CN109786745B - Iron-based negative plate of alkaline secondary battery, preparation method of iron-based negative plate and alkaline secondary battery using iron-based negative plate - Google Patents
Iron-based negative plate of alkaline secondary battery, preparation method of iron-based negative plate and alkaline secondary battery using iron-based negative plate Download PDFInfo
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Abstract
The invention discloses an iron-based negative plate of an alkaline secondary battery, a preparation method thereof and the alkaline secondary battery using the iron-based negative plate, belonging to the technical field of alkaline secondary batteries. The technical scheme provided by the invention has the key points that: an iron-based negative plate of an alkaline secondary battery comprises 1-20 parts by weight of elemental sulfur, 50-90 parts by weight of an iron-based active material, 1-15 parts by weight of an additive, 1-15 parts by weight of a conductive agent and 0.1-6 parts by weight of a binder, wherein the elemental sulfur is simultaneously used as the additive and a pore-forming agent. The invention also discloses a preparation method of the iron-based negative plate of the alkaline secondary battery and the alkaline secondary battery using the iron-based negative plate. The alkaline secondary battery of the present invention has excellent safety, an ultra-long cycle life and good charge and over-discharge resistance, and further can meet special requirements in the industrial field.
Description
Technical Field
The invention belongs to the technical field of alkaline secondary batteries, and particularly relates to an iron-based negative plate of an alkaline secondary battery, a preparation method of the iron-based negative plate and the alkaline secondary battery using the iron-based negative plate.
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 alkaline secondary battery comprises a hydrogen nickel battery, a zinc nickel battery, an iron nickel battery and the like, has the advantages of safety, low cost, greenness, no pollution, environmental friendliness and the like, and is continuously developed in a plurality of application fields. Among them, the alkaline secondary battery (iron-nickel battery) using the iron-based negative electrode has unique advantages of abundant material sources, low price, good safety, environmental protection, overcharge resistance, deep discharge resistance, long cycle life and the like, and thus has become a hot point of research. In recent years, with the increasing attention of people to green energy, iron-based alkaline secondary batteries are receiving the attention of researchers as green and environment-friendly batteries. However, the iron electrode generates an iron hydroxide insulating layer in the using process, and has the problems of easy passivation and easy hydrogen evolution, so that the iron-nickel battery has poor rate performance, low charging and discharging efficiency, large self-discharge and low utilization rate of active substances, and the application and development of the iron-based alkaline secondary battery are severely 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, there is still a large room for improvement in capacity performance and rate performance of the iron electrode, and it is still difficult to make up for 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 suitable iron negative electrode modification method is an important way for improving the electrical property of the iron-based alkaline secondary battery.
Disclosure of Invention
The invention provides an iron-based negative plate of an alkaline secondary battery, a preparation method thereof and the alkaline secondary battery using the iron-based negative plate, aiming at the problems of poor rate performance, difficult application in the fields of energy storage and the like of the iron-based negative plate of the alkaline secondary battery at present.
The invention adopts the following technical scheme for solving the technical problems, and the iron-based negative plate of the alkaline secondary battery is characterized in that: the negative active material of the iron-based negative plate of the iron-based alkaline secondary battery comprises elemental sulfur which is simultaneously used as an additive and a pore-forming agent.
More preferably, the negative active material of the iron-based negative plate of the iron-based alkaline secondary battery comprises 1-20 parts by weight of elemental sulfur, 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.
Preferably, 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, and the conductive agent is one or more of conductive graphite, acetylene black, conductive carbon black, carbon nano tube, graphene, carbon fiber, titanium oxide, copper powder, nickel powder, cobalt powder or tin powder; the binder is one or more of sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene, hydroxypropyl methylcellulose, sodium polyacrylate, polyethylene oxide or styrene butadiene rubber.
Further preferably, the elemental sulfur is preferably sublimed sulfur, and the average particle size diameter of the elemental sulfur after being added to the negative plate is controlled to be 0.5 to 30 μm.
Further preferably, the average particle size diameter of the sublimed sulfur added to the negative plate is controlled to 10 to 20 μm.
Further preferably, the elemental sulfur is added by directly mechanically mixing with other active materials or by mixing with other active materials and then ball-milling into a composite material.
Further preferably, the negative active material 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 belt, a three-dimensional steel belt, a nickel plated stainless steel net, foamed nickel, foamed copper, foamed iron or copper net.
