CN107887575A - A kind of polyaniline prepares and the method for modification negative plate of lead storage battery - Google Patents
A kind of polyaniline prepares and the method for modification negative plate of lead storage battery Download PDFInfo
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- CN107887575A CN107887575A CN201711157226.2A CN201711157226A CN107887575A CN 107887575 A CN107887575 A CN 107887575A CN 201711157226 A CN201711157226 A CN 201711157226A CN 107887575 A CN107887575 A CN 107887575A
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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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
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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
- H01M4/14—Electrodes for lead-acid accumulators
- H01M4/16—Processes of manufacture
- H01M4/20—Processes of manufacture of pasted electrodes
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/72—Grids
- H01M4/73—Grids for lead-acid accumulators, e.g. frame plates
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
A kind of method for being prepared the invention discloses polyaniline and modifying negative plate of lead storage battery, aniline is aoxidized and polymerisation occurs in sulfuric acid solution as oxidant using brown lead oxide polyaniline is made, polyaniline is obtained to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material as battery terminal negative active material raw material on negative electrode grid, by filling and solidification drying, polyaniline-modified negative pole green plate is prepared, negative pole green plate is that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, in electrochemistry formation process, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Reduction reaction generation rare earth low price material RE occurs in negative electrode2+, the rare earth low price material of generation further modified the negative electrode grid and negative electrode active material of negative plate, realizes polyaniline and the synergistically modified negative material of rare earth, improves negative plate of lead storage battery performance.
Description
Technical field
The invention belongs to technical field of material, especially belongs to negative plate of lead storage battery preparing technical field and lead carbon
Electrode material preparing technical field, and in particular to a kind of polyaniline prepares and the method for modification negative plate of lead storage battery.
Background technology
1. lead accumulator
Lead accumulator has the advantages that simple in construction, easy to use, dependable performance, price are relatively low, therefore in national economy
All departments are used widely, and are always that yield is big in electrochmical power source, the product that has a wide range of application, with new material and new technology
Research and development and application, the properties of lead accumulator, which have, to be increased substantially, and lead accumulator is in some special application fields
Advantage more show, as Moped Scooter, extraordinary electric car, new automobile power supply, the nearly stage is still main flow power supply.But
It is that the power-type lead accumulator that existing market uses is in the characteristic of heavy-current discharge, the spy of heavy-current discharge particularly under low temperature
Property is far apart with alkaline storage battery, and the service life of lead accumulator is limited.
The operation principle of lead accumulator is to realize that matter and energy converts using electrochemical principle, the boundary of electrode and electrolyte
Face response characteristic is core and the essence place for influenceing accumulator property.Therefore, ground for lead accumulator, its functional electrode
Send out, the use of the electrolyte of function admirable and the matching optimization of electrode and electrolyte are extremely heavy in lead accumulator research and development
The key issue wanted.
The basic element of character and material for forming monomer lead accumulator include：Negative plate, negative plate, sulfuric acid solution, dividing plate, electric power storage
Pond groove etc..
Negative plate of lead storage battery is the important component for forming monomer lead accumulator.Negative plate of lead storage battery is by negative electrode grid
Formed with negative electrode active material.The characteristic of negative plate/electrolyte interface, particularly negative electrode grid/electrolyte interface and negative pole are lived
Property material/electrolyte interface be influence battery performance an important factor for.Generally, the life-span of negative electrode grid is to influence negative pole
The major influence factors of plate service life, the microstructure and pattern of active material are to influence cell active materials utilization rate, electricity
The another important parameter of pole electric conductivity and service life.
2. the composition of negative plate of lead storage battery
Main the forming by negative electrode grid and negative electrode active material of negative plate of lead storage battery, its main function is respectively negative pole
The effect of grid and negative electrode active material.
2.1 negative grid of lead storage battery main functions
The main function of negative grid of lead storage battery has：
(1) colleeting comb skeleton:Negative electrode grid is the current collection skeleton of electrode, plays conduction, collects electric current and make CURRENT DISTRIBUTION equal
It is even, improve the utilization rate of negative electrode active material；
(2) the support carrier of negative electrode active material:Negative electrode grid plays support by frame and rib to negative electrode active material
Effect.
The main function of 2.2 lead accumulator negative electrode active materials
The main function of lead accumulator negative electrode active material：
(1) electrochemical reaction is participated in, non-conductive lead sulfate is converted into electric conductivity spongy lead during charging；During electric discharge
Electric conductivity spongy lead is converted into non-conductive lead sulfate.
(2) negative electrode active material is porous active material, and the spongy lead active material of partially electronically conductive property does not participate in electrification
Reaction is learned, the electric pathway led as offer reflecting point to grid, and be used merely to maintain structural integrity and electric conductivity good conductor.
Therefore, the active material of negative plate of lead storage battery has claimed below：Hydrogen-evolution overpotential is high, and corrosion resistance is good, good conductivity,
High current can be passed through.
2. the composition of negative plate of lead storage battery
Main the forming by negative electrode grid and negative electrode active material of negative plate of lead storage battery, its main function is respectively negative pole
The effect of grid and negative electrode active material.
2.1 negative grid of lead storage battery main functions
The main function of negative grid of lead storage battery has：
(1) colleeting comb skeleton:Negative electrode grid is the current collection skeleton of electrode, plays conduction, collects electric current and make CURRENT DISTRIBUTION equal
It is even, improve the utilization rate of negative electrode active material；
(2) the support carrier of negative electrode active material:Negative electrode grid plays support by frame and rib to negative electrode active material
Effect.
The main function of 2.2 lead accumulator negative electrode active materials
The main function of lead accumulator negative electrode active material：
(1) electrochemical reaction is participated in, non-conductive lead sulfate is converted into electric conductivity spongy lead during charging；During electric discharge
Electric conductivity spongy lead is converted into non-conductive lead sulfate.
(2) negative electrode active material is porous active material, and the spongy lead active material of partially electronically conductive property does not participate in electrification
Reaction is learned, the electric pathway led as offer reflecting point to grid, and be used merely to maintain structural integrity and electric conductivity good conductor.
Therefore, the active material of negative plate of lead storage battery has claimed below：Hydrogen-evolution overpotential is high, and corrosion resistance is good, good conductivity,
High current can be passed through.
