CN106207131A - Accumulator Graphene/β PbO2the preparation method of nano composite material - Google Patents

Accumulator Graphene/β PbO2the preparation method of nano composite material Download PDF

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CN106207131A
CN106207131A CN201610792124.7A CN201610792124A CN106207131A CN 106207131 A CN106207131 A CN 106207131A CN 201610792124 A CN201610792124 A CN 201610792124A CN 106207131 A CN106207131 A CN 106207131A
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solution
graphene
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王自强
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Jiangsu Unionkeepower New Mateiral Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Composite Materials (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of accumulator Graphene/β PbO2The preparation method of nano composite material, comprises the steps: 1) material preparation: graphite oxide water dissolution, it is configured to solution；Preparation dissoluble lead saline solution, alkaline solution, reductant solution；2) mixed material: graphite oxide is ultrasonic, is dispersed into homogeneous graphene oxide colloid solution, then is added thereto to lead salt solution, alkaline solution, ultrasonic vibration, adds reductant solution, ultrasonic shake；3) chemical reaction: mixed solution is put into and carries out water-bath in water-bath；4) material processes: take out mixed liquor, and cooling stands, and sucking filtration rinses repeatedly, until PH is 7；Again material is put in baking oven and dry, i.e. obtain final Graphene/β PbO2Nano composite material.Preparation method of the present invention, it has the advantages such as efficiency height, environmental protection, gained Graphene/β PbO2Nano composite material homogeneity is good, and stability is high, and application prospect is extensive.

Description

Accumulator Graphene/β-PbO2The preparation method of nano composite material
Technical field
The present invention relates to accumulator Graphene/β-PbO2The preparation method of nano composite material.
Background technology
Lead-acid accumulator, is widely used in start and stop, energy storage, communication, illumination, automobile, low-speed electronic at past nearly two a century The multiple fields such as car.Because of the advantage such as its technology maturation, low cost, safety be good, the most still widely applying, China is currently the whole world Maximum lead-acid storage battery production state and maximum lead-acid accumulator consume state.
Anode plate for lead acid accumulator presents two kinds of crystal habits after chemical conversion: α-PbO2With β-PbO2, at different conditions Formed and change.Both variant structures are all that lead ion is positioned at octahedra center, but to contact with each other be to have difference to octahedron , according to many researcher the data obtaineds, the density of PbO2 crystal modification is also not quite similar, α-PbO2Density is than β-PbO2Height, α- PbO2Intercrystalline is completely embedded, better mechanical property, PbO2Intercrystalline combines more loose, and intensity is the most poor.Grind with ultramicroscope Study carefully α-PbO2With β-PbO2Crystallization shape show, α-PbO2Crystallite dimension relatively big, grain surface is smooth；And β-PbO2Crystal grain Tiny.Owing to two kinds of crystal formation crystalline particles vary in size, therefore its each gram of i.e. specific surface area of the surface area being had is the most different, and α- PbO2Than β-PbO2There is less real density.
Although the molecular formula of Lead oxide brown is written to PbO2, but researcher is it is generally believed that wherein the ratio of lead and oxygen is not 1:2, but the anoxia structure that n is less than 2, in this molecule, element ratio is not according to the situation of chemical formula ratio of integers, the most non- Stoichiometry.PbOx X < 2 event later is at PbO2Crystal there will be O2-space, O2-space and free electron can make O2-become O2.Under electric field action, electronics flows, it addition, O2O around-space2-this space can be flowed into, it is allowed to cause PbO2In have micro- Amount OH-, also produces free electron while producing the OH-of trace, makes crystal conduction increase.Free electron flows in lattice Dynamic speed compares O2-fast, and in crystal, free electronic concentration compares O2-much higher, therefore PbO2Mainly by electronic conduction, it is a kind of n Type quasiconductor.
