEG C, obtains PbO/ graphene nanocomposite material.
It addition, in prepared PbO/ graphene nanocomposite material, the mass percentage content of PbO is 80～99.9%, the mass percentage content of Graphene is 0.1～20%；
Wherein, each graphene film comprises 1-80 carbon atomic layer, and homogeneous scattered PbO particle is nano spherical particle, and its particle diameter is 50～1000nm.
Preparation method based on above-mentioned PbO/ graphene nanocomposite material, the embodiment of the present invention additionally provides the cathode lead plaster of a kind of plumbous charcoal superbattery, described cathode lead plaster include Hydrocerussitum (Ceruse), method prepared as described above prepare PbO/ graphene nanocomposite material, acetylene black, barium sulfate, lignin, chopped fiber, sodium carboxymethyl cellulose (CMC, Carboxymethylcellulosesodium), sulphuric acid and water, wherein:
The quality of described PbO/ graphene nanocomposite material is the 0.1%～20% of described Hydrocerussitum (Ceruse) quality；The quality of described acetylene black is the 0.5%～5% of described Hydrocerussitum (Ceruse) quality；The quality of described barium sulfate is the 0.1%～2.0% of described Hydrocerussitum (Ceruse) quality；The quality of described lignin is the 0.1%～2.0% of described Hydrocerussitum (Ceruse) quality；The quality of described chopped fiber is the 0.01%～0.1% of described Hydrocerussitum (Ceruse) quality；The quality of described CMC is the 0.5%～2% of described Hydrocerussitum (Ceruse) quality；The quality of described sulphuric acid is the 4%～12% of described Hydrocerussitum (Ceruse) quality；The quality of described water is the 5%～15% of described Hydrocerussitum (Ceruse) quality.
It addition, described cathode lead plaster is further used for preparing the negative pole of plumbous charcoal superbattery, particularly as follows:
Being coated with to negative electrode grid by the cathode lead plaster comprising described PbO/ graphene nanocomposite material, wherein coating thickness is 1.9～2.2mm；
It is sequentially carried out solidification again and alienation processes, prepare the negative pole of plumbous charcoal superbattery.
Adopt the above-mentioned plumbous charcoal superbattery comprised made by PbO/ graphene nanocomposite material, after tested: the quality of this lead charcoal superbattery significantly improves than power.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.6V, and the cycle life of above-mentioned plumbous charcoal superbattery significantly improves.
Illustrate with the preparation process of the concrete example preparation process to above-mentioned PbO/ graphene nanocomposite material and plumbous charcoal superbattery more below:
Embodiment 1
(1) first, native graphite Hummers method is prepared into graphite oxide, then 50g graphite oxide is joined in 5L deionized water, sonic oscillation a period of time, obtain yellow solution；Being added in above-mentioned solution by 50mL hydrazine hydrate subsequently, be heated to 90 DEG C, reflux 24h, graphite oxide is reduced fully, graphene sol can be obtained, and in graphene sol, add 500mL, 0.25M Tetramethylammonium hydroxide (as surfactant), ultrasonic disperse, it is uniformly mixed.
(2) weighing the lead acetate of 65g in beaker, add 1.5L water, be configured to solution, then join in graphene sol by lead salt solution, at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L ammonia spirit to pH value is 9.5, and at room temperature stirring 2 hours, stand 1 hour；Sucking filtration, adds ultrasound wave with distilled water, ethanol respectively and product is washed 3 times and 2 times, vacuum drying 12 hours at 60 DEG C, in air atmosphere, and 170 DEG C of calcinations 1 hour, can be prepared by PbO/ graphene nanocomposite material, carbon content 7.8% in measuring and calculating complex.
(3) above-mentioned PbO/ graphene nanocomposite material is used to make plumbous charcoal superbattery, particularly as follows: 80wt.% Hydrocerussitum (Ceruse), 18wt.%PbO/ graphene nanocomposite material, 0.2wt.% barium sulfate, 0.4wt.% sodium lignosulfonate, 0.2wt.% acetylene black, 0.2wt.% chopped fiber and 1wt.%CMC mixing, be subsequently adding above-mentioned material gross mass 10%, 1.35g/cm3Sulphuric acid and the deionized water of above-mentioned material gross mass 10%, carry out and cream at 50～60 DEG C.
