CN111029563A - Preparation method of alkaline secondary battery iron negative electrode material - Google Patents

Preparation method of alkaline secondary battery iron negative electrode material Download PDF

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Publication number
CN111029563A
CN111029563A CN201911259055.3A CN201911259055A CN111029563A CN 111029563 A CN111029563 A CN 111029563A CN 201911259055 A CN201911259055 A CN 201911259055A CN 111029563 A CN111029563 A CN 111029563A
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iron
secondary battery
oxide
tin
negative electrode
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CN201911259055.3A
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CN111029563B (en
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杨玉锋
徐平
李群杰
彭英长
李喜歌
王晓燕
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Henan Troily New Energy Technology Co ltd
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Henan Troily New Energy Technology Co ltd
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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
    • H01M4/48—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
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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

Abstract

The invention discloses a preparation method of an iron cathode material of an iron-nickel secondary battery, which comprises the following specific steps: uniformly mixing iron oxide and tin oxide in proportion or co-precipitating iron salt and tin salt in proportion under an alkaline condition, and sintering the product at 700-1050 ℃ for 1-8 h in an inert or reducing atmosphere to prepare the alkaline secondary battery iron cathode material SnFe2O4Spinel structure material used as negative electrode active material or additive of iron-nickel secondary battery. Tin is beneficial to improving the hydrogen evolution overpotential of the cathode material during charging, so that the charging efficiency of the iron-nickel secondary battery is improved; during discharging, the interaction between tin ions and the discharge product ferric hydroxide is utilized to weaken the passivation phenomenon and prevent the increase of internal resistance, thereby improving the discharge efficiency and discharge platform of the iron-nickel secondary battery and eliminating the conventional iron negative electrode materialAnd a discharge second platform of the material electrode.