Subject matter be present in the negative plate of lead storage battery of 2.3 prior arts
Subject matter be present and have in the negative plate of lead storage battery of prior art：
(1) there is the reduction of conductance ability in negative electrode grid in use：Easily in plate during negative electrode grid use
The thick lead sulfate dendrite arm of grid Surface Creation, the resistivity of lead sulfate dendrite arm is high, and this thick lead sulfate is difficult charging, it is desirable to
The charging voltage of battery is very high, causes negative electrode grid conductance ability reduction property.
(2) negative electrode active material chemical property deterioration problem：For lead electrode in electric discharge, lead, which loses, is electronically generated electric conductivity
Very poor sulfuric acid leading crystal, sulfuric acid leading crystal are covered in negative electrode active material surface, when lead sulfate reaches certain thickness, cause
Negative electrode active material and electrolyte contacts are difficult, hinder negative electrode active material to continue to react, are passivated lead negative pole, with filling
The increase of discharge cycles number, discharge capacity gradually reduce；Electrode reaction is preferentially carried out in electrode surface, reaction product lead sulfate
For non-conductor, the internal resistance of battery is increased with electric discharge, make reactant H2SO4Be difficult to be diffused into electrode depths, cause residual compared with
More unreacting substances, cause the reduction of negative electrode active material utilization rate.
(3) matching problem of the active material of negative plate of lead storage battery and negative electrode grid：Negative electrode grid be present in prior art
With negative electrode active material be essentially machinery wrap up in it is attached, exist contact wrap up in attached power not enough, negative pole be present during lead accumulator use
The problem of coming off of active material.
Therefore, new negative electrode grid and negative electrode active material are researched and developed and improves the work of negative electrode grid and negative electrode active material
Skill matches, and the superior negative plate of processability is the performance for further improving current lead accumulator, it would be highly desirable to solves lead accumulator mesh
Before the problem of existing.
3. Modified by Rare Earth Elements negative plate of lead storage battery
In order to improve the performance of lead accumulator lead negative electrode active material, the side for improving electrode material using rare earth element have developed
Method.Rare earth element is a kind of additive of monosodium glutamate formula, and due to the special 4f electron structures of lanthanide series, it is special to determine that it has
The performances such as light, electricity, magnetic and many specific performances, it is widely used in magnetic, electricity, luminous, metallurgy, catalysis, nuclear energy, metal material
The field of new materials such as material.Using rare earth material modification negative plate, improve performance of lead-acid battery, solve conventional lead storage cells and compare energy
It is low, significantly improve the power characteristic of lead accumulator, the problems such as uniformity and cryogenic property are poor.Rare earth is referred to as new material
" treasure-house ".Rare earth modification negative plate, which improves performance of lead-acid battery, has wide application prospect.
Chinese invention patent:A kind of preparation method of negative grid of lead storage battery (ZL 201010183718.0) and one kind
The method (ZL 201010183712.3) of rare earth modification negative plate of lead storage battery is disclosed using electrochemical reduction technology, in sulphur
Rare earth ion is added in aqueous acid, using electrochemical reduction method, obtaining rare earth modification negative plate improves lead accumulator
Energy, improve the performance of negative plate.The Research idea of these patents be by adding rare earth ion in electrolyte sulfuric acid solution,
By changing the treatment conditions of the concentration and control negative plate of rare earth ion in different electrolytes, Applied Electrochemistry reduction skill
Art, improve the performance of electrode surface, so as to obtain the negative grid of lead storage battery of novel and high-efficiency；By in negative electrode active material
Add rare earth oxide or rare earth sulfuric acid salt additives, the rare earth element oxygenate particularly added in negative active core-shell material or sulphur
Acid rare earth sulfuric acid salt material, the performance of negative active core-shell material is significantly improved, improve conductive capability, the active material profit of negative pole
With rate and charge-discharge performance.
Chinese invention patent:The method (201410640843.8) and one kind of a kind of rare earth modification negative plate of lead storage battery are dilute
The method (ZL201410641311.6) of soil modification lead-acid battery electrode plate is using in lead-acid battery electrode electrochemistry formation process
In, add rare earth sulfate in electrochemistry forming liquid or rare earth oxide, variable high price rare earth ion reduce in negative electrode
In negative electrode reduction reaction modification negative plate of lead storage battery occurs for reaction modification negative plate of lead storage battery, variable low price rare earth ion,
While battery lead plate is melted into, rare earth modified electrode plate is realized, improves performance of lead-acid battery.
Using rare earth material modification cell negative plate, improve performance of lead-acid battery, fundamentally solve conventional lead storage cells
It is lower than energy, significantly improve the power characteristic of lead accumulator, the problems such as uniformity and cryogenic property are poor.
The principle of these technologies is the particularity using rare earth element, improves the performance of electrode material.Invention these
Technology is very effective method as solving lead-acid battery electrode without cadmium and lead minimizing key technology.But as lead
The negative electrode active material of battery spongy lead, particularly when lead accumulator is during fast charging and discharging, it is often more important that dynamic
In state charge and discharge process (during the startup of such as electric automobile, quick charge), most fast and effectively method is to utilize electric capacity
Device technology carries out fast charging and discharging, it is clear that the method for improving the performance of electrode material using rare earth element is difficult to meet quickly to fill
The requirement of electric discharge.Therefore, the technology of new modification spongy lead is researched and developed, is improving spongy lead as lead accumulator sea
Under conditions of the battery use of the negative electrode active material of continuous shape lead, while there is the electrode material of electrochemical capacitor technical principle again
Material disclosure satisfy that the electrode material of the requirement of dynamic charge and discharge process is further to improve current spongy lead electrode performance urgently
Solve the problems, such as.
Therefore, it is necessary to which a kind of method of new modification negative plate of lead storage battery is to solve the above problems.
The content of the invention
Goal of the invention：The problem of present invention exists for prior art, it is proposed that prepared by a kind of polyaniline and modification lead stores
The method of cell negative plate.