Pole plate after coating, at 30～50 DEG C, solidifies 20～30h when relative humidity 85～98%, then at 40～70 DEG C, dry 20～40h obtains raw negative plate, adopts tank formation method to obtain negative plate finished product.
Adopt above-mentioned negative plate and PbO again2Base positive plate is assembled into plumbous charcoal superbattery, and dividing plate adopts AGM dividing plate, and electrolyte adopts 1.338g/cm3Sulphuric acid.
After tested, the quality of this lead charcoal superbattery lead-acid accumulator raising 15% more existing than power ratio.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.6V;The cycle life of above-mentioned plumbous charcoal superbattery is 1.6 times of existing lead-acid accumulator.
Embodiment 2
Preparation graphene sol, preparation method is with embodiment 1, and adds 500mL, 0.25M Tetramethylammonium hydroxide, ultrasonic disperse in graphene sol, is uniformly mixed；Weighing the lead acetate of 65g in beaker, add 1.5L water, be configured to solution, then join in graphene sol by leaded solion, at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L sodium hydroxide solution to pH value is 9.0, and at room temperature stirring 2 hours, stand 1 hour；Sucking filtration, adds ultrasound wave with distilled water, ethanol respectively and product is washed 3 times and 2 times, vacuum drying 12 hours at 60 DEG C, in air atmosphere, and 160 DEG C of calcinations 1 hour, can be prepared by PbO/ graphene nanocomposite material.Carbon content 6.3% in measuring and calculating complex.
Use comprises above-mentioned PbO/ graphene nanocomposite material and makes plumbous charcoal superbattery, and manufacture method is with embodiment 1.After tested, the quality of this lead charcoal superbattery lead-acid accumulator raising 21% more existing than power ratio.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.7V;The cycle life of above-mentioned plumbous charcoal superbattery is 1.7 times of existing lead-acid accumulator.
Embodiment 3
Preparation graphene sol, preparation method is with embodiment 1, and adds 500mL, 0.25M Tetramethylammonium hydroxide, ultrasonic disperse in graphene sol, is uniformly mixed；Weighing the lead acetate of 65g in beaker, add 1.5L water, be configured to solution, then join in graphene sol by leaded solion, at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L ammonia spirit to pH value is 10.5, and at room temperature stirring 2 hours, stand 1 hour；Sucking filtration, adds ultrasound wave with distilled water, ethanol respectively and product is washed 3 times and 2 times, vacuum drying 12 hours at 60 DEG C, in air atmosphere, and 180 DEG C of calcinations 1 hour, can be prepared by PbO/ graphene nanocomposite material.Carbon content 4.8% in measuring and calculating complex.
Use comprises above-mentioned PbO/ graphene nanocomposite material and makes plumbous charcoal superbattery, and manufacture method is with embodiment 1.After tested, the quality of this lead charcoal superbattery lead-acid accumulator raising 25% more existing than power ratio.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.7V;The cycle life of above-mentioned plumbous charcoal superbattery is 1.5 times of existing lead-acid accumulator.
Embodiment 4
Preparation graphene sol, preparation method is with embodiment 1, and adds 500mL, 0.25M cetyl trimethylammonium bromide, ultrasonic disperse in graphene sol, is uniformly mixed；Weighing the lead acetate of 65g in beaker, add 1.5L water, be configured to solution, then join in graphene sol by leaded solion, at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L sodium hydroxide solution to pH value is 9.0, and at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L potassium hydroxide solution to pH value is 10.5, and at room temperature stirring 2 hours, stand 1 hour；Sucking filtration, adds ultrasound wave with distilled water, ethanol respectively and product is washed 3 times and 2 times, vacuum drying 12 hours at 60 DEG C, in air atmosphere, and 180 DEG C of calcinations 1 hour, can be prepared by PbO/ graphene nanocomposite material.Carbon content 5.8% in measuring and calculating complex.
Using above-mentioned PbO/ graphene nanocomposite material to make plumbous charcoal superbattery, manufacture method is with embodiment 1.After tested, the quality of this lead charcoal superbattery lead-acid accumulator raising 18% more existing than power ratio.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.7V;The cycle life of above-mentioned plumbous charcoal superbattery is 1.4 times of existing lead-acid accumulator.