Description

Preparation method of alkaline secondary battery iron negative electrode material
Technical Field
The invention belongs to the technical field of preparation of iron cathode materials of iron-nickel secondary batteries, and particularly relates to a preparation method of an iron cathode material of an alkaline secondary battery.
Background
The current available secondary batteries mainly comprise lead-acid storage batteries and lithium ion batteries, wherein the specific energy of the lead-acid storage batteries is low and generally can only reach 30-35 Wh/Kg, the cycle life is about 300-350 times, long charging time is needed, meanwhile, lead is toxic heavy metal, and if the lead is not properly treated during production and recovery, the lead can cause serious pollution to the environment, and the lead is limited by all countries in the world in production and use. The specific energy of the lithium ion battery is relatively high, but the lithium ion battery has the problems of high capacity, poor safety performance in a high-voltage use environment, difficulty in recycling the waste lithium ion battery, pollution and the like.
The raw materials of the iron-nickel secondary battery are easy to purchase and easy to obtain and are not controlled, and the iron-nickel secondary battery has the characteristics of environmental protection and safety in the production, use and recovery processes. However, the overpotential of hydrogen evolution of the iron cathode of the iron-nickel secondary battery is low, the second platform of discharging is obvious, a large amount of hydrogen can be evolved particularly in the later stage of charging, and the charging efficiency of the iron cathode of the iron-nickel secondary battery is reduced to a certain extent due to the generation of the hydrogen; and the high-current discharge performance, the low-temperature performance and the like can not be effectively solved. Most of the research at present focuses on the use of additives, and although the performance of the iron negative electrode is improved, the structure and inherent characteristics of the iron negative electrode material cannot be changed.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing the alkaline secondary battery iron cathode material which can effectively improve hydrogen evolution overpotential, reduce charging voltage and improve specific capacity of the battery, wherein the alkaline secondary battery iron cathode material prepared by the method is SnFe2O4The spinel structure utilizes the relatively high hydrogen evolution overpotential of tin to inhibit the hydrogen evolution of the iron cathode during charging, and can improve the charging efficiency and the formation rate. Tin ion is oxidized and dissolved out in situ and two farads are released during dischargingThe second electron capacity can improve the discharge efficiency.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the iron cathode material of the alkaline secondary battery is characterized by comprising the following specific processes: uniformly mixing iron oxide and tin oxide in proportion, and sintering at 700-1050 ℃ for 1-8 h in inert atmosphere or reducing atmosphere to obtain the alkaline secondary battery iron cathode material SnFe2O4A spinel structure material; or putting a product obtained by coprecipitation of soluble ferric salt and soluble tin salt in proportion under an alkaline condition into an inert or reducing atmosphere at 700-1050 ℃ for sintering for 1-8 h to prepare the alkaline secondary battery iron cathode material SnFe2O4A spinel structure material. The SnFe2O4Tin is beneficial to improving the hydrogen evolution overpotential of the cathode material during charging of the material, so that the charging efficiency is improved; during discharging, the interaction between tin ions and the discharge product iron hydroxide is utilized, so that the passivation phenomenon is weakened, the increase of internal resistance is prevented, and the discharge efficiency and the discharge platform of the iron-nickel secondary battery are improved.
Further preferably, the iron oxide is one or more of ferric oxide or ferroferric oxide; the tin oxide is one or more of stannous oxide or stannic oxide; the soluble ferric salt is one or more of ferric chloride or ferric sulfate; the soluble tin salt is one or more of stannous sulfate or stannous chloride.
Preferably, the inert atmosphere is one or more of nitrogen or argon, and the reducing atmosphere is hydrogen or a mixed gas of hydrogen and nitrogen.
Compared with the prior art, the invention has the following beneficial effects: the iron negative electrode material prepared by the invention can be used as a negative electrode active substance or an additive of an iron-nickel secondary battery, and compared with a conventional iron-nickel secondary battery which singly uses ferroferric oxide or iron powder as a negative electrode material, the iron negative electrode material can effectively improve the specific capacity of the iron-nickel secondary battery, reduce the electrode expansion, reduce the gassing amount and prolong the service life of the battery. Tin is beneficial to improving the hydrogen evolution overpotential of the cathode material during charging, so that the charging efficiency of the iron-nickel secondary battery is improved; during discharging, the action of tin ions and the discharge product ferric hydroxide is utilized, the passivation phenomenon is weakened, and the increase of internal resistance is prevented, so that the discharge efficiency and the discharge platform of the iron-nickel secondary battery are improved, and the discharge second platform of the conventional iron cathode material electrode is eliminated.
Drawings
FIG. 1 shows SnFe obtained in example 12O4The charge-discharge contrast curve of the negative electrode material and the common iron powder negative electrode material.
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 ferric oxide and tin dioxide in a ball mill according to the molar weight ratio of 1:1 for ball milling for 2h, then placing the uniformly mixed material in a sintering furnace, heating to 700 ℃ at the heating rate of 20 ℃/min in the mixed atmosphere of hydrogen and nitrogen, and sintering for 2h to obtain the alkaline secondary battery iron cathode material SnFe2O4A spinel structure material.
Example 2
Mixing and ball-milling ferroferric oxide and stannous oxide in a ball mill for 2h according to the molar weight ratio of 1:1, then placing the uniformly mixed materials in a sintering furnace, heating to 900 ℃ at the heating rate of 20 ℃/min in the nitrogen atmosphere, and sintering for 2h to obtain the alkaline secondary battery iron cathode material SnFe2O4A spinel structure material.
Example 3
Dissolving ferric sulfate and stannous sulfate in deionized water at 50 ℃ according to the molar weight ratio of 1:1, adding a sodium hydroxide aqueous solution under the condition of continuous stirring, stirring for 30min, standing for 2h, filtering and washing a precipitate to a pH value of 7, placing the dried material in a sintering furnace, heating to 700 ℃ at the heating rate of 20 ℃/min under the mixed atmosphere of hydrogen and nitrogen, and sintering for 1h to obtain the alkaline secondary battery iron cathode material SnFe2O4SpinelStructural crystal of SnFe2O4The spinel structure crystal is used as an active material or an additive of a cathode of an iron-nickel secondary battery.
Example 4
Dissolving ferric chloride and stannous chloride in deionized water at 50 ℃ according to the molar weight ratio of 1:1, adding sodium hydroxide aqueous solution under the condition of continuous stirring, stirring for 30min, standing for 2h, filtering and washing a precipitate to a pH value of 7, placing the dried material in a sintering furnace, heating to 700 ℃ at the heating rate of 20 ℃/min under the mixed atmosphere of hydrogen and nitrogen, and sintering for 1h to obtain the alkaline secondary battery iron cathode material SnFe2O4A spinel structure material.
Through comparison of charging curves, the iron cathode material SnFe prepared by the method2O4Compared with the conventional iron negative electrode material iron powder, the spinel structure material effectively reduces the charging voltage, improves the gram capacity, improves the formation speed and the discharge platform, and eliminates the discharge second platform of the conventional iron negative electrode material electrode.
The iron negative active material is SnFe containing iron and tin2O4The spinel structure crystal is beneficial to improving the hydrogen evolution overpotential of the negative electrode material during charging, so that the charging efficiency of the iron-nickel secondary battery is improved; during discharging, the interaction of tin ions and the discharge product iron hydroxide is utilized, the passivation phenomenon is weakened, and the increase of internal resistance is prevented, so that the discharge efficiency and the discharge platform of the iron-nickel secondary battery are improved, and the discharge second platform of the conventional iron cathode material electrode is eliminated.
While there have been shown and described what are at present considered the fundamental principles of the invention, its essential features and advantages, the invention further resides in various changes and modifications which fall within the scope of the invention as claimed.

Claims (3)

1. A preparation method of an iron negative electrode material of an alkaline secondary battery is characterized by comprising the following steps: mixing iron oxide and tin oxide in certain proportion, or adding soluble ferric salt and soluble tin salt in certain proportion into alkaliSintering the product after coprecipitation under the condition of nature for 1-8 h at 700-1050 ℃ in an inert or reducing atmosphere to prepare the alkaline secondary battery iron cathode material SnFe2O4Spinel structure material used as negative electrode active material or additive of iron-nickel secondary battery.
2. The method for preparing the iron anode material of the alkaline secondary battery according to claim 1, wherein: the iron oxide is one or more of ferric oxide or ferroferric oxide; the tin oxide is one or more of stannous oxide or stannic oxide; the soluble ferric salt is one or more of ferric chloride or ferric sulfate; the soluble tin salt is one or more of stannous sulfate or stannous chloride.
3. The method for preparing the iron anode material of the alkaline secondary battery according to claim 1, wherein: the inert atmosphere is one or more of nitrogen or argon, and the reducing atmosphere is hydrogen or a mixed gas of hydrogen and nitrogen.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113140708A (en) * 2021-03-22 2021-07-20 复旦大学 Alkaline storage battery based on tin cathode
CN113540431A (en) * 2021-07-09 2021-10-22 沈阳理工大学 Alkaline iron-nickel secondary battery negative electrode active material and preparation method thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113140708A (en) * 2021-03-22 2021-07-20 复旦大学 Alkaline storage battery based on tin cathode
CN113540431A (en) * 2021-07-09 2021-10-22 沈阳理工大学 Alkaline iron-nickel secondary battery negative electrode active material and preparation method thereof

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