CN110416502A - OMC/ sponge Pb sandwich lead plaster and its preparation method and application - Google Patents
OMC/ sponge Pb sandwich lead plaster and its preparation method and application Download PDFInfo
- Publication number
- CN110416502A CN110416502A CN201910564703.XA CN201910564703A CN110416502A CN 110416502 A CN110416502 A CN 110416502A CN 201910564703 A CN201910564703 A CN 201910564703A CN 110416502 A CN110416502 A CN 110416502A
- Authority
- CN
- China
- Prior art keywords
- omc
- sponge
- lead
- lead plaster
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/06—Lead-acid accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—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
- H01M4/48—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of OMC/ sponge Pb sandwich lead plaster and its preparation method and application；Preparation method includes the following steps: to be passivated moditied processing to OMC using hydrogen peroxide, obtains hydrophilic OMC；Hydrophilic OMC is configured as OMC dispersion liquid using deionized water；Wherein, the hydrophilic OMC and the mass ratio of the deionized water are 1:2000 to 1:3500；OMC dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, mixture is obtained；Sulfuric acid is added into mixture, carries out mechanical stirring and is mixed with to obtain OMC/ sponge Pb sandwich lead plaster.It is uniformly mixed in this way, being able to achieve OMC with lead powder, and can guarantee that negative OMC/ sponge Pb composite material applies the stability of cream and the binding ability of pole plate and lead plaster.
Description
Technical field
This application involves electrochemical technology field, more particularly to a kind of OMC/ sponge Pb sandwich lead plaster and its
Preparation method and application.
Background technique
By advantages such as low cost, technology maturations, be successfully applied to communication, electric car etc. is traditional lead acid batteries
System is a kind of energy-storage battery for meeting CHINESE INDUSTRIES layout and manufacture level.However, traditional lead acid batteries that there are specific energies is small,
The disadvantages of service life cycle is short is not able to satisfy demand of the modern society to long-life, high-capacity battery, the electrification of electrode material
Learning property has important influence to the performance of lead-acid battery, and has the negative electrode material of same status type in practical applications with Pb
Seldom, progress is slow.The lead plaster preparation method of traditional carbon material modified electrode is that carbon material and lead powder are mixed,
It adds water and sulfuric acid prepares lead plaster, in the lead plaster being prepared, the dispersion for being easy to appear carbon material is uneven, is thus made
The cathode of standby lead-acid battery be easy to cause pole plate local energy density relatively low.Ordered mesopore carbon (ordered mesoporous
Carbon, OMC), from the researcher by Mobil Oil Corporation (Mobil Oil Corporation) in 1992 report for the first time to
The present has rapidly become a new research hotspot, and has obtained biggish progress in some fields.Therefore, how OMC and lead to be improved
The uniformity of powder mixed process realizes that OMC forms uniform conductive network structure inside lead plaster, is carbon material modified electrode
Lead plaster prepares the serious problem faced.
Summary of the invention
Based on this, it is necessary to which providing one kind can make carbon material be distributed more uniform OMC/ sponge Pb sandwich
Lead plaster and its preparation method and application.
A kind of preparation method of OMC/ sponge Pb sandwich lead plaster, includes the following steps:
Moditied processing is passivated to OMC using hydrogen peroxide, obtains hydrophilic OMC；
Hydrophilic OMC is configured as OMC dispersion liquid using deionized water；Wherein, the hydrophilic OMC with it is described
The mass ratio of deionized water is 1:2000 to 1:3500；
OMC dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, mixture is obtained；
Sulfuric acid is added into mixture, carries out mechanical stirring and is mixed with to obtain OMC/ sponge Pb sandwich lead
Cream.
The density for the sulfuric acid being added in one of the embodiments, is 1.325 ± 0.01g/ml.
The mass ratio of the sulfuric acid and the lead powder is 0.1:1 to 0.12:1 in one of the embodiments,.
It is carried out at a temperature of the mechanical stirring is blended in 40 degrees Celsius to 70 degrees Celsius in one of the embodiments,.
It is carried out at a temperature of the mechanical stirring is blended in 65 degrees Celsius in one of the embodiments,.
The time of the mechanical stirring mixing is 20 minutes to 25 minutes in one of the embodiments,.
Described mix OMC dispersion liquid to 0.11:1 with lead powder 0.1:1 in mass ratio is stirred in one of the embodiments,
It mixes, obtains mixture, specifically:
OMC dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, and bonding material is added, is mixed
Close object.
The bonding material is staple fiber in one of the embodiments,.
A kind of OMC/ sponge Pb sandwich lead plaster, it is multiple using OMC/ sponge Pb described in any embodiment as above
The preparation method for closing structural material lead plaster is prepared.
Negative electrode active of the OMC/ sponge Pb sandwich lead plaster described in any embodiment as above in lead-acid battery
Application in material.
The preparation method of above-mentioned OMC/ sponge Pb sandwich lead plaster, is passivated modification to hydrophobic OMC first
Processing, obtains hydrophilic OMC；Will by Passivation modified, treated that OMC is mixed with deionized water, obtain uniform OMC and divide
Dispersion liquid；The OMC dispersion liquid and lead powder that are prepared are mixed again, so, it is possible to greatly improve OMC mixed with lead powder it is uniform
Property.This hybrid technology is able to achieve OMC and uniformly mixes with lead powder, and can guarantee that negative OMC/ sponge Pb composite material applies the steady of cream
The binding ability of solidity and pole plate and lead plaster is conducive to form OMC conductive network structure inside lead plaster, so as to improve
Its conductivity.
Compared with prior art, the present invention having the advantage that (1) OMC by surface passivation moditied processing, make to hate originally
Water and with inert OMC become it is hydrophilic and have certain chemical activity, be allowed to more easily disperse in deionized water, obtain
Uniform OMC dispersion liquid；(2) the lead plaster preparation method of traditional carbon material modified electrode is to mix carbon material with lead powder to stir
It mixes, adds water and sulfuric acid prepares lead plaster, the dispersion that will lead to carbon material in this way is uneven, causes pole plate local energy density inclined
It is low.The present invention preferentially prepares uniform OMC dispersion liquid, then OMC and lead powder are mixed, and finally mixes again with sulfuric acid.This mixing
Technology can be realized OMC and uniformly mix with lead powder, and can guarantee negative OMC/ sponge Pb composite material apply cream stability and
The binding ability of pole plate and lead plaster is conducive to form OMC conductive network structure inside lead plaster.
Detailed description of the invention
Fig. 1 a is H2O2(10%) Fourier transform infrared spectroscopy of surface treatment front and back ordered mesopore carbon (OMC)；
Fig. 1 b is H2O2(10%) Raman spectrogram of surface treatment front and back ordered mesopore carbon (OMC)；
Fig. 1 c is H2O2(10%) the low angle XRD diagram of surface treatment front and back ordered mesopore carbon (OMC)；
Fig. 2 a is scanning electron microscope (SEM) figure of hydrophilic OMC sample；
Fig. 2 b is transmission electron microscope (TEM) figure of hydrophilic OMC sample；
Fig. 3 is the schematic diagram for the conductive network structure that hydrophilic OMC is formed inside sponge Pb；
Fig. 4 is the carbon distribution map of OMC/ sponge Pb sandwich lead plaster；
Fig. 5 is the lead element distribution map of OMC/ sponge Pb sandwich lead plaster；
Fig. 6 is the electron-transport schematic diagram inside lead-acid battery；
Fig. 7 a is the lead element distribution map of OMC/ sponge Pb composite construction electrode (after loop test)；
Fig. 7 b is the element sulphur distribution map of OMC/ sponge Pb composite construction electrode (after loop test)；
Fig. 8 a is the lead element distribution map of traditional negative electrode material sponge Pb electrode (after loop test)；
Fig. 8 b is the element sulphur distribution map of traditional negative electrode material sponge Pb electrode (after loop test).
