CN110010856B - Preparation of conductive polyaniline modified titanium-based lead dioxide electrode by anodic oxidation codeposition method - Google Patents

Preparation of conductive polyaniline modified titanium-based lead dioxide electrode by anodic oxidation codeposition method Download PDF

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CN110010856B
CN110010856B CN201910311291.9A CN201910311291A CN110010856B CN 110010856 B CN110010856 B CN 110010856B CN 201910311291 A CN201910311291 A CN 201910311291A CN 110010856 B CN110010856 B CN 110010856B
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王雅琼
李成
张小兴
韩斌
许文林
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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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
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Abstract

A process for preparing the electrically conductive polyaniline modified Ti-base lead dioxide electrode by anode oxidizing codeposition method features that the Ti-base metal oxide electrode prepared by thermal decomposition of precursor is used as anode and Pb-contained metal oxide is used as anode2+And aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and the conductive polyaniline modified titanium-based lead dioxide electrode is prepared through anodic oxidation codeposition and electrochemical doping activation in sulfuric acid aqueous solution. The method can realize the in-situ preparation of the modified lead dioxide electrode by the aniline, simultaneously realize multiple functions of the construction of a conductive space network of the lead dioxide electrode, the inhibition of sulfation of the active substance, the regulation and control of the microstructure of the active substance and the like, and can effectively improve the performance of the lead dioxide electrode.

Description

Preparation of conductive polyaniline modified titanium-based lead dioxide electrode by anodic oxidation codeposition method
Technical Field
A process for preparing the electrically conductive polyaniline modified Ti-base lead dioxide electrode by anode oxidizing codeposition method features that the Ti-base metal oxide electrode prepared by thermal decomposition of precursor is used as anode and Pb-contained metal oxide is used as anode2+And aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and the conductive polyaniline modified titanium-based lead dioxide electrode is prepared through anodic oxidation codeposition and electrochemical doping activation in sulfuric acid aqueous solution. The electrode can be used as a positive plate of a lead storage battery, and belongs to the technical field of electrode material preparation and lead storage battery positive plate preparation.
Background
The lead storage battery utilizes the electrochemical principle to realize the conversion of substances and energy, and the characteristics of an electrode plate/electrolyte interface, particularly the characteristics of a positive electrode active substance/electrolyte interface are important factors influencing the performance of the battery; the microstructure and morphology of the electrode plate not only affects the characteristics of the electrode plate/electrolyte interface, but also affects the utilization rate of the battery active material, the conductivity of the electrode and the service life. Therefore, the research and development of novel lead storage battery electrode materials are of great significance.
1. Mechanism of action of positive active substance additive of lead storage battery
The characteristics of the lead battery electrode plate/electrolyte interface directly affect the performance of the battery. The capacity, energy, electricity output, cycle life and other properties of the positive plate of the lead storage battery are closely related to the interface reaction, electron transfer and substance (reactant and product) transfer rates, and the positive plate is a simultaneous electron and substance transfer process. The following factors are particularly closely related:
(1) interfacial reaction
The Positive Active Material (PAM) of lead accumulator is mainly composed of lead sulfate (PbSO) in discharge state4) The composition of the positive active material in the charging and discharging process has the following reaction formula:
Figure BDA0002031558000000011
the reaction takes place near the PAM/electrolyte interface, the reaction mechanism being Pb in solution 2+The oxidation/reduction reaction occurs, and the macroscopic rate of the reaction is determined by the interfacial reaction characteristics and the specific surface area of the reaction.
(2) Electronic transmission
Electrons are transferred at the PAM/electrolyte interface and are transmitted in solid PAM. Pb in lead dioxide crystals during discharge of the electrodes4+Receiving the electrons transmitted by the external line and reducing the electrons into Pb2+Transferring into solution; pb in solution when the electrode is charged2 +Oxidizing, and transferring electrons to the external circuit. The reaction generated at the PAM/electrolyte interface in the PAM must realize the directional movement of the electrons transferred by the electrochemical interface reaction and the electrons of an external circuit through the processes of electron migration, electron conduction, PAM and grid interface electron conduction and the like in the PAM.
(3) Mass transfer process
The mass transfer process is carried out in the liquid phase. Pb in lead dioxide crystals during discharge of the electrodes4+The obtained electrons are reduced to Pb2+Transferring into solution; pb2+With HSO in solution4 -To achieve PbSO4To precipitate PbSO4The solid crystallized out on the electrode. O in lead dioxide2-With H in solution+Synthetic water with continuous PbSO as the discharge progresses4Depositing; when the electrode is charged, dissolvePb in liquid2+Oxidation, H in solution2O molecule is substituted with H+The ions remaining in solution, O2-And Pb4+Into the lead dioxide crystal lattice. There must be mass transfer of reactants and products from the bulk of the liquid phase to the interior of the PAM and internal mass transfer from the exterior of the interface to the electrode surface near the PAM/electrolyte interface.