In electrochemistry, it is identical that we are frequently encountered by chemical composition, and the material that structure is different, their oxidoreduction energy Often there is bigger difference in power, the most so-called electro-chemical activity is different.For α-PbO2With β-PbO2The difference of electro-chemical activity can To characterize by flash-over characteristic.PbO for equal number2, α-PbO2 has relatively low discharge capacity, close at different electric currents The lower electric discharge of degree, β-PbO2The capacity be given is more than α-PbO2Provide 1.5-3 times of capacity.This depends on following factors:
(1)α-PbO2Crystallizing thick, crystalline size is about 10-6m, and β-PbO2Crystallizing tiny, size is about α-PbO2's Half, therefore, α-PbO2Than β-PbO2There is less real table area
(2)α-PbO2For orthorhombic forms and PbSO4Lattice parameter similar, both belong to crystal formation of the same race.Therefore, during electric discharge α-PbO2Can serve as PbSO4Crystal seed, and form tiny sulphuric acid salt deposit, along α-PbO2Generate, then cover in α-PbO2 Surface, there is difficulty in the depths making sulphuric acid be diffused into active substance, so that electrochemical reaction only limited at active substance The degree of depth is carried out, provides the least capacity.PbSO4For tetragonal structure and PbSO4Lattice parameter difference relatively big, therefore, electric discharge is produced Thing PbSO4It is impossible to and along β-PbO2Lattice growth, or form new crystal seed, or PbSO remaining in the electrodes4In Grow up.Then, at PbSO4Between leave gap, it is allowed to sulphuric acid, by reaching inside active substance, makes β-PbO2Utilization rate is higher than α-PbO2。
Summary of the invention
It is an object of the invention to provide a kind of accumulator Graphene/β-PbO2The preparation method of nano composite material, It has the advantages such as efficiency height, environmental protection, gained Graphene/β-PbO2Nano composite material homogeneity is good, and stability is high, should Extensive by prospect.
For achieving the above object, the technical scheme is that a kind of accumulator Graphene/β-PbO of design2Nanometer is multiple The preparation method of condensation material, comprises the steps:
1) material prepares: graphite oxide water dissolution, be configured to 1～10mg/ml solution；Compound concentration be 0.01～ The dissoluble lead saline solution of 2mol/l, compound concentration is the alkaline solution of 2～20mol/l, prepares reductant solution；
2) mixed material: graphite oxide is ultrasonic, is dispersed into homogeneous graphene oxide colloid solution, then is added thereto to Lead salt solution, alkaline solution, ultrasonic vibration 5～30min, add reductant solution, ultrasonic vibration 5～30min；
3) chemical reaction: put into by mixed solution and carry out water-bath in water-bath, stirs 6～12 hours；
4) material processes: take out mixed liquor, and cooling stands 5～10 hours, and sucking filtration rinses repeatedly, until PH is 7； Again material is put in baking oven and dry, i.e. obtain final Graphene/β-PbO2Nano composite material.
Preferably, described solubility lead salt be the nitrate containing lead element, acetate, carbonate, hydrochlorate, sulfate with And one or more in complex salt.
Preferably, one or more during described alkaline solution is sodium hydroxide, sodium hydroxide and strong aqua ammonia.
Preferably, one or more during described reductant solution is hydrogen peroxide, sodium peroxydisulfate solution and company's hydrazine etc..
Preferably, the dispersion liquid of described graphite oxide comes to be purchased with market, ultrasonic 2 hours, and is placed in frozen water In carry out.
Preferably, during water-bath, temperature controls between 60 DEG C-90 DEG C, is incubated 6～12 hours.
Preferably, in flushing process, repeatedly rinse with deionized water, then sucking filtration, the most repeatedly, until PH is equal to 7.
Preferably, the rotating speed of described stirring is 100～800r/min.
Preferably, graphene film grown a large amount of β-PbO2, it being mainly distributed on the edge of lamellar, mean diameter is 2 ～50 μm.
Advantages of the present invention and having the beneficial effects that: a kind of accumulator Graphene/β-PbO is provided2Nano composite material Preparation method, it has the advantages such as efficiency height, environmental protection, gained Graphene/β-PbO2Nano composite material homogeneity is good, Stability is high, and application prospect is extensive.