Specific embodiment
The application in order to facilitate understanding, in order to make the above objects, features, and advantages of the present application more apparent, under
Face is described in detail in conjunction with specific embodiment of the attached drawing to the application.It is explained in the following description many details
In order to fully understand the application, the better embodiment of the application is given in attached drawing.But the application can be with many not
With form realize, however it is not limited to embodiments described herein.On the contrary, the purpose of providing these embodiments is that making
Disclosure of this application is understood more thorough and comprehensive.The application can be to be much different from other way described herein
Implement, those skilled in the art can do similar improvement without prejudice to the application intension, therefore the application not by
The limitation of following public specific embodiment.Unless otherwise defined, all technical and scientific terms used herein and category
It is identical in the normally understood meaning of those skilled in the art of the application.Term used herein is intended merely to describe
The purpose of specific embodiment, it is not intended that in limitation the application.Term " and or " used herein includes one or more
Any and all combinations of a relevant listed item.
The application provides a kind of surface passivation moditied processing method of ordered mesopore carbon first.
It should be noted that existing OMC itself be hydrophobic and have it is inert so that its answering in some fields
With being restricted.Therefore, surface passivation moditied processing need to be carried out to OMC, OMC is made to become hydrophilic and has certain chemistry living
Property.Traditional carbon material surface Passivation modified processing method be using 80% concentrated nitric acid under 80 DEG C of hot conditions in carbon material
Oxidation reaction occurs for surface.This method the problem is that: concentrated nitric acid under the high temperature conditions be easy to volatilization cause concentration to change,
So that technical process is not easy to control, and will cause environmental pollution after doing nitric acid volatilization, the feature of environmental protection is poor, is also good for operator
Kang Buli.
In order to enable OMC has hydrophily, the surface passivation moditied processing method of ordered mesopore carbon includes the following steps:
Hydrogen peroxide and ordered mesopore carbon are mixed, is passivated and repairs under 55 degrees Celsius to 70 degrees Celsius of preset temperature
Decorations reaction, is prepared hydrophilic ordered mesopore carbon.
In the present embodiment, modification is passivated to ordered mesopore carbon by using the hydrogen peroxide with strong oxidizing property；
Reaction can be completed under more mild 55 degrees Celsius to 70 degrees Celsius of preset temperature in reaction, can greatly improve orderly Jie
The oxygen-containing group concentration of hole carbon surface, the presence of these oxygen-containing groups can improve the contact angle between electrolyte and electrode material,
Make script hydrophobic and becomes hydrophilic with inert OMC and there is certain chemical activity.The present invention is compared with traditional technology, tool
Have following advantage: (1) hydrogen peroxide cost of material is low and from a wealth of sources, not will cause energy waste；(2) reaction condition is mild,
Reaction temperature is only 55 degrees Celsius to 70 degrees Celsius, and technical process is easy to control safely；(3) by-product of surface passivation modification reaction
Object is oxygen, realizes zero waste gas emission, is not necessarily to subsequent supervision, maintenance cost.Hydrogen peroxide is relative to concentrated nitric acid, and hydrogen peroxide is not
Volatile, to volatilization gas is not likely to produce in the Passivation modified reaction process of OMC, smaller to environmental hazard, the feature of environmental protection is preferable.
The preset temperature is 60 degrees Celsius to 65 degrees Celsius in one of the embodiments,；It is described blunt in one embodiment
The reaction time for changing modification reaction is 2 hours to 4 hours.It so, it is possible preferably to be passivated modification reaction.One wherein
In embodiment, the hydrogen peroxide is the hydrogenperoxide steam generator that mass fraction is 10%.In this way, 10% hydrogenperoxide steam generator is former
Material is easy to get, and cost of material is low and from a wealth of sources, not will cause energy waste.
In order to improve the hydrophily of ordered mesopore carbon, in one of the embodiments, the hydrogenperoxide steam generator with it is described
The mass ratio of ordered mesopore carbon is 50:1 to 100:1.It so, it is possible the hydrophily for preferably improving ordered mesopore carbon.By Shen
It asks someone the study found that hydrophily is limited when the mass ratio of hydrogenperoxide steam generator and the ordered mesopore carbon is lower than 50:1, into
And its application is limited to a certain extent, cannot not especially have preferably applied in the negative electrode material of lead-acid battery
Conducive to absorption fixed electrolyte molecule.And when the mass ratio of hydrogenperoxide steam generator and the ordered mesopore carbon is 50:1 or more
When, there can be preferable hydrophily, and then be applied in the negative electrode material of lead-acid battery, can preferably adsorb solid
Electrolyte molecule is determined, so as to improve the specific surface utilization rate of cathode.And when hydrogenperoxide steam generator and the ordered mesopore carbon
Mass ratio be greater than 100:1 when, hydrogenperoxide steam generator is limited to the performance improvement of ordered mesopore carbon, will cause hydrogenperoxide steam generator
Waste.And when the mass ratio of the hydrogenperoxide steam generator and the ordered mesopore carbon is 50:1 to 100:1, it is more suitable
Preferably, the hydrophily that can preferably improve ordered mesopore carbon, is conducive to apply it in the negative electrode material of lead-acid battery, can
Fixed electrolyte molecule is preferably adsorbed, so as to improve the specific surface utilization rate of cathode, and then can be used in improving plumbic acid
The service life of battery.In one preferred embodiment, the mass ratio of the hydrogenperoxide steam generator and the ordered mesopore carbon is 40:1.
By applicants have found that, by being 40:1 by the mass ratio of the hydrogenperoxide steam generator and the ordered mesopore carbon, by it
When being subsequently applied in the negative electrode material of lead-acid battery, the raising in capacitance and service life can be realized, while improving electrode structure
Stability, so that material is adapted to big strain without causing material volume to expand, avoid material failure.
In one of the embodiments, in Passivation modified response lag, the surface passivation moditied processing method further includes
Following steps: the mixture obtained after Passivation modified reaction is carried out filtering operation and drying operation, is obtained described hydrophilic
Ordered mesopore carbon.The drying temperature of the drying operation is 55 degrees Celsius to 60 degrees Celsius in one of the embodiments,.Such as
This, can preferably carry out drying operation.In one of the embodiments, before carrying out the drying operation, the surface
Passivation modified processing method further includes following steps: being washed, and repeated with deionized water to the solid matter that operation obtains is filtered
Operation is filtered, until the water lotion of solid matter is neutrality.It so, it is possible so that being in acid hydrophilic ordered mesopore carbon
It is neutral.
The surface passivation moditied processing method of above-mentioned ordered mesopore carbon is come by using the hydrogen peroxide with strong oxidizing property
Modification is passivated to ordered mesopore carbon；Reaction can be complete under more mild 55 degrees Celsius to 70 degrees Celsius of preset temperature
At reaction, the oxygen-containing group concentration of order mesoporous carbon surface can be greatly improved, the presence of these oxygen-containing groups can improve electrolysis
Contact angle between liquid and electrode material makes script hydrophobic and becomes hydrophilic with inert OMC and have certain chemistry living
Property.The present invention has the advantage that (1) hydrogen peroxide cost of material is low and from a wealth of sources, not will cause compared with traditional technology
Energy waste；(2) reaction condition is mild, and reaction temperature is only 55 degrees Celsius to 70 degrees Celsius, and technical process is easy to control safely；
(3) by-product of surface passivation modification reaction is oxygen, realizes zero waste gas emission, is not necessarily to subsequent supervision, maintenance cost.Peroxidating
For hydrogen relative to concentrated nitric acid, hydrogen peroxide is not volatile, right to being not likely to produce volatilization gas in the Passivation modified reaction process of OMC
Environmental hazard is smaller, and the feature of environmental protection is preferable.
The application also provides a kind of hydrophilic ordered mesopore carbon, using ordered mesopore carbon described in any implementation as above
Surface passivation moditied processing method be prepared.
Hydrophilic ordered mesopore carbon in the application any embodiment as above is in the negative electrode active material of lead-acid battery
Application.Specifically, referring to hydrophilic OMC and cathode sponge Pb is compound, the OMC/ sponge Pb for preparing special construction type is multiple
Condensation material.