(4) Solid/liquid equilibrium
In the liquid phase near the PAM/electrolyte interface, solid phase PbSO is present4(S) and liquid phase PbSO4(L) in solution equilibrium with PbSO4(S) solubility in sulfuric acid solution is closely related, especially SO in the liquid phase near the PAM/electrolyte interface4 2-And H+The concentration and temperature of (A) determine the solid/liquid equilibrium characteristics, i.e. PbSO4(S) solubility in liquid phase sulfuric acid solution.
(5) Solid phase PbSO4(S) dissolution and PbSO in solution4(L) precipitation of
When Pb is contained in the solution2+Is consumed, solid phase PbSO4(S) continuously dissolving to lead Pb2+The oxidation process of (2) can be continued; when Pb is contained in the solution2+Upon formation, liquid phase PbSO4(L) precipitation of crystals. Apparently PbSO4The magnitude of solubility, dissolution rate and crystallization rate have a direct influence on the electrode charge and discharge rate.
(6) Liquid phase mass transfer process
The rate of transfer of reactants and products in solution directly affects the reaction rate at the PAM/electrolyte interface by affecting the concentration of the reaction site. Thus, there must be a problem of liquid phase mass transfer of reactants and products in the bulk liquid phase, the bulk liquid phase to the reaction zone, and the reaction zone to the PAM/electrolyte interface.
2. Types of additives for positive electrode active material of lead storage battery
In order to further improve the performance of the lead storage battery, improve the utilization rate of positive active substances of the lead storage battery and improve PbSO 4The rate of oxidative conversion to lead dioxide and the control of the microstructure of the active material, the most effective method being to use functional additives in the positive active material or in the electrolyte, depending on the positiveThe action mechanism of the functional additive of the polar active substance can be divided into the following categories:
(1) additive to build up a conductive space network: the additive can enable PAM to form a space network with conductivity before and after formation, has high conductivity and relatively small density, is stable in properties in the charge-discharge process, has corrosion resistance and certain mechanical strength, and can be tightly connected with a positive grid of a lead storage battery. The additives meeting these requirements mainly include conductive ceramics (e.g., barium plumbate), oxidants with strong oxidizing power (e.g., barium plumbate), conductive polymers (e.g., polyaniline), and the like. When the PAM lead paste is dispersed in the PAM lead paste, the conductivity of the positive active material is improved, and a conductive network is formed among the additives, so that the formation rate of the polar plate and the utilization rate of the active material can be effectively improved.
(2) Additives that inhibit sulfation of actives: in order to increase the reaction rate of the oxidative conversion of lead sulfate to lead dioxide, the most effective method is to increase the specific surface area of the reaction. In the reaction process of oxidizing and converting lead sulfate into lead dioxide, the reactant is solid-phase PbSO 4(S) and liquid phase H2O (L), only PbSO for increasing solid/liquid interfacial area4And (S) the specific surface area, and therefore, an additive for inhibiting sulfation of the active material is added to the positive electrode active material. The additive can be used as PbSO4Crystallization center and reduction of PbSO4The effect of solubility of (c). Typically, the solid phase additive is PbSO4A crystalline center; the additive dissolved in the sulfuric acid solution, and the sulfate, phosphoric acid and phosphate additive utilizing the same ion effect reduce the PbSO of the insoluble electrolyte by utilizing the same ion effect4The solubility of (a). When the storage battery is charged or discharged for a small part, the concentration of sulfuric acid is low, and the solubility of lead sulfate is high, so that the lead sulfate is easy to recrystallize. Small particle crystals dissolve to form large PbSO4Crystals are then accumulated into a layer of compact PbSO4Resulting in sulfation of the plates.
(3) Additives that regulate the microstructure of the active substance: in order to increase the lead dioxide/PbSO4Conversion rate (charge-discharge rate) of (1), increase of reactionConversion rate (energy density) of a reactant, stable microstructure (service life) obtained, and a functional additive for regulating and controlling the microstructure of an active substance is added into the PAM, so that the PAM has a specific and relatively stable microstructure. PAM is in a fixed bed structure (porous electrode), the added functional additive mainly controls the microstructure of PAM, and the specific surface area of a bed layer is controlled to be 1.0 multiplied by 10 6m2/m3The above.
3. Particularity of polyaniline as additive of positive active material of lead storage battery
The conductive polymer is an ideal additive with the three functions, polyaniline can have a conductive function after being doped and activated, and the polyaniline has the characteristics of strong reversibility of electrochemical oxidation/reduction cycling reaction, high chemical stability and the like, so that the conductive polymer additive is effectively used for improving the performance of electrode materials and is a modification material for electrochemical oxidation reaction, storage batteries and electrochemical capacitor electrodes. Therefore, the in-situ synthesis and electrochemical modification method of the conducting polymer is developed, and the performance of the lead dioxide electrode can be effectively improved by preparing the lead dioxide modified by polyaniline.