The present invention provides a kind of brand-new anode plate for lead acid accumulator preparation method, obtains dynamical positive plate, improves The utilization ratio of lead.Realized by following approach:
1, using Graphene as skeleton, β-PbO is supported2, to improve pole plate monolithic conductive performance；
2, by chemical synthesis beam system for β-PbO2；
3, Graphene is aoxidized, prepare graphene oxide mother solution, as preparation β-PbO2Base soln, make Graphene with β-PbO2The most compound；
In order to reach above-mentioned requirements simultaneously, inventor devises preferable material structure.Graphene is aoxidized, is allowed to surface With substantial amounts of oxygen-containing functional group, it is greatly increased its water solublity, is configured to colloid.Subsequently this kind of colloid is combined with saline solution, Make the solute in saline solution with graphene oxide colloid by electrostatical binding formation Graphene and the complex of inorganic salt, then pass through Oxidoreduction, pickling, separation, lyophilizing, sintering etc. process and obtain final composite.
Through fully experiment, techniques below means can obtain the material of design: is aoxidized by Graphene, is configured to homogeneous Colloid, then obtain final composite through process such as oxidization-reduction, pickling, separation, lyophilizing, sintering.This composite is mixed Electrode active material is made in conjunction, wherein β-PbO2Accounting for 90%-95%, Graphene accounts for 5%-10%.
Graphene/β-PbO2Unique structure of composite and performance are to ensure that the reason of superbattery performance.Specifically Ground is said, composite has good electric conductivity, structural stability and single high capacity characteristics.
Structurally, this composite is by high conductivity, high-specific surface area and the Graphene of stability and β-PbO2Material Material composition, wherein nanometer β-PbO2The weight ratio of material is 90%-95%.Through structural analysis, described Graphene/β-PbO2 Composite exists a small amount of α-PbO2, but content is little, after making battery, through repeatedly charge and discharge cycles, α-PbO2 It is automatically converted to β-PbO2。
Graphene/β-PbO2The preparation method of composite, is made up of the following steps: solubilized lead salt is configured to water-soluble Liquid, the molar concentration of lead is more than 0.1M until saturated solution.Graphene oxide colloid is joined in leaded middle solution, then In the case of water-bath, carry out redox reaction, then cool down, stand, wash, filter, be dried, obtain Graphene/β-PbO2Compound Material.
Described solubility lead salt is the source of lead in product material, for the nitrate containing lead element, acetate, carbonic acid One or more of salt, hydrochlorate, sulfate and complex salt.The presoma of these lead, because of dissolubility, ionization property, electronegativity Difference, the performance of product can be affected.By the adjustment to composition of raw materials, can optimize product structure further and performance.
Graphene oxide colloid derives from graphite oxide, through ultrasonic disperse, obtains Graphene colloid.Dispersion liquid oxidation stone Ink concentration is 1-3mg/ml, and variable concentrations graphite oxide solution eventually affects Graphene/β-PbO2Composite covered effect.
After above two raw material is compound, obtain Graphene/β-PbO2Composite, wherein β-PbO2Account for composite wood of the present invention The 90～95% of material gross weight.
The lead carbon composite obtained by above-mentioned technique, as lead-acid battery positive electrode, compared to the prior art, has Advantages below:
1, the utilization rate of lead is improved.Traditional lead acid batteries positive plate, through chemical conversion, is α-PbO2 and β-PbO2 Biphase combination, wherein α-PbO2The electric capacity of few quantity is provided, so causes substantial amounts of lead to be wasted.And Graphene/β-PbO2Multiple Only β-PbO in condensation material2, it is greatly improved the utilization ratio of lead.
2, lead-acid accumulator whole volume is improved.In traditional lead acid batteries positive plate, α-PbO2With β-PbO2Deposit simultaneously , pole plate monolithic conductive is poor, causes power reservoir capacity to decline, and Graphene/β-PbO2Composite, as the stone of skeleton character Ink alkene electric conductivity is strong, and the electric conductivity of the whole positive plate being greatly enhanced improves power reservoir capacity；On the other hand, more traditional positive pole For plate, composite provides the β-PbO of capacitance characteristic2Content is greatly improved, and improves battery capacity greatly.