Technical scheme：In order to solve the above technical problems, the present invention, which proposes a kind of polyaniline, prepares and modifies lead accumulator
The method of negative plate：Comprise the following steps：
1) polyaniline, is prepared：Water, sulfuric acid and aniline are mixed, form the aqueous solution of sulfuric acid and aniline sulfate, so
Afterwards, it is that aniline is aoxidized and polymerisation generation polyaniline occurs by oxidant to add brown lead oxide, while brown lead oxide changes
For lead sulfate, the mixture of formation polyaniline, lead sulfate and sulfuric acid；
2) negative pole green plate, is prepared：Lead is added in the mixture of polyaniline, lead sulfate and sulfuric acid that step 1) obtains
Powder, dispersion mixing is carried out, the lead plaster material of dispersing polyaniline is obtained, using the lead plaster material of dispersing polyaniline as battery terminal negative
Coated on negative electrode grid, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared in active material；
3), electrochemistry is melted into：Water, sulfuric acid and rare earth sulfate or rare earth oxide are subjected to mixed preparing, are prepared
Aqueous sulfuric acid containing rare earth ion is electrochemistry forming liquid, and in electrochemistry formation process, the sulfate on negative plate turns
While being changed into spongy lead, rare earth ion RE3+Reduction reaction generation rare earth low price material RE occurs in negative electrode2+, rare earth is at a low price
Material RE2+Negative electrode grid and negative electrode active material are modified, realize that polyaniline and rare earth collaboration improve lead accumulator negative pole
Plate.
Further, the concentration of sulfuric acid is 1.8mol/L-4.8mol/L in step 1).
Further, the concentration of the aniline sulfate aqueous solution is 0.001mol/L-0.10mol/L in step 1).
Further, the molal weight of brown lead oxide and aniline ratio is (0.8-1.2) in step 1):1.0.
Further, the mass percent of polyaniline is in the lead plaster material of dispersing polyaniline described in step 2)
0.02%-2.00%.
Further, step 3) rare earth elements include at least any one changeable valence rare earth in samarium Sm, europium Eu, ytterbium Yb
Element.
Further, step 3) rare earth elements also include lanthanum and/or yttrium.
Further, changeable valence rare earth ion RE in step 3)3+Total concentration in electrochemistry forming liquid is 0.001mol/
L-0.200mol/L, rare earth ion RE3+Be 0.001mol/L-0.200mol/ in the total concentration of electrochemistry forming liquid, sulfuric acid it is dense
Spend for 1.8mol/L-4.8mol/L.
Further, electrochemistry described in step 3) chemical conversion method include constant potential den process, constant current den process,
One or more combination in cyclic voltammetry and pulse charge scheme den process based on Maas theorem.
Further, the chemical conversion operation temperature of the chemical conversion of electrochemistry described in step 3) is 10 DEG C -60 DEG C.
Inventive principle：
(1) characteristic having using polyaniline (PAn)：The characteristic of polyaniline in its molecular chain structure with there are-NH2Base
It is electron-donating by close relationship with aromatic ring, so as to impart the unique chemistry of polyaniline, electrochemistry premium properties；Polyaniline passes through
Crossing into dopant activation has certain conducting function, and polyaniline due to the reversible degree of electrochemical oxidation/reduction circular response is strong,
The features such as chemical stability is high, turn into one of conducting polymer for being effectively improved electrode material performance, be electrochemical oxidation reactions,
Battery, the modification of electrochemical capacitor electrode and material modified.Therefore as its storage of the electrode active material used time of battery
Electricity is big, energy density is high, manufactured battery length, and self discharge is small.
(2) characteristic (chemical oxidization method) of aniline (An) oxidative polymerization generation PAn reactions is utilized：Using aniline in acid
Property under the conditions of, can occur under chemical oxidizing agent existence condition oxidation reaction generation with conducting function polyaniline product spy
Property.Therefore, the present invention is oxidant using brown lead oxide, brown lead oxide aoxidizes aniline, and generation has in aqueous sulfuric acid
The polyaniline product of conducting function, it is reduced to obtain nonconducting lead sulfate product and can adopts during brown lead oxide aoxidizes aniline
The technology of electricity consumption chemistry chemical conversion carries out electrochemical reducing and regenerates to obtain spongy lead.
(3) PAn dopant activation characteristics in acid medium are utilized：Polyaniline is particularly water-soluble in sulfuric acid in acid medium
There is its unique mechanism of doping effect and body phase reaction mechanism in liquid, make it have good oxidation/reduction invertibity.
(4) characteristic of appraising at the current rate of rare earth element is made full use of：The principle for improving negative plate using rare earth is peculiar based on rare earth
Physics, chemical property improve current lead accumulator negative plate performance method.Improve the principle of negative electrode grid using rare earth
It is the method for the negative electrode grid performance for improving current lead accumulator based on the distinctive physics of rare earth, chemical property.Positioned at La, Gd and
Lanthanide series beside Lu, which generates, to appraise at the current rate.Such as Ce3+、Pr3+、Tb3+And Dy3+Formation tetravalence, and Sm3+、Eu3+, ytterbium Yb3+Then shape
Into divalence.
(5) electrode/electrolyte interfacial reaction characteristic is made full use of:It is rare earth modified in electrode surface with electrochemical techniques：It is logical
Cross in electrolyte sulfuric acid solution and add different types of rare earth sulfate, using electrochemical reduction technology, utilize rare earth sulfuric acid
Salt is soluble in water, and precipitation reaction generation rare-earth hydroxide or rare earth oxide occurs in the basic conditions for rare-earth salts, and rare earth
Hydroxide or rare earth oxide are insoluble in water feature.Rare earth oxide separates out and deposits to electrode surface.
(6) the electrochemical reaction characteristic of lead electric power storage chemistry formation process is made full use of：Negative plate of lead storage battery is melted into fact
It is exactly the first time charging to cell negative plate, so the quality of chemical conversion by the performance of lead-acid battery for directly influencing production and makes
Use the life-span.
(7) Polyaniline-modified spongy lead active material：Polyaniline, which passes through, has certain conducting function into dopant activation,
And polyaniline due to the reversible degree of electrochemical oxidation/reduction circular response is strong, chemical stability it is high the features such as, turn into and effectively change
One of conducting polymer of kind electrode material performance, it is the modification of electrochemical oxidation reactions, battery, electrochemical capacitor electrode
With it is material modified.Polyaniline-modified spongy lead forms composite with unique characteristic with spongy lead, can be effective
Improve the performance of spongy lead electrode, be consistent novel lead carbon battery electrode material.
