CN104409783B

CN104409783B - A kind of rare earth modifies the method for lead-acid battery electrode plate

Info

Publication number: CN104409783B
Application number: CN201410641311.6A
Authority: CN
Inventors: 王雅琼; 许文林; 居春山; 贾哲华; 周寿斌; 范春红; 吕佳乐; 于尊奎; 魏迪
Original assignee: JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd; Yangzhou University
Current assignee: JIANGSU HUAFU STORAGE NEW TECHNOLOGY Co Ltd; Yangzhou University
Priority date: 2014-11-14
Filing date: 2014-11-14
Publication date: 2016-06-29
Anticipated expiration: 2034-11-14
Also published as: CN104409783A

Abstract

The invention discloses a kind of method that rare earth modifies lead-acid battery electrode plate, in lead-acid battery electrode plate battery forming process, Battery formation liquid adds rare earth sulfate or rare earth oxide, rare earth ion modifies positive plate of lead storage battery in anode generation oxidation reaction, realize rare earth and modify anode grid and positive active material, negative plate of lead storage battery is modified, it is achieved rare earth modifies battery cathode grid and negative electrode active material, improves performance of lead-acid battery in negative electrode generation reduction reaction.The method production cost that the rare earth of the present invention modifies lead-acid battery electrode plate is low, it is good that the rare earth prepared modifies lead-acid battery electrode plate chemical property, long service life, easily mix some trace rare-earths at electrode surface equal and quantitative, realizing the regulation and control of electrode surface performance, equipment investment is low, and process modification is big, it is suitable for Different electrodes, the consumption of rare earth is greatly reduced and improves the utilization rate of rare earth；Adopt electrochemical techniques at electrode surface rare-earth modification technology, the consumption of rare earth be greatly reduced and improve the utilization rate of rare earth, being conducive to heavy industrialization, it is achieved the regulation and control of electrode surface performance.

Description

A kind of rare earth modifies the method for lead-acid battery electrode plate

Technical field

The invention belongs to the preparing technical field of positive plate of lead storage battery, be specifically related to a kind of method that rare earth modifies lead-acid battery electrode plate.

Background technology

Lead battery has the advantages such as simple in construction, easy to use, dependable performance, price are relatively low, therefore it is used widely at each department of national economy, to be always up in electrochmical power source yield big, the product of applied range, research and development and application along with new material and new technique, the properties of lead battery has had and has increased substantially, lead accumulator manifests more in the advantage of some special application fields, and as Moped Scooter, extraordinary electric motor car, new automobile power supply, the nearly stage is still main flow power supply.But, power-type lead battery characteristic of heavy-current discharge under the characteristic, particularly low temperature of heavy-current discharge that existing market uses is far apart with alkaline storage battery, and the service life of lead battery is limited.

The operation principle of lead battery is to utilize electrochemical principle to realize matter and energy to convert, and electrode and electrolytical interfacial reaction characteristic are to affect core and the essence place of accumulator property.Therefore, for lead battery, the research and development of its functional electrode, the electrolytical use of function admirable and electrode and electrolytical matching optimization are extremely important key issues in lead accumulator research and development.

The basic element of character and the material that constitute monomer lead battery include: positive plate, negative plate, sulfuric acid solution, dividing plate, cell jar etc..

Positive plate of lead storage battery is the vitals constituting monomer lead battery.Positive plate of lead storage battery is made up of anode plate grid and positive active material.The characteristic of positive plate/electrolyte interface, particularly anode plate grid/electrolyte interface and positive active material/electrolyte interface are the key factors affecting battery performance.Generally, the life-span of anode plate grid is the major influence factors affecting positive plate service life, and the microstructure of active substance and pattern are the another important parameters affecting cell active materials utilization rate, electrode conductivity and service life.

Positive electrode grid of lead storage battery Main Function has:

(1) colleeting comb skeleton: anode plate grid is the current collection skeleton of electrode, plays conduction, collects electric current and make homogeneous current distribution, improves the utilization rate of positive active material；

(2) the support carrier of positive active material: positive active material is played the effect of support by anode plate grid by frame and rib.

Positive active material mainly has two kinds of functions:

(1) electrochemical reaction, electric conductivity PbO during electric discharge are participated in₂It is converted into non-conductive PbSO₄；

(2) for porous active material, it is achieved reflecting point provides conductive path to grid.Latter function requires the PbO of some electric conductivity₂Active substance does not participate in electrochemical reaction, and is used merely to maintain structural integrity and electric conductivity is good.

Therefore, the active substance of positive plate of lead storage battery has claimed below: oxygen evolution potential is high, and corrosion resistance is good, good conductivity, can lead to super-high-current.Current positive electode of lead battery active substance is PbO₂。

There is subject matter and have in the positive plate of lead storage battery of prior art:

(1) in use there is corrosion and conductance ability reduction problem in anode plate grid: in anode plate grid use procedure, particularly under the operating condition of overcharge, oxidation reaction easily occurs grid, and corrosion and conductance ability reduction property occur.

(2) positive active material degradation problem: along with the increase of charge and discharge cycles number of times, discharge capacity is gradually lowered.Subject matter is that diamond retention reduces, and electrical contact is destroyed, and resistance increases therewith.Additionally, in the later stage of charging every time, aerobic precipitates out on positive pole, under the impact of analysis oxygen, more promote weakening of active substance adhesion, caused the grid that comes off of active substance to be combined with active substance and die down, the easy softening and shedding of positive active material；Electrode reaction preferentially carries out at electrode surface, product PbSO₄For non-conductor, the internal resistance of battery is made to increase with electric discharge, simultaneously PbSO₄By PbO₂Encasing, molal volume is more than PbO₂PbSO₄Plug the aperture of porous electrode, make reactant H₂SO₄Electrode depths can not be diffused into smoothly, cause the unreacting substance that residual is more, cause positive electrode active material utilization to reduce.

(3) matching problem of the active substance of positive plate of lead storage battery and anode plate grid: prior art exists anode plate grid and wraps up in attached with positive active material essentially machinery, exist contact wrap up in attached power not, in lead battery use procedure, there is the problem come off of positive active material.

Rare earth is a kind of additive improving material property, due to the 4f electron structure that lanthanide series is special, determine that it has performance and many-sided specific performances such as special optical, electrical, magnetic, be widely used in the field of new such as magnetic, electricity, luminescence, metallurgy, catalysis, nuclear energy, metal material.Adopt rare earth material to modify battery positive plate, improve performance of lead-acid battery, fundamentally solve conventional lead storage cells specific energy low, significantly improve the problems such as the power characteristic of lead battery, concordance and cryogenic property be poor.Rare earth modification battery positive plate improves performance of lead-acid battery and is widely applied prospect.