It should be noted that applicant in order to improve the service life and charging capacity of lead-acid battery, attempts OMC and negative
Pole sponge Pb is compound, prepares the OMC/ sponge Pb composite material of special construction type., it is understood that due to OMC conductive mesh
Network structure, can play the synergistic effect of OMC Yu sponge Pb, increase reaction contact surface, thus improve charge and discharge invertibity and
Kinetics, to realize the raising of capacitance and service life.But OMC itself is hydrophobic and has inert, this hydrophobicity
Matter make OMC as OMC/ sponge Pb combination electrode raw material it is difficult to ensure that OMC/ sponge Pb composite material apply cream stability with
And the binding ability of pole plate and lead plaster.And the hydrophobic and inertia of OMC is formed inside lead plaster since siphonic effect will lead to
OMC conductive network structure feature is not conducive to adsorb fixed electrolyte molecule, to reduce the ratio of OMC/ sponge Pb combination electrode
Surface utilisation.Therefore, in the present embodiment, hydrophilic have by will pass through that the processing of hydrogen peroxide Passivation modified is prepared
Sequence mesoporous carbon makes it have preferable hydrophily, by hydrophilic OMC in conjunction with sponge Pb after, can guarantee OMC/ sponge
Pb composite material applies the stability of cream, and is conducive to adsorb fixed electrolyte molecule, and then it is compound to can be improved OMC/ sponge Pb
The specific surface utilization rate of electrode, so as to improve the service life and capacity of lead-acid battery.
In order to which the hydrophilicity further to above-mentioned hydrophilic ordered mesopore carbon is illustrated.It is given below one specifically
Embodiment.
Embodiment 1
The OMC of 50g is added to the H that the mass fraction of 2000ml is 10%2O2In solution, and stirring is accompanied by, reacts 2h,
Reaction temperature is 60 DEG C.Reactant is cooled to room temperature after reaction, removes upper layer clear solution, obtained suspension is centrifuged 3 times,
Suction filtration is washed repeatedly using deionized water to being in neutrality, being placed in drying box 60 DEG C, drying to constant weight；It obtains hydrophilic orderly
Mesoporous carbon.
Following method is respectively adopted in the characterizing method of OMC: (1) winning vertical leaf transformation infrared spectroscopy (FT-IR, Nicolet
6700) functional group of sample is characterized；(2) laser Raman spectrometer (Raman, Dilor LABRAM-1B microscopic) table
Levy the structure change of sample；(3) the crystal phase composition of X diffractometer (XRD, Philips XPert pro MPD) characterization sample；(4)
The surface topography of scanning electron microscope (SEM, JSM-7500F) characterization sample；(5) transmission electron microscope (TEM, Tecnai
G2F20S-Twin microscopic appearance and lattice form) are characterized.As a result as follows:
(1) with the functional group of rich vertical leaf transformation infrared spectroscopy (FT-IR, Nicolet 6700) characterization OMC.Fig. 1 a is OMC
By H2O2It is surface-treated the Fourier Transform Infrared Spectroscopy (FT-IR) of front and back.The figure shows OMC in Passivation Treatment front surface
Oxygen-containing functional group content is seldom, in 3438cm-1The broad band at place is due to-OH stretching vibration, 1576cm-1The bands of a spectrum at place are
Due to C=O carbon skeleton stretching vibration, and 1137cm-1The sharp bands of a spectrum at place are the stretching vibrations due to C-O.OMC is after Passivation Treatment
FT-IR figure show that the position of its aforementioned vibration peak does not have significant change, but its intensity obviously increases, and shows its surface oxygen-containing group
Group's concentration greatly improves, this is because H2O2Oxidation reaction has occurred with the surface OMC.The presence of these oxygen-containing groups can improve electricity
The contact angle between liquid and electrode material is solved, script hydrophobic is made and becomes hydrophilic with inert OMC and there is certain chemistry
Activity.
(2) structure of laser Raman spectrometer (Raman, Dilor LABRAM-1B microscopic) characterization OMC becomes
Change.Fig. 1 b is that OMC passes through H2O2It is surface-treated the Raman map of front and back.As seen from the figure, in 1320cm-1And 1580cm-1At left and right
There are two apparent absorption peaks, Raman line is more smooth, and the spectral line integral strength after Passivation Treatment is lower.Wherein,
1580cm-1The absorption peak (peak G) at place is the characteristic absorption peak of the graphite-structure sp2 hydridization of high-sequential, and 1320cm-1Place
Absorption peak (peak D) is the characteristic absorption peak of amorphous carbon.With the ratio between the halfwidth at the peak D and the peak G in Raman spectrum R (R=ID/IG)
The degree of graphitization of sample is evaluated, the relative intensity (ID/IG) at two peaks is higher to show that the degree of disorder is higher, the lower theory of relative intensity
Bright degree of graphitization is higher.For OMC after surface passivating treatment, ID/IG value is reduced to 1.06 by 1.11, shows its defect and nothing
Sequenceization is reduced to a certain extent.Since the power of the electric conductivity of carbon material depends on its degree of graphitization, so H2O2Surface
The degree of graphitization of OMC can be improved in processing, to improve its conductivity.It is possible thereby to see, H2O2Modification is passivated to OMC
After processing, additionally it is possible to improve the conductivity of OMC.
(3) crystalline substance of X diffractometer (XRD, Philips XPert pro MPD) the characterization resulting hydrophilic OMC of embodiment
Phase composition.Fig. 1 c is that OMC sample passes through H2O2It is surface-treated the low angle XRD diagram of front and back.Before OMC passes through Passivation Treatment, diffraction pattern exists
There is an obvious diffraction maximum at 2 θ=0.95 °, this is that the hexagonal mesoporous structural material of two dimension corresponds to Hexagonal lattice
(100) characteristic diffraction peak of crystal face.OMC passes through H2O2After surface treatment, two is increased newly at 1.68 ° and 2.23 ° and weaker have spread out
Peak is penetrated, corresponds respectively to (110) and (200) crystal face, and the diffraction maximum at 2 θ=0.95 ° becomes more sharp.This shows
OMC has hexagonal mesoporous (Hexagonal) structure of two dimension of high-sequential, belongs to P6mm space group.Above analysis shows, H2O2
Surface treatment can also improve its hydrophily and electric conductivity while keeping mesoporous material OMC order to a certain extent.
(4) the surface shape of scanning electron microscope (SEM, JSM-7500F) the characterization resulting hydrophilic OMC of embodiment 1
Looks.Fig. 2 a is that the SEM of hydrophilic OMC sample schemes.Vermiform pattern shows OMC specific surface area with higher and controllable knot
Structure, these structure features are conducive to adsorb fixed electrolyte.
(5) transmission electron microscope (TEM, Tecnai G2F20S-Twin) the characterization resulting hydrophilic OMC's of embodiment 1 is microcosmic
Pattern and lattice form.Fig. 2 b is that the TEM of OMC sample schemes.Order mesoporous hole is clearly seen in the TEM figure of OMC (100) crystal face
Road structure.Wherein, blackstreak represents mesoporous wall, and white stripes represent mesopore orbit.The mesopore orbit marshalling of OMC,
Two-dimentional hexagonal mesoporous structure and uniform pore-size distribution with high-sequential, pore-size distribution is mainly in 5~6nm.
From the above, it can be seen that the application is passivated moditied processing to OMC by using hydrogen peroxide, can preferably mention
The hydrophily and electric conductivity of high OMC, additionally it is possible to keep the vermiform pattern and ordered mesoporous pore canals structure of OMC, and then be conducive to
In the subsequent negative electrode material for applying it to lead-acid battery, the contact area with electrolyte is improved, is conducive to adsorb electrolyte, into
And it can be improved the service life and battery capacity of lead-acid battery.
