CN111146431B - Iron-nickel battery cathode composite material and preparation method thereof - Google Patents
Iron-nickel battery cathode composite material and preparation method thereof Download PDFInfo
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- CN111146431B CN111146431B CN202010085787.1A CN202010085787A CN111146431B CN 111146431 B CN111146431 B CN 111146431B CN 202010085787 A CN202010085787 A CN 202010085787A CN 111146431 B CN111146431 B CN 111146431B
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an iron-nickel battery cathode composite material and a preparation method thereof, wherein the cathode composite material consists of 5-30 wt% of stannate compound and 70-95 wt% of active ferroferric oxide, and the preparation method comprises the following specific steps: mixing trivalent metal oxide with a potassium stannate or sodium stannate aqueous solution to form slurry, evaporating, drying and sintering at high temperature to obtain a stannate compound; and mixing and ball-milling the stannate compound and the ferroferric oxide powder to obtain the iron-nickel battery cathode composite material. The iron-nickel battery prepared by the invention can effectively reduce the charging voltage and improve the gram capacity, can improve the formation speed and the discharge platform, and can reduce the gassing amount.
Description
Technical Field
The invention belongs to the technical field of preparation of iron-nickel secondary battery iron cathode materials, and particularly relates to an iron-nickel battery cathode composite material and a preparation method thereof.
Background
The currently available square secondary batteries mainly comprise lead-acid batteries and lithium ion batteries, wherein the lead-acid batteries have low specific energy which can only reach 30 to 35wh/Kg, the cycle life is about 300 to 350 times, long charging time is needed, lead is toxic heavy metal, and the production process and the recovery process can cause serious pollution to the environment if not properly treated, so the production and the use are limited by countries in the world. The specific energy of the lithium ion battery is relatively high, but the lithium ion battery has a large capacity, is poor in safety performance in a high-voltage use environment, and simultaneously faces a series of problems that the waste lithium ion battery is difficult to recycle, causes environmental pollution and the like. The nickel-hydrogen battery in the alkaline secondary battery uses rare earth and other noble metals, so the use cost is high, and the large-scale popularization and use are difficult; the zinc-nickel secondary battery has higher specific energy and specific power, but zinc dendrite is easy to generate when the zinc cathode material is used, so that the service life of the zinc-nickel secondary battery is shortened, and the problems that the large-capacity battery is difficult to manufacture and the like exist; the iron-nickel secondary battery has long service life, is safe and environment-friendly, but the iron negative electrode potential of the iron-nickel secondary battery is easy to separate hydrogen, and has the problems of low charging efficiency, easy hydrogen separation and water loss and the like. Currently, most of the main research on the iron-nickel secondary battery is focused on the iron negative electrode, the added elements are basically in the form of oxides, particularly, the addition of cobalt element is common, and if more noble metals are used as additives, the inherent advantage of low price of the iron-nickel secondary battery is lost.
Disclosure of Invention
The invention provides an iron-nickel battery cathode composite material capable of effectively improving hydrogen evolution overpotential and charging efficiency and a preparation method thereof by combining the characteristics of an iron-nickel secondary battery. The preparation method has the advantages of simple preparation process, no solid waste and waste water generation, environmental protection, safety, and cheap and easily-obtained raw materials.
The invention adopts the following technical scheme for solving the technical problems, and the cathode composite material for the iron-nickel battery comprises 5-30 wt% of stannate compound and 70-95 wt% of active ferroferric oxide.
Preferably, the stannate is one or two of antimony stannate and bismuth stannate.
Preferably, the negative electrode composite material consists of 7wt% of stannate compound and 93wt% of active ferroferric oxide.
The preparation method of the iron-nickel battery cathode composite material comprises the following specific steps: mixing trivalent metal oxide with potassium stannate or sodium stannate aqueous solution to form slurry, and heating and evaporating to form a solid precursor; and (3) placing the solid precursor in a high-temperature furnace, sintering at the temperature of 650-1050 ℃ for 1-10h to form a stannate compound, crushing the stannate compound, mixing with active ferroferric oxide powder according to the proportion of 5-30 wt%, and performing ball milling to form the stannate-containing iron-nickel battery cathode composite material.
Preferably, the trivalent metal oxide is Sb 2 O 3 Or Bi 2 O 3 One or two of them.
Preferably, the feeding molar ratio of the trivalent metal oxide to the potassium stannate or the sodium stannate is 1:2.
Compared with the prior art, the invention has the following beneficial effects: compared with a battery which singly uses ferroferric oxide or iron powder as a negative electrode material, the iron-nickel battery negative electrode composite material prepared by the invention can effectively improve the specific capacity of the iron-nickel battery, reduce the electrode expansion, reduce the gas evolution amount and prolong the service life of the battery. The negative electrode made of the material is beneficial to improving the hydrogen evolution overpotential of the negative electrode material during charging, thereby improving the charging efficiency of the battery; the passivation phenomenon can be weakened during discharging, and the increase of internal resistance is prevented, so that the discharging efficiency and the discharging platform of the battery are improved.
Drawings
FIG. 1 shows Sb contained in example 1 2 Sn 2 O 7 And the charge-discharge comparison curve of the composite material negative electrode and the common material negative electrode.
FIG. 2 shows Bi-containing samples obtained in example 2 2 Sn 2 O 7 And the charge-discharge comparison curve of the composite material negative electrode and the common material negative electrode.