Chinese invention patent: the preparation method (ZL201010183703.4) of a kind of positive electrode grid of lead storage battery, a kind of rare earth are modified the method (ZL201010183692.X) of lead-acid battery electrode plate and disclosed the use of electrochemical oxidation technology, aqueous sulfuric acid adds rare earth ion, obtain rare earth and modify battery positive plate, improve the performance of battery positive plate.The Research idea of these patents is by adding rare earth ion in electrolyte sulfuric acid solution, by changing the concentration of rare earth ion and controlling battery positive plate treatment conditions in different electrolytes, Applied Electrochemistry oxidation technology, improve the performance of electrode surface, thus obtaining the positive electrode grid of lead storage battery of novel and high-efficiency；By adding rare earth oxide or rare earth sulfuric acid salt additives in positive active material, particularly at PbO₂The rare earth oxide material that positive electrode active materials adds, improves PbO₂The performance of positive electrode active materials.Improve the conductive capability of positive pole, active material utilization and charge-discharge performance, the connection decreasing anode plate grid and positive active material in battery deeper cavity discharge process worsens.But, the subject matter that the method exists is as follows:

(1) electrode performance declines: at the positive plate adopting preelectrolysis to process in its use procedure, because the rare-earth substance on electrode surface is in charging, discharging electric batteries process, rare earth is easily accessible in sulfuric acid solution, reduce rare-earth substance content in battery positive plate, in battery use procedure, battery performance can decline.

(2) preparation condition is inconsistent with the condition of use: add rare earth in aqueous sulfuric acid, adopt electrochemistry preelectrolysis method to prepare rare earth modification battery positive plate and improve performance of lead-acid battery, but, modify battery positive plate when rare earth and improve performance of lead-acid battery in use, exist and reduce rare-earth substance content in battery positive plate, in battery use procedure, battery performance declines.

(3) process contamination: after preelectrolysis processes, it is necessary to carry out, through washing, the operating procedure such as dry, producing substantial amounts of acid mist, spent acid, not only makes the little reduction of the level of resources utilization, and contaminated environment temperature.

(4) preelectrolysis processes: carry out electrochemical treatments in preelectrolysis equipment, causes that equipment, operating unit operating process increase.

Accordingly, it would be desirable to a kind of new lead-acid battery electrode plate rare earth method of modifying is to solve the problems referred to above.

Summary of the invention

It is an object of the invention to modify the deficiency of battery positive plate for the rare earth of prior art, it is provided that the rare earth that a kind of chemical property is good, long service life, production cost are low modifies the method for lead-acid battery electrode plate.

For achieving the above object, the method for rare earth of the present invention modification lead-acid battery electrode plate can adopt the following technical scheme that

A kind of rare earth modifies the method for lead-acid battery electrode plate, and wherein, cell panel includes positive plate and negative plate, and positive plate includes anode plate grid and positive active material, and negative plate includes negative electrode grid and negative electrode active material, comprises the following steps:

1), in Battery formation liquid dosing apparatus, by water, H₂SO₄Carry out being mixed to get Battery formation liquid with rare earth compound, wherein, H in the Battery formation liquid obtained₂SO₄Concentration be 1.8mol/L-4.8mol/L, rare earth ion RE³⁺Concentration be 0.001mol/L-0.200mol/L, described rare earth compound is rare earth sulfate or rare earth oxide, described rare earth compound middle rare earth includes variable high price rare earth element and variable low price rare earth element wherein, variable high price rare earth element is one or more in cerium Ce, praseodymium Pr and terbium Tb, and variable low price rare earth element is one or more in samarium Sm, europium Eu and ytterbium Yb；

2) the Battery formation liquid that, by step 1) obtains adds in lead battery, keeps the temperature of Battery formation liquid to be 10-60 DEG C, positive active material and negative electrode active material respectively with H₂SO₄React, be respectively formed one layer of lead sulfate on the surface of positive plate and negative plate；

3), lead battery battery forming process is carried out, variable high price rare earth element ion RE in battery forming process³⁺The rare earth ion RE of high price is generated in anode generation oxidation reaction⁴⁺, variable low price rare earth element ion RE³⁺Rare earth ion RE at a low price is generated in negative electrode generation reduction reaction²⁺, the rare earth ion RE of high price⁴⁺Anode plate grid and positive active material to positive plate are modified, rare earth ion RE at a low price²⁺Negative electrode grid and the negative electrode active material of anticathode plate are modified, and obtain rare earth and modify positive plate of lead storage battery and negative plate.

Further, also including the second rare earth element, described second rare earth element is the one in lanthanum La and yttrium Y or two kinds.

Further, in step 1), variable high price rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.

Further, variable low price rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.

Further, the second rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.

Further, in step 3), battery forming process adopts the pulse charge method based on Maas theorem, and wherein, chemical conversion operation temperature is 10 DEG C-60 DEG C, chemical conversion operation electric current density 5mA/cm²-20mA/cm², when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, battery forming process is complete.

Further, described Battery formation liquid dosing apparatus is stirred tank or tubular-mix equipment.

Inventive principle:

(1) characteristic of appraising at the current rate of rare earth is made full use of:The principle of battery lead plate is based on the distinctive physics of rare earth, chemical property improves the method for electrode plate grid performance of current lead battery to adopt rare earth to improve.Rare earth element is arranged in periodic table of elements IIIB race, including lanthanide series from 57 to 71 of scandium, yttrium and atomic number, totally 17 metallic elements.The electron structure of rare earth atoms is (Xe) 4f^0-145d^0-16s², after losing two 6s and a 5d or 4f electronics, define modal Ln³⁺, wherein La³⁺,Gd³⁺And Lu³⁺4f subgrade respectively empty, half-full or full up state entirely.According to Hund's rule, these states are all most stable of, so+3 valencys of these three element are the most stable.It is positioned at the Ln of they both sides³⁺Have and obtain or lose electronics to reach or close to the trend of aforementioned stable state.This just makes the lanthanide series being positioned at La, Gd and Lu side create to appraise at the current rate.Such as Ce³⁺、Pr³⁺、Tb³⁺And Dy³⁺Formation tetravalence, and Sm³⁺、Eu³⁺、Tm³⁺、Yb³⁺Then define bivalence.

Make full use of electrode/electrolyte interfacial reaction characteristic:The characteristic of electrode/electrolyte interface is the key problem affecting battery performance.Therefore, in order to improve battery performance, to can pass through to improve the performance of the characteristic raising battery of electrode/electrolyte interface, Lead-Rare Earth alloy can significantly reduce plumbous corrosion rate in sulfuric acid solution and corrosive film impedance, thus enhancing the corrosion resisting property of metal and inhibiting the growth of high impedance insulator corrosion layer；Employing rare earth ion modifies lead-acid battery electrode plate at electrode generation oxidation/reduction reaction.The present invention utilizes while battery lead plate is melted into, it is achieved rare earth modified electrode plate, improves performance of lead-acid battery.Namely the characteristic of electrode/electrolyte interface equilibrium establishment is made full use of: there is rare earth element on electrode when electrolyte is electrochemically reacted, rare earth can add electrolyte, at electrode/electrolyte interface equilibrium establishment；Meanwhile, when electrode is absent from rare-earth substance, electrolyte exist rare earth ion reagent be electrochemically reacted time, rare earth can enter electrode surface from electrolyte, equally at electrode/electrolyte interface equilibrium establishment, it is achieved the rare earth modification of battery lead plate.