The preparation method of the iron-based negative plate of the alkaline secondary battery is characterized in that the negative plate with negative active substances loaded on a carrier is prepared by the following specific steps:
step S1, preparation of active material slurry: uniformly mixing 50-90 parts by weight of ferroferric oxide or carbonyl iron powder, 1-20 parts by weight of elemental sulfur, 1-15 parts by weight of additive and 1-15 parts by weight of conductive agent, adding a binder aqueous solution prepared from 0.1-6 parts by weight of binder, and uniformly stirring to obtain active substance slurry;
step S2, preparation of the iron-nickel secondary battery negative plate: and (4) scraping and coating the active substance slurry prepared in the step (S1) on a matrix of a punched nickel-plated or tin-plated steel strip, a three-dimensional steel strip, foamed nickel, foamed copper or nickel-plated foamed iron or copper mesh through a slurry drawing die, drying, rolling and cutting to obtain the negative plate of the iron-nickel secondary battery.
The preparation method of the iron-based negative plate of the alkaline secondary battery is characterized in that the negative plate with negative active substances filled in the middle of a carrier is prepared by the following specific steps:
step S1, preparation of active substance particles: uniformly mixing 50-90 parts by weight of ferroferric oxide or carbonyl iron powder, 1-20 parts by weight of elemental sulfur, 1-15 parts by weight of additive and 1-15 parts by weight of conductive agent, adding a binder aqueous solution prepared from 0.1-6 parts by weight of binder, uniformly stirring, drying and granulating to obtain active substance particles;
step S2, preparation of the iron-nickel secondary battery negative plate: and (4) wrapping the active substance particles prepared in the step (S1) in strip-shaped small boxes made of nickel-plated steel strips or copper strips through a powder wrapping machine, then drawing the plurality of strip-shaped small boxes, pressing transverse stripes on the surfaces of the strip-shaped small boxes for fixing, and finally performing spot welding on conductive tabs through wrapping ribs and current collecting plates to obtain the negative plate of the iron-nickel secondary battery.
The alkaline secondary battery comprises a battery shell, an electrode plate group and electrolyte, wherein the electrode plate group and the electrolyte are positioned in the battery shell, the electrode plate group comprises 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.
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 capability, low utilization rate of negative active materials, easy hydrogen evolution, large self-discharge and the like exist in the using process of an iron-based negative plate of an alkaline secondary battery, the application of the secondary battery is greatly limited due to the problems, and the technical problems cannot be well solved due to various defects of the existing improved method. According to the invention, through research, the elemental sulfur material can be used as an iron-based negative electrode additive of the alkaline secondary battery and a pore-forming agent, and the performance of the iron negative electrode can be effectively improved by controlling the appropriate addition amount and the appropriate addition size of the elemental sulfur material, particularly the passivation phenomenon of the iron negative electrode is reduced, so that 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 alkaline secondary battery prepared by the novel iron-based negative plate has the advantages of high specific energy, high specific power and long cycle life.
Drawings
FIG. 1 is a graph of rate capability of an iron negative electrode made in example 9;
FIG. 2 is an SEM image of an electrode prepared in example 9 after 100 cycles containing 0 wt% S and 10 wt% S;
FIG. 3 is an XRD pattern during cycling of the 10 wt% S iron containing negative electrode made in example 9;
fig. 4 is a schematic diagram of the effect of elemental sulfur during use of an iron anode.
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 sublimed sulphur (average diameter 0.5-3 μm):
the sublimed sulfur purchased was ball-milled for 4 hours using a ball mill, and sublimed sulfur particles having an average diameter of 0.5 to 3 μm were prepared by sieving.
Preparing an iron-based negative plate:
uniformly mixing 62g of ferroferric oxide powder, 8g of sublimed sulfur (the average diameter is 0.5-3 mu m), 11g of conductive graphite, 4g of yttrium oxide, 2g of nickel sulfate, 8g of PVA solution with the mass concentration of 2.5% and 2g of SBR aqueous solution with the mass concentration of 2% to prepare negative electrode slurry; and coating a slurry layer on the nickel-plated steel strip by adopting a slurry drawing mode, and drying, cutting and welding a connecting plate to obtain the negative plate for later use.