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
Mixing antimony trioxide and potassium stannate or sodium stannate in a container according to the molar ratio of 1:2, pouring deionized water into the container, stirring the mixture to form slurry, and drying the slurry at the temperature of 100 ℃; then placing the dried product in a high temperature furnace to sinter for 1.5h at the temperature of 650 ℃, and crushing to form Sb 2 Sn 2 O 7 A material; adding Sb 2 Sn 2 O 7 The material is mixed with ferroferric oxide according to the proportion of 7 weight percent, and the mixture is ball-milled in a ball mill for 1 hour to form the mixture containing Sb 2 Sn 2 O 7 The iron-nickel battery cathode composite material.
Will contain Sb 2 Sn 2 O 7 The composite material and the binder are stirred into slurry and then coated on a nickel-plated steel belt, an electrode plate is formed after drying and rolling, the electrode plate and a nickel hydroxide positive plate are assembled into a full cell, and a charge-discharge test is carried out after the electrode plate and the nickel hydroxide positive plate are formed in 6M KOH solution.
Example 2
Mixing bismuth trioxide and potassium stannate or sodium stannate in a container according to the molar ratio of 1:2, pouring deionized water into the container, stirring the mixture to form slurry, and drying the slurry at the temperature of 100 ℃; then the dried product is put into a high temperature furnace to be sintered for 1.5h at the temperature of 650 ℃, and is crushed to form Bi 2 Sn 2 O 7 A material; adding Bi to the mixture 2 Sn 2 O 7 The material is mixed with ferroferric oxide according to the proportion of 7 weight percent, and is ball-milled in a ball mill for 1 hour to form the Bi-containing material 2 Sn 2 O 7 The iron-nickel battery cathode composite material.
Will contain Bi 2 Sn 2 O 7 The composite material and the binder are stirred into slurry and then coated on a nickel-plated steel belt, an electrode plate is formed after drying and rolling, the electrode plate and a nickel hydroxide positive plate are assembled into a full cell, and a charge-discharge test is carried out after the electrode plate and the nickel hydroxide positive plate are formed in 6M KOH solution.
After the composite material prepared by the invention is used as the cathode of the iron-nickel battery, the comparison with the charging and discharging curve of the cathode material of the conventional iron-nickel battery shows that the battery containing the composite material can effectively reduce the charging voltage, improve the gram capacity, improve the formation speed and the discharging platform and reduce the gassing amount.
While there have been shown and described the fundamental principles, essential features and advantages of this invention, there are various changes and modifications that can be made without departing from the spirit and scope of the invention, and it is intended that all such changes and modifications be included within the scope of the invention as claimed.
Claims (4)
1. The application of the cathode composite material in the cathode of the iron-nickel battery is characterized in that: the cathode composite material is composed of 5-30 wt% of stannate compound and 70-95 wt% of active ferroferric oxide, wherein the stannate is antimony stannate.
2. Use according to claim 1, characterized in that: the negative electrode composite material consists of 7wt% of stannate compound and 93wt% of active ferroferric oxide.
3. The application of the anode composite material as claimed in claim 1, wherein the specific preparation process of the anode composite material is as follows: mixing trivalent metal oxide with potassium stannate or sodium stannate aqueous solution to form slurry, wherein the trivalent metal oxide is Sb 2 O 3 Heating and evaporating to form a solid precursor; and (3) placing the solid precursor in a high-temperature furnace, sintering at the temperature of 650-1050 ℃ for 1-10h to form a stannate compound, crushing the stannate compound, mixing with active ferroferric oxide powder according to the proportion of 5-30 wt%, and performing ball milling to form the stannate-containing iron-nickel battery cathode composite material.
4. Use according to claim 3, characterized in that: the feeding molar ratio of the trivalent metal oxide to the potassium stannate or the sodium stannate is 1:2.
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| JP4852713B2 (en) * | 2000-03-29 | 2012-01-11 | Ｄｏｗａエレクトロニクス株式会社 | Zinc alloy powder for alkaline batteries and method for producing the same |
| CN101422703A (en) * | 2007-10-30 | 2009-05-06 | 赢创德固赛有限责任公司 | Ionic conduction type substance permeability composite material, preparation method and use thereof |
| CN101613122B (en) * | 2008-06-27 | 2011-08-17 | 比亚迪股份有限公司 | Method for preparing stibium-doped stannic oxide materials |
| CN101651208B (en) * | 2008-12-17 | 2011-12-28 | 成都和能科技有限公司 | Low self-discharge ferrous electrode material |
| US8501351B2 (en) * | 2009-05-18 | 2013-08-06 | Powergenix Systems, Inc. | Pasted zinc electrode for rechargeable nickel-zinc batteries |
| CN102214822A (en) * | 2010-04-09 | 2011-10-12 | 国立清华大学 | Cathode electrode composite material and preparation method thereof and electrochemical device applying same |
| KR20140068850A (en) * | 2011-06-15 | 2014-06-09 | 유니버시티 오브 써던 캘리포니아 | High efficiency iron electrode and additives for use in rechargeable iron-based batteries |
| CN105552325B (en) * | 2015-12-18 | 2018-10-02 | 电子科技大学 | Iron electrode composite material and preparation method |
| CN107349943A (en) * | 2017-08-10 | 2017-11-17 | 南京理工大学 | The preparation method of bismuth stannate/silver-colored silver chlorate plasma nano composite photocatalyst material |
| 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 |
| CN109755498B (en) * | 2018-12-03 | 2022-04-19 | 河南师范大学 | Iron-based negative electrode additive for alkaline secondary battery, preparation method, iron-based negative plate using additive and application of iron-based negative plate |
| CN110690446A (en) * | 2019-09-29 | 2020-01-14 | 蔚蓝(广东)新能源科技有限公司 | Preparation method of carbon-coated ferroferric oxide for iron-nickel battery |
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| 圆柱密封铁镍碱性蓄电池研制;阎登明等;《电源技术》;20161220;第40卷(第12期);2361-2363，2404 * |
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