CN107887575B - Method for modifying lead storage battery negative plate by polyaniline and rare earth together - Google Patents
Method for modifying lead storage battery negative plate by polyaniline and rare earth together Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/14—Electrodes for lead-acid accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/20—Processes of manufacture of pasted electrodes
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- H—ELECTRICITY
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- 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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
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Abstract
The invention discloses a method for preparing and modifying a negative plate of a lead storage battery by polyaniline, which comprises the steps of oxidizing aniline in sulfuric acid solution by using lead dioxide as an oxidant and carrying out polymerization reaction to prepare polyaniline, mixing the obtained polyaniline with lead powder to obtain a polyaniline dispersed lead plaster material, coating the obtained lead plaster material on a negative plate grid as a raw material of a negative active material of the storage battery, coating, filling, curing and drying to prepare a polyaniline modified negative green plate, carrying out electrochemical formation on the negative green plate in sulfuric acid aqueous solution containing rare earth ions as a formation solution, and carrying out electrochemical formation while a lead compound on the negative green plate is converted into spongy lead by using variable-valence rare earth ions RE in the electrochemical formation process3+The reduction reaction is carried out at the cathode to generate rare earth low-valence substance RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved.
Description
Technical Field
The invention belongs to the technical field of material preparation, particularly belongs to the technical field of preparation of negative plates of lead storage batteries and the technical field of preparation of lead-carbon electrode materials, and particularly relates to a method for jointly modifying negative plates of lead storage batteries by polyaniline and rare earth.
Background
Lead-acid battery
The lead storage battery has the advantages of simple structure, convenient use, reliable performance, lower price and the like, is widely applied to various departments of national economy, is a product with large yield and wide application range in chemical power supplies all the time, and along with the research and development and application of new materials and new technologies, the various performances of the lead storage battery are greatly improved, the advantages of the novel lead storage battery in some special application fields are more shown, and the lead storage battery is still a mainstream power supply in the near stage as an electric power-assisted vehicle, a special electric vehicle and a novel automobile power supply. However, the power type lead storage battery used in the market has a far distance from the alkaline storage battery in terms of the characteristics of large-current discharge, particularly the characteristics of large-current discharge at low temperature, and the service life of the lead storage battery is limited.
The working principle of the lead storage battery is to realize substance and energy conversion by utilizing an electrochemical principle, and the interface reaction characteristics of electrodes and electrolyte are the core and essence influencing the performance of the storage battery. Therefore, for lead storage batteries, the development of functional electrodes, the use of electrolyte with excellent performance and the matching optimization of the electrodes and the electrolyte are very important key problems in the development of novel lead storage batteries.
The basic components and materials that make up a single lead battery include: negative plate, sulfuric acid solution, separator, accumulator tank, etc.
The negative electrode plate of the lead storage battery is an important component constituting the single lead storage battery. The negative plate of lead accumulator is composed of negative plate grid and negative active material. The characteristics of the negative plate/electrolyte interface, particularly the negative plate grid/electrolyte interface and the negative active material/electrolyte interface, are important factors that affect the performance of the battery. In general, the service life of a negative plate grid is a main influence factor influencing the service life of a negative plate, and the microstructure and the morphology of an active substance are another important parameter influencing the utilization rate of the active substance of a battery, the conductivity of an electrode and the service life of the electrode.
Composition of negative plate of lead storage battery
The negative plate of the lead storage battery mainly comprises a negative plate grid and a negative active material, and the main functions of the negative plate grid and the negative active material are respectively functions of the negative plate grid and the negative active material.
The main function of the negative grid of the lead storage battery
The negative grid of the lead storage battery has the following main functions:
(1) the current collecting framework is used for conducting and collecting current and enabling the current to be distributed uniformly, and the utilization rate of the negative active material is improved;
(2) and the support carrier of the negative active material is a negative grid which plays a role of supporting the negative active material through a frame and ribs.
The main function of the negative active material of the lead storage battery
The main functions of the negative active material of the lead storage battery are as follows:
(1) participating in electrochemical reaction, and converting non-conductive lead sulfate into conductive spongy lead during charging; the conductive spongy lead is converted to non-conductive lead sulfate during discharge.
(2) The negative active material is porous active material, and the partially conductive spongy lead active material does not participate in electrochemical reaction, is used as an electric path for providing the conduction from the reaction point to the grid, and is only used for maintaining the structural integrity and good conductivity.
Therefore, the following requirements are imposed on the active material of the negative electrode plate of a lead storage battery: high hydrogen evolution potential, good corrosion resistance, good conductivity and large current passing.
Composition of negative plate of lead storage battery
The negative plate of the lead storage battery mainly comprises a negative plate grid and a negative active material, and the main functions of the negative plate grid and the negative active material are respectively functions of the negative plate grid and the negative active material.
The main function of the negative grid of the lead storage battery
The negative grid of the lead storage battery has the following main functions:
(1) the current collecting framework is used for conducting and collecting current and enabling the current to be distributed uniformly, and the utilization rate of the negative active material is improved;
(2) and the support carrier of the negative active material is a negative grid which plays a role of supporting the negative active material through a frame and ribs.
The main function of the negative active material of the lead storage battery
The main functions of the negative active material of the lead storage battery are as follows:
(1) participating in electrochemical reaction, and converting non-conductive lead sulfate into conductive spongy lead during charging; the conductive spongy lead is converted to non-conductive lead sulfate during discharge.
(2) The negative active material is porous active material, and the partially conductive spongy lead active material does not participate in electrochemical reaction, is used as an electric path for providing the conduction from the reaction point to the grid, and is only used for maintaining the structural integrity and good conductivity.