The application continues with the cathode for being applied to lead-acid battery to the hydrophilic OMC being prepared in any implementation as above
Application in active material is explained.More specifically, hydrophilic OMC is mixed with lead powder to prepare lead plaster, in other words,
For OMC/ sponge Pb sandwich lead plaster.
It should be noted that the negative electrode active material of traditional lead-acid battery is mainly spongy lead (Pb), existing for it
Key problem is that the sulfation of spongy lead (referred to as sponge Pb).Incorporated by reference to Fig. 6, under high-multiplying power discharge mode,
HSO4 -With the supply mismatch of sponge Pb, a part of irreversible conversion reaction occur leads to PbSO4Nucleation rate is too fast, generation
PbSO4It is covered on negative electrode active material surface and forms irreversible SEI (Solid electrolyte interface, solid
Electrolyte interface) passivating film, the bulky grain PbSO of Surface Creation4Stack layer significantly reduces electronics transfer rate and effecting reaction table
Area, and material part volume expansion can be caused.So that the sulfation of sponge Pb cannot be by ideal situation negative
Extremely internal uniform generation, or the velvet-like PbSO that fine uniform is easy reduction is only generated on surface4, so that in negative plate
Portion's active material cannot leak active site cruelly, and subsequent reactions are more difficult, influence electrochemical process, and then influence the use of battery
And the service life.And in charging, because of PbSO4It itself is electrically inactive, conductive capability is poor, and shear stress can only be leaned on to go back oxidation
Original matter is as PbSO4The exotic matter of film pulls in film, and the charge transfer of electrode interior is by ion or electroactive particle
Diffusion and adjacent redox center transfer and carry out, such charge need to pass through PbSO4Film passes to internal sea again
Continuous Pb.Because of surface PbSO4Layer hinders the generation of lead-acid battery bulk reaction, and the bias for being applied to cathode at this time leads to liberation of hydrogen
It reacts (hydrogen-evolution reaction, HER) to occur, causes concentration of electrolyte to change, vicious circle is further led
Cause reduced performance, the lost of life of battery performance.Therefore, surface PbSO4Layer can hinder electrolyte in the effective of the surface sponge Pb
Infiltration, causes specific surface area utilization rate very low, so that electrolyte and interelectrode electronics transfer are hindered, to electrochemical reaction mistake
Charge in journey has transmitted inhibiting effect.The disadvantages of traditional lead acid batteries specific energy is small, service life cycle is short is not able to satisfy existing
Demand of the generation society to long-life, high-capacity battery, the performance of the electrochemistry confrontation lead-acid battery of electrode material has important
It influences, and has the negative electrode material of same status with Pb type is seldom in practical applications, progress is slow.
Ordered mesopore carbon is reported so far from the researcher by Mobil Oil Corporation in 1992, for the first time since it is orderly
Cellular structure, high ratio pore volume, big specific surface area and adsorption capacity, low-resistivity and high electron mobility and chemical inertness
Deng there is it in numerous areas such as absorption, chemical sensor, catalyst carrier, energy storage and new function composite materials
Potential application value.With glass carbon, fullerene, even compared with carbon nanotube, ordered mesopore carbon CMK-3 can be mentioned ordered mesopore carbon
For faster electron transfer rate, to reduce the overpotential of electrode polarization and electrochemical reaction.Such as with the glass carbon electricity of OMC modification
Pole (OMCs/GCE) helps to strengthen the oxidation reaction of Ractopamine, is remarkably improved its electro-chemical activity, and certain
It can reduce the oxidation overpotential of phenolic substances in degree, improve current-responsive.In view of the good adsorptivity of OMC, electric conductivity and
Storage/release electronic capability, this kind of material can effectively improve the absorption and chemical reaction in mesoporous, and catalysis is promoted to react crucial base
The charge transfer effciency of first step, and then strengthen corresponding chemical reaction process significantly.
Based on this, the application attempts to be applied to OMC in the negative electrode active material of lead-acid battery.However, due to traditional
Common OMC has stronger hydrophobicity and is inert in itself, so that it is restricted in some applications.Therefore, it needs
Surface passivation moditied processing is carried out to OMC.In such as preceding description, applicant is passivated OMC by using hydrogen peroxide
Moditied processing, and then hydrophilic OMC has been obtained, and the preparation process for obtaining hydrophilic OMC is more mild.However, traditional
The lead plaster preparation method of carbon material modified electrode be that carbon material and lead powder are mixed, add water and sulfuric acid prepare lead
Cream, in the lead plaster being prepared, the dispersion for being easy to appear carbon material is uneven, and the cathode for thus being prepared lead-acid battery is easy
Cause pole plate local energy density relatively low.
In order to keep carbon material distribution more uniform, this application provides a kind of preparation methods of lead plaster, more specifically,
This application provides a kind of preparation methods of OMC/ sponge Pb sandwich lead plaster.It should be noted that the application provides
OMC/ sponge Pb sandwich lead plaster preparation method, it is main using as preceding any as described in the examples order mesoporous
Carbon is raw material, or it is also understood that as described in preceding any implementation ordered mesopore carbon is used to be prepared for raw material
OMC/ sponge Pb sandwich lead plaster, and apply it in the negative electrode active material of lead-acid battery.For example, as preceding any
Application of the hydrophilic ordered mesopore carbon as described in the examples in the negative electrode active material of lead-acid battery, including by hydrophily
Ordered mesopore carbon be used to OMC/ sponge Pb sandwich lead plaster is prepared, wherein by hydrophilic ordered mesopore carbon
It is specially a kind of OMC/ sponge Pb sandwich lead plaster for OMC/ sponge Pb sandwich lead plaster is prepared
Preparation method.
In one embodiment, a kind of preparation method of OMC/ sponge Pb sandwich lead plaster includes the following steps: to use
Hydrogen peroxide is passivated moditied processing to OMC, obtains hydrophilic OMC；Hydrophilic OMC is configured to using deionized water
For OMC dispersion liquid；Wherein, the hydrophilic OMC and the mass ratio of the deionized water are 1:2000 to 1:3500；By OMC
Dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, and obtain mixture；Sulfuric acid is added into mixture, carries out
Mechanical stirring is mixed with to obtain OMC/ sponge Pb sandwich lead plaster.
In order to further illustrate the preparation method of above-mentioned OMC/ sponge Pb sandwich lead plaster, another example is,
The preparation method of OMC/ sponge Pb sandwich lead plaster includes the following steps:
S110: moditied processing is passivated to OMC using hydrogen peroxide, obtains hydrophilic OMC；
Hydrophilic OMC how is obtained, the surface passivation such as preceding any ordered mesopore carbon as described in the examples is please referred to
Moditied processing method.Details are not described herein for the present embodiment.
S120: hydrophilic OMC is configured as OMC dispersion liquid using deionized water；Wherein, the hydrophilic OMC
Mass ratio with the deionized water is 1:2000 to 1:3500；
In the present embodiment, hydrophilic OMC is configured as by OMC dispersion liquid using deionized water, water can be reduced
The influence of ion or impurity to OMC.By being 1:2000 to 1 by the mass ratio of hydrophilic OMC and the deionized water:
3500, it so, it is possible that OMC dispersion liquid is preferably prepared.
In one preferable implementation, during hydrophilic OMC is configured as OMC dispersion liquid using deionized water, companion is gone back
There is stirring operation, for example, mixing time is 30 points to 60 minutes.For another example, it is normal for being configured as the configuration temperature of OMC dispersion liquid
Temperature.For example, room temperature is 25 ± 5 DEG C；OMC dispersion liquid is prepared with so, it is possible, and dispersion liquid is more uniform.