Make full use of the electrochemical reaction characteristic of lead battery formation process:Plate formation of lead accumulator is exactly charge the first time to battery pole plates in fact, so the quality of chemical conversion will directly influence performance of lead-acid battery and the service life of production.And electric current uneven on pole plate and Potential distribution can significantly affect the utilization rate of active substance, especially positive plate.Traditional plate formation of lead accumulator technique is to be placed on the green plate (not being melted into pole plate) being completely dried in dilute sulfuric acid electrolyte to be melted into, carry out respectively aoxidizing and reduction reaction through green plate, make the lead monoxide of positive plate be changed to Lead oxide brown and make the lead monoxide of negative plate be changed to the process that biscuit is plumbous respectively.Battery formation charging/discharging thereof meets green plate charge-discharge characteristic, and charging current is all the time in the acceptable scope of lead battery, and discharges in good time, quickly and effectively eliminates polarizing voltage, and charging rate is fast, and the chemical conversion time is short.

The present invention by adding rare earth sulfate or rare earth oxide in Battery formation liquid, by changing kind and the concentration of rare earth ion, in lead-acid battery electrode electrochemical cell formation process, Battery formation liquid adds rare earth sulfate or rare earth oxide, in electrochemical cell formation process, make the RE in Battery formation liquid³⁺RE is generated respectively in anode generation oxidation reaction⁴⁺Modifying positive plate of lead storage battery, rare earth ion modifies positive plate of lead storage battery in anode generation oxidation reaction；At negative electrode generation reduction reaction RE²⁺Modify lead battery negative electrode plate rare earth ion and modify negative plate of lead storage battery in negative electrode generation reduction reaction, while battery lead plate is melted into, it is achieved rare earth modified electrode plate improves performance of lead-acid battery, improves performance of lead-acid battery.

The present invention by adding rare earth sulfate or rare earth oxide, charge and discharge process in lead battery use procedure, the particularly RE in charging process, electrolyte in Battery formation liquid³⁺RE is generated further respectively in anode generation oxidation reaction⁴⁺Modifying positive plate of lead storage battery, rare earth ion modifies positive plate of lead storage battery in anode generation oxidation reaction；At negative electrode generation reduction reaction RE²⁺Modify lead battery negative electrode plate rare earth ion further and modify negative plate of lead storage battery in negative electrode generation reduction reaction, while realizing lead battery charging, complete rare earth modified electrode plate further and improve performance of lead-acid battery, improve performance of lead-acid battery.In the charging process of lead battery, further electrochemical reaction characteristic Applied Electrochemistry oxidation/reduction technology, and in the charging process of lead battery, further Applied Electrochemistry response characteristic Applied Electrochemistry oxidation/reduction technology.

Make full use of Ce ³⁺ Characteristic of appraising at the current rate Deng rare earth:Owing to anode plate grid is unique electronic conductor in positive plate, the sulfation of basic lead sulphate and lead monoxide is caused by battery lead plate pickling process and sulphuric acid generation chemical reaction, modifying in coupling process at electrochemistry chemical conversion-rare earth, first rare earth carries out the response characteristic of electrode surface and electrolyte interface on anode plate grid is the key problem affecting battery performance.The performance on anode plate grid surface is improved, thus obtaining the positive electrode grid of lead storage battery of novel and high-efficiency by anode plate grid surface modification；Then prepare in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface, plays conduction, collects electric current and make homogeneous current distribution, improves the utilization rate of positive active material；Ce³⁺Etc. can only in anode generation oxidisability, in the operating condition, an electrode is not produced impact；, utilize rare earth sulfate soluble in water, rare-earth salts occurs precipitation to generate rare-earth hydroxide or rare earth oxide in the basic conditions, and rare-earth hydroxide or rare earth oxide are insoluble in water feature.In sulphuric acid character aqueous solution, preparing in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface；

The addition of rare earth elements of the present invention can reduce the hazardness of anode plate grid general corrosion speed and corrosion, can suppress the corrosion rate of anode plate grid and the hazardness of corrosion, improve the performance of anode plate grid.Documents 1 being thought, the reason that positive material(PAM) softening comes off is mainly, as active substance skeletonα-PbO₂It is gradually converted intoβ-PbO₂, so that positive active material skeleton is weakened and destroys, ultimately results in softening and come off, rare earth compound can delay the softening of positive active material.

Make full use of Eu ³⁺ Characteristic of appraising at the current rate Deng rare earth:The chemical conversion of negative plate is also be initially from negative electrode grid surface, the sulfation of basic lead sulphate and lead monoxide is caused by negative plate pickling process and sulphuric acid generation chemical reaction, modify in coupling process at electrochemistry chemical conversion-rare earth, first rare earth carries out electrode face finish on negative electrode grid, by negative electrode grid surface modification, improve the performance on negative electrode grid surface, thus obtaining the negative grid of lead storage battery of novel and high-efficiency；Then prepare in metallic lead process in cathodic reduction, the generation reduction reaction of rare earth ion, the rare-earth hydroxide precipitation produced through reduction deposits to electrode surface, has improved conduction, collects electric current and has made homogeneous current distribution further, has improved the utilization rate of negative electrode active material.Eu³⁺Etc. can only in negative electrode generation reduction reaction, in the operating condition, an electrode is not produced impact；, utilize rare earth sulfate soluble in water, rare-earth salts occurs precipitation to generate rare-earth hydroxide or rare earth oxide in the basic conditions, and rare-earth hydroxide or rare earth oxide are insoluble in water feature.In sulphuric acid character aqueous solution, preparing in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface；

Battery formation liquid adds rare earth sulfate or rare earth oxide, adopts electrochemical oxidation/cathode technique to modify lead-acid battery electrode plate performance.The reproducibilities such as Eu3+, Eu3+ etc. can only in negative electrode generation reproducibility.It is characterized in that rare earth oxide or sulfate that described rare earth sulfate or rare earth oxide are at least any one rare earth formation in europium Eu, samarium Sm, yttrium Y, neodymium Nd, praseodymium Pr.Electrochemical cathode method of reducing anticathode grid is adopted to carry out finishing.Hydrion or water, in negative electrode generation reduction reaction, release hydrogen, generate one layer of alkaline solution at electrode/electrolyte near interface simultaneously, and rare earth ion generates rare-earth hydroxide or rare earth oxide precipitation in the basic conditions, and deposits to cathode electrode surface.The sulfuric acid solution of high concentration adds rare earth oxide or rare earth sulfate, carries out Eu³⁺Electrochemical reduction, electrolyte generates the precipitation of this rare earth really, finds that what generate being deposited on electrode and adsorbing by scanning electron microscope, and cause that tank voltage is sharply upper long, rare earth achieves electrode surface reforming in the deposition of electrode surface；With metal negative electrode grid for negative electrode, rare earth sulfate and aqueous sulfuric acid are electrolyte, adopt electrochemical cathode method of reducing anticathode grid to carry out finishing.Generating one layer of alkaline solution at electrode/electrolyte near interface, rare earth ion generates rare-earth hydroxide or rare earth oxide precipitation in the basic conditions, and deposits to cathode electrode surface.