Embodiment 5
Preparation graphene sol, preparation method is with embodiment 1, and adds 500mL, 0.25M cetyl trimethylammonium bromide, ultrasonic disperse in graphene sol, is uniformly mixed；Weighing the plumbi nitras of 66.2g in beaker, add 1.5L water, be configured to solution, add in graphene sol by leaded solion subsequently, at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L potassium hydroxide solution to pH value is 8.9, and at room temperature stirring 2 hours, stand 1 hour；Sucking filtration, adds ultrasound wave with distilled water, ethanol respectively and product is washed 3 times and 2 times, vacuum drying 12 hours at 60 DEG C, in air atmosphere, and 190 DEG C of calcinations 1 hour, can be prepared by PbO/ graphene nanocomposite material.Carbon content 5.9% in measuring and calculating complex.
Using above-mentioned PbO/ graphene nanocomposite material to make plumbous charcoal superbattery, manufacture method is with embodiment 1.After tested, the quality of this lead charcoal superbattery lead-acid accumulator raising 16% more existing than power ratio.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.7V;The cycle life of above-mentioned plumbous charcoal superbattery is 1.3 times of existing lead-acid accumulator.
Embodiment 6
Preparation graphene sol, preparation method is with embodiment 1, and adds 500mL, 0.25M cetyl trimethylammonium bromide, ultrasonic disperse in graphene sol, is uniformly mixed；Weighing the plumbi nitras of 66.2g in beaker, add 1.5L water, be configured to solution, join in graphene sol by leaded solion subsequently, at room temperature constant temperature stirs 1 hour, stands 1 hour；Under agitation instilling 1mol/L potassium hydroxide solution to pH value is 8.5, and at room temperature stirring 2 hours, stand 1 hour；Sucking filtration, adds ultrasound wave with distilled water, ethanol respectively and product is washed 3 times and 2 times, vacuum drying 12 hours at 60 DEG C, in air atmosphere, and 190 DEG C of calcinations 1 hour, can be prepared by PbO/ graphene nanocomposite material.Carbon content 6.8% in measuring and calculating complex.
Using above-mentioned PbO/ graphene nanocomposite material to make plumbous charcoal superbattery, manufacture method is with embodiment 1.After tested, the quality of this lead charcoal superbattery lead-acid accumulator raising 20% more existing than power ratio.Charge and discharge cycles in the following ways: 2C 20s → stop 10s → 1C 42s → stop 10s → 2C that charges that discharges discharges 20s, electric discharge cut-off 1.7V;The cycle life of above-mentioned plumbous charcoal superbattery is 1.5 times of existing lead-acid accumulator.
In sum, the PbO/ graphene nanocomposite material prepared by this method embodiment can realize effective combination of PbO granule and graphene film, it is possible to embodies capacitive property and the battery performance of composite more fully；This composite is as one plumbous charcoal superbattery cathode additive agent efficiently, more lead sulfate growing point is provided for plumbous charcoal superbattery negative pole, suppress the sulfation of lead-acid battery cathode in big multiplying power pulse charge and discharge process, greatly improve the big multiplying power discharging property of superbattery and extend cycle life.
The above; being only the present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, any those familiar with the art is in the technical scope of present disclosure; the change that can readily occur in or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (5)
1. the preparation method for the lead oxide/graphene nanocomposite material of plumbous charcoal superbattery, it is characterised in that described preparation method includes:
Utilize native graphite to prepare graphene sol, in described graphene sol, add certain surfactant；
Solubility lead salt is dissolved in deionized water, is configured to the leaded solion that solubility is 0.5～5mol/L；
The described leaded solion of 1L is slowly added in described graphene sol, ultrasonic 30～60min, and stand 1 hour, form stable colloidal sol；
In described colloidal sol, under agitation drip aqueous slkali, regulate the pH value of described colloidal sol to 8～14, at room temperature stir 1～2 hour, then stand 1～2 hour；
Filter solid reaction product, by described solid reaction product after deionized water and dehydrated alcohol alternate repetition wash, vacuum drying 12 hours at 60 DEG C；In air atmosphere, dried solid reaction product is calcined 1 hour at 150-200 DEG C, obtain lead oxide PbO/ graphene nanocomposite material；
Wherein, described utilize native graphite to prepare graphene sol, specifically include:
First native graphite Hummers method is prepared into graphite oxide；
Graphite oxide prepared by 50g is joined in the deionized water of 5L, after sonic oscillation a period of time, obtain yellow solution；
The hydrazine hydrate of 50mL is joined in described yellow solution, is heated to 90 DEG C, and the 24h that refluxes, graphite oxide is reduced fully, obtains graphene sol；
Further, in described PbO/ graphene nanocomposite material, the mass percentage content of PbO is 80～99.9%, and the mass percentage content of Graphene is 0.1～20%；
Wherein, each graphene film comprises 1-80 carbon atomic layer, and homogeneous scattered PbO particle is nano spherical particle, and its particle diameter is 50～1000nm.