S130: OMC dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, mixture is obtained；
In order to improve the binding force of hydrophilic OMC and lead powder, one implements, described OMC dispersion liquid and lead powder are pressed matter
Amount is mixed than 0.1:1 to 0.11:1, obtains mixture, specifically: extremely by OMC dispersion liquid and lead powder 0.1:1 in mass ratio
0.11:1 is mixed, and bonding material is added, and obtains mixture.In this way, can be improved hydrophilic by the way that binder is added
The binding force of OMC and lead powder.For example, the binder is water-soluble carboxymethyl cellulose, polyvinyl alcohol, starch, staple fiber
And dextrin etc..Preferably, the binder is staple fiber.It so, it is possible the combination for preferably improving hydrophilic OMC and lead powder
Power.For another example, the additional amount of the binder is 0.014%-0.02%, that is, its mass percent in the mixture is
0.014%-0.02% so, it is possible the binding force for preferably improving hydrophilic OMC and lead powder.For another example, for example, 1000kg
The staple fiber of 150g to 200g is added in mixture.
S140: sulfuric acid being added into mixture, carries out mechanical stirring and is mixed with to obtain OMC/ sponge Pb composite construction material
Expect lead plaster.
In the present embodiment, by the way that sulfuric acid is added into mixture, mechanical stirring mixing is carried out, OMC/ sponge is prepared
Pb sandwich lead plaster.In this way, the preparation method of OMC/ sponge Pb sandwich lead plaster provided by the present application, first
Moditied processing is passivated to hydrophobic OMC, obtains hydrophilic OMC；The OMC being prepared and lead powder are mixed again, in turn
The uniformity that OMC is mixed with lead powder can be greatly improved.This hybrid technology is able to achieve OMC and uniformly mixes with lead powder, and can
Guarantee that negative OMC/ sponge Pb composite material applies the stability of cream and the binding ability of pole plate and lead plaster, is conducive to inside lead plaster
OMC conductive network structure is formed, so as to improve its conductivity.It should be noted that traditional carbon material modified electrode
Lead plaster preparation method is that carbon material and lead powder are mixed, and adds water and sulfuric acid prepares lead plaster, will lead to carbon material in this way
Dispersion it is uneven, cause pole plate local energy density relatively low.The present invention preferentially prepares uniform OMC dispersion liquid, especially makes
It is standby to obtain the OMC dispersion liquid of hydrophilic OMC, then OMC and lead powder are mixed.This hybrid technology can be realized OMC and lead powder
Uniformly mixing, and can guarantee that negative OMC/ sponge Pb composite material applies the stability of cream and the binding ability of pole plate and lead plaster,
Be conducive to form OMC conductive network structure inside lead plaster.The OMC/ sponge Pb sandwich being prepared in this implementation
The apparent density of lead plaster is 4.25~4.3g/cm3。
In one embodiment, the density of the sulfuric acid of addition is 1.325 ± 0.01g/ml.It is described in one of the embodiments,
The mass ratio of sulfuric acid and the lead powder is 0.1:1 to 0.12:1.It so, it is possible that OMC/ sponge Pb composite junction is preferably prepared
Structure material lead plaster.At a temperature of the mechanical stirring is blended in 40 degrees Celsius to 70 degrees Celsius in one of the embodiments, into
Row.It so, it is possible preferably to carry out mechanical stirring hybrid manipulation, be conducive to preferably generate OMC/ sponge Pb sandwich
Lead plaster, and OMC is enabled to uniformly to mix with lead powder, and can guarantee negative OMC/ sponge Pb composite material apply the stability of cream with
And the binding ability of pole plate and lead plaster, be conducive to form OMC conductive network structure inside lead plaster.For example, the mechanical stirring
It is carried out at a temperature of being blended in 65 degrees Celsius.For example, the time of the mechanical stirring mixing is 20 minutes to 25 minutes, in this way,
It can preferably mechanical stirring mix, be conducive to that OMC/ sponge Pb sandwich lead plaster is prepared.
The preparation method of above-mentioned OMC/ sponge Pb sandwich lead plaster, is passivated modification to hydrophobic OMC first
Processing, obtains hydrophilic OMC；The OMC being prepared and lead powder are mixed again, so, it is possible to greatly improve OMC and lead powder is mixed
The uniformity of conjunction.This hybrid technology is able to achieve OMC and uniformly mixes with lead powder, and can guarantee negative OMC/ sponge Pb composite material
The stability of cream and the binding ability of pole plate and lead plaster are applied, is conducive to form OMC conductive network structure inside lead plaster, thus
It can be improved its conductivity.
Compared with prior art, the present invention having the advantage that (1) OMC by surface passivation moditied processing, make to hate originally
Water and with inert OMC become it is hydrophilic and have certain chemical activity, be allowed to more easily disperse in deionized water, obtain
Uniform OMC dispersion liquid；(2) the lead plaster preparation method of traditional carbon material modified electrode is to mix carbon material with lead powder to stir
It mixes, adds water and sulfuric acid prepares lead plaster, the dispersion that will lead to carbon material in this way is uneven, and the lead plaster being prepared is used to prepare
After negative plates, it be easy to cause pole plate local energy density relatively low.The present invention preferentially prepares uniform OMC dispersion liquid, then by OMC
It is mixed with lead powder.This hybrid technology can be realized OMC and uniformly mix with lead powder, and can guarantee negative OMC/ sponge Pb composite wood
Material applies the stability of cream and the binding ability of pole plate and lead plaster, is conducive to form OMC conductive network structure inside lead plaster.
The present invention also provides a kind of OMC/ sponge Pb sandwich lead plasters, using described in any implementation as above
The preparation method of OMC/ sponge Pb sandwich lead plaster is prepared.
Negative electrode active material of the OMC/ sponge Pb sandwich lead plaster described in any implementation as above in lead-acid battery
Application in material.More specifically, negative electrode active material of the OMC/ sponge Pb sandwich lead plaster in lead-acid battery
In application specifically: OMC/ sponge Pb sandwich lead plaster is used to prepare to the cathode of lead-acid battery, is conducive to improve
The local energy density of negative plates, and then be conducive to improve the service life and battery capacity of lead-acid battery.
The OMC/ being prepared in order to further illustrate the preparation method of above-mentioned OMC/ sponge Pb sandwich lead plaster
Sponge Pb sandwich lead plaster.It continues with and provides a specific embodiment and continue to be explained.
Embodiment 2
It weighs the hydrophilic OMC being prepared in 50g embodiment 1 to be added in the deionized water of 100kg, in room temperature 25
30min is stirred at DEG C obtains uniform OMC dispersion liquid.
OMC dispersion liquid is added in paste mixing machine and is mixed with 1000kg lead powder, mixture is obtained.In order to realize OMC
It is uniformly mixed with lead powder, and can guarantee that negative OMC/ sponge Pb composite material lead plaster applies the stability of cream, the knot of pole plate and lead plaster
Conjunction ability, is added bonding material staple fiber in OMC dispersion liquid and lead powder mixing process, and additional amount is the whole of mixture
The 0.015% of weight.
Into the mixture of the OMC and lead powder that mix, the sulfuric acid that 100kg density is 1.325g/ml and stirring is added
20min, reaction temperature are controlled at 65 DEG C, obtained OMC/ sponge Pb composite material lead plaster, apparent density 4.28g/cm3。
Using the surface-element distribution of EDS mapping (JSM-7500F) characterization OMC/ sponge Pb composite material lead plaster.Figure
4 and Fig. 5 is the distribution diagram of element of OMC/ sponge Pb sandwich lead plaster, and wherein Fig. 4 is the distribution of carbon, and Fig. 5 is point of Pb
Cloth.As can be seen that Pb element almost covers whole region, the distributed areas of C element are wider, and opposite with the distribution of Pb element
It answers.It is possible thereby to confirm, what the preparation method of OMC/ sponge Pb sandwich lead plaster provided by the present application was prepared
OMC/ sponge Pb sandwich lead plaster, can greatly improve the uniformity that OMC is mixed with lead powder.This hybrid technology can be real
Existing OMC is uniformly mixed with lead powder, and can guarantee the stability and pole plate and lead plaster of negative OMC/ sponge Pb composite material painting cream
Binding ability, be conducive to form OMC conductive network structure inside lead plaster, referring to Fig. 3, it is forms inside lead plaster
The schematic diagram of OMC conductive network structure, to improve its conductivity.It should be noted that Fig. 3's forms OMC inside lead plaster
The schematic diagram of conductive network structure, predominantly 1 experimental result and experimental result Fig. 4 and Fig. 5 of this implementation are pushed away in conjunction with the embodiments
Export.