The technology of the present invention has taken into full account following characteristic：
(1) characteristic (chemical oxidization method) of aniline (An) oxidative polymerization generation PAn reactions is utilized：Using aniline in acid
Property under the conditions of, can occur under chemical oxidizing agent existence condition oxidation reaction generation with conducting function polyaniline product spy
Property.Therefore, for the present invention in aqueous sulfuric acid, the brown lead oxide using electrode surface is oxidant, and brown lead oxide is by aniline oxygen
Change, polyaniline product of the generation with conducting function, realize Polyaniline-modified brown lead oxide, improve the property of lead dioxide electrode
Energy；It is reduced to obtain nonconducting lead sulfate product during brown lead oxide aoxidizes aniline using the technology of electrochemistry chemical conversion to enter
Row electrochemical reducing regenerates to obtain lead.
(2) nonconducting PbSO is made full use of4The characteristics of can regenerating to obtain the lead of electric conductivity using electrochemical reduction：Utilize
PbSO4Reduction reaction generation conductive material Pb occurs in negative electrode, in PbSO4/H2SO4Reduction reaction, which occurs, for interface makes PbSO4It is raw
Into Pb.In electrochemical cathode oxidizing process, only reacted on electrode/electrolyte interface, reactant and product are on boundary
Face is carried out, and the Pb that cathodic reduction is prepared is directly as electro catalytic electrode material.
(3) the electrochemical reaction characteristic of lead sulfate chemical conversion-PA dopant activation coupling techniques is utilized：Using lead sulfate in sulfuric acid
PAn dopant activations in sulfuric acid medium obtain the polymer of conduction while chemical conversion obtains lead in medium, and lead sulfate is in sulphur
Transformation and PAn in acid medium with the lead oxidation/reduction of dopant activation and polyaniline in sulfuric acid medium all have excellent
React invertibity.While electrode is melted into, PAn dopant activations are realized, further improve lead electrode performance.
(4) rare earth sulfate or rare earth oxide are added in electrochemistry forming liquid, by the species for changing rare earth ion
And concentration, in lead-acid battery electrode battery forming process, rare earth sulfate or rare-earth oxidation are added in electrochemistry forming liquid
Thing, in battery forming process, make the RE in electrochemistry forming liquid3+Reduction reaction generation RE occurs in negative electrode respectively2+Modify lead
Accumulator negative plate, realize that rare earth modification GND grid and negative electrode active material improve performance of lead-acid battery, further change
Kind performance of lead-acid battery.
(5) RE is made full use of3+Deng appraise at the current rate characteristic and the rare earth modification lead accumulator cell negative plate cooperative effect of rare earth：
Eu3+Etc. can only negative electrode occur reduction reaction, in the operating condition, an electrode is not had an impact, utilizes rare earth sulfate
Soluble in water, precipitation reaction generation rare-earth hydroxide or rare earth oxide occurs in the basic conditions for rare-earth salts, and rare earth hydrogen
Oxide or rare earth oxide are insoluble in water feature.Rare earth sulfate or rare earth oxide are added in electrochemistry forming liquid, is adopted
Negative plate of lead storage battery performance is modified with electrochemical cathode technology.Eu3+Etc. can only negative electrode occur reproducibility, Sm3+、Eu3+, ytterbium
Yb3+Then form divalence.Surface modification is carried out to negative electrode grid using electrochemical cathode restoring method.Hydrogen ion or water are in negative electrode
Generation reduction reaction, hydrogen is released, while one layer of alkaline solution, rare earth ion are generated in electrode/electrolyte near interface
Rare-earth hydroxide or rare earth oxide precipitation are generated in the basic conditions, and deposit to cathode electrode surface.In high concentration
Rare earth oxide or rare earth sulfate are added in sulfuric acid solution, carries out Eu3+Deng electrochemical reduction, rare earth is heavy electrode surface
Product realize electrode surface reforming, using electrochemical cathode restoring method to negative electrode grid carry out surface modification, while electrode/
Electrolyte interface nearby generates one layer of alkaline solution, and rare earth ion generates rare-earth hydroxide or rare earth in the basic conditions
Oxide precipitation, and deposit to cathode electrode surface.
Beneficial effect：Prepared by the polyaniline of the present invention and the method for modification negative plate of lead storage battery using brown lead oxide is oxygen
Aniline is aoxidized in sulfuric acid solution and polymerisation occurs by agent is made polyaniline, obtains polyaniline and is mixed with lead powder, is obtained
In the lead plaster material of dispersing polyaniline, the lead plaster material for obtaining dispersing polyaniline carries out original as battery terminal negative active material
Coated on negative electrode grid, by filling and solidifying drying, polyaniline-modified negative pole green plate, negative pole life pole is prepared in material
The aqueous sulfuric acid that plate contains rare earth ion carries out electrochemistry chemical conversion for electrochemistry forming liquid, in electrochemistry formation process,
While lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+It is anti-that reduction occurs in negative electrode
RE should be generated2+, the rare earth high price material of generation is further modified the negative electrode grid and negative electrode active material of negative plate, real
Existing polyaniline and rare earth element collaboration improves performance of lead-acid battery, realizes Polyaniline-modified GND grid and negative electrode active material
Matter, improve performance of lead-acid battery, significantly improve the performance of cell negative plate, improve conductive capability, the active material of electrode
Utilization rate and charge-discharge performance.
Embodiment
With reference to specific embodiment, the present invention is furture elucidated.