Therefore, the following requirements are imposed on the active material of the negative electrode plate of a lead storage battery: high hydrogen evolution potential, good corrosion resistance, good conductivity and large current passing.
The negative plate of the lead storage battery in the prior art has the main problems
The negative plate of the lead storage battery in the prior art has the main problems that:
(1) the negative grid has the problem of reduced conductivity in the use process: coarse lead sulfate crystal branches are easily generated on the surface of the negative plate grid in the using process, the resistivity of the lead sulfate crystal branches is high, the coarse lead sulfate is difficult to charge, the charging voltage of the battery is required to be high, and the grid conductivity of the negative plate is reduced.
Problem of deterioration of electrochemical properties of negative electrode active material: when the lead electrode discharges, lead loses electrons to generate lead sulfate crystals with poor conductivity, the lead sulfate crystals cover the surface of the negative active material, and when the lead sulfate crystals reach a certain thicknessLeading to difficult contact between the negative active material and the electrolyte, hindering the continuous reaction of the negative active material, leading the lead negative electrode to be passivated, and the discharge capacity is gradually reduced along with the increase of the charge-discharge cycle times; the electrode reaction is preferentially carried out on the surface of the electrode, the lead sulfate as a reaction product is a poor conductor, so that the internal resistance of the battery is increased along with the discharge, and the reactant H2SO4And the diffusion to the deep part of the electrode is difficult, so that more unreacted materials are remained, and the utilization rate of the negative electrode active material is reduced.
The matching problem of the active material of the negative plate of the lead storage battery and the negative plate grid is as follows: the prior art has the problems that a negative grid and a negative active material are basically mechanically wrapped, the contact wrapping force is not enough, and the negative active material falls off in the use process of a lead storage battery.
Therefore, the research and development of a novel negative plate grid and a negative active material and the process matching of the negative plate grid and the negative active material are realized, and the preparation of the negative plate with excellent performance is to further improve the performance of the current lead storage battery, so that the current problems of the lead storage battery are urgently solved.
Rare earth element modified lead storage battery negative plate
In order to improve the performance of lead negative electrode active materials of lead storage batteries, a method for improving electrode materials by adopting rare earth elements is developed. The rare earth element is a flavor type additive, and the lanthanide element has special optical, electric, magnetic and other properties and specific properties in various aspects due to the special 4f electronic layer structure of the lanthanide element, and is widely applied to the fields of new materials such as magnetism, electricity, luminescence, metallurgy, catalysis, nuclear energy, metal materials and the like. The negative plate is modified by rare earth materials, the performance of the lead storage battery is improved, and the problems that the specific energy of the traditional lead storage battery is low, the power characteristic, the consistency and the low-temperature performance of the lead storage battery are poor are solved. Rare earths are called "treasuries" of new materials. The rare earth modified negative plate has wide application prospect in improving the performance of the lead storage battery.
The invention discloses a preparation method of a lead storage battery negative plate grid (ZL 201010183718.0) and a method for modifying a lead storage battery negative plate (ZL 201010183712.3), which adopt an electrochemical reduction technology, add rare earth ions into a sulfuric acid aqueous solution, and adopt an electrochemical reduction method to obtain a rare earth modified negative plate to improve the performance of the lead storage battery and the performance of the negative plate. The research and development ideas of the patents are that rare earth ions are added into a sulfuric acid electrolyte solution, the concentration of the rare earth ions is changed, the processing conditions of a negative plate in different electrolytes are controlled, an electrochemical reduction technology is applied, and the surface performance of an electrode is improved, so that a novel and efficient lead storage battery negative plate grid is obtained; by adding rare earth oxide or rare earth sulfate additive into the negative active material, especially rare earth element oxide or rare earth sulfate material added into the negative active material, the performance of the negative active material is obviously improved, and the conductivity, active material utilization rate and charge-discharge performance of the negative electrode are improved.
The invention discloses a method (201410640843.8) for modifying a negative plate of a lead storage battery by rare earth and a method (ZL201410641311.6) for modifying a positive plate of the lead storage battery by the rare earth, which are invented by Chinese patents, wherein in the electrochemical formation process of the lead storage battery electrode, rare earth sulfate or rare earth oxide is added into an electrochemical formation liquid, variable high-valence rare earth ions generate a reduction reaction at a cathode to modify the negative plate of the lead storage battery, variable low-valence rare earth ions generate a reduction reaction at the cathode to modify the negative plate of the lead storage battery, and the rare earth modified positive plate is realized while the positive plate is formed, so that the performance of the lead.
The rare earth material is adopted to modify the negative plate of the battery and improve the performance of the lead storage battery, thereby fundamentally solving the problems of low specific energy of the traditional lead storage battery, obviously improving the power characteristic, consistency and low-temperature performance of the lead storage battery and the like.
The principle of the technologies is to improve the performance of the electrode material by utilizing the particularity of the rare earth elements. These invented techniques are very effective as key techniques for solving the problems of cadmium-free lead-acid battery electrodes and lead reduction. However, as the negative electrode active material of spongy lead of lead-acid battery, especially when the lead-acid battery is in the process of rapid charge and discharge, and more importantly in the process of dynamic charge and discharge (such as the process of starting and rapid charge of electric vehicle), the method for rapidly and effectively carrying out rapid charge and discharge by using capacitor technology is the fastest method, and obviously, the method for improving the performance of electrode material by using rare earth element is difficult to meet the requirement of rapid charge and discharge. Therefore, the development of a novel process technology for modifying spongy lead is an electrode material which has the technical principle of an electrochemical capacitor and can meet the requirements of a dynamic charge-discharge process under the condition of improving the use condition of a storage battery with the spongy lead as a negative electrode active substance of the spongy lead of the lead storage battery, and the problem to be solved is to further improve the performance of the current spongy lead electrode.