Make full use of rare earth and modify lead-acid battery electrode plate cooperative effect: adopt rare earth element at battery lead plate,Form at electrode/electrolyte interface that response speed is fast, reversibility is high solid-solution interface, improve the microscopic crystalline structure of battery lead plate simultaneously, improve electric conductivity and the utilization rate of active substance.

Beneficial effect: the method production cost that the rare earth of the present invention modifies lead-acid battery electrode plate is low, it is good that the rare earth prepared modifies lead-acid battery electrode plate chemical property, long service life, easily mix some trace rare-earths at electrode surface equal and quantitative, realizing the regulation and control of electrode surface performance, equipment investment is low, and process modification is big, it is suitable for Different electrodes, the consumption of rare earth is greatly reduced and improves the utilization rate of rare earth；Adopt electrochemical techniques at electrode surface rare-earth modification technology, the consumption of rare earth be greatly reduced and improve the utilization rate of rare earth, being conducive to heavy industrialization, it is achieved the regulation and control of electrode surface performance.

Accompanying drawing explanation

Fig. 1 is the process chart of the method for the rare earth modification lead-acid battery electrode plate of the present invention.

Detailed description of the invention

Below in conjunction with the drawings and specific embodiments, it is further elucidated with the present invention, it should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention, after having read the present invention, the amendment of the various equivalent form of values of the present invention is all fallen within the application claims limited range by those skilled in the art.

Referring to shown in Fig. 1, the rare earth of the present invention modifies the method for lead-acid battery electrode plate, wherein, cell panel includes positive plate and negative plate, positive plate includes anode plate grid and positive active material, and negative plate includes negative electrode grid and negative electrode active material, comprises the following steps:

1), in Battery formation liquid dosing apparatus, by water, H₂SO₄Carry out being mixed to get Battery formation liquid with rare earth compound, wherein, H in the Battery formation liquid obtained₂SO₄Concentration be 1.8mol/L-4.8mol/L, rare earth ion RE³⁺Concentration be 0.001mol/L-0.200mol/L, rare earth compound is rare earth sulfate or rare earth oxide, rare earth compound middle rare earth includes variable high price rare earth element and variable low price rare earth element wherein, variable high price rare earth element is one or more in cerium Ce, praseodymium Pr and terbium Tb, and variable low price rare earth element is one or more in samarium Sm, europium Eu and ytterbium Yb.Also including the second rare earth element, the second rare earth element is the one in lanthanum La and yttrium Y or two kinds.In step 1), variable high price rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.Variable low price rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.Second rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.Wherein, becoming liquid dosing apparatus is stirred tank or tubular-mix equipment.

3), lead battery battery forming process is carried out, variable high price rare earth element ion RE in battery forming process³⁺The rare earth ion RE of high price is generated in anode generation oxidation reaction⁴⁺, variable low price rare earth element ion RE³⁺Rare earth ion RE at a low price is generated in negative electrode generation reduction reaction²⁺, the rare earth ion RE of high price⁴⁺Anode plate grid and positive active material to positive plate are modified, rare earth ion RE at a low price²⁺Negative electrode grid and the negative electrode active material of anticathode plate are modified, and obtain rare earth and modify positive plate of lead storage battery and negative plate.Wherein, becoming process to adopt the pulse charge method based on Maas theorem, wherein, chemical conversion operation temperature is 10 DEG C-60 DEG C, chemical conversion operation electric current density 5mA/cm²-20mA/cm², when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, battery forming process is complete.

The method production cost that the rare earth of the present invention modifies lead-acid battery electrode plate is low, it is good that the rare earth prepared modifies lead-acid battery electrode plate chemical property, long service life, easily mix some trace rare-earths at electrode surface equal and quantitative, realizing the regulation and control of electrode surface performance, equipment investment is low, and process modification is big, it is suitable for Different electrodes, the consumption of rare earth is greatly reduced and improves the utilization rate of rare earth；Adopt electrochemical techniques at electrode surface rare-earth modification technology, the consumption of rare earth be greatly reduced and improve the utilization rate of rare earth, being conducive to heavy industrialization, it is achieved the regulation and control of electrode surface performance.

Major process unit is: stirred tank or tubular-mix forming liquid dosing apparatus, electrochemical reactor, metal fusion apparatus, metal grid former and cream equipment and positive plate formation device etc..

Embodiment 1:

A kind of rare earth modifies the method for lead-acid battery electrode plate, in lead-acid battery electrode electrochemical cell formation process, Battery formation liquid adds rare earth sulfate or rare earth oxide, variable high price rare earth ion modifies positive plate of lead storage battery in anode generation oxidation reaction, variable low price rare earth ion modifies negative plate of lead storage battery in negative electrode generation reduction reaction, while battery lead plate is melted into, it is achieved rare earth modified electrode plate, improve performance of lead-acid battery, it is characterised in that described method step is as follows:

(1) Battery formation liquid preparation: in stirred tank forming liquid dosing apparatus, water, sulphuric acid and cerous sulfate and europium sulfate are mixed, prepares 1.8mol/L sulphuric acid, 0.001mol/LCe³⁺And 0.001mol/LEu³⁺Battery formation liquid；

(2) battery lead plate pickling process: adopt raw positive plate and raw negative plate, every tablet quality error is less than ± 2%, the Battery formation liquid that previous step preparation obtains is added in lead battery, while adding forming liquid, controlling pickling temperature is 10 DEG C, battery electrode plate generation pickling process, electrode active material and sulphuric acid generation chemical reaction, battery lead plate pickling process is the lead monoxide in pole plate and sulphuric acid generation chemical reaction, cause the sulfation of basic lead sulphate and lead monoxide, form the region rich in lead sulfate at battery lead plate；

(3) electrochemistry chemical conversion-rare earth modifies coupling process: in battery forming process, it is adopted as potentiostatic method, the operation temperature of chemical conversion is 10 DEG C for chemical conversion operation temperature, the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, positive plate is all in sepia, rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, while lead compound on positive plate is changed into Lead oxide brown, variable valency rare earth ion RE³⁺RE is generated in anode generation oxidation reaction⁴⁺Anode plate grid and the positive active material of positive plate are modified by the rare earth high price material generated, negative plate is cinerous, first rare earth carries out the positive electrode grid of lead storage battery of electrode surface and the reaction acquisition novel and high-efficiency of electrolyte interface on anode plate grid, then prepare in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface, play conduction, collect electric current and make homogeneous current distribution, improve the utilization rate of positive active material, improve performance of lead-acid battery；While lead compound on negative plate is changed into porous metals lead, variable valency rare earth ion RE³⁺RE is generated in negative electrode generation reduction reaction²⁺Negative electrode grid and the negative electrode active material of the rare earth generated material anticathode plate at a low price are modified, first rare earth carries out the negative grid of lead storage battery of electrode surface and the reaction acquisition novel and high-efficiency of electrolyte interface on responsible grid, then prepare in rare earth oxide process in cathodic reduction, the generation reduction reaction of rare earth ion, the rare earth oxide precipitation produced through reduction deposits to electrode surface, play conduction, collect electric current and make homogeneous current distribution, improve the utilization rate of negative electrode active material, improve performance of lead-acid battery.