The preparation method of OMC/ sponge Pb sandwich lead plaster of the invention compared with prior art, has following excellent
Gesture: (1) OMC passes through surface passivation moditied processing, makes script hydrophobic and becomes hydrophilic with inert OMC and have certain change
Activity is learned, is allowed to more easily disperse in deionized water, obtains uniform OMC dispersion liquid；(2) traditional carbon material modified electrode
Lead plaster preparation method be that carbon material and lead powder are mixed, add water and sulfuric acid prepare lead plaster, will lead to carbon materials in this way
The dispersion of material is uneven, causes pole plate local energy density relatively low.The present invention preferentially prepares uniform OMC dispersion liquid, then by OMC
It is mixed with lead powder.This hybrid technology can be realized OMC and uniformly mix with lead powder, and can guarantee negative OMC/ sponge Pb composite wood
Material applies the stability of cream and the binding ability of pole plate and lead plaster, is conducive to form OMC conductive network structure inside lead plaster.
The present invention continues to attempt to for OMC/ sponge Pb sandwich lead plaster described in any implementation as above being applied to
In the negative electrode active material of lead-acid battery.
The present invention also provides a kind of OMC base composite negative pole, the OMC/ sponge in any embodiment as above is used
Pb sandwich lead plaster is prepared.In other words, the composite construction material of OMC/ sponge Pb described in any embodiment as above
Material lead plaster is used to prepare to obtain OMC base composite negative pole.
In one implementation, the OMC based combined electrode includes negative electrode grid and OMC/ sponge Pb sandwich lead plaster, is incited somebody to action
OMC/ sponge Pb sandwich lead plaster is coated on negative electrode grid, and the OMC base Compound Negative is made after cured and dry
Pole.
Specifically, OMC/ sponge Pb sandwich lead plaster is coated on negative electrode grid, can all be coated with；Or
It is coated in regional area, and other regions are coated with traditional common lead-acid battery negative pole plate lead plaster, the regional area refers to
A region or more than two regions in the upper and lower, left and right of negative electrode grid and intermediate and corner；Or first coating OMC/ is extra large
After continuous Pb sandwich lead plaster, traditional common plumbic acid is coated in the appearance of OMC/ sponge Pb sandwich lead plaster
Accumulator negative plate lead plaster；Or it is first coated with traditional common lead-acid battery negative pole plate lead plaster, and in traditional common plumbic acid
The appearance of accumulator negative plate lead plaster is coated OMC/ sponge Pb sandwich lead plaster；Either traditional common plumbic acid stores
Cell negative plate lead plaster replaces coating with OMC/ sponge Pb sandwich lead plaster multilayer.Preferably, complete on negative electrode grid
Portion is coated with the OMC/ sponge Pb sandwich lead plaster in as above any implementation.For example, the OMC/ sponge Pb composite construction
The apparent density range of material lead plaster is 4.25~4.3g/cm3, in other words, by the view of OMC/ sponge Pb sandwich lead plaster
Density domination is in 4.25~4.3g/cm3。
In one embodiment, the material of the negative electrode grid is pure lead, alternatively, the material of the negative electrode grid is the conjunction of polynary lead
Gold.For example, in the multicomponent lead alloy in addition to Element Lead also comprising in Elements C a, As, Sn, S, Al, Sb, Bi, Si at least
A kind of element.For example, the negative electrode grid can be common casting grid, or lead foil punching grid can also be punching
Cut seine grid, the grid that lead fabric plate or other cathode can use.
Above-mentioned OMC base composite negative pole is passed through by the way that OMC/ sponge Pb sandwich lead plaster to be coated on negative electrode grid
The OMC base composite negative pole is made after solidification and drying；Wherein, OMC/ sponge Pb sandwich lead plaster, by first modifying
OMC makes it have hydrophily, then preferentially prepares uniform OMC dispersion liquid, then OMC and lead powder are mixed, finally mixed with sulfuric acid again
It closes.This hybrid technology can be realized OMC and uniformly mix with lead powder, and can guarantee that negative OMC/ sponge Pb composite material applies cream
The binding ability of stability and pole plate and lead plaster is conducive to form OMC conductive network structure inside lead plaster, by OMC/ sponge
It after Pb sandwich lead plaster is coated on negative electrode grid, is confirmed through follow-up test, is conducive to the specific volume for improving lead-acid battery
Amount and service life.It is above-mentioned to blend both traditional lead acid batteries negative electrode and supercapacitors technology, both have battery spy
Property energy advantage but also with double layer capacitor instantaneous power large capacity charging characteristic, thus improve conventional lead acid electricity
The specific capacity in pond and service life.
The synergistic effect between OMC and sponge Pb is based on the principle that (1) compares greatly table using OMC it has been confirmed by experiments that
Area, the gas for accelerating to be precipitated during electro-catalysis speed away electrode surface, electrode stability energy；(2) OMC has a large amount of
Faceted pebble defect changes the band structure of sponge Pb electrode as dopant, electrode is made to show different characteristic of semiconductor；(3)
There is provided chain carrier by OMC: multilayered structure OMC is that electrode and electrolyte contacts interface increase more haptoreaction sites,
These carbon particles form uniform mass transfer network structure in electrode interior, promote electrochemical reaction uniform in electrode surface, inside
It carries out, to mitigate PbSO4Concentration on surface is precipitated, and buffers pole plate Study of Volume Expansion in charge and discharge process；(4)OMC
With compound band curvature and the electrochemical active surface for improving electrode and electrolyte liquor and electrode surface of cathode sponge Pb, electrode is reduced
Process impedance reduces charge in the accumulation of electrode surface, accelerates alternate transfer of the electronics from electrolyte to electrode surface and in electricity
Extremely internal transmission reduces electrode polarization degree, strengthens electrode process；(5) OMC improves active material point as dissimilar materials
It dissipates, improves active material utilization, inhibit surface PbSO4Particle growth, it is suppressed that the volume change in charge and discharge process, it is dual
Structure feature postpones material failure；(6) it is adjusted by the electronic structure to sponge Pb electrode, to catalyst surface reactant
Combination can be carried out optimization, form difunctional composite negative pole, the intermediate and repository by OMC as electronics transfer, and adjusting
Control the Interface Electronic States between carrier and active sites, strengthening electronic toward activated centre transfer, to promote entire catalytic process；
(7) OMC base energy-storage battery is during high power charging-discharging, mainly by the OMC material release with capacitance characteristic/reception electricity
Son, OMC play buffer function, improve charge acceptance and high rate during charging-discharging；When battery low current work when,
Mainly energy is persistently provided by sponge Pb.
OMC/ sponge Pb composite construction electrode of the invention, i.e. OMC base composite negative pole and traditional negative electrode material sponge Pb electricity
Pole is compared, and is had the advantage that
1, OMC has biggish specific surface area, Kong Rong and controlled architecture, these structure features are conducive to adsorb stationary electrolysis
Liquid molecule is conducive to the transmission and absorption of electrolyte ion, specific surface utilization rate is improved, to improve the electrochemical capacitor of electrode
Performance enhances the electrochemical properties of electrode.
2, the vector charge transfer effect of OMC, charge is in the internal transmission of electrode, electrolyte and OMC table during HER
The alternate processes such as pass through in face are reinforced, and are improved the activated centre density of electro-catalysis process, are reduced the polarization journey of electrochemical process
Degree.
3, OMC has excellent thermal stability, the high-velocity electrons mobility not being affected by temperature, thermal expansion coefficient small and machine
The features such as chemical stability, shows the great advantage as thermoelectric material.OMC/ sponge Pb combines the two advantage, high temperature
Cycle performance is accelerated to improve.