Therefore, a new method for modifying the negative plate of the lead storage battery is required to solve the above problems.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a method for modifying a negative plate of a lead storage battery by polyaniline and rare earth together, aiming at the problems in the prior art.
The technical scheme is as follows: in order to solve the technical problem, the invention provides a method for jointly modifying a negative plate of a lead storage battery by polyaniline and rare earth, which comprises the following steps: the method comprises the following steps:
1) preparing polyaniline: mixing water, sulfuric acid and aniline to form an aqueous solution of sulfuric acid and aniline sulfate, adding lead dioxide as an oxidant to oxidize aniline and perform a polymerization reaction to generate polyaniline, and simultaneously converting lead dioxide into lead sulfate to form a mixture of polyaniline, lead sulfate and sulfuric acid;
2) preparing a negative green plate: adding lead powder into the mixture of polyaniline, lead sulfate and sulfuric acid obtained in the step 1), dispersing and mixing to obtain a polyaniline dispersed lead plaster material, coating the polyaniline dispersed lead plaster material on a negative plate grid as a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a polyaniline modified negative green plate;
3) electrochemical formation: mixing water, sulfuric acid and rare earth sulfate or rare earth oxide to prepare a sulfuric acid aqueous solution containing rare earth ions as an electrochemical formation solution, wherein in the electrochemical formation process, the rare earth ions RE are rare earth ions while the sulfate on a negative plate is converted into spongy lead3+Reduction reaction at cathodeRare earth low-valent substance RE should be generated2+Rare earth low-valent substance RE2+And modifying a negative plate grid and a negative active substance to realize the synergistic improvement of the negative plate of the lead storage battery by the polyaniline and the rare earth.
Further, the concentration of the sulfuric acid in the step 1) is 1.8mol/L-4.8 mol/L.
Further, the concentration of the aniline sulfate aqueous solution in the step 1) is 0.001mol/L-0.10 mol/L.
Further, the molar ratio of the lead dioxide to the aniline in the step 1) is (0.8-1.2): 1.0.
Further, the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline in the step 2) is 0.02-2.00%.
Furthermore, the rare earth element in the step 3) comprises at least one variable valence rare earth element of samarium Sm, europium Eu and ytterbium Yb.
Furthermore, the rare earth element in the step 3) also comprises lanthanum and/or yttrium.
Further, the valence rare earth ion RE in the step 3)3+The total concentration in the electrochemical forming liquid is 0.001mol/L-0.200mol/L, and the rare earth ions RE3+The total concentration of the electrochemical formation solution is 0.001-0.200 mol/, and the concentration of the sulfuric acid is 1.8-4.8 mol/L.
Further, the electrochemical formation method in the step 3) includes one or more of potentiostatic formation method, galvanostatic formation method, cyclic voltammetry method and pulse charging scheme formation method based on the gauss theorem.
Furthermore, the formation operation temperature of the electrochemical formation in the step 3) is 10-60 ℃.
The invention principle is as follows:
(1) the characteristics of polyaniline (PAn) are utilized: the characteristics of polyaniline and the existence of-NH in the molecular chain structure2The groups and the aromatic ring have close relation in the electricity supply property, thereby endowing the polyaniline with unique chemical and electrochemical excellent performances; the polyaniline has certain conductive function after adulteration and activation, and the polyaniline has strong reversibility and chemical stability due to electrochemical oxidation/reduction cycle reactionThe conductive polymer is one of conductive polymers which can effectively improve the performance of electrode materials, and is a modification material for electrochemical oxidation reaction, storage batteries and electrochemical capacitor electrodes. Therefore, when used as an electrode active material for a secondary battery, the material has a large amount of stored electricity, a high energy density, and a long service life and a low self-discharge property.
Utilizing the characteristic of aniline (An) oxidation polymerization reaction to generate PAn (chemical oxidation method): the characteristic that aniline can be oxidized under acidic condition and in the presence of chemical oxidant to generate polyaniline product with conductive function is utilized. Therefore, in the sulfuric acid aqueous solution, lead dioxide is used as an oxidant, aniline is oxidized by the lead dioxide to generate a polyaniline product with a conductive function, the polyaniline product is reduced in the process of oxidizing aniline by the lead dioxide to obtain a non-conductive lead sulfate product, and spongy lead can be obtained by regenerating the non-conductive lead sulfate product by an electrochemical reduction method by adopting an electrochemical formation technology.
The PAn is utilized to dope the activation characteristic in an acidic medium: polyaniline has a unique doping mechanism and a bulk phase reaction mechanism in an acidic medium, particularly in a sulfuric acid aqueous solution, so that the polyaniline has good oxidation/reduction reversibility.
The valence-variable characteristics of the rare earth elements are fully utilized: the principle of adopting rare earth to improve the negative plate is a method for improving the performance of the negative plate of the current lead storage battery based on the specific physical and chemical properties of the rare earth. The principle of adopting rare earth to improve the negative plate grid is a method for improving the negative plate grid performance of the current lead storage battery based on the specific physical and chemical properties of the rare earth. The lanthanides beside La, Gd and Lu produce valence changes. Such as Ce3+、Pr3+、Tb3+And Dy3+Form a tetravalent, but Sm3+、Eu3+Yb, Yb of Yb3+A divalent state is formed.