Example 2
Preparation of sublimed sulphur (average diameter 4-9 μm) material:
the sublimed sulfur purchased was ball-milled for 0.5 hour using a ball mill, and particles of sublimed sulfur having an average diameter of 4 to 9 μm were prepared by sieving.
Preparing an iron-based negative plate:
uniformly mixing 60g of ferroferric oxide powder, 10g of sublimed sulfur (the average diameter is 4-9 mu m), 10g of conductive carbon black, 5g of cuprous oxide, 3g of zirconium oxide, 2g of nickel hydroxide, 9g of PVA solution with the mass concentration of 2.5% and 1g of SBR aqueous solution with the mass concentration of 2% to prepare negative electrode slurry; and coating a slurry layer on the nickel-plated steel strip by adopting a slurry drawing mode, and drying, cutting and welding a connecting plate to obtain a negative plate for later use.
Example 3
Preparation of sublimed sulphur (average diameter 10-15 μm) material:
the sublimed sulfur purchased was directly sieved to prepare sublimed sulfur particles having an average diameter of 10 to 15 μm.
Preparing an iron-based negative plate:
uniformly mixing 55g of ferric oxide powder, 10g of sublimed sulfur (the average diameter is 10-15 mu m), 15g of conductive graphite, 5g of cuprous oxide, 3g of erbium oxide, 2g of nickel sulfate, 8g of HPMC solution with the mass concentration of 2.5% and 2g of PTFE aqueous solution with the mass concentration of 60% to prepare negative electrode slurry; and coating a slurry layer on the nickel-plated steel strip by adopting a slurry drawing mode, and drying, cutting and welding a connecting plate to obtain a negative plate for later use.
Example 4
Preparation of sublimed sulphur (average diameter 16-25 μm) material:
the sublimed sulfur purchased was directly sieved to prepare sublimed sulfur particles having an average diameter of 16 to 25 μm.
Preparing an iron-based negative plate:
uniformly mixing 57g of ferroferric oxide, 8g of sublimed sulfur (the average diameter is 16-25 mu m), 12g of conductive graphite, 5g of copper hydroxide, 5g of zirconium hydroxide, 2g of ytterbium hydroxide, 1g of nickel sulfate, 8g of CMC solution with the mass concentration of 2.5% and 2g of PTFE aqueous solution with the mass concentration of 60% to prepare negative electrode slurry; and coating a slurry layer on the nickel-plated steel strip by adopting a slurry drawing mode, and drying, cutting and welding a connecting plate to obtain a negative plate for later use.
Example 5
The procedure of example 1 was repeated except that the powdered magnetite of example 1 was replaced with carbonyl iron powder.
Example 6
The same procedure as in example 1 was repeated except that 50 wt% of the powdered ferric oxide powder in example 1 was replaced with ferrous sulfide powder.
Example 7
Uniformly mixing 70g of ferroferric oxide powder, 10g of sublimed sulfur (the average diameter is 10-15 mu m), 10g of conductive graphite, 3g of cerium oxide, 2g of nickel hydroxide, 4g of CMC solution with the mass concentration of 2.5% and 1g of PTFE aqueous solution with the mass concentration of 60%, rolling, drying and granulating; and (3) wrapping active substance particles into the steel strip pole box through a powder wrapping machine, and performing the working procedures of strip splicing, embossing, cutting, welding and the like to prepare the bag-type iron negative plate.
Example 8
Preparing a sublimed sulfur and ferroferric oxide composite material:
mixing the purchased sublimed sulfur and ferroferric oxide according to the weight ratio of 77:10, ball-milling for 4 hours by adopting a ball mill, and preparing the composite material of the ferroferric oxide and the sublimed sulfur by screening.
Preparing an iron-based negative plate:
uniformly mixing 87g of ferroferric oxide and sublimed sulfur composite material, 10g of conductive graphite and 3g of PTFE aqueous solution with the mass concentration of 10% to prepare negative electrode slurry; and coating the slurry on the foamed nickel by adopting a slurry scraping mode, and drying, cutting and welding a connecting plate to obtain a negative plate for later use.
Example 9
The purchased sublimed sulfur is directly used in the preparation of the negative electrode of the battery, and the weight proportions of different sublimed sulfur additions are adjusted to be 0 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt% and 13 wt%.