Embodiment 2:

(1) Battery formation liquid preparation: in stirred tank or tubular-mix forming liquid dosing apparatus, the rare earth sulfate that water, sulphuric acid and cerium Ce, the variable high price rare earth element of praseodymium Pr bis-kinds and europium Eu, bis-kinds of step-down valency rare earth elements of samarium Sm are formed with lanthanum is mixed, prepares 4.8mol/L sulphuric acid, 0.010mol/LCe³⁺、0.001mol/LPr³⁺、0.010mol/LEu³⁺、0.001mol/LSm³⁺And 0.090mol/LLa³⁺Battery formation liquid；

(2) battery lead plate pickling process: adopt raw positive plate and raw negative plate, every tablet quality error is less than ± 2%, the Battery formation liquid that previous step preparation obtains is added in lead battery, while adding forming liquid, controlling pickling temperature is 60 DEG C, battery electrode plate generation pickling process, electrode active material and sulphuric acid generation chemical reaction, battery lead plate pickling process is the lead monoxide in pole plate and sulphuric acid generation chemical reaction, cause the sulfation of basic lead sulphate and lead monoxide, form the region rich in lead sulfate at battery lead plate；

(3) electrochemistry chemical conversion-rare earth modifies coupling process: in battery forming process, adopts galvanostatic method, and the operation temperature of chemical conversion is 60 DEG C for chemical conversion operation temperature, chemical conversion operation electric current density 20mA/cm², when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, and positive plate is all in sepia, and negative plate is cinerous.Rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, while the lead compound on positive plate is changed into Lead oxide brown, and variable valency rare earth ion RE³⁺RE is generated in anode generation oxidation reaction⁴⁺Anode plate grid and the positive active material of positive plate are modified by the rare earth high price material generated, first rare earth carries out the positive electrode grid of lead storage battery of electrode surface and the reaction acquisition novel and high-efficiency of electrolyte interface on anode plate grid, then prepare in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface, play conduction, collect electric current and make homogeneous current distribution, improve the utilization rate of positive active material, improve performance of lead-acid battery；While lead compound on negative plate is changed into porous metals lead, variable valency rare earth ion RE³⁺RE is generated in negative electrode generation reduction reaction²⁺Negative electrode grid and the negative electrode active material of the rare earth generated material anticathode plate at a low price are modified, first rare earth carries out the negative grid of lead storage battery of electrode surface and the reaction acquisition novel and high-efficiency of electrolyte interface on responsible grid, then prepare in rare earth oxide process in cathodic reduction, the generation reduction reaction of rare earth ion, the rare earth oxide precipitation produced through reduction deposits to electrode surface, play conduction, collect electric current and make homogeneous current distribution, improve the utilization rate of negative electrode active material, improve performance of lead-acid battery.

Embodiment 3:

(1) Battery formation liquid preparation: in stirred tank or tubular-mix forming liquid dosing apparatus, the rare earth sulfate that three kinds of step-down valency rare earth elements in water, sulphuric acid and cerium Ce, praseodymium Pr, terbium Tb cerium Ce, the variable high price rare earth element of praseodymium Pr tri-kinds and europium Eu, samarium, Sm, ytterbium Yb are formed with lanthanum is mixed, prepares 2.8mol/L sulphuric acid, 0.010mol/LCe³⁺、0.001mol/LPr³⁺、0.001mol/LTb³⁺、0.010mol/LEu3+、0.001mol/LPr³⁺、0.001mol/LYb³⁺And 0.080mol/LLa³⁺Battery formation liquid；

(2) battery lead plate pickling process: adopt raw positive plate and raw negative plate, every tablet quality error is less than ± 2%, the Battery formation liquid that previous step preparation obtains is added in lead battery, while adding forming liquid, controlling pickling temperature is 40 DEG C, battery electrode plate generation pickling process, electrode active material and sulphuric acid generation chemical reaction, battery lead plate pickling process is the lead monoxide in pole plate and sulphuric acid generation chemical reaction, cause the sulfation of basic lead sulphate and lead monoxide, form the region rich in lead sulfate at battery lead plate；

(3) electrochemistry chemical conversion-rare earth modifies coupling process: in battery forming process, adopt based in the pulse charge scheme of Maas theorem, the operation temperature of chemical conversion is 40 DEG C for chemical conversion operation temperature, when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, positive plate is all in sepia, and negative plate is cinerous.

Rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, while the lead compound on positive plate is changed into Lead oxide brown, and variable valency rare earth ion RE³⁺RE is generated in anode generation oxidation reaction⁴⁺Anode plate grid and the positive active material of positive plate are modified by the rare earth high price material generated, first rare earth carries out the positive electrode grid of lead storage battery of electrode surface and the reaction acquisition novel and high-efficiency of electrolyte interface on anode plate grid, then prepare in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface, play conduction, collect electric current and make homogeneous current distribution, improve the utilization rate of positive active material, improve performance of lead-acid battery；While lead compound on negative plate is changed into porous metals lead, variable valency rare earth ion RE³⁺RE is generated in negative electrode generation reduction reaction²⁺Negative electrode grid and the negative electrode active material of the rare earth generated material anticathode plate at a low price are modified, first rare earth carries out the negative grid of lead storage battery of electrode surface and the reaction acquisition novel and high-efficiency of electrolyte interface on responsible grid, then prepare in rare earth oxide process in cathodic reduction, the generation reduction reaction of rare earth ion, the rare earth oxide precipitation produced through reduction deposits to electrode surface, play conduction, collect electric current and make homogeneous current distribution, improve the utilization rate of negative electrode active material, improve performance of lead-acid battery.

Embodiment 4:

(1) Battery formation liquid preparation: in stirred tank or tubular-mix forming liquid dosing apparatus, mixed by the oxide of water, sulphuric acid and cerium Ce, prepares 1.8mol/L sulphuric acid, 0.001mol/LCe³⁺And 0.001mol/LEu³⁺Battery formation liquid；

(3) electrochemistry chemical conversion-rare earth modifies coupling process: in battery forming process, it is adopted as potentiostatic method, the operation temperature of chemical conversion is 10 DEG C for chemical conversion operation temperature, chemical conversion operation electric current density 5, when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, and positive plate is all in sepia, and negative plate is cinerous.

Embodiment 5:

(3) electrochemistry chemical conversion-rare earth modifies coupling process: in battery forming process, adopts galvanostatic method, and the operation temperature of chemical conversion is 60 DEG C for chemical conversion operation temperature, chemical conversion operation electric current density 20mA/cm², when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, rare earth modification and the chemical conversion coupling of rare earth modification-electrochemistry are complete, and positive plate is all in sepia, and negative plate is cinerous.