Embodiment 1：
It is a kind of prepare polyaniline and modify negative plate of lead storage battery method, using aniline oxidation and polymerization-polyaniline with
The negative plate of lead storage battery of Polyaniline-modified is prepared in lead powder dispersion mixing-pole plate preparation and electrochemistry chemical conversion coupling technique
Method, particularly aniline is aoxidized in sulfuric acid solution as oxidant using brown lead oxide and the obtained polyaniline of polymerisation occurs,
Obtain polyaniline to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material is lived as battery terminal negative
Property material raw material on negative electrode grid, through filling with solidification drying, polyaniline-modified negative pole life pole is prepared
Plate, negative pole green plate are that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, are melted into electrochemistry
Cheng Zhong, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Occur in negative electrode
Reduction reaction generates RE2+, the rare earth low price material of generation carries out further to the negative electrode grid and negative electrode active material of negative plate
Modification, polyaniline and the synergistically modified negative material of rare earth are realized, improve negative plate of lead storage battery performance.Comprise the following steps：
(1) prepared by polyaniline：Using oxidation-oxidation technology, by water, sulfuric acid and aniline with it is secondary be added to polyaniline and prepare set
Mixed in standby, form 1.8mol/L sulfuric acid, the aqueous solution of 0.01mol/L aniline sulfates composition, then, add titanium dioxide
Lead is that oxidant aoxidizes aniline, and the molal weight ratio of brown lead oxide and aniline is 0.8:1.0, aniline is oxidized and gathered
Reaction generation polyaniline is closed, while brown lead oxide is changed into lead sulfate, forms polyaniline, lead sulfate, aniline sulfate and sulfuric acid
Mixture；
(2) prepared by negative pole green plate：Using dispersion mixing technology, the lead powder of preparation is added in above-mentioned material, continue into
Row dispersion mixing, obtains the lead plaster material of dispersing polyaniline, the mass percent of polyaniline in the lead plaster material of dispersing polyaniline
For 0.02%, the lead plaster material of dispersing polyaniline is obtained as the raw material of battery terminal negative active material in negative electrode grid
On, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared；
(3) electrochemistry is melted into：Using electrochemistry forming technology, in electrochemistry forming liquid dosing apparatus, by water, sulfuric acid and
Rare earth sulfate or rare earth oxide carry out mixed preparing, be prepared 0.001mol/L Sm, 0.001mol/L La and
The electrochemistry forming liquid of 1.8mol/L sulfuric acid, in electrochemistry formation process, using 2.80V constant potential den processes, the behaviour of chemical conversion
It is 10 DEG C to make temperature, in electrochemistry formation process, while the sulfate on negative plate is changed into spongy lead, and rare earth
Ion RE3+Reduction reaction generation RE occurs in negative electrode2+, the rare earth low price material of generation is to negative electrode grid and negative electrode active material
Carrying out further modification improves performance of lead-acid battery, realizes that polyaniline and rare earth collaboration improve lead accumulator negative material performance.
Embodiment 2：
It is a kind of prepare polyaniline and modify negative plate of lead storage battery method, using aniline oxidation and polymerization-polyaniline with
The negative plate of lead storage battery of Polyaniline-modified is prepared in lead powder dispersion mixing-pole plate preparation and electrochemistry chemical conversion coupling technique
Method, particularly aniline is aoxidized in sulfuric acid solution as oxidant using brown lead oxide and the obtained polyaniline of polymerisation occurs,
Obtain polyaniline to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material is lived as battery terminal negative
Property material raw material on negative electrode grid, through filling with solidification drying, polyaniline-modified negative pole life pole is prepared
Plate, negative pole green plate are that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, are melted into electrochemistry
Cheng Zhong, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Occur in negative electrode
Reduction reaction generates RE2+, the rare earth low price material of generation carries out further to the negative electrode grid and negative electrode active material of negative plate
Modification, polyaniline and the synergistically modified negative material of rare earth are realized, improve negative plate of lead storage battery performance.Comprise the following steps：
(1) prepared by polyaniline：Water, sulfuric acid and aniline are mixed with secondary be added in polyaniline Preparation equipment, formed
The aqueous solution of 4.8mol/L sulfuric acid, 0.10mol/L aniline sulfates composition, then, it is oxidant by aniline to add brown lead oxide
The molal weight ratio of oxidation, brown lead oxide and aniline is 1.2:1.0, aniline is oxidized and polymerisation generation polyphenyl occurs
Amine, while brown lead oxide is changed into lead sulfate, forms the mixture of polyaniline, lead sulfate and sulfuric acid；
(2) prepared by negative pole green plate：Using dispersion mixing technology, the lead powder of preparation is added in above-mentioned material, continue into
Row dispersion mixing, obtains the lead plaster material of dispersing polyaniline, the mass percent of polyaniline in the lead plaster material of dispersing polyaniline
For 2.00%, the lead plaster material of dispersing polyaniline is obtained as the raw material of battery terminal negative active material in negative electrode grid
On, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared；
(3) electrochemistry is melted into：Using electrochemistry forming technology, in electrochemistry forming liquid dosing apparatus, by water, sulfuric acid and
Rare earth sulfate or rare earth oxide carry out mixed preparing, are prepared 0.001mol/L Eu, 0.019mol/L Y and
4.8mol/L sulfuric acid is electrochemistry forming liquid, in electrochemistry formation process, using constant current den process, the operation temperature of chemical conversion
For for 60 DEG C, operation electric current density 5mA/cm2, in electrochemistry formation process, the sulfate on negative plate is changed into sponge
While shape lead, rare earth ion RE3+Reduction reaction generation RE occurs in negative electrode2+, the rare earth low price material of generation is to negative electrode grid
Carrying out further modification with negative electrode active material improves performance of lead-acid battery, realizes that polyaniline and rare earth collaboration improve lead accumulator
Negative material performance.