4. The main problems of the prior art for preparing polyaniline modified lead dioxide
The traditional technique for preparing polyaniline modified lead dioxide mainly adopts aniline chemical oxidation polymerization to prepare polyaniline, or aniline electrochemical polymerization to prepare polyaniline, and then the polyaniline is mixed with lead dioxide and added with specific dopant for modification.
The invention relates to a method for modifying a positive plate of a lead storage battery by polyaniline (201711158874.X), which is invented by China (Wangyueqiong, etc.); a method (201711158870.1) for preparing and modifying a lead storage battery positive plate by polyaniline aims at the problems of the traditional process technology for preparing polyaniline modified lead dioxide, aniline is added into a formed liquid in the battery formation process of the lead storage battery positive plate, the aniline is subjected to oxidation reaction at an anode to generate the polyaniline modified lead storage battery positive plate, and a lead compound on the positive plate is converted into lead dioxide, and meanwhile, a positive plate grid and a positive active substance of the polyaniline modified battery are realized, so that the performance of the lead storage battery is improved.
The main problem in the process of adding aniline into the battery formation solution to realize polyaniline modification of the positive grid and the positive active material of the battery is that only polyaniline modification can be carried out on the active surfaces of the positive grid and the positive electrode, and multiple functions of constructing a conductive space network, inhibiting sulfation of the active material, regulating and controlling the microstructure of the active material and the like are difficult to realize at the same time.
Therefore, aiming at the particularity of preparation and use of the lead dioxide of the lead storage battery positive plate active substance, the preparation of the lead dioxide, the preparation of polyaniline and the modification of the polyaniline are organically combined together, so that the lead dioxide electrode is modified by aniline in situ polymerization, and multiple effects of construction of a lead dioxide electrode conductive space network, inhibition of sulfation of the active substance, regulation and control of an active substance microstructure and the like are realized.
Disclosure of Invention
The invention aims to provide a method for preparing a conductive polyaniline modified titanium-based lead dioxide electrode by an anodic oxidation codeposition method, which adopts a precursor thermal decomposition-anodic oxidation codeposition-doping activation coupling technology to prepare a titanium-based electrode, a metal oxide-based intermediate layer and a lead dioxide-polyaniline-based electrode, wherein the titanium-based electrode can be used as a positive plate of a lead storage battery.
The technical scheme is as follows: a method for preparing a conductive polyaniline modified titanium-based lead dioxide electrode by an anodic oxidation codeposition method is particularly characterized in that a titanium-based metal oxide electrode prepared by precursor thermal decomposition is used as an anode, and Pb-containing metal oxide is used as a cathode2+Aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and an anodic oxidation codeposition technology is adopted to generate Pb at an electrode/electrolyte interface2+Respectively obtaining lead dioxide and polyaniline through electrochemical oxidation reaction with aniline, co-depositing the generated lead dioxide and polyaniline on the surface of a titanium-based metal oxide electrode to prepare a polyaniline modified titanium-based lead dioxide electrode, and then washing, removing impurities and electrochemically doping and activating in a sulfuric acid aqueous solution to prepare the conductive polyaniline modified titanium-based lead dioxide electrode, wherein the preparation of the electrode comprises the following steps:
(1) preparation of titanium-based metal oxide electrode
The preparation method of the titanium-based metal oxide electrode comprises the following steps:
surface treatment: mechanically polishing the titanium substrate, removing oil on the surface of an alkaline solution, etching the titanium substrate by an oxalic acid solution, and washing to obtain a surface-treated titanium substrate;
coating the intermediate layer: coating the intermediate layer precursor on the titanium substrate subjected to surface treatment;
Curing: heating and curing the titanium substrate coated with the intermediate layer precursor in an oven;
roasting: and roasting the solidified precursor in roasting equipment. And repeating the coating, curing and roasting operations for 5-50 times to obtain the titanium-based metal oxide electrode.
(2) Anodic oxidation co-deposition
The titanium-based metal oxide electrode prepared in the previous step is taken as an anode and contains Pb2+Aqueous solution of aniline and alkali metal nitrate as electrolyte, Pb2+And carrying out oxidation reaction on the titanium-based lead dioxide electrode and aniline at the anode, and carrying out codeposition to obtain the polyaniline-modified titanium-based lead dioxide electrode.
(3) Washing to remove impurities
And in washing and impurity removing equipment, washing and impurity removing treatment is carried out on the polyaniline-modified lead dioxide electrode obtained in the last step, and nitrate impurities in the electrode are removed.
