CN109534406A - Preparation method of electrode material ferrous acid europium and products thereof and application - Google Patents

Preparation method of electrode material ferrous acid europium and products thereof and application Download PDF

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Publication number
CN109534406A
CN109534406A CN201811391938.5A CN201811391938A CN109534406A CN 109534406 A CN109534406 A CN 109534406A CN 201811391938 A CN201811391938 A CN 201811391938A CN 109534406 A CN109534406 A CN 109534406A
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China
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electrode material
preparation
europium
eufeo
acid europium
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Inventor
何丹农
吴晓燕
张芳
卢玉英
张道明
王亚坤
金彩虹
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0054—Mixed oxides or hydroxides containing one rare earth metal, yttrium or scandium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides preparation method of a kind of electrode material ferrous acid europium and products thereof and application, molecular formula EuFeO3, EuFeO is prepared using Freeze Drying Technique auxiliary microemulsion method3, microemulsion method is conducive to prepare the controllable nano-scale particle of size, and Freeze Drying Technique can make preparation have loose continuous shape structure, be conducive to the refinement of particle in calcination process.The two is combined with controllable, the lesser nanometer EuFeO conducive to preparation particle size3The specific surface area of particle, material is larger, is conducive to the chemical property for improving material.Under 5 mA/g current density conditions, first discharge specific capacity is 320 mAh/g, and specific discharge capacity is about 100 mAh/g or so after 20 circulations.