Preparing an iron-based negative plate:
uniformly mixing ferroferric oxide (87-X) wt%, sublimed sulfur X wt%, conductive graphite 10 wt% and 10% PTFE aqueous solution 3 wt%, wherein X is 0, 3, 5, 7, 10 or 13, and preparing into negative electrode slurry; and coating the slurry on the foamed nickel by adopting a slurry scraping mode, and drying, cutting and welding a connecting plate to obtain a negative plate for later use.
Comparative example 1
Preparing a bag type iron negative plate:
uniformly mixing 88g of ferroferric oxide powder, 10g of conductive graphite and 2g of nickel sulfate, spraying a sodium hydroxide solution, rolling, drying and granulating; and (3) wrapping active substance particles into the steel strip pole box through a powder wrapping machine, and performing the processes of splicing, embossing, cutting, welding and the like to prepare the bag-type negative plate.
Comparative example 2
Preparing a slurry-drawing iron negative plate:
84g of ferroferric oxide powder, 10g of conductive graphite, 2g of nickel sulfate, 9.5g of PVA solution with the mass concentration of 2.5% and 2g of SBR solution with the mass concentration of 2% are uniformly mixed, a slurry layer is coated on a nickel-plated steel strip in 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, 8g of HPMC (hydroxy propyl methyl cellulose) with the mass concentration of 2.5% and 1g of PTFE (polytetrafluoroethylene) aqueous solution with the mass concentration of 60% to prepare anode slurry; the positive plate is coated on a foam nickel-based belt in a slurry drawing mode, and the positive plate is obtained for later use after drying, cutting, powder cleaning and welding of a connecting plate.
Preparing an electrolyte: dissolving potassium hydroxide and lithium hydroxide into deionized water to prepare a solution with the total molar concentration of 6.0M.
The positive and negative plates of the battery are separated by a sulfonated polypropylene diaphragm 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 the diaphragm bag into an electrode group by lamination, putting the electrode group into a square battery case, 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.
To pair
Electrode gram capacity and rate performance test: the negative electrode plates and the batteries prepared in examples 1 to 9 and comparative examples 1 to 2 were activated at 0.2C, charged at 0.2C for 6 hours, and then 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 mode is adopted, and the gram capacity of the active material of the battery plate is evaluated.
And (3) testing the cycle performance of the battery: the batteries prepared in examples 1-8, 9(10 wt% S) and 1-2 were subjected to 2C charge-discharge cycles at 25 ℃ ambient temperature, respectively, for 500 cycles, and the capacity retention rate was calculated.
TABLE 1 Battery and plate Performance test
In example 9, different contents of sublimed sulfur are directly adopted to carry out a comparative experiment, the rate performance is shown in figure 1, and the doping of sublimed sulfur greatly improves the rate performance of the material. From the above test results, it can be seen that the diameter size of the sublimed sulfur particles affects the cycle performance of the electrode to some extent. Through carrying out scanning electron microscope test to the electrode after the circulation, when discovering that large granule sublimed sulphur uses as the additive, can form porous structure on the electrode at the circulation in-process, this will greatly improve electrode surface and inner structure, and then reduce its passivation phenomenon. And XRD test is carried out on the structural change of the electrode in the circulating process, and the result shows that an FeS active layer is formed on the surface of the electrode, so that the formation of an iron hydroxide passivation layer is greatly inhibited. FIG. 4 is a schematic diagram of the mechanism of action of elemental sulfur based on the findings of the above studies. 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 polar plate is greatly reduced, the electrode reaction between electrolyte and electrodes is accelerated, and the rate capability of the battery is improved.
The iron cathode of the alkaline secondary battery prepared by the invention has higher utilization rate of cathode active materials, 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 the elemental sulfur with proper amount and particle size can inhibit the passivation of the polar plate, optimize the electrode structure and inhibit the caking and inactivation phenomena of the iron electrode in the circulation process, thereby improving the multiplying power and the circulation performance and improving the anti-hardening capacity of the iron electrode. The anode active material prepared by the technical scheme has the advantages of high utilization rate, excellent cathode 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 (4)
1. An iron-based negative plate for an alkaline secondary battery, characterized in that: the negative active material of the alkaline secondary battery iron-based negative plate comprises 1-20 parts by weight of sublimed sulfur, 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, the sublimed sulfur is simultaneously used as the additive and pore-forming agent, the sublimed sulfur is added in a mode of being directly mechanically mixed with other active materials or being mixed with other active materials and then being ball-milled into a composite material, the average particle size diameter of the sublimed sulfur added to the negative plate is controlled to be 10-20 mu m, 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 tubes, graphene, carbon fibers, titanium monoxide, copper powder, nickel powder, cobalt powder or tin powder, the binder is one or more of sodium carboxymethylcellulose, polyvinyl alcohol, polytetrafluoroethylene, hydroxypropyl methyl cellulose, sodium polyacrylate, polyethylene oxide or styrene butadiene rubber, the negative active substance is loaded on a carrier or filled in the middle of the carrier or loaded and wrapped in the carrier, and the carrier is perforated nickel plating, tinned steel strip, three-dimensional steel strip, nickel-plated stainless steel mesh, foamed nickel, foamed copper, foamed iron or copper mesh.
