CN109686978B - Alkaline secondary battery iron electrode additive, preparation method, iron-based negative plate using additive and application - Google Patents
Alkaline secondary battery iron electrode additive, preparation method, iron-based negative plate using additive and application Download PDFInfo
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- CN109686978B CN109686978B CN201811467449.3A CN201811467449A CN109686978B CN 109686978 B CN109686978 B CN 109686978B CN 201811467449 A CN201811467449 A CN 201811467449A CN 109686978 B CN109686978 B CN 109686978B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel 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
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/248—Iron electrodes
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Abstract
The invention discloses an alkaline secondary battery iron electrode additive, a preparation method, an iron-based negative plate using the additive and application, and belongs to the technical field of alkaline secondary battery negative electrodes. The technical scheme provided by the invention has the key points that: the alkaline secondary battery iron electrode additive is a S@M composite material which is composed of elemental sulfur and one or more of metal or metal hydroxide and has a core-shell coating structure, wherein the elemental sulfur S is a core, and the metal or/and metal hydroxide M is a coating layer. The invention also discloses a preparation method of the iron electrode additive, an iron-based negative plate using the additive and an alkaline secondary battery using the iron-based negative plate. The alkaline secondary battery prepared by the iron electrode additive has excellent safety, ultra-long cycle life and good over-charge and over-discharge resistance, and can further meet the special requirements of the industrial field.
Description
Technical Field
The invention belongs to the technical field of alkaline secondary batteries, and particularly relates to an alkaline secondary battery iron electrode additive, a preparation method, an iron-based negative plate using the additive and application.
Background
With the increasing environmental and energy crisis, the development, transformation and storage of renewable energy has become an important aspect of the development of human society. Chemical power source is used as a novel energy storage device, has the characteristics of convenient operation, high conversion efficiency and the like, and is widely used in various social fields at present. As is well known, lithium ion batteries have high energy density and are widely used in various fields. However, the method has the defects of high production cost, easy combustion of electrolyte, potential safety hazard and the like which are difficult to overcome. At present, the development of low-cost, environment-friendly and high-efficiency energy storage systems is a key point of research of researchers.
The traditional bag-type iron-nickel secondary battery has the unique advantages of abundant material sources, low price, good safety, environmental protection, overcharge resistance, deep discharge resistance, long cycle life and the like, and is rapidly developed in a plurality of application fields. In recent years, with the increasing attention of people to green energy, the iron-nickel secondary battery is receiving the attention of researchers as a green environmental protection battery. However, iron electrodes generate iron hydroxide insulating layers in the using process, and the problems of easy passivation and easy hydrogen evolution exist, so that the rate performance of the iron-nickel battery is poor, the charging and discharging efficiency is low, the self-discharge is large, and the utilization rate of active substances is low, and the application and the development of the iron-based alkaline secondary battery are seriously restricted by the problems. In recent years, many studies have been made on the process for producing an iron electrode, and progress has been made in the capacity performance and rate performance of the iron electrode. However, the capacity performance and rate performance of the iron electrode still have a large promotion space, and it is still difficult to make up the difference between the iron electrode and other alkaline secondary batteries in terms of energy density and power density, and further development is still needed. At present, exploring a proper iron negative electrode additive is an important way for improving the electrical property of the iron-based alkaline secondary battery.
Disclosure of Invention
The invention provides an alkaline secondary battery iron electrode additive, a preparation method thereof, an iron-based negative plate using the additive and application thereof, aiming at the problems of poor negative electrode rate performance, difficulty in meeting the application in the fields of energy storage and the like of the existing alkaline iron electrode.
The invention adopts the following technical scheme to solve the technical problems, and the alkaline secondary battery iron electrode additive is characterized in that: the iron electrode additive is a S@M composite material with a core-shell coating structure, wherein the composite material is composed of elemental sulfur and one or more of metal or metal hydroxide, the elemental sulfur S is a core, and the metal or/and the metal hydroxide M is a coating layer.
More preferably, the elemental sulfur is sublimed sulfur, the mass percentage of the sublimed sulfur in the S@M composite material is 40% -99%, and the average diameter of the sublimed sulfur in particle size is controlled to be 50nm-30 μm.
Further preferably, the metal is conductive metal copper, nickel or tin, the metal hydroxide is one or more of hydroxides of copper, nickel, tin, ytterbium, erbium and indium, and the metal or/and metal hydroxide coating layer is a single layer or a plurality of layers.