The electrode/electrolyte interface reaction characteristics are fully utilized, and the electrochemical technology is used for rare earth modification on the surface of the electrode: by adding different types of rare earth sulfate into a sulfuric acid electrolyte solution, adopting an electrochemical reduction technology, and utilizing the characteristics that the rare earth sulfate is easily soluble in water, the rare earth salt is subjected to precipitation reaction under an alkaline condition to generate rare earth hydroxide or rare earth oxide, and the rare earth hydroxide or the rare earth oxide is difficultly soluble in water. The rare earth oxide is precipitated and deposited on the surface of the electrode.
The electrochemical reaction characteristics of the lead storage chemical formation process are fully utilized: the formation of the negative plate of the lead storage battery is actually the first charging of the negative plate of the battery, so the performance and the service life of the produced lead storage battery are directly influenced by the quality of the formation.
(7) Polyaniline-modified spongy lead active substance: polyaniline has a certain conductive function after adulteration and activation, and is one of conductive polymers for effectively improving the performance of electrode materials due to the characteristics of strong reversibility of electrochemical oxidation/reduction cycling reaction, high chemical stability and the like, and is a modification and modification material for electrochemical oxidation reaction, storage batteries and electrochemical capacitor electrodes. The spongy lead modified by polyaniline or the composite material formed by the polyaniline and the spongy lead has unique characteristics, can effectively improve the performance of the spongy lead electrode, and is a consistent and novel lead-carbon battery electrode material.
The process technology of the invention fully considers the following characteristics:
(1) utilizing the characteristic of aniline (An) oxidation polymerization reaction to generate PAn (chemical oxidation method): the characteristic that aniline can be oxidized under acidic condition and in the presence of chemical oxidant to generate polyaniline product with conductive function is utilized. Therefore, in the sulfuric acid aqueous solution, lead dioxide on the surface of the electrode is used as an oxidant, and the lead dioxide oxidizes aniline to generate a polyaniline product with a conductive function, so that the lead dioxide is modified by polyaniline, and the performance of the lead dioxide electrode is improved; the lead sulfate product which is reduced in the process of oxidizing the aniline by the lead dioxide and is not conductive is regenerated by an electrochemical reduction method by adopting an electrochemical formation technology to obtain the lead.
Make full use of the PbSO which is not conductive4The conductive lead can be obtained by electrochemical reduction regeneration: by using PbSO4Reduction reaction at the cathode to generate conductive material Pb in PbSO4/H2SO4The interface is subjected to reduction reaction to lead PbSO4Pb is produced. In cathodic electrochemical oxidation processes, only the electrode/electricityReacting on the interface of the electrolyte, carrying out reactants and products on the interface, and directly using Pb prepared by cathode reduction as an electrocatalytic electrode material.
The electrochemical reaction characteristics of the lead sulfate formation-PA doping activation coupling technology are utilized: lead is obtained by utilizing the formation of lead sulfate in a sulfuric acid medium, and PAn is doped and activated in the sulfuric acid medium to obtain a conductive polymer, and the conversion of lead sulfate in the sulfuric acid medium and lead, the doping and activation of PAn in the sulfuric acid medium and the oxidation/reduction of polyaniline have excellent reaction reversibility. And during electrode formation, PAn doping activation is realized, and the performance of the lead electrode is further improved.
Adding rare earth sulfate or rare earth oxide into electrochemical formation liquid, and changing the type and concentration of rare earth ions to add rare earth sulfate or rare earth oxide into the electrochemical formation liquid in the formation process of lead storage battery electrode battery, so that RE in the electrochemical formation liquid is added in the formation process of battery3+Respectively generate RE by reduction reaction at the cathode2+The negative plate of the lead storage battery is modified, the rare earth modified negative plate grid and the negative active material of the battery are used for improving the performance of the lead storage battery, and the performance of the lead storage battery is further improved.
Make full use of RE3+Equivalent valence property of rare earth and synergistic effect of rare earth modified negative plate of lead storage battery: eu (Eu)3+The rare earth sulfate is easy to dissolve in water, the rare earth salt is subjected to precipitation reaction under an alkaline condition to generate rare earth hydroxide or rare earth oxide, and the rare earth hydroxide or rare earth oxide is difficult to dissolve in water. Rare earth sulfate or rare earth oxide is added into the electrochemical formation solution, and the performance of the negative plate of the lead storage battery is modified by adopting an electrochemical cathode technology. Eu (Eu)3+Sm capable of reducing at the cathode3+、Eu3+Yb, Yb of Yb3+A divalent state is formed. And (3) performing surface modification on the negative grid by adopting a cathodic electrochemical reduction method. Hydrogen ions or water are reduced at the cathode to release hydrogen, and simultaneously a layer of alkaline solution is generated near the interface of the electrode/electrolyte, and rare earth metal ions are generated under alkaline conditionsAnd generating rare earth hydroxide or rare earth oxide precipitate, and depositing the rare earth hydroxide or rare earth oxide precipitate on the surface of the cathode electrode. Adding rare earth oxide or rare earth sulfate into high-concentration sulfuric acid solution to perform Eu3+And the electrochemical reduction is carried out, the deposition of rare earth on the surface of the electrode realizes the modification of the surface of the electrode, the cathode electrochemical reduction method is adopted to carry out surface modification on a negative plate grid, a layer of alkaline solution is generated near an electrode/electrolyte interface, and rare earth metal ions generate rare earth hydroxide or rare earth oxide precipitate under the alkaline condition and deposit the rare earth hydroxide or rare earth oxide precipitate on the surface of the cathode electrode.