3, energy-conserving and environment-protective.Traditional lead acid batteries positive plate way includes, refining lead, pours that molding, lead pig be broken, lead powder Broken, oxidation and cream, be dried, solidify, the operation such as chemical conversion, this serial procedures is the process of a highly energy-consuming high pollution, especially Lead discharges, and pollutes soil property and water quality greatly.And Graphene/β-PbO2Composite preparation process is to carry out in the solution, only Having the water-bath less than 100 DEG C, greatly reduce energy consumption, and eliminate chemical synthesis technology, powder is directly and cream is fabricated to battery, rule Keep away a series of complex process, additionally, efficiency is high, there is not situation of arranging outside lead simultaneously, protect water and soil greatly.
The present invention has a characteristic that
1, positive plate directly can prepare positive electrode material Lead oxide brown by the method for chemosynthesis, gets around tradition chemical conversion Link, reduces energy consumption.
2, battery positive plate electrode material is Graphene and β-PbO2Composite, on the one hand, Graphene formed lead Electric network improves the monolithic conductive of pole plate, on the other hand, high capacitance β-PbO2α after replacement tradition process chemical conversion- PbO2, improve the service efficiency of battery lead, improve pole plate specific capacity.
3, positive electrode material, Graphene/β-PbO2Composite, oxidized reduction bonding forms；Wherein, Hydrocerussitum (Ceruse) accounts for 91%～99.5%, Graphene accounts for 0.5～9%.
4, accumulator Graphene/β-PbO2Composite, relatively through positive plate, the lamellar of interlinkage obtained by tradition chemical conversion Graphene plays skeleton function, greatly improves pole plate monolithic conductive；And as carbon skeleton, replace the tradition ripe pole of positive pole Low capacity α-PbO in plate2Effect, increase high power capacity β-PbO2Content, improve overall plate active material utilization rate.
5, Graphene/β-PbO2Composite is to utilize graphite oxide and lead salt to be composited through oxidization-reduction, is not Simple mechanical mixture, this composite biphase, nonmetal graphite alkene and metal-oxide β-PbO2Between exist bonding Effect, is therefore evenly distributed, and is firmly combined with.
6, Graphene forms skeleton conductive network, supports the β-PbO of high capacitance characteristic2。
Accompanying drawing explanation
Fig. 1 is Graphene of the present invention/β-PbO2The XRD figure of composite；
Fig. 2 is Graphene of the present invention/β-PbO2The SEM figure of composite；
Fig. 3 is Graphene of the present invention/β-PbO2The TEM figure of composite；
Fig. 4 is Graphene of the present invention/β-PbO2The electrode constant current charge-discharge curve of composite.
Detailed description of the invention
Below in conjunction with the accompanying drawings and embodiment, the detailed description of the invention of the present invention is further described.Following example are only For technical scheme is clearly described, and can not limit the scope of the invention with this.
The present invention provides a kind of accumulator Graphene/β-PbO2The preparation method of nano composite material, including walking as follows Rapid:
1) material prepares: graphite oxide water dissolution, be configured to 1～10mg/ml solution；Compound concentration be 0.01～ The dissoluble lead saline solution of 2mol/l, compound concentration is the alkaline solution of 2～20mol/l, prepares reductant solution；
2) mixed material: graphite oxide is ultrasonic, is dispersed into homogeneous graphene oxide colloid solution, then is added thereto to Lead salt solution, alkaline solution, ultrasonic vibration 5～30min, add reductant solution, ultrasonic vibration 5～30min；
3) chemical reaction: put into by mixed solution and carry out water-bath in water-bath, stirs 6～12 hours；
4) material processes: take out mixed liquor, and cooling stands 5～10 hours, and sucking filtration rinses repeatedly, until PH is 7； Again material is put in baking oven and dry, i.e. obtain final Graphene/β-PbO2Nano composite material.