2. according to claim 1 for the preparation method of the lead oxide/graphene nanocomposite material of plumbous charcoal superbattery, it is characterised in that described surfactant includes one or more of:
Cetyl trimethylammonium bromide, Tetramethylammonium hydroxide, dodecyl sodium sulfate and polyvinylpyrrolidone.
3. according to claim 1 for the preparation method of the lead oxide/graphene nanocomposite material of plumbous charcoal superbattery, it is characterised in that
Described solubility lead salt includes: plumbi nitras or lead acetate；
Described aqueous slkali includes: NaOH aqueous solution, KOH aqueous solution or ammonia spirit.
4. the cathode lead plaster of a plumbous charcoal superbattery, it is characterized in that, PbO/ graphene nanocomposite material, acetylene black, barium sulfate, lignin, chopped fiber, sodium carboxymethyl cellulose CMC, sulphuric acid and the water that described cathode lead plaster includes Hydrocerussitum (Ceruse), prepares such as claim 1-4 preparation method as described in one of them, wherein:
The quality of described PbO/ graphene nanocomposite material is the 0.1%～20% of described Hydrocerussitum (Ceruse) quality；The quality of described acetylene black is the 0.5%～5% of described Hydrocerussitum (Ceruse) quality；The quality of described barium sulfate is the 0.1%～2.0% of described Hydrocerussitum (Ceruse) quality；The quality of described lignin is the 0.1%～2.0% of described Hydrocerussitum (Ceruse) quality；The quality of described chopped fiber is the 0.01%～0.1% of described Hydrocerussitum (Ceruse) quality；The quality of described CMC is the 0.5%～2% of described Hydrocerussitum (Ceruse) quality；The quality of described sulphuric acid is the 4%～12% of described Hydrocerussitum (Ceruse) quality；The quality of described water is the 5%～15% of described Hydrocerussitum (Ceruse) quality；
Further, each graphene film comprises 1-80 carbon atomic layer, and homogeneous scattered PbO particle is nano spherical particle, and its particle diameter is 50～1000nm.
5. the cathode lead plaster of plumbous charcoal superbattery as claimed in claim 4, it is characterised in that described cathode lead plaster is further used for preparing the negative pole of plumbous charcoal superbattery, particularly as follows:
Being coated with to negative electrode grid by the cathode lead plaster comprising described PbO/ graphene nanocomposite material, wherein coating thickness is 1.9～2.2mm；
It is sequentially carried out solidification again and alienation processes, prepare the negative pole of plumbous charcoal superbattery.
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| CN106531972B (en) * | 2016-08-17 | 2022-07-26 | 重庆大学 | Preparation method of lead-graphene composite material for lead-carbon battery |
| CN109860531A (en) * | 2018-12-16 | 2019-06-07 | 浙江工业大学 | A kind of nanometer of lead/carbon composite preparation method and application |
| CN110212172B (en) * | 2019-05-10 | 2021-06-04 | 重庆大学 | Carbon material in-situ deposition nano-lead crystal grain/lead oxide composite material and preparation method thereof |
| CN112928261B (en) * | 2021-02-24 | 2022-08-05 | 超威电源集团有限公司 | Lead powder with lead oxide activated carbon graphene core-shell structure and preparation method thereof |
| CN113903915B (en) * | 2021-09-14 | 2023-05-09 | 浙江大学 | Preparation method of graphene-coated porous lead oxide-lead sulfide composite material |
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