CN111029563B - 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
CN111029563B
CN111029563B CN201911259055.3A CN201911259055A CN111029563B CN 111029563 B CN111029563 B CN 111029563B CN 201911259055 A CN201911259055 A CN 201911259055A CN 111029563 B CN111029563 B CN 111029563B
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iron
secondary battery
oxide
tin
negative electrode
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CN111029563A (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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

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 to 1050 ℃ for 1 to 8 hours in an inert or reducing atmosphere to prepare the alkaline secondary battery iron cathode material SnFe 2 O 4 Spinel 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 negative electrode 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, 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.

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 currently available 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 generally, the cycle life is about 300 to 350 times, long charging time is needed, lead is a toxic heavy metal, and the production process and recovery process are limited by countries all over the world if the lead is improperly treated, so that the production and use of the lead-acid batteries are limited. 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 iron-nickel secondary battery raw material is easy to purchase and is easy to obtain and is not controlled, and the characteristics of environmental protection and safety are displayed 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 the preparation method of the alkaline secondary battery iron cathode material which can effectively improve hydrogen evolution overpotential, reduce charging voltage and improve battery specific capacity, and the alkaline secondary battery iron cathode material prepared by the method is SnFe 2 O 4 The 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 ions are oxidized and dissolved out in situ during discharging, two Faraday electron capacities are released, and the discharging efficiency can be improved.
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 the iron oxide and the tin oxide according to a proportion, and then placing the mixture in an inert atmosphere or a reducing atmosphere to be sintered for 1 to 8h at the temperature of 700 to 1050 ℃ to prepare the alkaline secondary battery iron cathode material SnFe 2 O 4 A spinel structure material; or putting a product obtained by coprecipitation of soluble iron salt and soluble tin salt in proportion under an alkaline condition into an inert or reducing atmosphere and sintering at 700 to 1050 ℃ for 1 to 8h to prepare the alkaline secondary battery iron negative material SnFe 2 O 4 A spinel structure material. The SnFe 2 O 4 Tin 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 the 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 gas evolution rate and prolong the service life of the battery. Tin 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 action 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.
Drawings
FIG. 1 shows SnFe obtained in example 1 2 O 4 The 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 understood that the scope of the subject matter of the present invention is limited to the examples below, and any technique realized based on the above contents of the present invention falls within the scope of the present invention.
Example 1
Mixing and ball-milling ferric oxide and tin dioxide in a ball mill for 2h according to the molar weight ratio of 1 2 O 4 A 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 2 O 4 A spinel structure material.
Example 3
Dissolving ferric sulfate and stannous sulfate in deionized water at 50 ℃ according to the molar weight of 1 2 O 4 Crystal of spinel structure, the SnFe 2 O 4 The 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 of 1Placing the obtained material in a sintering furnace, heating to 700 ℃ at a 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 SnFe 2 O 4 A spinel structure material.
Through comparison of charging curves, the iron cathode material SnFe prepared by the method 2 O 4 Compared 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 electrode active material is SnFe containing iron and tin 2 O 4 The 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 to be the principles of the invention, its essential features and advantages, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (3)

1.SnFe 2 O 4 The application of spinel structure material as negative electrode active material of iron-nickel secondary battery is characterized by that it contains SnFe 2 O 4 The specific preparation process of the spinel structure material comprises the following steps: uniformly mixing iron oxide and tin oxide in proportion, or co-precipitating soluble iron salt and soluble tin salt in proportion under an alkaline condition, and sintering the product in an inert or reducing atmosphere at 700 to 1050 ℃ for 1 to 8h to prepare SnFe 2 O 4 A spinel structure material.
2. Use according to claim 1, characterized in that: 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. Use according to claim 1, characterized in that: 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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Publication number Priority date Publication date Assignee Title
CN113140708B (en) * 2021-03-22 2022-08-19 复旦大学 Alkaline storage battery based on tin negative electrode
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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CN1260069A (en) * 1997-05-05 2000-07-12 化学能量有限公司 Iron-based storage battery
CN1645530A (en) * 2004-11-12 2005-07-27 清华大学 Method for synthesizing series single-dispersed ferrite nanometer magnetic beads
CN102923786A (en) * 2012-11-29 2013-02-13 江苏技术师范学院 Method for preparing nano ferrite by molten salt method
CN106129361A (en) * 2016-07-25 2016-11-16 北京化工大学 A kind of lithium ion battery anode active material and preparation method
CN106431379A (en) * 2016-09-05 2017-02-22 中南大学 Method for preparing Sn-Fe spinel material through low-temperature solid-phase reaction
CN109449379A (en) * 2018-09-12 2019-03-08 华南师范大学 A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof

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JP3951363B2 (en) * 1996-06-26 2007-08-01 宇部興産株式会社 Non-aqueous secondary battery
JP2013077456A (en) * 2011-09-30 2013-04-25 Fdk Twicell Co Ltd Alkaline secondary battery
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CN1260069A (en) * 1997-05-05 2000-07-12 化学能量有限公司 Iron-based storage battery
CN1645530A (en) * 2004-11-12 2005-07-27 清华大学 Method for synthesizing series single-dispersed ferrite nanometer magnetic beads
CN102923786A (en) * 2012-11-29 2013-02-13 江苏技术师范学院 Method for preparing nano ferrite by molten salt method
CN106129361A (en) * 2016-07-25 2016-11-16 北京化工大学 A kind of lithium ion battery anode active material and preparation method
CN106431379A (en) * 2016-09-05 2017-02-22 中南大学 Method for preparing Sn-Fe spinel material through low-temperature solid-phase reaction
CN109449379A (en) * 2018-09-12 2019-03-08 华南师范大学 A kind of SnFe that nitrogen-doped carbon is compound2O4Lithium ion battery negative material and the preparation method and application thereof

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