Embodiment 6:

(1) Battery formation liquid preparation: in stirred tank or tubular-mix forming liquid dosing apparatus, the rare earth sulfate that three kinds of step-down valency rare earth elements in water, sulphuric acid and cerium Ce, praseodymium Pr, terbium Tb cerium Ce, the variable high price rare earth element of praseodymium Pr tri-kinds and europium Eu, samarium, Sm, ytterbium Yb are formed with lanthanum is mixed, prepares 2.8mol/L sulphuric acid, 0.010mol/LCe³⁺、0.001mol/LPr³⁺、0.001mol/LTb³⁺、0.010mol/LEu³⁺、0.001mol/LPr³⁺、0.001mol/LYb³⁺And 0.080mol/LLa³⁺Battery formation liquid；

Embodiment 7:

(1) Battery formation liquid preparation: in stirred tank or tubular-mix forming liquid dosing apparatus, three kinds of step-down valency rare earth elements in water, sulphuric acid and cerium Ce, praseodymium Pr, terbium Tb cerium Ce, the variable high price rare earth element of praseodymium Pr tri-kinds and europium Eu, samarium, Sm, ytterbium Yb are mixed with the rare earth sulfate of lanthanum and yttrium formation, prepares 2.8mol/L sulphuric acid, 0.010mol/LCe³⁺、0.001mol/LPr³⁺、0.001mol/LTb³⁺、0.010mol/LEu³⁺、0.001mol/LPr³⁺、0.001mol/LYb³⁺And 0.080mol/LLa³⁺0.080mol/LY³⁺Battery formation liquid；

Embodiment 8:

(1) Battery formation liquid preparation: in stirred tank or tubular-mix forming liquid dosing apparatus, the rare earth sulfate that three kinds of step-down valency rare earth elements in water, sulphuric acid and cerium Ce, praseodymium Pr, terbium Tb cerium Ce, the variable high price rare earth element of praseodymium Pr tri-kinds and europium Eu, samarium, Sm, ytterbium Yb are formed by lanthanum and yttrium is mixed, prepares 2.8mol/L sulphuric acid, 0.010mol/LCe³⁺、0.001mol/LPr³⁺、0.001mol/LTb³⁺、0.010mol/LEu³⁺、0.001mol/LPr³⁺、0.001mol/LYb³⁺、0.080mol/LLa³⁺And 0.080mol/LY³⁺Aqueous solution be Battery formation liquid；

Measure the performance obtaining battery with comprehensive tester, result shows to adopt technical side's peace of the present invention, makes battery specific energy promote more than 30% than conventional batteries, and cycle life improves more than 40%, under optimal conditions, reaches more than 3 times of like products。The invention is not restricted to above-described embodiment, all employings are equal to replacement or equivalence is replaced the technical scheme formed and belonged to the scope of protection of present invention.Except the various embodiments described above, embodiment of the present invention also have a lot, and the equivalent or equivalent technical scheme replaced of all employings, all within protection scope of the present invention.

The present invention, by adding rare earth sulfate or rare earth oxide in Battery formation liquid, significantly improves the performance of positive plate of lead storage battery, improves the conductive capability of electrode, active material utilization and charge-discharge performance.

The know-why that the present invention adopts has:

(1) characteristic of appraising at the current rate of rare earth element is made full use of:The principle of positive plate is based on the distinctive physics of rare earth, chemical property improves the method for positive plate performance of current lead battery to adopt rare earth to improve.Rare earth element is arranged in periodic table of elements IIIB race, including lanthanide series from 57 to 71 of scandium, yttrium and atomic number, totally 17 metallic elements.The electron structure of rare earth atoms is (Xe) 4f^0-145d^0-16s², after losing two 6s and a 5d or 4f electronics, define modal Ln³⁺, wherein La³⁺,Gd³⁺And Lu³⁺4f subgrade respectively empty, half-full or full up state entirely.According to Hund's rule, these states are all most stable of, so+3 valencys of these three element are the most stable.It is positioned at the Ln of they both sides³⁺Have and obtain or lose electronics to reach or close to the trend of aforementioned stable state.This just makes the lanthanide series being positioned at La, Gd and Lu side create to appraise at the current rate.Such as Ce³⁺、Pr³⁺、Tb³⁺And Dy³⁺Form tetravalence.The changeable valence rare earth element that the present invention selects and typical metallic element, the electron configuration basic simlarity of they outermost two-layers, chemical reaction shows typical metalline, easily lose three electronics, in positive trivalent, rare earth element is the element that comparison is active, and their metal activity is only second to alkali and alkaline earth metal ions element, and more active than other metal.

Make full use of electrode/electrolyte interfacial reaction characteristic:The characteristic of electrode/electrolyte interface is the key problem affecting battery performance.Therefore, in order to improve battery performance, improve the performance of battery by improving the characteristic of electrode/electrolyte interface.Employing rare earth ion modifies lead battery battery positive plate at electrode generation oxidation/reduction reaction.The present invention utilizes while battery positive plate is melted into, it is achieved rare earth modifies anode grid and positive active material, improves performance of lead-acid battery.Namely the characteristic of electrode/electrolyte interface equilibrium establishment is made full use of: there is rare earth element on electrode when electrolyte is electrochemically reacted, rare earth carries out electrolyte, at electrode/electrolyte interface equilibrium establishment；Meanwhile, when electrode is absent from rare-earth substance, electrolyte exist rare earth ion be electrochemically reacted time, rare earth can enter electrode surface from electrolyte, equally at electrode/electrolyte interface equilibrium establishment, it is achieved the rare earth modification of battery positive plate.

Make full use of the electrochemical reaction characteristic of lead battery formation process:Positive plate of lead storage battery chemical conversion is exactly charge the first time to battery positive plate in fact, so the quality of chemical conversion will directly influence performance of lead-acid battery and the service life of production.And electric current uneven on positive plate and Potential distribution can significantly affect the utilization rate of active substance, especially positive plate.Traditional positive plate of lead storage battery chemical synthesis technology is to be placed on the raw positive plate (not being melted into positive plate) being completely dried in dilute sulfuric acid electrolyte to be melted into, carry out respectively aoxidizing and reduction reaction through raw positive plate, make the lead monoxide of positive plate be changed to Lead oxide brown and make the lead monoxide of positive plate be changed to the process that biscuit is plumbous respectively.Battery formation charging/discharging thereof meets raw positive plate charge-discharge characteristic, and charging current is all the time in the acceptable scope of lead battery, and discharges in good time, quickly and effectively eliminates polarizing voltage, and charging rate is fast, and the chemical conversion time is short.

The present invention by adding rare earth sulfate or rare earth oxide in Battery formation liquid, by changing kind and the concentration of rare earth ion, in lead-acid battery electrode battery forming process, Battery formation liquid adds rare earth sulfate or rare earth oxide, in battery forming process, make the RE in Battery formation liquid³⁺RE is generated respectively in anode generation oxidation reaction⁴⁺Modifying positive plate of lead storage battery, rare earth ion modifies positive plate of lead storage battery in anode generation oxidation reaction, it is achieved rare earth modifies anode grid and positive active material improves performance of lead-acid battery, improves performance of lead-acid battery.