4, in view of the good adsorptivity of OMC and storage/release electronic capability, this kind of material can effectively improve the suction in mesoporous
Chemical reaction is echoed, promotes catalysis to react the charge transfer effciency of crucial primitive step, then improves cycle life.
5, OMC/ sponge Pb composite material generates electronics: the electrochemical oxidation reactions on the surface sponge Pb by two kinds of approach
(Pb+HSO4 -→PbSO4+2e+H+) generate electronics.Charge transport layer and electrochemical reaction interface of the OMC as sponge Pb, In
The surface OMC occurs anode reaction and generates electronics.The electronics that two kinds of approach generate converges, and the electronics for substantially increasing electrode interior is dense
Degree can effectively facilitate the charge transfer effciency that crucial primitive step is reacted in catalysis, then greatly improve reaction rate.Promote catalysis
The charge transfer effciency for reacting crucial primitive step, promotes kinetics.
6, OMC has preferable electron propagation ducts as charge-conduction carrier, strengthens the electrochemical reaction of electrode surface
With electrolyte/electrode surface two-phase interface electric charge transfer, the ability enhancing of electronics is conducted.In charge and discharge process, charge is first
Into the sp of OMC2In the carbon atom of track, accelerate charge-discharge velocity, reduce the diffusional resistance between electrode and electrolyte, increases
The storage capacity of charge improves battery portion state-of-charge, to improve the capacitance of electrode material.
7, OMC is added and inhibits negative electrode volume variation in charge and discharge process, to improve the effective of electrode surface and electrolyte
Contact area, specific surface area needed for providing reaction and electric double layer capacitance, promote electrolyte permeability to the efficiency of electrode interior.
8, the biggish specific surface area of OMC is conducive to the contact and diffusion of electrolyte, and is conducive to yin during electro-catalysis
The hydrogen that pole is precipitated speeds away the surface of electrode, improves the stability of electrode.
The present invention also provides a kind of lead-acid accumulators, including OMC base composite negative pole described in any implementation as above.Example
Such as, the lead-acid accumulator includes multiple negative plates, wherein at least one piece in multiple negative plates is any implementation as above
OMC base composite negative pole described in example.Preferably, when with multiple negative plates, the whole in multiple negative plates is as above
OMC base composite negative pole described in any embodiment.It should be noted that the positive plate of lead-acid accumulator, partition, electrolyte
Deng refer to the prior art, and details are not described herein by the application.
Continue with provide specific embodiment come to the application OMC base composite negative pole and lead-acid accumulator be explained.
Embodiment 3
The negative plate of machine coated plate preparation: the apparent density that embodiment 2 is prepared is 4.28g/cm3OMC/ sponge Pb
Composite material lead plaster is to prepare OMC base composite negative pole, and in other words, OMC base composite negative pole is OMC/ sponge Pb combination electrode.Its
In, OMC/ sponge Pb composite material lead plaster is all coated on negative electrode grid, negative electrode grid size are as follows: 68mm × 44mm ×
1.7mm, using calcium content 0.09%, the lead-calcium-tin alloy of Theil indices 0.3% is made.Certainly, the tab part of negative electrode grid is then
Without coating.The negative electrode grid of coated sponge Pb composite material lead plaster is lasting to solidify under the conditions of 60 DEG C, humidity 85-95%
24 hours；Then it under conditions of 60 DEG C, humidity are less than 50%, continues drying out and negative plate is made within 24 hours, as OMC base is compound
Cathode.By the combination electrode after carrying out tank formation, surface does not have carbon material precipitation, and it is existing grid dilatancy do not occur
As.
The OMC/ sponge Pb combination electrode being prepared is assembled into lead-acid accumulator.
Comparative example
One comparative example is provided simultaneously, uses traditional negative electrode material sponge Pb electrode assembling at lead acid storage battery in comparative example
Pond.
The lead-acid accumulator that will implement 3 and comparative example is carried out charge acceptance, cycle life detection, is studied with this
The electrochemical properties of combination electrode.The standard of the main foundation of test is GB/T 19639.1-2014.The test knot of embodiment 3
Fruit are as follows: charge acceptance Ica >=3 of battery, cycle life 50%DOD are greater than 600 times.And the test result of comparative example are as follows:
Charge acceptance Ica >=2.4 of battery, cycle life 50%DOD are 480 times.It can thus be seen that provided by the present application
OMC base composite negative pole can be improved specific capacity and the service life of traditional lead acid batteries.
The table of OMC/ sponge Pb composite construction electrode after characterizing loop test using EDS mapping (JSM-7500F)
Surface element distribution.Fig. 7 a and Fig. 7 b are the distribution diagram of element of OMC/ sponge Pb composite construction electrode (after loop test).Pb element
Distributed areas it is wider, and the distributed areas of S element are diluter, and the distributed areas of Pb element can cover S element.Illustrate S and Pb member
Element is combined together, and illustrates that S, Pb element are combined together to form a small amount of PbSO4, Pb element is largely with the shape of sponge Pb
Formula exists.
EDS mapping (JSM-7500F) characterizes the surface element of traditional negative electrode material sponge Pb electrode after loop test
Element distribution.Fig. 8 a and Fig. 8 b are the distribution diagram of element of traditional negative electrode material sponge Pb electrode (after loop test).S and Pb element
Distributed areas are relatively wide and distribution is almost the same, and the distributed areas of Pb element can cover S element, illustrate that S, Pb element are combined together
Form a large amount of PbSO4.There is many places aggregation in the distributed areas of S and Pb element, the cathode material after further illustrating loop test
Expect that sponge Pb electrode surface forms bulky grain PbSO4Stack layer.
Through the foregoing embodiment 3 and comparative example can be seen that OMC base composite negative pole provided by the present application, be applied to plumbic acid electricity
Chi Hou can reduce bulky grain PbSO4The formation of stack layer.
Above-mentioned OMC base composite negative pole is passed through by the way that OMC/ sponge Pb sandwich lead plaster to be coated on negative electrode grid
The OMC base composite negative pole is made after solidification and drying；Wherein, OMC/ sponge Pb sandwich lead plaster, by first modifying
OMC makes it have hydrophily, then preferentially prepares uniform OMC dispersion liquid, then OMC and lead powder are mixed, finally mixed with sulfuric acid again
It closes.This hybrid technology can be realized OMC and uniformly mix with lead powder, and can guarantee that negative OMC/ sponge Pb composite material applies cream
The binding ability of stability and pole plate and lead plaster is conducive to form OMC conductive network structure inside lead plaster, by OMC/ sponge
It after Pb sandwich lead plaster is coated on negative electrode grid, is confirmed through follow-up test, is conducive to the specific volume for improving lead-acid battery
Amount and service life.It is above-mentioned to blend both traditional lead acid batteries negative electrode and supercapacitors technology, both have battery spy
Property energy advantage but also with double layer capacitor instantaneous power large capacity charging characteristic, thus improve conventional lead acid electricity
The specific capacity in pond and service life.
The present invention is compound by OMC and cathode sponge Pb, prepares the OMC/ sponge Pb composite material of special construction type, assembling
At OMC base energy-storage battery, the synergistic effect of OMC and sponge Pb are played, improves the contact area of sponge Pb and electrolyte, is increased anti-
Contact surface is answered, the invertibity and kinetics of charge and discharge are improved, to realize the raising of capacitance and service life.Electrode is improved simultaneously
The stability of structure makes material adapt to big strain without causing material volume to expand, avoids material failure.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.It should be noted that " in an embodiment ", " example of the application
Such as ", " for another example ", it is intended to the application is illustrated, rather than for limiting the application.Embodiment described above only table
The several embodiments of the application are reached, the description thereof is more specific and detailed, and but it cannot be understood as to applying for a patent
The limitation of range.It should be pointed out that for those of ordinary skill in the art, in the premise for not departing from the application design
Under, various modifications and improvements can be made, these belong to the protection scope of the application.Therefore, the protection of the application patent
Range should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of OMC/ sponge Pb sandwich lead plaster, which comprises the steps of:
Moditied processing is passivated to OMC using hydrogen peroxide, obtains hydrophilic OMC；
Hydrophilic OMC is configured as OMC dispersion liquid using deionized water；Wherein, the hydrophilic OMC and it is described go from
The mass ratio of sub- water is 1:2000 to 1:3500；
OMC dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, mixture is obtained；
Sulfuric acid is added into mixture, carries out mechanical stirring and is mixed with to obtain OMC/ sponge Pb sandwich lead plaster.