2. A method for preparing an iron-based negative plate for an alkaline secondary battery according to claim 1, wherein the negative plate with a negative active material supported on a carrier is prepared by the following steps:
step S1, preparation of active material slurry: uniformly mixing 50-90 parts by weight of ferroferric oxide or carbonyl iron powder, 1-20 parts by weight of sublimed sulfur, 1-15 parts by weight of additive and 1-15 parts by weight of conductive agent, adding a binder aqueous solution prepared from 0.1-6 parts by weight of binder, and uniformly stirring to obtain active substance slurry;
step S2, preparation of the iron-nickel secondary battery negative plate: and (4) scraping and coating the active substance slurry prepared in the step (S1) on a matrix of a punched nickel-plated or tin-plated steel strip, a three-dimensional steel strip, foamed nickel, foamed copper or nickel-plated foamed iron or copper mesh through a slurry drawing die, drying, rolling and cutting to obtain the negative plate of the iron-nickel secondary battery.
3. A method for preparing an iron-based negative plate of an alkaline secondary battery according to claim 1, wherein the negative plate with the negative active material filled in the middle of the carrier is prepared by the following steps:
step S1, preparation of active substance particles: uniformly mixing 50-90 parts by weight of ferroferric oxide or carbonyl iron powder, 1-20 parts by weight of sublimed sulfur, 1-15 parts by weight of additive and 1-15 parts by weight of conductive agent, adding a binder aqueous solution prepared from 0.1-6 parts by weight of binder, uniformly stirring, drying and granulating to obtain active substance particles;
step S2, preparation of the iron-nickel secondary battery negative plate: and (4) wrapping the active substance particles prepared in the step (S1) in strip-shaped small boxes made of nickel-plated steel strips or copper strips through a powder wrapping machine, then drawing the plurality of strip-shaped small boxes, pressing transverse stripes on the surfaces of the strip-shaped small boxes for fixing, and finally performing spot welding on conductive tabs through wrapping ribs and current collecting plates to obtain the negative plate of the iron-nickel secondary battery.
4. 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 includes positive plate, negative plate and sets up diaphragm or the baffle 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 claim 1.
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| US3853624A (en) * | 1970-07-17 | 1974-12-10 | Westinghouse Electric Corp | High energy density iron-nickel battery |
| CN107681118A (en) * | 2017-09-03 | 2018-02-09 | 河南师范大学 | Iron nickel secondary batteries negative plate and preparation method thereof and the iron nickel secondary batteries using the negative plate |
| CN108878786A (en) * | 2018-06-01 | 2018-11-23 | 河南师范大学 | High-power iron nickel secondary batteries of a kind of list pocket type and preparation method thereof |
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| US9935312B2 (en) * | 2013-09-05 | 2018-04-03 | Encell Technology, Inc. | Nickel-iron battery with a chemically pre-formed (CPF) iron negative electrode |
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| US3853624A (en) * | 1970-07-17 | 1974-12-10 | Westinghouse Electric Corp | High energy density iron-nickel battery |
| CN107681118A (en) * | 2017-09-03 | 2018-02-09 | 河南师范大学 | Iron nickel secondary batteries negative plate and preparation method thereof and the iron nickel secondary batteries using the negative plate |
| CN108878786A (en) * | 2018-06-01 | 2018-11-23 | 河南师范大学 | High-power iron nickel secondary batteries of a kind of list pocket type and preparation method thereof |
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| 李青松.铁镍蓄电池铁负极性能研究.《中国优秀硕士学位论文全文数据库电子期刊工程科技II辑》.2012,(第6期), * |
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