The preparation method of the alkaline secondary battery iron electrode additive is characterized by comprising the following specific steps:
step S1, preparing a sulfur material: grinding elemental sulfur, and then screening to obtain elemental sulfur particles with the average particle size diameter of 50nm-30 mu m for later use;
step S2, preparation of S@M composite material: and (2) taking the elemental sulfur particles obtained in the step (S1) as a matrix, and forming a single-layer or multi-layer metal or/and metal hydroxide coating layer on the surface of the elemental sulfur particles by adopting a single or multiple chemical plating or chemical coprecipitation method.
The invention relates to an iron-based negative plate of an alkaline secondary battery, which is characterized in that: the active substance of the iron-based negative plate comprises the iron electrode additive S@M composite material, and the S@M composite material is added in a mechanical doping mode.
More preferably, the active substance of the iron-based negative plate comprises 1-20 parts by weight of S@M composite material, 50-90 parts by weight of iron-based active material, 1-15 parts by weight of additive, 1-15 parts by weight of conductive agent and 0.1-6 parts by weight of binder, wherein the iron-based active material is one or two of ferroferric oxide, ferric oxide, carbonyl iron powder or ferrous sulfide, the additive is one or more of cerium oxide, yttrium oxide, zirconium oxide, erbium oxide, cuprous oxide, nickel sulfide, nickel hydroxide or nickel sulfate, the conductive agent is one or more of conductive graphite, acetylene black, conductive carbon black, carbon nano tube, graphene, carbon fiber, titanium monoxide, copper powder, nickel powder, cobalt powder or tin powder, and the binder is one or more of sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene, hydroxypropyl methylcellulose, sodium polyacrylate, polyethylene oxide or styrene butadiene rubber.
More preferably, the active material of the iron-based negative plate is loaded on a carrier or filled in the middle of the carrier or loaded and wrapped in the carrier, and the carrier is a perforated nickel or tin plated steel strip, a three-dimensional steel strip, a nickel-plated stainless steel mesh, foamed nickel, foamed copper, foamed iron or copper mesh.
The alkaline secondary battery comprises a battery shell, an electrode plate group and electrolyte, wherein the electrode plate group is positioned in the battery shell and consists of a positive plate, a negative plate and a diaphragm or a separator arranged between the positive plate and the negative plate, and the alkaline secondary battery is characterized in that: the negative plate adopts the iron-based negative plate of the alkaline secondary battery.
In summary, compared with the prior art, the invention has the following beneficial effects: in the prior art, it is known that the problems of easy passivation, poor rate performance, low utilization rate of negative active materials, easy hydrogen evolution, self-discharge and the like exist in the use process of the iron negative electrode of the alkaline secondary battery, and the application of the type of secondary battery is greatly limited due to the problems, but the existing improvement method has various defects and cannot well solve the problems. According to the invention, through research, elemental sulfur can be used as not only an iron-based negative electrode additive of the alkaline secondary battery but also a pore-forming agent, and the performance of the iron negative electrode can be effectively improved by controlling the appropriate dosage and the appropriate addition size of the elemental sulfur, particularly the passivation phenomenon of the iron negative electrode is reduced, the gram volume of the iron negative electrode is improved, and the rate capability and the cycle performance of the iron negative electrode are improved. The S@M composite material provided by the invention can improve the conductivity of the composite material and reduce adverse effects caused by poor conductivity of elemental sulfur by modifying the beneficial metal and the hydroxide coating layer of the beneficial metal, can control the release speed of sulfur ions in the use process of a battery, provides long-term sustainable sulfur ion supply, improves the hydrogen evolution behavior of an electrode, and prolongs the service life of the electrode. The invention improves the problems of the original iron-nickel battery through the optimization of the cathode formula, greatly improves the charging efficiency and the rate capability of the iron cathode, and greatly improves the anti-hardening capability of the iron cathode. The iron electrode additive is cheap, easy to obtain and efficient, and is very beneficial to preparing a high-performance iron cathode. The iron cathode active material prepared by the technical scheme has high utilization rate and excellent rate capability, and the prepared iron-nickel alkaline secondary battery has the advantages of low internal resistance, good rate capability, long cycle life and the like.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Preparation of S @ Cu composite material:
after grinding the sublimed sulfur, screening the particles with the average diameter of 15-20 μm for later use. With 0.1mol L -1 SnCl of 2 、0.1mol L -1 Carrying out sensitization treatment on the HCl solution; then 0.001mol L of -1 PdCl of (2) 2 、0.25mol L -1 The HCl solution is taken out after being activated and is washed to be neutral by deionized water. Putting the cleaned sublimed sulfur into a copper plating solution (copper sulfate pentahydrate 25g L) -1 60ml of formaldehyde L -1 10g ml of sodium potassium tartrate L -1 Sodium hydroxide 20g L -1 Sodium potassium tartrate 20g L -1 Potassium ferrocyanide 20g L -1 ) Carrying out chemical copper plating, washing the copper plate to be neutral by deionized water after chemical plating, and drying the copper plate.