Based on Battery formation technique, lead battery is carried out formation charging, is primarily present problems with:

1. in Battery formation charging process, lead battery internal temperature is too high.In Battery formation charging process, the temperature within lead battery is generally no more than 60 DEG C.If temperature is too high, the activity of the various active substances within lead battery will increase, it is possible to can cause the possibility producing crystallization and over-charging of battery on positive plate, thus damaging lead battery.Owing to Battery formation technique is compared to tank formation technique, it does not have special tank is lowered the temperature to battery, therefore, a great problem that the temperature rise in charging process is puzzlement Battery formation charge technology how is controlled.

2. the polarization phenomena in charging process.Polarization phenomena are also the big factors affecting charge efficiency.In charging process, electrochemical reaction inside lead battery, can be there is, thus producing polarization.Polarization phenomena mainly have three kinds: ohmic polarization, concentration polarization and activation polarization.If the polarization phenomena can not controlled well in charging process, then causing that lead battery internal temperature raises, acceptable charging current diminishes, thus affecting charge efficiency.

3. lead battery capacity not easily be full of and the charging interval long.Due to temperature rise in the existence of polarization phenomena and charging process, the lead battery not being melted into is when first time formation charging, and its electricity is not easy to be full of and exist charging interval long problem.If electricity is not full of, then can in follow-up charging process, the electricity of lead battery is also not easy to be filled, thus causing that the service efficiency of lead battery declines, and affects the use time of lead battery.

For solving the difficult point in Battery formation battery charge technology, the present invention adopts the pulse charge scheme based on Mas law:

(I) Mas law

Each lead battery has its specific intrinsic charging curve, only when the value of charging current is less than the value of its peculiar charging curve electric current, just without influence on charge efficiency, otherwise, have a large amount of gassing inside lead battery to produce, hinder charging current to flow into lead battery, affect charge efficiency.Mas law is pointed out, in charging process, when the intrinsic charging curve current value of lead battery is down near the value of charging current, lead battery is carried out the electric discharge in short-term of appropriateness, the intrinsic charging curve of lead battery can be made to move to right, improve the value of lead battery acceptable charging current, it is thus possible to make lead battery keep large current charge, improve charge efficiency.Meanwhile, electric discharge in short-term, it is possible to removing activation polarization and concentration polarization that lead battery produces in charging process, the temperature within lead battery also can reduce, thus promoting charge efficiency further, reduces the charging interval.

(II) charging scheme design

The present invention, on the basis of Mas law, devises a kind of new charging scheme, in the starting stage of charging, first adopts the constant-current charge of small area analysis.This is because the charging incipient stage, the polarization reaction that battery produces is less, now adopts constant-current charge, it is possible to effectively promote the capacity of lead battery at short notice, and can reduce the vulcanization reaction within lead battery.

In constant-current charge process, lead battery voltage can continue to rise.When lead battery voltage rises to certain numerical value, beginning with pulse charge, the complete procedure of pulse charge is, after first lead battery being continued constant-current charge a period of time, to stop charging, static lead battery, it is therefore an objective to eliminate ohmic polarization and concentration polarization.Relief lead battery carried out the repid discharge of short time by discharge loop, to eliminate the activation polarization of accumulation in charging process, and discharge the gas produced in positive plate hole, control battery temperature rise.After lead battery discharge cycle terminates, then lead battery is stood a period of time, it is therefore an objective to avoid the electric current reverse impact in the short time that lead battery is impacted.After standing terminates, namely complete a complete pulse charge cycle.Carry out the constant-current charge-standing-electric discharge-standing process of next cycle afterwards again, so move in circles.

When rechargeable electrical energy is close to the rated capacity of lead battery, stop pulse charges, and starts the constant-current charge of final stage.The small area analysis constant-current charge Main Function of final stage is to ensure that the electricity of lead battery is sufficient, it is prevented that battery void electricity or situation about being not fully filled occur, also referred to as supplying charging.Owing to, in second charging stage, employing is pulse charge, and the temperature rise of inside battery will not be too high, polarization reaction without it is obvious that therefore the constant-current charge of final stage ensure that battery capacity is full of.

Make full use of the electrochemical reaction characteristic of charge and discharge process in lead battery use procedure:The present invention by adding rare earth sulfate or rare earth oxide, charge and discharge process in lead battery use procedure, the particularly RE in charging process, electrolyte in Battery formation liquid³⁺RE is generated further respectively in anode generation oxidation reaction⁴⁺Modifying positive plate of lead storage battery, rare earth ion modifies positive plate of lead storage battery in anode generation oxidation reaction；At negative electrode generation reduction reaction RE²⁺Modify lead battery negative battery positive plate rare earth ion further and modify lead battery negative material in negative electrode generation reduction reaction, while realizing lead battery charging, complete rare earth modification battery positive plate further and improve performance of lead-acid battery, improve performance of lead-acid battery.In the charging process of lead battery, further electrochemical reaction characteristic Applied Electrochemistry oxidation/reduction technology, and in the charging process of lead battery, further Applied Electrochemistry response characteristic Applied Electrochemistry oxidation/reduction technology.

Make full use of RE ³⁺ Appraise at the current rate characteristic and rare earth modification lead battery battery positive plate cooperative effect Deng rare earth:Owing to anode plate grid is unique electronic conductor in positive plate, the sulfation of basic lead sulphate and lead monoxide is caused by positive plate pickling process and sulphuric acid generation chemical reaction, modifying in coupling process at electrochemistry chemical conversion-rare earth, first rare earth carries out the response characteristic of electrode surface and electrolyte interface on anode plate grid is the key problem affecting battery performance.The performance on anode plate grid surface is improved, thus obtaining the positive electrode grid of lead storage battery of novel and high-efficiency by anode plate grid surface modification；Then prepare in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface, plays conduction, collects electric current and make homogeneous current distribution, improves the utilization rate of positive active material；RE³⁺Etc. can only in anode generation oxidisability, in the operating condition, an electrode is not produced impact；, utilize rare earth sulfate soluble in water, rare-earth salts occurs precipitation to generate rare-earth hydroxide or rare earth oxide in the basic conditions, and rare-earth hydroxide or rare earth oxide are insoluble in water feature.In sulphuric acid character aqueous solution, preparing in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface.Such as La₂O₃、Ce₂O₃、Pr₂O₃、Nd₂O₃Deng, improve the conductive capability of positive pole, active material utilization and charge-discharge performance, the connection decreasing anode plate grid and positive active material in battery deeper cavity discharge process worsens.The addition of rare earth elements of the present invention can reduce the hazardness of anode plate grid general corrosion speed and corrosion, can suppress the corrosion rate of anode plate grid and the hazardness of corrosion, improve the performance of anode plate grid.The reason that positive material(PAM) softening comes off is mainly, as active substance skeletonα-PbO₂It is gradually converted intoβ-PbO₂, so that positive active material skeleton is weakened and destroys, ultimately results in softening and come off, rare earth compound can delay the softening of positive active material.Rare earth element achieves electrode surface reforming in the deposition of electrode surface.Form at electrode/electrolyte interface that response speed is fast, reversibility is high solid-solution interface, improve the microscopic crystalline structure of battery positive plate simultaneously, improve electric conductivity and the utilization rate of active substance.