(4) Doping activation
And in a sulfuric acid aqueous solution, performing electrochemical doping activation on the titanium-based lead dioxide electrode modified by the polyaniline obtained in the previous step as an anode to obtain the conductive polyaniline-modified titanium-based lead dioxide electrode.
Further, in the step (2), the Pb-containing layer is formed by anodic oxidation codeposition2+Aniline and alkali metal nitrate in an aqueous solution, Pb (NO)3)2The concentration of the alkali metal nitrate is 0.10 mol/L-1.0 mol/L, the concentration of the aniline is 0.01 mol/L-0.80 mol/L, and the alkali metal nitrate is LiNO 3、NaNO3、KNO3In any combination, the total concentration of the alkali metal nitrates is between 0.1mol/L and 1.0 mol/L.
Further, in the step (2), the anodic oxidation codeposition method is any one or combination of potentiostatic method, galvanostatic method, cyclic voltammetry and pulsed amperometry, the operating temperature is 10-60 ℃, and the operating current density is 200A/m2～2000A/m2。
Further, in the step (4), the concentration of the sulfuric acid aqueous solution is between 0.10mol/L and 6.0mol/L, the doping activation adopts any one method or combination of electrochemical oxidation, electrochemical oxidation to potentiostatic method, or galvanostatic method, or cyclic voltammetry, or pulsed current method, the operating temperature is 10-60 ℃, and the operating current density is 50A/m2～1000A/m2。
Further, in the step (1), the precursor of the intermediate layer is composed of chlorides of Sn and Sb and salts of any metal of Pb, Y and La, the precursor also comprises citric acid and glycol, and the molar ratio of the citric acid to the glycol is (2.0-6.0): 1.
Further, in the intermediate layer precursor in the step (1), the molar ratio of Sn to glycol is 1 (6.0-24.0), and the total molar ratio of other metal salts to glycol is 1 (6.0-24.0).
Further, in the step (1), the curing temperature is 60-120 ℃, and the roasting temperature is 380-620 ℃.
Further, the geometry of the titanium substrate in the step (1) of preparing the titanium-based metal oxide electrode may be any one of a plate, a wire, a rod and a mesh.
The invention adopts the technical principle that:
(1) utilizing Pb2+And aniline can generate electrochemical oxidation reaction on the anode to co-deposit the product on the anode, and the anode oxidation co-deposition technology is adopted to realize Pb at the electrode/electrolyte interface2+Respectively obtaining lead dioxide and polyaniline by electrochemical oxidation of aniline, and co-depositing the produced lead dioxide and polyaniline on titanium-based metal oxideThe titanium-based lead dioxide electrode modified by polyaniline is obtained on the surface of the electrode, and meanwhile, the lead dioxide can also oxidize the aniline to prepare the polyaniline, so that the polyaniline can modify the lead dioxide electrode in the three-dimensional space of the lead dioxide, thereby realizing the construction of a conductive space network, the sulfation inhibition of active substances and the microstructure regulation and control of the active substances.
(2) Utilizing Pb2+The lead dioxide is deposited on the surface of a titanium-based lead dioxide electrode by the characteristic that an electrochemical oxidation reaction is generated at an anode to generate a lead dioxide precipitate, and the lead dioxide as the positive active material of the lead storage battery is prepared by a formation method.
(3) The characteristic that aniline generates electrochemical oxidation reaction under the condition of neutral medium to generate polyaniline is utilized, so that aniline directly generates electrochemical oxidation reaction on an electrode to generate polyaniline, and the generated polyaniline is difficult to dissolve in electrolyte and is deposited on the electrode, thereby realizing lead dioxide modified by polyaniline.
(4) The main causes of failure of metal oxide anodes are dissolution consumption of the oxide layer, exfoliation and the formation of a passive film between the active layer and the substrate. The invention designs the electrode with a multilayer structure, utilizes the characteristic that titanium has excellent corrosion resistance in a sulfuric acid aqueous solution, and adopts titanium as an electrode base material; the anti-passivation performance of the electrode is improved through the corrosion-resistant conductive intermediate coating, the falling and inactivation of the active layer of the electrode are prevented, and the prepared polyaniline modified lead dioxide not only has high reaction activity, but also has long electrode service life. Particularly, the titanium matrix metal oxide electrode is adopted as the positive grid material of the lead storage battery, the problem of corrosion damage of the conventional positive grid is fundamentally solved, the weight of the lead storage battery is reduced, the energy density of the lead storage battery is improved, and favorable conditions are created for recycling and cyclic utilization of the electrode material of the lead storage battery.