Preparing a negative plate:
mixing 58g of ferroferric oxide powder, 10g of S @ Cu composite material, 5g of iron powder, 10g of conductive graphite, 5g of bismuth oxide, 10g of PVA solution with the mass concentration of 2.5 percent and 2g of SBR aqueous solution with the mass concentration of 2 percent uniformly to prepare negative electrode slurry, coating a slurry layer on a nickel-plated steel strip by adopting a slurry pulling mode, and drying, cutting and welding a connecting plate to prepare the negative electrode plate for later use.
Example 2
S@Ni(OH) 2 Preparing a composite material:
after grinding the sublimed sulfur, screening the particles with the average diameter of 10-15 μm for later use. Dispersing sublimed sulfur into deionized water, slowly dropwise adding a nickel sulfate solution with the concentration of 2mol/L and a sodium hydroxide solution with the concentration of 2mol/L into the solution under the condition of vigorous stirring, wherein the reaction temperature is 50 ℃, the pH of the mixture after the reaction is finally =10.0, after the reaction is finished, aging the mother liquor at 50 ℃ for 5h, then filtering, and drying at 100 ℃ for 2h to obtain S @ Ni (OH) 2 A composite material.
Preparing a negative plate:
60g of ferroferric oxide powder, S @ Ni (OH) 2 Mixing 10g of composite material, 10g of conductive carbon black, 5g of cuprous oxide, 5g of ytterbium hydroxide, 2.5 percent of PVA solution 9g and 2 percent of SBR aqueous solution 1g to prepare negative pole slurry, coating a slurry layer on a nickel-plated steel strip by adopting a slurry drawing mode, and drying, cutting and welding a connecting plate to obtain the negative pole plate for later use.
Example 3
S@Cu@SnO 2 Preparing a composite material:
after grinding the sublimed sulfur, screening the particles with the average diameter of 15-20 μm for later use. With 0.1mol L -1 SnCl of 2 、0.1mol L -1 Carrying out sensitization treatment on the HCl solution; then 0.001mol L of -1 PdCl of (2) 2 、0.25mol L -1 The HCl solution is taken out after being activated and is washed to be neutral by deionized water. Putting the cleaned sublimed sulfur into a copper plating solution (copper sulfate pentahydrate 25g L) -1 Formaldehyde 60ml L -1 10g ml of sodium potassium tartrate L -1 Sodium hydroxide 20g L -1 Sodium potassium tartrate 20g L -1 Potassium ferrocyanide 20g L -1 ) Carrying out chemical copper plating, and washing the copper plate to be neutral by using deionized water after chemical plating. Then dispersed to deionizationAdding proper amount of dilute hydrochloric acid into the seed water, and then adding a certain amount of SnCl 2 Stirring for 1 hr, filtering, washing, and drying at 90 deg.C for 6 hr to obtain S @ Cu @ SnO 2 A composite material.
Preparing a negative plate:
65g of ferroferric oxide powder, S @ Cu @ SnO 2 Mixing 8g of composite material, 10g of conductive graphite, 5g of ytterbium hydroxide, 2g of nickel sulfate, 2.5 percent of HPMC solution 8g and 60 percent of PTFE aqueous solution 2g uniformly to prepare negative electrode slurry, coating a layer of slurry layer on a nickel-plated steel strip by adopting a slurry drawing mode, and drying, cutting and welding a connecting plate to obtain the negative electrode plate for later use.
Example 4
S@Ni@Sn 6 O 4 (OH) 4 Preparing a composite material:
after grinding the sublimed sulfur, screening the particles with the average diameter of 3-6 μm for later use. Preparing a plating solution: dissolving a proper amount of sodium citrate, sodium potassium tartrate, nickel sulfate and thiourea in deionized water to prepare a solution, then dropwise adding concentrated ammonia water, and adjusting the pH value of the solution to be alkaline. An appropriate amount of hydrazine (40 wt%) was measured, diluted with a small amount of distilled water, and slowly added to the prepared solution under vigorous stirring. Adding the sublimed sulfur into the plating solution, and heating in a water bath. Then adjusting the pH value of the solution by using NaOH solution to carry out chemical nickel plating. Then, dispersing the obtained sample into deionized water, and preparing SnCl with certain concentration 2 Dripping solution (prepared with dilute hydrochloric acid) and sodium hydroxide solution into the solution simultaneously, stirring, controlling pH at 12, aging for 5 hr, filtering, washing, and vacuum drying at 90 deg.C for 6 hr to obtain S @ Ni @ Sn 6 O 4 (OH) 4 A composite material.