Has the advantages that: the method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth utilizes lead dioxide as an oxidant to oxidize aniline in sulfuric acid solution and perform polymerization reaction to prepare polyaniline, the obtained polyaniline is mixed with lead powder to obtain polyaniline dispersed lead plaster materials, the polyaniline dispersed lead plaster materials are used as raw materials of negative active materials of the storage battery to be coated on a negative plate grid, coating, filling, curing and drying are performed to prepare a polyaniline modified negative green plate, the sulfuric acid aqueous solution of the negative green plate containing the rare earth ions is used as electrochemical formation liquid to perform electrochemical formation, and in the electrochemical formation process, when the lead compound on the negative green plate is converted into spongy lead, the variable valence rare earth ions RE are converted into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth high-price substance further modifies a negative plate grid and a negative active substance of the negative plate, thereby realizing the synergistic improvement of the lead storage battery performance by polyaniline and rare earth elements, realizing the polyaniline modification of the negative plate grid and the negative active substance of the battery, improving the lead storage battery performance, remarkably improving the performance of the negative plate of the battery, and improving the conductivity, the active substance utilization rate and the charging and discharging performance of the electrode.
Detailed Description
The invention will be further elucidated with reference to the following specific examples.
Example 1:
a process for preparing polyaniline and modifying negative plate of lead accumulator includes oxidizing and polymerizing aniline, dispersing and mixing polyaniline and lead powder, preparing plate and electrochemical couplingA process for preparing negative plate of lead accumulator modified by polyaniline includes such steps as oxidizing aniline in sulfuric acid solution by lead dioxide as oxidant, polymerizing to obtain polyaniline, mixing polyaniline with lead powder to obtain dispersed lead paste, coating the lead paste on negative plate grid, coating it on negative plate grid, coating, solidifying and drying to obtain raw negative plate modified by polyaniline, electrochemical formation of rare-earth ions in sulfuric acid solution, and converting the lead compound on negative plate into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved. The method comprises the following steps:
(1) preparing polyaniline: adding water, sulfuric acid and aniline into polyaniline preparation equipment in sequence by adopting an oxidation-oxidation technology for mixing to form an aqueous solution consisting of 1.8mol/L sulfuric acid and 0.01mol/L aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline, wherein the molar ratio of lead dioxide to aniline is 0.8:1.0, aniline is oxidized and undergoes a polymerization reaction to generate polyaniline, and lead dioxide is converted into lead sulfate to form a mixture of polyaniline, lead sulfate, aniline sulfate and sulfuric acid;
(2) preparing a negative green plate: adding the prepared lead powder into the materials by adopting a dispersion mixing technology, continuously performing dispersion mixing to obtain a lead plaster material with dispersed polyaniline, wherein the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline is 0.02%, coating the lead plaster material with dispersed polyaniline on a negative plate grid as a raw material of a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a negative green plate modified by the polyaniline;
(3) electrochemical formation: adopting electrochemical formation technology, mixing and preparing water, sulfuric acid and rare earth sulfate or rare earth oxide in electrochemical formation liquid preparation equipment,preparing electrochemical formation liquid of 0.001mol/L Sm, 0.001mol/L La and 1.8mol/L sulfuric acid, adopting a 2.80V constant potential formation method in the electrochemical formation process, wherein the formation operation temperature is 10 ℃, and in the electrochemical formation process, when sulfate on a negative plate is converted into spongy lead, rare earth ions RE are simultaneously converted into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance to improve the performance of the lead storage battery, and the polyaniline and the rare earth are used for improving the performance of the negative material of the lead storage battery cooperatively.
Example 2:
a method for preparing polyaniline and modifying lead storage battery negative plate, adopting aniline oxidation and polymerization-polyaniline and lead powder dispersion mixing-plate preparation and electrochemical formation coupling technology to prepare polyaniline modified lead storage battery negative plate, especially using lead dioxide as oxidant to oxidize aniline in sulfuric acid solution and make polymerization reaction to obtain polyaniline, mixing polyaniline and lead powder to obtain polyaniline dispersed lead plaster material, using the obtained lead plaster material as raw material of storage battery negative active material to coat on negative plate grid, coating, filling, curing and drying to obtain polyaniline modified negative green plate, electrochemically forming negative green plate in sulfuric acid aqueous solution containing rare earth ions as forming solution, in the course of electrochemical formation, at the same time of converting lead compound on the negative green plate into spongy lead, variable valence rare earth ion RE3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved. The method comprises the following steps:
(1) preparing polyaniline: adding water, sulfuric acid and aniline into polyaniline preparation equipment in batches for mixing to form an aqueous solution consisting of 4.8mol/L sulfuric acid and 0.10mol/L aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline, wherein the molar ratio of lead dioxide to aniline is 1.2:1.0, aniline is oxidized and undergoes a polymerization reaction to generate polyaniline, and lead dioxide is converted into lead sulfate to form a mixture of polyaniline, lead sulfate and sulfuric acid;
(2) preparing a negative green plate: adding the prepared lead powder into the materials by adopting a dispersion mixing technology, continuously performing dispersion mixing to obtain a lead plaster material with dispersed polyaniline, wherein the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline is 2.00%, coating the lead plaster material with dispersed polyaniline on a negative plate grid as a raw material of a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a negative green plate modified by the polyaniline;
(3) electrochemical formation: adopting an electrochemical formation technology, mixing and preparing water, sulfuric acid and rare earth sulfate or rare earth oxide in electrochemical formation solution preparation equipment to prepare 0.001mol/L Eu, 0.019 mol/L Y and 4.8mol/L sulfuric acid as electrochemical formation solutions, and adopting a constant current formation method in the electrochemical formation process, wherein the formation operation temperature is 60 ℃, and the operation current density is 5mA/cm2During electrochemical formation, the rare earth ion RE is converted into spongy lead while the sulfate on the negative plate is converted into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance to improve the performance of the lead storage battery, and the polyaniline and the rare earth are used for improving the performance of the negative material of the lead storage battery cooperatively.