The process technology of the invention fully considers the following characteristics:
(1) the characteristics that lead nitrate and aniline respectively generate lead dioxide and polyaniline by electrochemical oxidation reaction under the condition of neutral medium are utilized, aniline directly generates electrochemical oxidation reaction on an electrode to generate polyaniline, and Pb simultaneously2+Electrochemical deviceAnd (4) carrying out chemical oxidation reaction to generate lead dioxide, thus forming the polyaniline modified lead dioxide composite material. As the polyaniline obtained under the reaction condition is an insulating material, the polyaniline with conductivity can be obtained by doping and activating the polyaniline in a sulfuric acid aqueous solution, so that the lead dioxide electrode modified by the polyaniline is obtained to improve the performance of the lead dioxide electrode.
(2) Make full use of the PbSO which is not conductive4Lead dioxide with conductivity is obtained by electrochemical oxidation regeneration, so that PbSO4Oxidation reaction takes place at the anode and conversion to lead dioxide takes place.
(3) By utilizing the characteristic that the anodic oxidation of lead sulfate and the electrochemical doping activation of polyaniline can be carried out simultaneously, lead sulfate is converted into lead dioxide in a sulfuric acid medium, polyaniline is doped and activated in the sulfuric acid medium to obtain a conductive polymer, and the conversion of lead sulfate and lead dioxide in the sulfuric acid medium, the doping activation of polyaniline in the sulfuric acid medium and the oxidation-reduction of polyaniline have excellent reaction reversibility. And doping and activating the polyaniline while performing electrode formation.
The invention has the following beneficial effects:
(1) by anodic oxidation co-deposition technique, Pb2+And aniline are subjected to electrochemical reaction on the anode, and the product is co-deposited on the anode, so that the polyaniline modifies the lead dioxide electrode in a lead dioxide three-dimensional space, and multiple functions of conductive space network construction, active substance sulfation inhibition, active substance microstructure regulation and the like are realized.
(2) The polyaniline modified lead dioxide electrode has good oxidation-reduction reversibility and pseudocapacitance performance, can be used as a positive active substance of a lead storage battery, can enable the positive active substance of the traditional lead storage battery to have capacitor characteristics, and can also be used as an electrocatalytic material for oxygen evolution reaction in a sulfuric acid solution.
(3) With Pb2+The lead dioxide prepared by the method of anodic electrodeposition in nitrate aqueous solution has a more balanced proton distribution structure.
(4) The invention designs the electrode with a multilayer structure, utilizes the characteristic that titanium has excellent corrosion resistance in a sulfuric acid aqueous solution, and adopts titanium as an electrode base material; the anti-passivation performance of the electrode is improved through the corrosion-resistant conductive intermediate coating, the falling and inactivation of the active layer of the electrode are prevented, and the prepared polyaniline modified lead dioxide not only has high reaction activity, but also has long electrode service life. Particularly, the titanium matrix metal oxide electrode is adopted as the positive grid material of the lead storage battery, the problem of corrosion damage of the conventional positive grid is fundamentally solved, the weight of the lead storage battery is reduced, the energy density of the lead storage battery is improved, and favorable conditions are created for recycling and cyclic utilization of the electrode material of the lead storage battery.
(5) The multi-element mixed metal oxide is used as the intermediate layer, so that the binding force between the lead dioxide active layer and the substrate can be improved, the service life of the electrode is prolonged, and the electrochemical performance of the electrode is improved.
Drawings
The attached figure is a process flow schematic diagram of preparing the conductive polyaniline modified titanium-based lead dioxide electrode by an anodic oxidation codeposition method.
Example 1
As shown in the attached drawing, a method for preparing a titanium-based lead dioxide electrode modified by conductive polyaniline by an anodic oxidation codeposition method, in particular to a method for preparing a titanium-based metal oxide electrode by thermal decomposition of a precursor as an anode and Pb-containing metal oxide electrode2+The aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and the anodic oxidation codeposition technique is adopted to generate Pb at the interface of electrode/electrolyte2+Respectively obtaining lead dioxide and polyaniline through electrochemical oxidation reaction with aniline, co-depositing the generated lead dioxide and polyaniline on the surface of a titanium-based metal oxide electrode to obtain a polyaniline-modified titanium-based lead dioxide electrode, and then washing to remove impurities and electrochemically doping and activating in sulfuric acid aqueous solution to obtain the conductive polyaniline-modified titanium-based lead dioxide electrode, wherein the preparation method of the electrode is characterized by comprising the following steps of:
(1) Preparation of titanium-based metal oxide electrode
The method is characterized in that the titanium-based metal oxide electrode is prepared by taking flat titanium as an electrode substrate through surface treatment, middle layer coating, curing and roasting, and the method comprises the following specific steps:
surface treatment: mechanically polishing the titanium substrate, removing oil on the surface of alkaline solution, etching oxalic acid solution and washing to obtain a titanium substrate with a treated surface;
coating the intermediate layer: coating an intermediate layer precursor on the titanium electrode substrate subjected to the surface coating treatment in the previous step by adopting a coating method, wherein the intermediate layer precursor consists of chlorides of Sn and Sb, the precursor also comprises citric acid and glycol, the molar ratio of the citric acid to the glycol is 2.0:1, and the molar ratio of the Sn to the glycol in the intermediate layer precursor is 1: 6.0;
curing: heating and curing the titanium substrate coated with the intermediate layer precursor in an oven at the curing temperature of 70 ℃;
and fourthly, roasting: roasting the cured precursor in roasting equipment, wherein the roasting temperature is 430 ℃; the coating-curing-baking operation was repeated 10 times to obtain a titanium-based metal oxide electrode.