Preparing a negative plate:
40g of ferrous sulfide, 25g of ferroferric oxide, S @ Cu @ Sn 6 O 4 (OH) 4 Mixing 10g of composite material, 12g of conductive graphite, 3g of nickel hydroxide, 2.5% of CMC solution 8g and 60% of PTFE aqueous solution 2g uniformly to prepare negative electrode slurry, coating a slurry layer on a nickel-plated steel strip by slurry drawing, and bakingAnd drying, cutting and welding the connecting plate to obtain a negative plate for later use.
Example 5
S@In(OH) 3 Preparation of @ Ag composite material:
after grinding the sublimed sulfur, screening the particles with the average diameter of 8-12 μm for later use. An appropriate amount of sublimed sulfur was dispersed in an appropriate amount of 0.5M NaOH solution as a base solution. Stirring at room temperature, adding 0.05M In (NO) 3 ) 3 ·5H 2 And dropwise adding the O solution into the base solution, continuing stirring for 1 hour after the O solution is added, filtering, washing and drying for later use. Prepared S @ in (OH) 3 Adding the material into 0.04mol L under the ultrasonic condition -1 Glucose and 0.08mol L -1 AgNO 3 Aging for 20 hr, filtering, washing, and vacuum drying to obtain S @ in (OH) 3 @ Ag composite material.
Comparative example 1
Preparing a bag type iron negative plate:
88g of ferroferric oxide powder, 10g of conductive graphite and 2g of nickel sulfate are uniformly mixed, sodium hydroxide solution is sprayed, rolling and drying granulation are carried out, active substance particles are wrapped in a steel strip electrode box through a powder wrapping machine, and the bag type negative plate is prepared through the working procedures of strip splicing, embossing, cutting, welding and the like.
Comparative example 2
Preparing a slurry-drawing iron negative plate:
84g of ferroferric oxide powder, 10g of conductive graphite and 2g of nickel sulfate, 9.5g of PVA solution with the mass concentration of 2.5 percent and 2g of SBR solution with the mass concentration of 2 percent are uniformly mixed, a slurry layer is coated on a nickel-plated steel strip by adopting a slurry drawing mode, and the nickel-plated steel strip is dried, cut and welded with a connecting plate to obtain a negative plate for later use.
Preparing a positive plate:
uniformly mixing 80g of cobalt-coated spherical nickel hydroxide, 6g of cobaltous oxide, 5g of nickel powder, 2.5 percent of HPMC 8g in mass concentration and 1g of PTFE aqueous solution in mass concentration of 60 percent to prepare positive electrode slurry, coating the positive electrode slurry on a foam nickel-based belt in a slurry drawing mode, and drying, cutting, cleaning powder and welding a connecting plate to obtain the positive electrode plate for later use.
Preparing an electrolyte: potassium hydroxide and lithium hydroxide were dissolved in deionized water to make a solution with a total molar concentration of 6.0M.
The positive and negative plates of the battery are isolated by sulfonated polypropylene diaphragms with the thickness of about 0.18 mm. And (3) putting the prepared positive plate and the prepared negative plate into a diaphragm bag, assembling a motor set by lamination, putting the motor set into a square battery shell, filling alkaline electrolyte, activating, sealing and assembling into a 10AH battery. The designed capacity of the negative electrode is 1.5 times that of the positive electrode.
And (3) testing gram capacity and rate performance of a counter electrode: the electrodes and batteries prepared using specific examples 1 to 5 and comparative examples 1 to 2 were activated at 0.2C, charged at 0.2C for 6 hours, and then the batteries were left to stand for 10 minutes, and then discharged at 0.2C and 2C to voltages of 1.0V and 0.8V, respectively, to obtain room-temperature discharge capacities. The positive electrode excess was used and the unipolar plates were evaluated for active material gram capacity.
And (3) testing the cycle performance of the battery: the batteries prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to 2C charge-discharge cycles at an ambient temperature of 25C, respectively, and the capacity retention rate was calculated after 500 cycles.