Example 3:
a process for preparing polyaniline and modified negative plate of lead accumulator includes such steps as oxidizing aniline in sulfuric acid solution by lead dioxide as oxidant, polymerizing to obtain polyaniline, mixing it with lead powder to obtain dispersed lead paste, coating it on negative plate grid, solidifying, drying to obtain modified negative plate, electrochemical conversion of said plate in sulfuric acid solution containing rare-earth ions, and electrochemical conversionIn the formation process, the lead compound on the negative electrode green plate is converted into spongy lead, and simultaneously, the variable-valence rare earth ions RE3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved. The method comprises the following steps:
(1) preparing polyaniline: adding water, sulfuric acid and aniline into polyaniline preparation equipment in sequence by adopting an oxidation-oxidation technology for mixing to form an aqueous solution consisting of 2.8mol/L sulfuric acid and 0.06mol/L aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline, wherein the molar ratio of lead dioxide to aniline is 1.0:1.0, aniline is oxidized and undergoes a polymerization reaction to generate polyaniline, and lead dioxide is converted into lead sulfate to form a mixture of polyaniline, lead sulfate and sulfuric acid;
(2) preparing a negative green plate: adding the prepared lead powder into the materials by adopting a dispersion mixing technology, continuously performing dispersion mixing to obtain a lead plaster material with dispersed polyaniline, wherein the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline is 1.00%, coating the lead plaster material with dispersed polyaniline on a negative plate grid as a raw material of a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a negative green plate modified by the polyaniline;
(3) electrochemical formation: adopting an electrochemical formation technology, mixing and preparing water, sulfuric acid and rare earth sulfate or rare earth oxide in electrochemical formation liquid preparation equipment to prepare electrochemical formation liquid of 0.001mol/L Yb, 0.018mol/L Y and 2.8mol/L sulfuric acid, and adopting a constant current formation method in the electrochemical formation process, wherein the formation operation temperature is 50 ℃, and the operation current density is 20mA/cm2During electrochemical formation, the rare earth ion RE is converted into spongy lead while the sulfate on the negative plate is converted into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance to improve the performance of the lead storage battery, and the polyaniline and the rare earth are used for improving the lead storage battery synergisticallyAnd (4) performance of a battery negative electrode material.
Example 4:
a method for preparing polyaniline and modifying lead storage battery negative plate, adopting aniline oxidation and polymerization-polyaniline and lead powder dispersion mixing-plate preparation and electrochemical formation coupling technology to prepare polyaniline modified lead storage battery negative plate, especially using lead dioxide as oxidant to oxidize aniline in sulfuric acid solution and make polymerization reaction to obtain polyaniline, mixing polyaniline and lead powder to obtain polyaniline dispersed lead plaster material, using the obtained lead plaster material as raw material of storage battery negative active material to coat on negative plate grid, coating, filling, curing and drying to obtain polyaniline modified negative green plate, electrochemically forming negative green plate in sulfuric acid aqueous solution containing rare earth ions as forming solution, in the course of electrochemical formation, at the same time of converting lead compound on the negative green plate into spongy lead, variable valence rare earth ion RE3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved. The method comprises the following steps:
(1) preparing polyaniline: adding water, sulfuric acid and aniline into polyaniline preparation equipment in sequence by adopting an oxidation-oxidation technology for mixing to form an aqueous solution consisting of 4.8mol/L sulfuric acid and 0.06mol/L aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline, wherein the molar ratio of lead dioxide to aniline is 0.9:1.0, aniline is oxidized and undergoes a polymerization reaction to generate polyaniline, and lead dioxide is converted into lead sulfate to form a mixture of polyaniline, aniline sulfate, lead sulfate and sulfuric acid;
(2) preparing a negative green plate: adding the prepared lead powder into the materials by adopting a dispersion mixing technology, continuously performing dispersion mixing to obtain a lead plaster material with dispersed polyaniline, wherein the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline is 1.20%, coating the lead plaster material with dispersed polyaniline on a negative plate grid as a raw material of a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a negative green plate modified by the polyaniline;
(3) electrochemical formation: adopting an electrochemical formation technology, mixing and preparing water, sulfuric acid and rare earth sulfate or rare earth oxide in electrochemical formation liquid preparation equipment to prepare electrochemical formation liquid with the concentration of 0.001mol/L Sm, 0.001mol/L Eu, 0.009mol/L La, 0.009mol/L Y and 4.8mol/L sulfuric acid, adopting a cyclic voltammetry method in the electrochemical formation process, wherein the formation operation temperature is 40 ℃, and rare earth ions RE are converted into spongy lead while sulfate on a negative plate is converted into the spongy lead in the electrochemical formation process3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance to improve the performance of the lead storage battery, and the polyaniline and the rare earth are used for improving the performance of the negative material of the lead storage battery cooperatively.