(2) Anodic oxidation co-deposition
The titanium-based metal oxide electrode prepared in the previous step is taken as an anode, and 0.10mol/L Pb (NO) is used 3)20.01mol/L aniline and 0.1mol/L NaNO3The water solution is electrolyte, and the anodic oxidation codeposition operation is carried out by adopting a constant current method, wherein the operation temperature is 10 ℃, and the operation current density is 200A/m2Pb in solution2+And aniline generates electrochemical oxidation reaction at an electrode/solution interface to respectively generate lead dioxide and polyaniline to be co-deposited on the titanium-based metal oxide electrode, and the reaction lasts for 10.0h to prepare the polyaniline modified titanium-based lead dioxide electrode.
(3) Washing to remove impurities
And (3) in washing impurity removal equipment, washing and impurity removal treatment are carried out on the polyaniline-modified lead dioxide electrode obtained in the last step, so as to remove nitrate impurities in the electrode.
(4) Doping activation
In sulfuric acid aqueous solution, the polyaniline modified lead dioxide electrode obtained in the previous step is taken as an anode, electrochemical doping activation is carried out by adopting a constant current method, the concentration of the sulfuric acid aqueous solution is 1.0mol/L, and the operation temperature isAt 20 ℃ and an operating current density of 500A/m2And obtaining the conductive polyaniline modified titanium-based lead dioxide electrode.
Example 2
As shown in the attached drawing, a method for preparing a titanium-based lead dioxide electrode modified by conductive polyaniline by an anodic oxidation codeposition method, in particular to a method for preparing a titanium-based metal oxide electrode by thermal decomposition of a precursor as an anode and Pb-containing metal oxide electrode 2+The aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and the anodic oxidation codeposition technique is adopted to generate Pb at the interface of electrode/electrolyte2+Respectively obtaining lead dioxide and polyaniline through electrochemical oxidation reaction with aniline, co-depositing the generated lead dioxide and polyaniline on the surface of a titanium-based metal oxide electrode to prepare a polyaniline modified titanium-based lead dioxide electrode, and then washing, removing impurities and electrochemically doping and activating in a sulfuric acid aqueous solution to prepare the conductive polyaniline modified titanium-based lead dioxide electrode, wherein the preparation of the electrode comprises the following steps:
(1) preparation of titanium-based metal oxide electrode
The method comprises the following steps of preparing a titanium-based metal oxide electrode by taking screen-shaped titanium as an electrode substrate through surface treatment, interlayer coating, curing and roasting, and specifically comprises the following steps:
surface treatment: mechanically polishing the titanium substrate, removing oil on the surface of an alkaline solution, etching the titanium substrate by an oxalic acid solution, and washing to obtain a surface-treated titanium substrate;
coating the intermediate layer: coating an intermediate layer precursor on the titanium substrate subjected to the surface treatment in the last step by adopting a coating method, wherein the intermediate layer precursor consists of chlorides of Sn and Sb and lead chloride, the precursor also comprises citric acid and glycol, the molar ratio of the citric acid to the glycol is 6.0:1, the molar ratio of the Sn to the glycol in the intermediate layer precursor is 1:24.0, and the molar ratio of the lead chloride to the glycol is 1: 24.0;
Curing: heating and curing the titanium substrate coated with the intermediate layer precursor in an oven at the curing temperature of 120 ℃;
and fourthly, roasting: roasting the cured precursor in roasting equipment, wherein the roasting temperature is 500 ℃; the coating-curing-baking operation was repeated 20 times to obtain a titanium-based metal oxide electrode.
(2) Anodic oxidation co-deposition
The titanium-based metal oxide electrode prepared in the previous step is taken as an anode, and 1.0mol/L Pb (NO) is used3)20.80mol/L aniline and 1.0mol/L NaNO3The water solution is used as electrolyte, and the anodic oxidation codeposition operation is carried out by adopting a constant current method, wherein the operation temperature is 60 ℃, and the operation current density is 2000A/m2Pb in solution2+And aniline generates electrochemical oxidation reaction at an electrode/solution interface to respectively generate lead dioxide and polyaniline to be codeposited on the titanium-based metal oxide electrode, and the titanium-based lead dioxide electrode modified by polyaniline is prepared after reaction for 1.0 h.