Embodiment 3：
It is a kind of prepare polyaniline and modify negative plate of lead storage battery method, using aniline oxidation and polymerization-polyaniline with
The negative plate of lead storage battery of Polyaniline-modified is prepared in lead powder dispersion mixing-pole plate preparation and electrochemistry chemical conversion coupling technique
Method, particularly aniline is aoxidized in sulfuric acid solution as oxidant using brown lead oxide and the obtained polyaniline of polymerisation occurs,
Obtain polyaniline to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material is lived as battery terminal negative
Property material raw material on negative electrode grid, through filling with solidification drying, polyaniline-modified negative pole life pole is prepared
Plate, negative pole green plate are that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, are melted into electrochemistry
Cheng Zhong, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Occur in negative electrode
Reduction reaction generates RE2+, the rare earth low price material of generation carries out further to the negative electrode grid and negative electrode active material of negative plate
Modification, polyaniline and the synergistically modified negative material of rare earth are realized, improve negative plate of lead storage battery performance.Comprise the following steps：
(1) prepared by polyaniline：Using oxidation-oxidation technology, by water, sulfuric acid and aniline with it is secondary be added to polyaniline and prepare set
Mixed in standby, form 2.8mol/L sulfuric acid, the aqueous solution of 0.06mol/L aniline sulfates composition, then, add titanium dioxide
Lead is that oxidant aoxidizes aniline, and the molal weight ratio of brown lead oxide and aniline is 1.0:1.0, aniline is oxidized and gathered
Reaction generation polyaniline is closed, while brown lead oxide is changed into lead sulfate, forms the mixture of polyaniline, lead sulfate and sulfuric acid；
(2) prepared by negative pole green plate：Using dispersion mixing technology, the lead powder of preparation is added in above-mentioned material, continue into
Row dispersion mixing, obtains the lead plaster material of dispersing polyaniline, the mass percent of polyaniline in the lead plaster material of dispersing polyaniline
For 1.00%, the lead plaster material of dispersing polyaniline is obtained as the raw material of battery terminal negative active material in negative electrode grid
On, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared；
(3) electrochemistry is melted into：Using electrochemistry forming technology, in electrochemistry forming liquid dosing apparatus, by water, sulfuric acid and
Rare earth sulfate or rare earth oxide carry out mixed preparing, be prepared 0.001mol/L Yb, 0.018mol/L Y and
The electrochemistry forming liquid of 2.8mol/L sulfuric acid, in electrochemistry formation process, using constant current den process, the operation temperature of chemical conversion
For for 50 DEG C, operation electric current density 20mA/cm2, in electrochemistry formation process, the sulfate on negative plate is changed into sponge
While shape lead, rare earth ion RE3+Reduction reaction generation RE occurs in negative electrode2+, the rare earth low price material of generation is to negative electrode grid
Carrying out further modification with negative electrode active material improves performance of lead-acid battery, realizes that polyaniline and rare earth collaboration improve lead accumulator
Negative material performance.
Embodiment 4：
It is a kind of prepare polyaniline and modify negative plate of lead storage battery method, using aniline oxidation and polymerization-polyaniline with
The negative plate of lead storage battery of Polyaniline-modified is prepared in lead powder dispersion mixing-pole plate preparation and electrochemistry chemical conversion coupling technique
Method, particularly aniline is aoxidized in sulfuric acid solution as oxidant using brown lead oxide and the obtained polyaniline of polymerisation occurs,
Obtain polyaniline to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material is lived as battery terminal negative
Property material raw material on negative electrode grid, through filling with solidification drying, polyaniline-modified negative pole life pole is prepared
Plate, negative pole green plate are that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, are melted into electrochemistry
Cheng Zhong, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Occur in negative electrode
Reduction reaction generates RE2+, the rare earth low price material of generation carries out further to the negative electrode grid and negative electrode active material of negative plate
Modification, polyaniline and the synergistically modified negative material of rare earth are realized, improve negative plate of lead storage battery performance.Comprise the following steps：
(1) prepared by polyaniline：Using oxidation-oxidation technology, by water, sulfuric acid and aniline with it is secondary be added to polyaniline and prepare set
Mixed in standby, form 4.8mol/L sulfuric acid, the aqueous solution of 0.06mol/L aniline sulfates composition, then, add titanium dioxide
Lead is that oxidant aoxidizes aniline, and the molal weight ratio of brown lead oxide and aniline is 0.9:1.0, aniline is oxidized and gathered
Reaction generation polyaniline is closed, while brown lead oxide is changed into lead sulfate, forms polyaniline, aniline sulfate, lead sulfate and sulfuric acid
Mixture；
(2) prepared by negative pole green plate：Using dispersion mixing technology, the lead powder of preparation is added in above-mentioned material, continue into
Row dispersion mixing, obtains the lead plaster material of dispersing polyaniline, the mass percent of polyaniline in the lead plaster material of dispersing polyaniline
For 1.20%, the lead plaster material of dispersing polyaniline is obtained as the raw material of battery terminal negative active material in negative electrode grid
On, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared；
(3) electrochemistry is melted into：Using electrochemistry forming technology, in electrochemistry forming liquid dosing apparatus, by water, sulfuric acid and
Rare earth sulfate or rare earth oxide carry out mixed preparing, be prepared 0.001mol/L Sm, 0.001mol/L Eu,
0.009mol/L La, 0.009mol/L Y and the dense electrochemistry forming liquid for being of 4.8mol/L sulfuric acid, in electrochemistry formation process
In, using cyclic voltammetry, the operation temperature of chemical conversion is 40 DEG C, in electrochemistry formation process, the sulfuric acid on negative plate
While salt is changed into spongy lead, rare earth ion RE3+Reduction reaction generation RE occurs in negative electrode2+, the rare earth low price thing of generation
Confrontation negative electrode grid and negative electrode active material, which carry out further modification, improves performance of lead-acid battery, realizes polyaniline and rare earth collaboration
Improve lead accumulator negative material performance.