Preferably, described solubility lead salt be the nitrate containing lead element, acetate, carbonate, hydrochlorate, sulfate with And one or more in complex salt.
Preferably, one or more during described alkaline solution is sodium hydroxide, sodium hydroxide and strong aqua ammonia.
Preferably, one or more during described reductant solution is hydrogen peroxide, sodium peroxydisulfate solution and company's hydrazine etc..
Preferably, the dispersion liquid of described graphite oxide comes to be purchased with market, ultrasonic 2 hours, and is placed in frozen water In carry out.
Preferably, during water-bath, temperature controls between 60 DEG C-90 DEG C, is incubated 6～12 hours.
Preferably, in flushing process, repeatedly rinse with deionized water, then sucking filtration, the most repeatedly, until PH is equal to 7.
Preferably, the rotating speed of described stirring is 100～800r/min.
Preferably, graphene film grown a large amount of β-PbO2, it being mainly distributed on the edge of lamellar, mean diameter is 2 ～50 μm.
Reference example is as follows:
Embodiment 1
Configuration lead acetate water solution, concentration is 0.1M, adds the Graphene colloid that concentration is 1mg/ml.Solution and material with carbon element Weight ratio 85:15.Mixing suspension stirring in water bath 7 hours, cooling, static, wash, filter.Do under 80 DEG C of air conditionses Dry, obtain lead/carbon composite.
Embodiment 2
Configuration plumbi nitras aqueous solution, concentration is 0.1M, adds the Graphene colloid that concentration is 2mg/ml.Solution and material with carbon element Weight ratio 85:15.Mixing suspension stirring in water bath 7 hours, cooling, static, wash, filter.Do under 80 DEG C of air conditionses Dry, obtain lead/carbon composite.
Embodiment 3
Configuration plumbi nitras aqueous solution, concentration is 0.1M, adds the Graphene colloid that concentration is 3mg/ml.Solution and material with carbon element Weight ratio 85:15.Mixing suspension stirring in water bath 7 hours, cooling, static, wash, filter.Do under 80 DEG C of air conditionses Dry, obtain lead/carbon composite.
Embodiment 4
Compound is spray-dried at 100～200 DEG C, prepares the mean diameter micro powder granule in 5～100 μm, by institute The modified carbonaceous components obtained is fully ground, and i.e. prepares accumulator lead/carbon composite.Then, by the Pb/C composite of preparation As positive plate material, carry out lead plaster and system.The lead plaster obtained is coated to anode plate grid again, manufactures super accumulator positive pole Plate.
Test result:
As it is shown in figure 1, the XRD diffracting diagram of this material reveals β-PbO2, faint α-PbO2Characteristic peaks, the non-spy of carbon Levy peak, illustrate that the material of preparation is conductive carbon material and PbO2Material is combined into entirety.
As shown in Figures 2 and 3, this material microstructure is flake graphite alkene coating beta-PbO2, β-PbO simultaneously2It is more prone to growth In the edge zone of flake graphite alkene, also there is internal cladding situation simultaneously.
By embodiment 4 method, after being respectively prepared half lead carbon battery, carry out capacity check to judge that its active substance utilizes Rate, as shown in Figure 4.Lead carbon battery shows the discharge performance better than conventional lead acid battery.Normal plate active substance utilizes Rate is 30%, graphene coated β-PbO2Active material utilization is 40-45%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For Yuan, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvements and modifications, these improvements and modifications Also should be regarded as protection scope of the present invention.