(3) Washing to remove impurities
And in washing and impurity removing equipment, washing and impurity removing treatment is carried out on the polyaniline-modified lead dioxide electrode obtained in the last step, and nitrate impurities in the electrode are removed.
(4) Doping activation
In sulfuric acid aqueous solution, the polyaniline-modified lead dioxide electrode obtained in the previous step is used as an anode, electrochemical doping activation is carried out by adopting a constant current method, the concentration of the sulfuric acid aqueous solution is 6.0mol/L, the operating temperature is 60 ℃, and the operating current density is 1000A/m 2And preparing the conductive polyaniline modified titanium-based lead dioxide electrode.
Example 3
As shown in the attached drawing, a method for preparing a titanium-based lead dioxide electrode modified by conductive polyaniline by an anodic oxidation codeposition method, in particular to a method for preparing a titanium-based metal oxide electrode by thermal decomposition of a precursor as an anode and Pb-containing metal oxide electrode2+The aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and the anodic oxidation codeposition technique is adopted to generate Pb at the interface of electrode/electrolyte2+Respectively obtaining lead dioxide and polyaniline by electrochemical oxidation reaction of the lead dioxide and the polyaniline, co-depositing the generated lead dioxide and the polyaniline on the surface of a titanium-based metal oxide electrode to prepare a polyaniline modified titanium-based lead dioxide electrode, washing to remove impurities, and electrochemically doping and activating in sulfuric acid aqueous solution to prepare conductive polyaniline modified lead dioxide electrodeThe titanium-based lead dioxide electrode is characterized by comprising the following preparation steps:
(1) preparation of titanium-based metal oxide electrode
The preparation method comprises the following steps of taking round bar-shaped titanium as an electrode substrate, and preparing the titanium-based metal oxide electrode through surface treatment, interlayer coating, curing and roasting, wherein the preparation method comprises the following specific steps:
surface treatment: mechanically polishing the titanium substrate, removing oil on the surface of alkaline solution, etching oxalic acid solution and washing to obtain a titanium substrate with a treated surface;
Coating the middle layer: coating an intermediate layer precursor on the titanium substrate subjected to the surface treatment in the last step by adopting a coating method, wherein the intermediate layer precursor consists of chlorides of Sn and Sb and lead chloride, the precursor also comprises citric acid and glycol, the molar ratio of the citric acid to the glycol is 4.0:1, the molar ratio of the Sn to the glycol in the intermediate layer precursor is 1:12.0, and the molar ratio of the lead chloride to the glycol is 1: 10.0;
curing: heating and curing the titanium substrate coated with the intermediate layer precursor in an oven at 100 ℃;
roasting: roasting the cured precursor in roasting equipment at the roasting temperature of 600 ℃; the coating-curing-baking operation was repeated 10 times to obtain a titanium-based metal oxide electrode.
(2) Anodic oxidation co-deposition
The titanium-based metal oxide electrode prepared in the previous step is taken as an anode, and 0.6mol/L Pb (NO) is used3)20.1mol/L aniline, 0.1mol/L LiNO3、0.1mol/L NaNO3、0.1mol/LKNO3The water solution is used as electrolyte, and the anodic oxidation codeposition operation is carried out by adopting a constant current method, the operation temperature is 40 ℃, and the operation current density is 1000A/m2Pb in solution2+And aniline generates electrochemical oxidation reaction at an electrode/solution interface to respectively generate lead dioxide and polyaniline to be codeposited on the titanium-based metal oxide electrode, and the titanium-based lead dioxide electrode modified by polyaniline is prepared after 24.0h of reaction.
(3) Washing to remove impurities
And in washing and impurity removing equipment, washing and impurity removing treatment is carried out on the polyaniline-modified lead dioxide electrode obtained in the last step, and nitrate impurities in the electrode are removed.
(4) Doping activation
In sulfuric acid aqueous solution, the polyaniline modified lead dioxide electrode obtained in the previous step is taken as an anode, electrochemical doping activation is carried out by adopting a constant current method, the concentration of the sulfuric acid aqueous solution is 1.0mol/L, the operating temperature is 40 ℃, and the operating current density is 600A/m2And obtaining the conductive polyaniline modified titanium-based lead dioxide electrode.
The prepared electrode is used as a positive electrode plate of the lead storage battery, and the performance of the battery is measured by adopting a comprehensive tester, and the result shows that the electrode prepared by the technical scheme of the invention is used as the positive electrode plate of the lead storage battery, the capacity of the electrode is improved by more than 30%, and the cycle life of the electrode is improved by more than 100%.