Embodiment 5：
It is a kind of prepare polyaniline and modify negative plate of lead storage battery method, using aniline oxidation and polymerization-polyaniline with
The negative plate of lead storage battery of Polyaniline-modified is prepared in lead powder dispersion mixing-pole plate preparation and electrochemistry chemical conversion coupling technique
Method, particularly aniline is aoxidized in sulfuric acid solution as oxidant using brown lead oxide and the obtained polyaniline of polymerisation occurs,
Obtain polyaniline to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material is lived as battery terminal negative
Property material raw material on negative electrode grid, through filling with solidification drying, polyaniline-modified negative pole life pole is prepared
Plate, negative pole green plate are that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, are melted into electrochemistry
Cheng Zhong, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Occur in negative electrode
Reduction reaction generates RE2+, the rare earth low price material of generation carries out further to the negative electrode grid and negative electrode active material of negative plate
Modification, polyaniline and the synergistically modified negative material of rare earth are realized, improve negative plate of lead storage battery performance.Comprise the following steps：
(1) prepared by polyaniline：Using oxidation-oxidation technology, by water, sulfuric acid and aniline with it is secondary be added to polyaniline and prepare set
Mixed in standby, form 3.8mol/L sulfuric acid, the aqueous solution of 0.06mol/L aniline sulfates composition, then, add titanium dioxide
Lead is that oxidant aoxidizes aniline, and the molal weight ratio of brown lead oxide and aniline is 1.1:1.0, aniline is oxidized and gathered
Reaction generation polyaniline is closed, while brown lead oxide is changed into lead sulfate, forms the mixture of polyaniline, lead sulfate and sulfuric acid；
(2) prepared by negative pole green plate：Using dispersion mixing technology, the lead powder of preparation is added in above-mentioned material, continue into
Row dispersion mixing, obtains the lead plaster material of dispersing polyaniline, the mass percent of polyaniline in the lead plaster material of dispersing polyaniline
For 1.00%, the lead plaster material of dispersing polyaniline is obtained as the raw material of battery terminal negative active material in negative electrode grid
On, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared；
(3) electrochemistry is melted into：Using electrochemistry forming technology, in electrochemistry forming liquid dosing apparatus, by water, sulfuric acid and
Rare earth sulfate or rare earth oxide carry out mixed preparing, be prepared 0.001mol/L Sm, 0.001mol/L Eu,
0.001mol/L Yb, 0.008mol/L La, 0.006mol/L Y and 2.8mol/L sulfuric acid are electrochemistry forming liquid, in electrification
Learn in formation process, the method for electrochemistry chemical conversion is constant potential den process, using the pulse charge scheme based on Maas theorem
Cheng Fa, the operation temperature of chemical conversion is 40 DEG C, operation electric current density 5mA/cm2-20mA/cm2, in electrochemistry formation process,
While sulfate on negative plate is changed into spongy lead, rare earth ion RE3+Reduction reaction generation RE occurs in negative electrode2+, it is raw
Into rare earth low price material further modification carried out to negative electrode grid and negative electrode active material improve performance of lead-acid battery, realize poly-
Aniline and rare earth collaboration improve lead accumulator negative material performance.
Embodiment 6：
It is a kind of prepare polyaniline and modify negative plate of lead storage battery method, using aniline oxidation and polymerization-polyaniline with
The negative plate of lead storage battery of Polyaniline-modified is prepared in lead powder dispersion mixing-pole plate preparation and electrochemistry chemical conversion coupling technique
Method, particularly aniline is aoxidized in sulfuric acid solution as oxidant using brown lead oxide and the obtained polyaniline of polymerisation occurs,
Obtain polyaniline to mix with lead powder, obtain the lead plaster material of dispersing polyaniline, obtained lead plaster material is lived as battery terminal negative
Property material raw material on negative electrode grid, through filling with solidification drying, polyaniline-modified negative pole life pole is prepared
Plate, negative pole green plate are that forming liquid carries out electrochemistry chemical conversion in the aqueous sulfuric acid containing rare earth ion, are melted into electrochemistry
Cheng Zhong, while the lead compound on negative pole green plate is changed into spongy lead, variable valency rare earth ion RE3+Occur in negative electrode
Reduction reaction generates RE2+, the rare earth low price material of generation carries out further to the negative electrode grid and negative electrode active material of negative plate
Modification, polyaniline and the synergistically modified negative material of rare earth are realized, improve negative plate of lead storage battery performance.Comprise the following steps：
(1) prepared by polyaniline：Using oxidation-oxidation technology, by water, sulfuric acid and aniline with it is secondary be added to polyaniline and prepare set
Mixed in standby, form 2.8mol/L sulfuric acid, the aqueous solution of 0.10mol/L aniline sulfates composition, then, add titanium dioxide
Lead is that oxidant aoxidizes aniline, and the molal weight ratio of brown lead oxide and aniline is 1.0:1.0, aniline is oxidized and gathered
Reaction generation polyaniline is closed, while brown lead oxide is changed into lead sulfate, forms the mixture of polyaniline, lead sulfate and sulfuric acid；
(2) prepared by negative pole green plate：Using dispersion mixing technology, the lead powder of preparation is added in above-mentioned material, continue into
Row dispersion mixing, obtains the lead plaster material of dispersing polyaniline, the mass percent of polyaniline in the lead plaster material of dispersing polyaniline
For 0.80%, the lead plaster material of dispersing polyaniline is obtained as the raw material of battery terminal negative active material in negative electrode grid
On, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared；
(3) electrochemistry is melted into：Using electrochemistry forming technology, in electrochemistry forming liquid dosing apparatus, by water, sulfuric acid and
Rare earth sulfate or rare earth oxide carry out mixed preparing, be prepared 0.0006mol/L Sm, 0.0004mol/L Eu,
0.016mol/L La and 1.8mol/L sulfuric acid are electrochemistry forming liquid, in electrochemistry formation process, the side of electrochemistry chemical conversion
Method is the combination in constant potential den process and pulse charge scheme den process based on Maas theorem, the operation temperature of chemical conversion be for
40 DEG C, operation electric current density 5mA/cm2-20mA/cm2, in electrochemistry formation process, the sulfate on negative plate is changed into
While spongy lead, rare earth ion RE3+Reduction reaction generation RE occurs in negative electrode2+, the rare earth low price material of generation is to negative pole
Grid and negative electrode active material, which carry out further modification, improves performance of lead-acid battery, realizes that polyaniline and rare earth collaboration improve lead and stored
Cell negative electrode material performance.
Determined to obtain the performance of battery with comprehensive tester, the results showed that, pacified using the technical side of the present invention, follow battery
The ring life-span improves more than 100%, under optimal conditions, reaches more than 3 times of like products.
Beneficial effects of the present invention are embodied in：
(1) lead electrode of Polyaniline-modified uses as the negative electrode active material of lead accumulator, because with good oxygen
Change/reduction invertibity and fake capacitance performance.
(2) polyaniline is used with fake capacitance performance characteristics as electrode material, and the compound of PAn and carbon material can have
The capacitance behavior of the improvement PAn base electrodes of effect.On the one hand, the presence of lead can make electrode be easier to electric conductivity in combination electrode, especially
It is when PAn is in neutral state；On the other hand, additive for electrode can effectively be weakened PAn in charge and discharge process by lead
Volume Changes degree, improve its cycle performance.
(3) use brown lead oxide for oxidant by aniline aoxidize and occur polymerization generation polyaniline, it is not necessary to separation and
Refinement treatment, the preparation technology of polyaniline is significantly simplify, the polyaniline and the material of course of reaction being prepared directly are made
Used to improve the raw material of electrode active material.