Claims (9)

1. accumulator Graphene/β-PbO2The preparation method of nano composite material, it is characterised in that comprise the steps:
1) material prepares: graphite oxide water dissolution, be configured to 1～10mg/ml solution；Compound concentration is 0.01～2mol/l Dissoluble lead saline solution, compound concentration is the alkaline solution of 2～20mol/l, prepare reductant solution；
2) mixed material: graphite oxide is ultrasonic, is dispersed into homogeneous graphene oxide colloid solution, then is added thereto to lead salt Solution, alkaline solution, ultrasonic vibration 5～30min, add reductant solution, ultrasonic vibration 5～30min；
3) chemical reaction: put into by mixed solution and carry out water-bath in water-bath, stirs 6～12 hours；
4) material processes: take out mixed liquor, and cooling stands 5～10 hours, and sucking filtration rinses repeatedly, until PH is 7；Again will Material is put in baking oven and is dried, and i.e. obtains final Graphene/β-PbO2Nano composite material.
Accumulator Graphene/β-PbO the most according to claim 12The preparation method of nano composite material, its feature exists In, described solubility lead salt is in the nitrate containing lead element, acetate, carbonate, hydrochlorate, sulfate and complex salt One or more.
Accumulator Graphene/β-PbO the most according to claim 22The preparation method of nano composite material, its feature exists In, described alkaline solution is one or more in sodium hydroxide, sodium hydroxide and strong aqua ammonia.
Accumulator Graphene/β-PbO the most according to claim 32The preparation method of nano composite material, its feature exists In, described reductant solution is one or more in hydrogen peroxide, sodium peroxydisulfate solution and company's hydrazine etc..
Accumulator Graphene/β-PbO the most according to claim 42The preparation method of nano composite material, its feature exists In, the dispersion liquid of described graphite oxide comes to be purchased with market, ultrasonic 2 hours, and is placed in frozen water and carries out.
Accumulator Graphene/β-PbO the most according to claim 52The preparation method of nano composite material, its feature exists In, during water-bath, temperature controls between 60 DEG C-90 DEG C, is incubated 6～12 hours.
Accumulator Graphene/β-PbO the most according to claim 62The preparation method of nano composite material, its feature exists In, in flushing process, repeatedly rinse with deionized water, then sucking filtration, the most repeatedly, until PH is equal to 7.
Accumulator Graphene/β-PbO the most according to claim 72The preparation method of nano composite material, its feature exists In, the rotating speed of described stirring is 100～800r/min.
Accumulator Graphene/β-PbO the most according to claim 82The preparation method of nano composite material, its feature exists In, graphene film grown a large amount of β-PbO2, it being mainly distributed on the edge of lamellar, mean diameter is 2～50 μm.
CN201610792124.7A 2016-08-31 2016-08-31 Accumulator Graphene/β PbO2the preparation method of nano composite material Withdrawn CN106207131A (en)

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CN108425132A (en) * 2018-02-11 2018-08-21 中氧科技（广州）有限公司 A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate
CN108886174A (en) * 2016-03-30 2018-11-23 日立化成株式会社 Lead storage battery, ultralight hybrid car and idling system vehicle
CN109970155A (en) * 2019-01-28 2019-07-05 中南大学 A kind of preparation method of graphene oxide modification lead dioxide electrode
CN114276850A (en) * 2021-12-24 2022-04-05 安徽工业大学 Fluorine-doped graphene-loaded Pb composite material and preparation method and application thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108886174A (en) * 2016-03-30 2018-11-23 日立化成株式会社 Lead storage battery, ultralight hybrid car and idling system vehicle
CN108425132A (en) * 2018-02-11 2018-08-21 中氧科技（广州）有限公司 A kind of preparation method of ozone electrolytic cell anode catalyst diaphragm plate
CN109970155A (en) * 2019-01-28 2019-07-05 中南大学 A kind of preparation method of graphene oxide modification lead dioxide electrode
CN109970155B (en) * 2019-01-28 2022-01-04 中南大学 Preparation method of lead dioxide electrode modified by graphene oxide
CN114276850A (en) * 2021-12-24 2022-04-05 安徽工业大学 Fluorine-doped graphene-loaded Pb composite material and preparation method and application thereof
CN114276850B (en) * 2021-12-24 2023-02-07 安徽工业大学 Fluorine-doped graphene-loaded Pb composite material and preparation method and application thereof

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