2. preparation method according to claim 1, which is characterized in that the density of the sulfuric acid of addition is 1.325 ± 0.01g/
ml。
3. preparation method according to claim 2, which is characterized in that the mass ratio of the sulfuric acid and the lead powder is 0.1:
1 to 0.12:1.
4. preparation method according to claim 1, which is characterized in that the mechanical stirring is blended in 40 degrees Celsius to 70 and takes the photograph
It is carried out at a temperature of family name's degree.
5. the preparation method according to claim 4, which is characterized in that the mechanical stirring is blended in 65 degrees Celsius of temperature
Lower progress.
6. the preparation method according to claim 4, which is characterized in that the time of mechanical stirring mixing be 20 minutes extremely
25 minutes.
7. preparation method according to claim 1, which is characterized in that it is described by OMC dispersion liquid and lead powder in mass ratio
0.1:1 to 0.11:1 is mixed, and obtains mixture, specifically:
OMC dispersion liquid and lead powder 0.1:1 in mass ratio to 0.11:1 are mixed, and bonding material is added, obtains mixture.
8. preparation method according to claim 7, which is characterized in that the bonding material is staple fiber.
9. a kind of OMC/ sponge Pb sandwich lead plaster, which is characterized in that using such as institute in any one of claim 1 to 8
The preparation method for the OMC/ sponge Pb sandwich lead plaster stated is prepared.
10. OMC/ sponge Pb sandwich lead plaster as claimed in claim 9 is in the negative electrode active material of lead-acid battery
Application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910564703.XA CN110416502A (en) | 2019-06-27 | 2019-06-27 | OMC/ sponge Pb sandwich lead plaster and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910564703.XA CN110416502A (en) | 2019-06-27 | 2019-06-27 | OMC/ sponge Pb sandwich lead plaster and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110416502A true CN110416502A (en) | 2019-11-05 |
Family
ID=68358377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910564703.XA Pending CN110416502A (en) | 2019-06-27 | 2019-06-27 | OMC/ sponge Pb sandwich lead plaster and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110416502A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111816847A (en) * | 2020-07-08 | 2020-10-23 | 肇庆理士电源技术有限公司 | Lead paste for preparing positive plate and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282918A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Li-air battery negative electrode, Li-air battery and Li-air battery electrode preparation method |
| CN105024046A (en) * | 2015-07-31 | 2015-11-04 | 湘潭大学 | Preparation method of lead-carbon battery cathode |
| CN108743960A (en) * | 2018-07-04 | 2018-11-06 | 中国人民解放军第二军医大学第二附属医院 | A kind of mesoporous carbon nanoparticle and its application |
| CN109081325A (en) * | 2018-08-10 | 2018-12-25 | 湖南大学 | A kind of preparation method of carbon material |
| CN109390561A (en) * | 2018-09-27 | 2019-02-26 | 泉州市凯鹰电源电器有限公司 | A kind of lead negative and preparation method thereof of graphene lead carbon battery |
| CN109585806A (en) * | 2018-11-02 | 2019-04-05 | 双登集团股份有限公司 | Lead carbon capacitor batteries are rich in active material cathode lead plaster formula and preparation method |
-
2019
- 2019-06-27 CN CN201910564703.XA patent/CN110416502A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104282918A (en) * | 2013-07-02 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Li-air battery negative electrode, Li-air battery and Li-air battery electrode preparation method |
| CN105024046A (en) * | 2015-07-31 | 2015-11-04 | 湘潭大学 | Preparation method of lead-carbon battery cathode |
| CN108743960A (en) * | 2018-07-04 | 2018-11-06 | 中国人民解放军第二军医大学第二附属医院 | A kind of mesoporous carbon nanoparticle and its application |
| CN109081325A (en) * | 2018-08-10 | 2018-12-25 | 湖南大学 | A kind of preparation method of carbon material |
| CN109390561A (en) * | 2018-09-27 | 2019-02-26 | 泉州市凯鹰电源电器有限公司 | A kind of lead negative and preparation method thereof of graphene lead carbon battery |
| CN109585806A (en) * | 2018-11-02 | 2019-04-05 | 双登集团股份有限公司 | Lead carbon capacitor batteries are rich in active material cathode lead plaster formula and preparation method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111816847A (en) * | 2020-07-08 | 2020-10-23 | 肇庆理士电源技术有限公司 | Lead paste for preparing positive plate and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Huang et al. | Self-assembled large-area Co (OH) 2 nanosheets/ionic liquid modified graphene heterostructures toward enhanced energy storage | |
| CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| Xue et al. | Decoration of nickel hexacyanoferrate nanocubes onto reduced graphene oxide sheets as high-performance cathode material for rechargeable aqueous zinc-ion batteries | |
| US9515310B2 (en) | V2O5 electrodes with high power and energy densities | |
| Zhu et al. | Multifunctional vanadium nitride@ N-doped carbon composites for kinetically enhanced lithium–sulfur batteries | |
| Chen et al. | Mesoporous spinel LiMn2O4 cathode material by a soft-templating route | |
| CN110391401A (en) | OMC based combined electrode and lead-acid battery | |
| CN113410443B (en) | Preparation method and application of high-stability copper intercalation manganese dioxide electrode material | |
| CN106006599A (en) | Synthesizing method and application of high-S-content P-S-N-codoped mesoporous carbon material | |
| CN109713279A (en) | The preparation method of the lithium ion battery negative material of foam copper oxide-base | |
| CN114400309A (en) | Sodium ion positive electrode material and preparation method and application thereof | |
| CN111211273A (en) | Lithium-sulfur battery with iron nitride nanoparticles growing in situ on reduced graphene oxide as modified diaphragm material and preparation method thereof | |
| CN110600697A (en) | Sulfur positive electrode material with core-shell structure, preparation method of sulfur positive electrode material, lithium-sulfur battery positive electrode piece and lithium-sulfur battery | |
| CN109301254A (en) | A kind of lithium sulfur battery anode material, anode and its preparation and application | |
| Zhang et al. | Design and synthesis of novel pomegranate-like TiN@ MXene microspheres as efficient sulfur hosts for advanced lithium sulfur batteries | |
| CN113571841B (en) | Lithium-sulfur battery composite diaphragm and preparation method thereof | |
| CN109786769A (en) | A kind of carbon supported noble metal oxide bifunctional catalyst and its preparation method and application | |
| CN113436905A (en) | Preparation method of carbon/nickel oxide composite electrode material | |
| CN110416502A (en) | OMC/ sponge Pb sandwich lead plaster and its preparation method and application | |
| Shen et al. | Enhanced polysulfide regulation of lithium-sulfur batteries by ZnS-SnO2 nano-heterostructures | |
| CN110407188A (en) | Passivation modified processing method, hydrophilic ordered mesopore carbon and its application of order mesoporous carbon surface | |
| KR102519029B1 (en) | Manufacturing method of pitch coated silicon/carbon composites as anode material of secondary battery | |
| Xu et al. | Core–shell structured S@ CuO/δ-MnO 2 composites as cathodes for lithium–sulfur batteries | |
| Wang et al. | Boosting the kinetics with graphene quantum dots (GQDs)-decorated NiCo2O4 nanosheets towards high-performance Li-O2 batteries | |
| CN109920986B (en) | Preparation method and application of three-dimensional porous structure composite electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191105 |
|
| RJ01 | Rejection of invention patent application after publication |