(4) using substep preparation and pre-dispersed hybrid technique technology, polyaniline dispersion mixing in lead plaster is uniform, material profit
With rate height.First water, sulfuric acid and aniline are added sequentially to be mixed in polyaniline Preparation equipment, form sulfuric acid and aniline sulphur
The aqueous solution of hydrochlorate composition, then, it is that aniline is aoxidized and polymerization generation polyaniline occurs by oxidant to add brown lead oxide, together
When brown lead oxide be changed into lead sulfate, form the material of polyaniline, lead sulfate and sulfuric acid, polyaniline is realized pre-dispersed mixing；
The lead powder of preparation is added in above-mentioned material, continues dispersion mixing, the lead plaster material of dispersing polyaniline is obtained, obtains polyphenyl
The scattered lead plaster material of amine carries out the raw material as battery terminal negative active material on negative electrode grid, by filling and admittedly
Change drying, polyaniline-modified negative pole green plate is prepared, polyaniline is uniformly distributed in electrode active material.
(5) fully applying rare earth and mainly improving negative electrode grid and polyaniline mainly improves the performance of electrode active material,
The grid of battery lead plate and active material is set to be obtained for sufficient improvement.And preparation method is simple, convenient operation and control, easily
Polyaniline is uniformly distributed in some trace rare-earths of the incorporation of electrode surface equal and quantitative and in electrode active material, realizes electricity
The regulation and control of the improvement performance of pole, preparation method of the present invention is simple, and it is convenient to prepare, and process safety is reliable.
(6) fully applying rare earth and mainly improving negative electrode grid and polyaniline mainly improves the performance of electrode active material,
The grid of battery lead plate and active material is set to be obtained for sufficient improvement.And preparation method is simple, convenient operation and control, easily
Polyaniline is uniformly distributed in some trace rare-earths of the incorporation of electrode surface equal and quantitative and in electrode active material, realizes electricity
The regulation and control of the improvement performance of pole, preparation method of the present invention is simple, and it is convenient to prepare, and process safety is reliable.
The invention is not restricted to above-described embodiment, all technical schemes formed using equivalent substitution or equivalence replacement belong to this
The claimed scope of invention.Except the various embodiments described above, embodiment of the present invention is also a lot, all using equivalent or equivalent replace
The technical scheme changed, within protection scope of the present invention.
Claims (10)
1. a kind of polyaniline prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Comprise the following steps：
1) polyaniline, is prepared：Water, sulfuric acid and aniline are mixed, form the aqueous solution of sulfuric acid and aniline sulfate, then,
It is that aniline is aoxidized and polymerisation generation polyaniline occurs by oxidant to add brown lead oxide, while brown lead oxide is changed into sulphur
Lead plumbate, form the mixture of polyaniline, lead sulfate and sulfuric acid；
2) negative pole green plate, is prepared：Lead powder is added in the mixture of polyaniline, lead sulfate and sulfuric acid that step 1) obtains, is entered
Row dispersion mixing, the lead plaster material of dispersing polyaniline is obtained, using the lead plaster material of dispersing polyaniline as battery terminal negative activity
On negative electrode grid, by filling with solidifying drying, polyaniline-modified negative pole green plate is prepared in coating substance；
3), electrochemistry is melted into：Water, sulfuric acid and rare earth sulfate or rare earth oxide are subjected to mixed preparing, are prepared containing dilute
The aqueous sulfuric acid of native ion is electrochemistry forming liquid, and in electrochemistry formation process, the sulfate on negative plate is changed into
While spongy lead, changeable valence rare earth ion RE3+Reduction reaction generation rare earth low price material RE occurs in negative electrode2+, rare earth is at a low price
Material RE2+Negative electrode grid and negative electrode active material are modified, realize that polyaniline and rare earth collaboration improve lead accumulator negative pole
Plate.
2. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
1) concentration of sulfuric acid is 1.8mol/L-4.8mol/L in.
3. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
1) concentration of the aniline sulfate aqueous solution is 0.001mol/L-0.10mol/L in.
4. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
1) molal weight of brown lead oxide and aniline ratio is (0.8-1.2) in:1.0.
5. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
2) mass percent of polyaniline is 0.02%-2.00% in the lead plaster material of dispersing polyaniline described in.
6. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
3) rare earth elements include at least any one changeable valence rare earth element in samarium Sm, europium Eu, ytterbium Yb.
7. polyaniline according to claim 6 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
3) rare earth elements also include lanthanum or yttrium.
8. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
3) changeable valence rare earth ion RE in3+Total concentration in electrochemistry forming liquid is 0.001mol/L-0.200mol/L, rare earth ion
RE3+It is 0.001mol/L-0.200mol/ in the total concentration of electrochemistry forming liquid, the concentration of sulfuric acid is 1.8mol/L-4.8mol/
L。
9. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
3) method of the chemical conversion of electrochemistry described in is included constant potential den process, constant current den process, cyclic voltammetry and determined based on Maas
One or more combination in the pulse charge scheme den process of reason.
10. polyaniline according to claim 1 prepares and the method for modification negative plate of lead storage battery, it is characterised in that：Step
It is rapid 3) described in electrochemistry chemical conversion chemical conversion operation temperature be 10 DEG C -60 DEG C.
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| CN110085938A (en) * | 2019-04-10 | 2019-08-02 | 刘孝军 | A kind of waste and old lead acid accumulator sulfuric acid circulation utilization method |
| CN113782750A (en) * | 2021-09-17 | 2021-12-10 | 广西鑫锋环保科技有限公司 | Metal @ copolymer composite grid, preparation thereof and application thereof in lead-acid battery |
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| CP02 | Change in the address of a patent holder |
Address after: 225603 Gaoyou Battery Industrial Park, Gaoyou Economic Development Zone, Yangzhou City, Jiangsu Province Co-patentee after: YANGZHOU University Patentee after: JIANGSU HUAFU STORAGE NEW TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 225603 Jiangsu Huafu storage energy new technology Limited by Share Ltd of Gaoyou City Battery Industrial Park, Gaoyou City, Zhenjiang City, Jiangsu Province Co-patentee before: YANGZHOU University Patentee before: JIANGSU HUAFU STORAGE NEW TECHNOLOGY DEVELOPMENT Co.,Ltd. |