Example 5:
a method for preparing polyaniline and modifying lead storage battery negative plate, adopting aniline oxidation and polymerization-polyaniline and lead powder dispersion mixing-plate preparation and electrochemical formation coupling technology to prepare polyaniline modified lead storage battery negative plate, especially using lead dioxide as oxidant to oxidize aniline in sulfuric acid solution and make polymerization reaction to obtain polyaniline, mixing polyaniline and lead powder to obtain polyaniline dispersed lead plaster material, using the obtained lead plaster material as raw material of storage battery negative active material to coat on negative plate grid, coating, filling, curing and drying to obtain polyaniline modified negative green plate, electrochemically forming negative green plate in sulfuric acid aqueous solution containing rare earth ions as forming solution, in the course of electrochemical formation, at the same time of converting lead compound on the negative green plate into spongy lead, variable valence rare earth ion RE3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved. The method comprises the following steps:
(1) preparing polyaniline: adding water, sulfuric acid and aniline into polyaniline preparation equipment in sequence by adopting an oxidation-oxidation technology for mixing to form an aqueous solution consisting of 3.8mol/L sulfuric acid and 0.06mol/L aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline, wherein the molar ratio of lead dioxide to aniline is 1.1:1.0, aniline is oxidized and undergoes a polymerization reaction to generate polyaniline, and lead dioxide is converted into lead sulfate to form a mixture of polyaniline, lead sulfate and sulfuric acid;
(2) preparing a negative green plate: adding the prepared lead powder into the materials by adopting a dispersion mixing technology, continuously performing dispersion mixing to obtain a lead plaster material with dispersed polyaniline, wherein the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline is 1.00%, coating the lead plaster material with dispersed polyaniline on a negative plate grid as a raw material of a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a negative green plate modified by the polyaniline;
(3) electrochemical formation: adopting an electrochemical formation technology, mixing and preparing water, sulfuric acid and rare earth sulfate or rare earth oxide in electrochemical formation liquid preparation equipment to prepare 0.001mol/L Sm, 0.001mol/L Eu, 0.001mol/L Yb, 0.008mol/L La, 0.006mol/L Y and 2.8mol/L sulfuric acid as electrochemical formation liquid, wherein in the electrochemical formation process, the electrochemical formation method is a constant potential formation method, a pulse charging scheme formation method based on the Masson theorem is adopted, the operation temperature of formation is 40 ℃, and the operation current density is 5mA/cm2-20mA/cm2During electrochemical formation, the rare earth ion RE is converted into spongy lead while the sulfate on the negative plate is converted into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance to improve the performance of the lead storage battery, and the polyaniline and the rare earth are used for improving the performance of the negative material of the lead storage battery cooperatively.
Example 6:
a process for preparing polyaniline and modified negative plate of lead accumulator includes oxidizing and polymerizing aniline, dispersing and mixing polyaniline and lead powder, preparing electrode plate and electrochemical couplingA negative plate of battery is prepared through oxidizing phenylamine in sulfuric acid solution by using lead dioxide as oxidant, polymerizing to obtain polyaniline, mixing it with lead powder to obtain dispersed lead paste, coating it on negative plate grid, solidifying and drying to obtain modified negative plate, electrochemical formation of negative plate in the aqueous solution of sulfuric acid containing rare-earth ions, and converting the lead compound on negative plate into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance of the negative plate, so that the polyaniline and the rare earth are used for modifying the negative material cooperatively, and the performance of the negative plate of the lead storage battery is improved. The method comprises the following steps:
(1) preparing polyaniline: adding water, sulfuric acid and aniline into polyaniline preparation equipment in sequence by adopting an oxidation-oxidation technology for mixing to form an aqueous solution consisting of 2.8mol/L sulfuric acid and 0.10mol/L aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline, wherein the molar ratio of lead dioxide to aniline is 1.0:1.0, aniline is oxidized and undergoes a polymerization reaction to generate polyaniline, and lead dioxide is converted into lead sulfate to form a mixture of polyaniline, lead sulfate and sulfuric acid;
(2) preparing a negative green plate: adding the prepared lead powder into the materials by adopting a dispersion mixing technology, continuously performing dispersion mixing to obtain a lead plaster material with dispersed polyaniline, wherein the mass percent of the polyaniline in the lead plaster material with dispersed polyaniline is 0.80%, coating the lead plaster material with dispersed polyaniline on a negative plate grid as a raw material of a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a negative green plate modified by the polyaniline;
(3) electrochemical formation: adopting electrochemical formation technology, mixing and preparing water, sulfuric acid and rare earth sulfate or rare earth oxide in electrochemical formation liquid preparation equipment to obtain 0.0006mol/L Sm, 0.0004mol/L Eu and 0.016mol/L oxideLa and 1.8mol/L sulfuric acid are used as electrochemical formation liquid, in the electrochemical formation process, the electrochemical formation method is a combination of a constant potential formation method and a pulse charging scheme formation method based on the Masson's theorem, the operation temperature of formation is 40 ℃, and the operation current density is 5mA/cm2-20mA/cm2During electrochemical formation, the rare earth ion RE is converted into spongy lead while the sulfate on the negative plate is converted into spongy lead3+The reduction reaction is carried out at the cathode to generate RE2+The generated rare earth low-price substance further modifies a negative plate grid and a negative active substance to improve the performance of the lead storage battery, and the polyaniline and the rare earth are used for improving the performance of the negative material of the lead storage battery cooperatively.
The performance of the battery is measured by a comprehensive tester, and the result shows that the cycle life of the battery is prolonged by more than 100% by adopting the technical scheme of the invention and reaches more than 3 times of the same product under the optimized condition.
The invention has the beneficial effects that:
(1) the lead electrode modified by polyaniline is used as a negative active material of a lead storage battery because of good oxidation/reduction reversibility and pseudocapacitance performance.