Besides the above examples, the present invention has many embodiments, and all the technical solutions using equivalent or equivalent substitution are within the protection scope of the present invention.

Claims (5)

1. A process for preparing the electrically conductive polyaniline modified Ti-base lead dioxide electrode by anode oxidizing codeposition features that the Ti-base metal oxide electrode prepared by thermal decomposition of precursor is used as anode and Pb-contained metal oxide is used as anode 2+Aqueous solution of aniline and alkali metal nitrate is used as electrolyte, and an anodic oxidation codeposition technology is adopted to generate Pb at an electrode/electrolyte interface2+Respectively obtaining lead dioxide and polyaniline through electrochemical oxidation reaction with aniline, co-depositing the generated lead dioxide and polyaniline on the surface of a titanium-based metal oxide electrode to prepare a polyaniline modified titanium-based lead dioxide electrode, and then washing, removing impurities and electrochemically doping and activating in a sulfuric acid aqueous solution to prepare the conductive polyaniline modified titanium-based lead dioxide electrode, wherein the preparation of the electrode comprises the following steps:
(1) preparing a titanium-based metal oxide electrode: firstly, mechanically polishing a titanium substrate, removing oil on the surface of an alkaline solution, etching by an oxalic acid solution, and washing to obtain a surface-treated titanium substrate; coating the intermediate layer precursor on the titanium substrate subjected to surface treatment; thirdly, heating and curing the titanium substrate coated with the intermediate layer precursor in an oven; fourthly, roasting the solidified precursor in roasting equipment; repeating the coating, curing and roasting operation for 5-50 times to obtain the titanium-based metal oxide electrode;
(2) anodic oxidation codeposition: the titanium-based metal oxide electrode prepared in the previous step is taken as an anode and contains Pb 2+Aqueous solution of aniline and alkali metal nitrate as electrolyte, Pb2+Carrying out oxidation reaction on the titanium-based lead dioxide electrode and aniline at an anode, and carrying out codeposition to obtain a polyaniline-modified titanium-based lead dioxide electrode; in the electrolyte, Pb (NO)3)2The concentration of the alkali metal nitrate is 0.10 mol/L-1.0 mol/L, the concentration of the aniline is 0.01 mol/L-0.80 mol/L, and the alkali metal nitrate is LiNO3、NaNO3、KNO3The total concentration of the alkali metal nitrate is between 0.1mol/L and 1.0 mol/L; the anodic oxidation codeposition method is any one method or combination of a potentiostatic method, a galvanostatic method, a cyclic voltammetry method or a pulse current method, the operating temperature is 10-60 ℃, and the operating current density is 200A/m2～2000A/m2；
(3) Washing to remove impurities: in washing and impurity removing equipment, washing and impurity removing treatment is carried out on the polyaniline-modified lead dioxide electrode obtained in the last step, and nitrate impurities in the electrode are removed;
(4) doping activation: in the aqueous solution with sulfuric acid concentration of 0.10-6.0 mol/L, the titanium-based lead dioxide electrode modified by polyaniline obtained in the previous step is used as an anode for electrochemical doping activation, the electrochemical doping activation adopts any one method or combination of a constant potential method, a constant current method, cyclic voltammetry or a pulse current method scheme, the operating temperature is 10-60 ℃, and the operating current density is 50A/m 2～1000A/m2To prepare the sulfate radical doped conductive polyaniline modified titanium-based lead dioxide electrode.
2. The method for preparing the conductive polyaniline-modified titanium-based lead dioxide electrode by the anodic oxidation codeposition method according to claim 1, which is characterized in that: the intermediate layer precursor in the step (1) of preparing the titanium-based metal oxide electrode consists of chlorides of Sn and Sb and salts of any metal of Pb, Y and La, and further comprises citric acid and ethylene glycol, wherein the molar ratio of the citric acid to the ethylene glycol is (2.0-6.0): 1.
3. The method for preparing the conductive polyaniline-modified titanium-based lead dioxide electrode by the anodic oxidation codeposition method according to claim 1, which is characterized in that: in the intermediate layer precursor prepared in the step (1), the molar ratio of Sn to ethylene glycol is 1 (6.0-24.0), and the total molar ratio of other metal salts to ethylene glycol is 1 (6.0-24.0).
4. The method for preparing the conductive polyaniline-modified titanium-based lead dioxide electrode by the anodic oxidation codeposition method according to claim 1, which is characterized in that: in the step (1), the curing temperature is 60-120 ℃, and the roasting temperature is 380-620 ℃.
5. The method for preparing the conductive polyaniline-modified titanium-based lead dioxide electrode by the anodic oxidation codeposition method according to claim 1, which is characterized in that: the geometry of the titanium substrate in the step (1) of preparing the titanium-based metal oxide electrode can be any one of a plate, a wire, a rod and a net.
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