TABLE 1 Battery and plate Performance test
From the test results, the iron electrode additive provided by the invention can greatly improve the rate performance of the material. The stability of the composite material may affect the cycling performance of the electrode to some extent. Research shows that elemental sulfur in the iron electrode can not only provide sustainable supply of beneficial sulfur elements, but also form a porous structure in the circulating process, so that the hardening condition of the negative plate is greatly reduced, the electrode reaction between electrolyte and electrodes is accelerated, and the rate capability is improved.
The alkaline secondary battery iron negative plate prepared by the invention has higher negative active material utilization rate, excellent rate capability and cycle stability, and can meet the requirements of commercial batteries, especially high-power long-life batteries. The improvement in these properties is mainly attributed to: the addition of a proper amount of elemental sulfur with a proper particle size can inhibit the passivation of a polar plate, optimize the electrode structure and inhibit the caking and inactivation phenomena of an iron electrode in the circulation process, thereby improving the multiplying power and the circulation performance of the battery and improving the anti-hardening capacity of the battery. The negative plate prepared by the technical scheme has the advantages of high utilization rate of active substances, excellent negative capacity performance and rate capability, low internal resistance, good rate performance, long cycle life and the like.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (6)
1. An alkaline secondary battery iron electrode additive, characterized in that: the iron electrode additive is S@M composite material with a core-shell coating structure, wherein the S@M composite material is composed of elemental sulfur and one or more of metal or metal hydroxide, the elemental sulfur is a core, the metal or/and the metal hydroxide M is a coating layer, the elemental sulfur is sublimed sulfur, the mass percentage of the sublimed sulfur in the S@M composite material is 40% -99%, the average particle size diameter of the sublimed sulfur is controlled to be 50nm-30 mu M, the metal is conductive metal copper, nickel or tin, the metal hydroxide is one or more of hydroxides of copper, nickel, tin, ytterbium, erbium and indium, the coating layer of the metal or/and the metal hydroxide is single-layer or multi-layer, the iron electrode comprises S@M composite material in 1-20 parts by weight and iron-based active material in 50-90 parts by weight, and the iron electrode additive is used as a pore-forming agent at the same time.
2. The method for preparing the iron electrode additive of the alkaline secondary battery according to claim 1, which is characterized by comprising the following steps:
step S1, preparing a sulfur material: grinding elemental sulfur, and then screening to obtain elemental sulfur particles with the average particle size diameter of 50nm-30 mu m for later use;
step S2, preparation of S@M composite material: and (2) taking the elemental sulfur particles obtained in the step (S1) as a matrix, and forming a single-layer or multi-layer metal or/and metal hydroxide coating layer on the surfaces of the elemental sulfur particles by adopting a single or multiple chemical plating or chemical coprecipitation method.
3. An iron-based negative plate for an alkaline secondary battery, characterized in that: the active substance of the iron-based negative plate comprises S@M composite material of the iron electrode additive of claim 1, and the S@M composite material is added in a mechanical doping mode.
4. The iron-based negative plate for the alkaline secondary battery according to claim 3, wherein: the active substance of the iron-based negative plate comprises 1-20 parts by weight of S@M composite material, 50-90 parts by weight of iron-based active material, 1-15 parts by weight of additive, 1-15 parts by weight of conductive agent and 0.1-6 parts by weight of binder, wherein the iron-based active material is one or two of ferroferric oxide, ferric oxide, carbonyl iron powder or ferrous sulfide, the additive is one or more of cerium oxide, yttrium oxide, zirconium oxide, erbium oxide, cuprous oxide, nickel sulfide, nickel hydroxide or nickel sulfate, the conductive agent is one or more of conductive graphite, conductive carbon black, carbon nano tube, graphene, carbon fiber, copper powder, nickel powder, cobalt powder or tin powder, and the binder is one or more of carboxymethylcellulose sodium, polyvinyl alcohol, polytetrafluoroethylene, hydroxypropyl methylcellulose, sodium polyacrylate, polyethylene oxide or styrene-butadiene rubber.
5. The iron-based negative plate for alkaline secondary batteries according to claim 3 or 4, wherein: the active substance of the iron-based negative plate is loaded on a carrier or filled in the middle of the carrier or loaded and wrapped in the carrier, and the carrier is a perforated nickel-plated or tin-plated steel belt, a three-dimensional steel belt, a nickel-plated stainless steel net, foamed nickel, foamed copper, foamed iron or copper net.
6. The utility model provides an alkaline secondary battery, includes battery case and is located polar plate group and electrolyte of battery case, and wherein the polar plate group comprises positive plate, negative plate and the diaphragm or the baffle that sets up between positive plate and negative plate, its characterized in that: the negative plate is an iron-based negative plate for an alkaline secondary battery according to any one of claims 3 to 5.
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