The main advantage of the present invention:

(1) characteristic of electrode surface in positive plate use procedure is fully applied: the response characteristic of electrode surface and electrolyte interface is the key problem affecting battery performance.The performance on anode plate grid surface is improved, thus obtaining the positive plate of lead storage battery of novel and high-efficiency by anode plate grid surface modification.

(2) rare earth modified at electrode surface by electrochemical techniques: the present invention by adding different types of rare earth sulfate in electrolyte sulfuric acid solution, by changing concentration and battery positive plate preconditioning technique in different electrolytes of rare earth sulfate, Applied Electrochemistry oxidation technology, improves the performance on positive plate surface.

(3) pulse charge based on Maas theorem is adopted to be melted into scheme.Mas law is pointed out, in charging process, when the intrinsic charging curve current value of lead battery is down near the value of charging current, lead battery is carried out the electric discharge in short-term of appropriateness, the intrinsic charging curve of lead battery can be made to move to right, improve the value of lead battery acceptable charging current, it is thus possible to make lead battery keep large current charge, improve charge efficiency.Meanwhile, electric discharge in short-term, it is possible to removing activation polarization and concentration polarization that lead battery produces in charging process, the temperature within lead battery also can reduce, thus promoting charge efficiency further, reduces the charging interval.This charging scheme is: in the starting stage of charging, first adopt the constant-current charge of small area analysis.This is because the charging incipient stage, the polarization reaction that battery produces is less, now adopts constant-current charge, it is possible to effectively promote the capacity of lead battery at short notice, and can reduce the vulcanization reaction within lead battery.Based on the pulse charging method of Mas law, not only effectively follow the tracks of the optimal charge curve of lead battery, controlled the temperature rise of inside battery preferably, and served lifting charge efficiency, save the effect of charging interval and energy-conserving and environment-protective.

(4) adopting electrochemical oxidation technology, utilize rare earth sulfate soluble in water, rare-earth salts occurs precipitation to generate rare-earth hydroxide or rare earth oxide in the basic conditions, and rare-earth hydroxide or rare earth oxide are insoluble in water feature.In sulphuric acid character aqueous solution, preparing in rare earth oxide process in anodic oxidation, the generation oxidation reaction of rare earth ion, the rare earth oxide precipitation produced through peroxidating deposits to electrode surface.

(5) adopt electrochemistry at electrode surface rare-earth modification technology, prepare in rare earth oxide process in cathodic reduction method, hydrion or water are in negative electrode generation reduction reaction, release hydrogen, generate one layer of alkaline solution at electrode/electro solution near interface simultaneously, rare earth ion generates rare-earth hydroxide or rare earth oxide in the basic conditions, generate rare-earth hydroxide or rare earth oxide produces precipitation, precipitation deposits to cathode electrode surface, the consumption of rare earth is greatly reduced and improves rare earth utilization rate.

(6) method is simple, convenient operation and control: easily mix some trace rare-earths at electrode surface equal and quantitative, it is achieved the regulation and control of electrode surface performance；Equipment investment is low, and process modification is big: not needing complicated reaction reagent and special reaction condition, cost is low, and equipment is simple.

(7) convenient, flexible, it is suitable for Different electrodes (by changing electrolyte and operating condition), the consumption of rare earth is greatly reduced and improves the utilization rate of rare earth；Adopt electrochemical techniques at electrode surface rare-earth modification technology, the consumption of rare earth is greatly reduced and improves the utilization rate of rare earth, it is possible to be constant potential operation, constant current operation or circulation peace operation；Method is simple, convenient operation and control, it is to avoid the difficulty of lead-rare earth (Pb-RE) reasonable offer；Easily mix some trace rare-earths at electrode surface equal and quantitative, it is achieved the regulation and control of electrode surface performance.

(8) advantages such as the rare earth oxide purity that electrochemical production rare earth oxide has operating condition gentleness, simple, preparation cost is low and prepared is high, the domain structure controllable of rare earth oxide.

(9) being conducive to heavy industrialization: preparation method of the present invention is simple, preparation is convenient, and process safety is reliable.

Claims

1. the method that rare earth modifies lead-acid battery electrode plate, wherein, cell panel includes positive plate and negative plate, and positive plate includes anode plate grid and positive active material, and negative plate includes negative electrode grid and negative electrode active material, it is characterised in that: comprise the following steps:

1), in Battery formation liquid dosing apparatus, by water, H₂SO₄Carry out being mixed to get Battery formation liquid with rare earth compound, wherein, H in the Battery formation liquid obtained₂SO₄Concentration be 1.8mol/L-4.8mol/L, rare earth ion RE³⁺Concentration 0.001mol/L-0.200mol/L, described rare earth compound is rare earth sulfate or rare earth oxide, described rare earth compound middle rare earth includes variable high price rare earth element and variable low price rare earth element, wherein, variable high price rare earth element is one or more in cerium Ce, praseodymium Pr and terbium Tb, and variable low price rare earth element is one or more in samarium Sm, europium Eu and ytterbium Yb；

2), by step 1) the Battery formation liquid that obtains adds in lead battery, keeps the temperature of Battery formation liquid to be 10-60 DEG C, positive active material and negative electrode active material respectively with H₂SO₄React, be respectively formed one layer of lead sulfate on the surface of positive plate and negative plate；

2. the method that rare earth as claimed in claim 1 modifies lead-acid battery electrode plate, it is characterised in that: also including the second rare earth element, described second rare earth element is the one in lanthanum La and yttrium Y or two kinds.

3. the method that rare earth as claimed in claim 1 modifies lead-acid battery electrode plate, it is characterised in that: step 1) in variable high price rare earth element ion be 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.

4. the method that rare earth as claimed in claim 1 modifies lead-acid battery electrode plate, it is characterised in that: variable low price rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.

5. the method that rare earth as claimed in claim 2 modifies lead-acid battery electrode plate, it is characterised in that: the second rare earth element ion is 0.001mol/L-0.200mol/L in the total concentration of Battery formation liquid.

6. the method that rare earth as claimed in claim 1 modifies lead-acid battery electrode plate, it is characterized in that: step 3) in battery forming process adopt based on the pulse charge method of Maas theorem, wherein, chemical conversion operation temperature is 10 DEG C-60 DEG C, chemical conversion operation electric current density 5mA/cm²-20mA/cm², when the cell tank voltage of electrolytic bath is stable when 2.6V-2.8V, battery forming process is complete.

7. the method that rare earth as claimed in claim 1 modifies lead-acid battery electrode plate, it is characterised in that: described Battery formation liquid dosing apparatus is stirred tank or tubular-mix equipment.