(2) Polyaniline used as an electrode material has the characteristic of pseudo-capacitance performance, and the capacitance behavior of the PAn-based electrode can be effectively improved by compounding the PAn and a carbon material. On the one hand, the presence of lead in the composite electrode may make the electrode more conductive, especially when the PAn is in a neutral state; on the other hand, the lead electrode additive can effectively weaken the volume change degree of the PAn in the charge and discharge process and improve the cycle performance of the PAn.
(3) Lead dioxide is used as an oxidant to oxidize aniline and polymerize to generate polyaniline, separation and refining are not needed, the preparation process of polyaniline is obviously simplified, and the prepared polyaniline and materials in the reaction process are directly used as raw materials for improving electrode active substances.
(4) By adopting the technology of step-by-step preparation and pre-dispersion mixing, the polyaniline is uniformly dispersed and mixed in the lead plaster, and the material utilization rate is high. Firstly, sequentially adding water, sulfuric acid and aniline into polyaniline preparation equipment for mixing to form an aqueous solution consisting of sulfuric acid and aniline sulfate, then adding lead dioxide as an oxidant to oxidize aniline and polymerize to generate polyaniline, and simultaneously converting lead dioxide into lead sulfate to form materials of polyaniline, lead sulfate and sulfuric acid so as to realize pre-dispersion mixing of polyaniline; adding the prepared lead powder into the materials, continuously carrying out dispersion mixing to obtain a lead plaster material with polyaniline dispersed, coating the lead plaster material with polyaniline dispersed as a raw material of a negative electrode active material of a storage battery on a negative electrode grid, carrying out coating, curing and drying to prepare a negative electrode green plate modified by polyaniline, and uniformly distributing the polyaniline in the electrode active material.
(5) The rare earth is fully applied to mainly improve the negative grid and the polyaniline mainly improves the performance of the electrode active substance, so that the grid and the active substance of the electrode plate are fully improved. The preparation method is simple, the operation and the control are convenient, some trace rare earth is easily uniformly and quantitatively doped on the surface of the electrode, and polyaniline is uniformly distributed in the electrode active substance, so that the regulation and the control of the improvement performance of the electrode are realized.
(6) The rare earth is fully applied to mainly improve the negative grid and the polyaniline mainly improves the performance of the electrode active substance, so that the grid and the active substance of the electrode plate are fully improved. The preparation method is simple, the operation and the control are convenient, some trace rare earth is easily uniformly and quantitatively doped on the surface of the electrode, and polyaniline is uniformly distributed in the electrode active substance, so that the regulation and the control of the improvement performance of the electrode are realized.
The present invention is not limited to the above embodiments, and all technical solutions formed by using equivalents or equivalent substitutions belong to the scope of the claims of the present invention. 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 (10)
1. A method for modifying a negative plate of a lead storage battery by polyaniline and rare earth is characterized by comprising the following steps: the method comprises the following steps:
1) preparing polyaniline: mixing water, sulfuric acid and aniline to form an aqueous solution of sulfuric acid and aniline sulfate, adding lead dioxide as an oxidant to oxidize aniline and perform a polymerization reaction to generate polyaniline, and simultaneously converting lead dioxide into lead sulfate to form a mixture of polyaniline, lead sulfate and sulfuric acid;
2) preparing a negative green plate: adding lead powder into the mixture of polyaniline, lead sulfate and sulfuric acid obtained in the step 1), dispersing and mixing to obtain a polyaniline dispersed lead plaster material, coating the polyaniline dispersed lead plaster material on a negative plate grid as a negative active material of a storage battery, and performing coating, filling, curing and drying to prepare a polyaniline modified negative green plate;
3) electrochemical formation: mixing water, sulfuric acid and rare earth sulfate or rare earth oxide to prepare a sulfuric acid aqueous solution containing rare earth ions as an electrochemical formation solution, wherein in the electrochemical formation process, the sulfate on a negative plate is converted into spongy lead, and simultaneously, the valence-variable rare earth ions RE3+The reduction reaction is carried out at the cathode to generate rare earth low-valence substance RE2+Rare earth low-valent substance RE2+And modifying a negative plate grid and a negative active substance to realize the synergistic improvement of the negative plate of the lead storage battery by the polyaniline and the rare earth.
2. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: the concentration of the sulfuric acid in the step 1) is 1.8-4.8 mol/L.
3. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: the concentration of the aniline sulfate aqueous solution in the step 1) is 0.001mol/L-0.10 mol/L.
4. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: the molar ratio of the lead dioxide to the aniline in the step 1) (0.8-1.2) is 1.0.
5. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: the mass percentage of the polyaniline in the lead plaster material with dispersed polyaniline in the step 2) is 0.02-2.00%.
6. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: in the step 3), the rare earth element in the rare earth sulfate or the rare earth oxide comprises at least one variable valence rare earth element of samarium Sm, europium Eu and ytterbium Yb.
7. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 6, wherein the method comprises the following steps: the rare earth element in the step 3) also comprises lanthanum or yttrium.
8. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: in step 3), the variable rare earth ion RE3+The total concentration in the electrochemical forming solution is 0.001-0.200 mol/L, and the concentration of the sulfuric acid is 1.8-4.8 mol/L.
9. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: the electrochemical formation method in the step 3) comprises one or more of potentiostatic formation method, galvanostatic formation method, cyclic voltammetry and pulse charging formation method based on the Mass theorem.
10. The method for jointly modifying the negative plate of the lead storage battery by the polyaniline and the rare earth as recited in claim 1, characterized by comprising the following steps: the formation operation temperature of the electrochemical formation in the step 3) is 10-60 ℃.
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