Description

Preparation method of electrode material ferrous acid europium and products thereof and application
Technical field
The present invention relates to preparation methods of a kind of electrode material and products thereof and application, more particularly to a kind of electrode material Preparation method of ferrous acid europium and products thereof and application.
Background technique
With the development of society, lithium ion battery is concerned.Lithium ion battery be it is ideal in the world at present can Rechargeable battery, it not only has many advantages, such as that energy density is big, has extended cycle life, memory-less effect and pollution are small.With technology Progress, lithium ion battery will be widely used in the fields such as electric car, aerospace and biological medicine, therefore, research and development Power is of great significance with lithium ion battery and associated materials.For power lithium ion battery, key is to mention High power density and energy density, and what power density and energy density improved is electrode material at all, especially negative electrode material Improvement.
From the beginning of the nineties in last century, Japanese scientific worker has developed the carbon material of layer structure, and carbon material is most The early material being studied for people and being applied to lithium ion battery and be commercialized, be still so far everybody concern and the emphasis studied it One, but there are some defects for carbon negative pole material: it when Battery formation, reacts to form SEI film with electrolyte, leads to disappearing for electrolyte Consumption and lower coulombic efficiency for the first time；When over-charging of battery, it may form Li dendrite at carbon electrodes precipitating metal lithium and cause Short circuit causes temperature to increase, battery explosion；In addition, diffusion coefficient of the lithium ion in carbon material is smaller, cause battery real Existing high current charge-discharge, to limit the application range of lithium ion battery.
EuFeO3It is a kind of perovskite structural material of distortion with orthorhombic space group, which fires in soild oxide Expect that there is certain application in battery, it, at present can also be with since the structure of the material can allow lithium ion to carry out insertion and deintercalation As lithium ion battery negative material, but how the control material particle size, be a problem to increase its specific surface area also.
Summary of the invention
In order to overcome the deficiencies of the prior art, it is an object of that present invention to provide a kind of preparation methods of electrode material ferrous acid europium.
Another object of the present invention is: providing a kind of electrode material ferrous acid europium product of above method preparation.
Another object of the present invention is to: a kind of application of the said goods is provided.
The object of the invention is realized by following proposal: a kind of preparation method of electrode material ferrous acid europium, molecular formula are EuFeO3, it is characterised in that EuFeO is prepared using Freeze Drying Technique auxiliary microemulsion method3, the specific steps of this method are as follows:
(1) n-butanol, cationic surfactant and epoxychloropropane 50g:1.5g:3g in mass ratio are added in beaker, It stirs to uniformly mixed；
(2) 0.02 mol solubility europium salt and 0.02 mol soluble ferric iron salt are dissolved in deionized water, magnetic agitation 10-20 The uniform salting liquid is added into above-mentioned steps (1) homogeneous solution, then ultrasound 10-20 min in min；
(3) culture dish for placing above-mentioned solution is covered with preservative film, is freezed at -80 DEG C, the sample freezed is put into cold Lyophilizer freeze-drying, is put into crucible for the sample being freeze-dried, 500 ~ 800 DEG C of 5 ~ 10h of calcining in Muffle furnace are obtained EuFeO3。
The present invention prepares EuFeO using Freeze Drying Technique auxiliary microemulsion method3, microemulsion method is conducive to preparation size can The nano-scale particle of control, Freeze Drying Technique can make preparation have loose continuous shape structure, be conducive in calcination process The refinement of grain, the two are combined with controllable, the lesser nanometer EuFeO of particle conducive to preparation size3, obtained EuFeO3Material Specific surface area is larger, is conducive to the chemical property for improving material.
On the basis of above scheme, the cationic surfactant is cetyl trimethylammonium bromide, hexadecane One of base trimethyl ammonium chloride, dodecyldimethylamine oxide or combinations thereof.
The soluble europium salt is one of acetic acid europium, europium nitrate or oxalic acid europium or combinations thereof.
The soluble ferric iron salt is one of ferric acetate, ferric nitrate or ferric oxalate or combinations thereof.
The freeze-drying condition is to vacuumize, freeze-drying 10 ~ for 24 hours.
The present invention provides a kind of electrode material ferrous acid europium, is prepared according to any of the above-described the method.
The present invention provides a kind of electrode material ferrous acid europium in lithium ion battery as the application of negative electrode material.
The new electrode materials EuFeO that the present invention is prepared using Freeze Drying Technique auxiliary microemulsion method3, prepare particle ruler Very little controllable, lesser nanometer EuFeO3The specific surface area of particle, material is larger, is conducive to the chemical property for improving material.5 Under mA/g current density condition, first discharge specific capacity is 320 mAh/g, and specific discharge capacity is about 100 after 20 circulations MAh/g or so.
Detailed description of the invention
Fig. 1 is embodiment 1EuFeO3The cycle life figure of material；
Fig. 2 is embodiment 2EuFeO3The high rate performance figure of material；
Fig. 3 is embodiment 3EuFeO3The SEM of material schemes.
Specific embodiment
The present invention is described in detail by following specific example, but protection scope of the present invention is not only restricted to these Examples of implementation.
Embodiment 1
A kind of preparation method of electrode material ferrous acid europium, molecular formula EuFeO3, microemulsion legal system is assisted using freeze-drying Standby EuFeO3, include the following steps:
(1) n-butanol, cetyl trimethylammonium bromide and epoxychloropropane are added in beaker by 50g:1.5g:3g, are stirred It mixes to mixed solution；
(2) 0.02 mol acetic acid europium and 0.02 mol ferric acetate are dissolved in deionized water, 20 min of magnetic agitation is obtained uniformly The uniform salting liquid is added into above-mentioned steps (1) homogeneous solution in salting liquid, and then the solution of 20 min of ultrasound is transferred to training It supports in ware；
(3) culture dish for placing above-mentioned solution is covered with preservative film, is freezed at -80 DEG C, the sample freezed is put into cold Lyophilizer vacuumizes, and dry 10 h, dried sample is put into crucible, and 600 DEG C of 10 h of calcining in Muffle furnace are obtained EuFeO3。
Fig. 1 is EuFeO3The cycle life figure of material.Under 5 mA/g current density conditions, first discharge specific capacity is 320 mAh/g, specific discharge capacity is about 100 mAh/g or so after 20 circulations.
Embodiment 2
A kind of preparation method of electrode material ferrous acid europium, it is approximate with embodiment, include the following steps:
(1) n-butanol, cetyl trimethylammonium bromide and epoxychloropropane are added in beaker by 50g:1.5g:3g, are stirred It mixes to mixed solution；
(2) 0.02 mol europium nitrate and 0.02 mol ferric nitrate are dissolved in deionized water, 20 min of magnetic agitation is obtained uniformly The uniform salting liquid is added into above-mentioned steps (1) homogeneous solution in salting liquid, and then the solution of 20 min of ultrasound is transferred to training It supports in ware；
(3) culture dish for placing above-mentioned solution is covered with preservative film, is freezed at -80 DEG C, the sample freezed is put into cold Lyophilizer vacuumizes, and dry 10 h, dried sample is put into crucible, and 600 DEG C of 10 h of calcining in Muffle furnace are obtained EuFeO3。
Fig. 2 is EuFeO3The high rate performance figure of material, under 5 mA/g current density conditions, 10 circulation specific discharge capacities Between 115 ~ 120 mAh/g, under 10 mA/g current density conditions, specific discharge capacity is on the left side 96 mAh/g after 10 circulations The right side, under 20 mA/g current density conditions, specific discharge capacity is in 87 mAh/g or so.
Embodiment 3
A kind of preparation method of electrode material ferrous acid europium, molecular formula EuFeO3, it is approximate with embodiment 1, include the following steps:
(1) n-butanol, hexadecyltrimethylammonium chloride and epoxychloropropane are added in beaker by 50g:1.5g:3g, are stirred It mixes to mixed solution；
(2) 0.02 mol europium nitrate and 0.02 mol ferric nitrate are dissolved in deionized water, 20 min of magnetic agitation is obtained uniformly The uniform salting liquid is added into above-mentioned steps (1) homogeneous solution in salting liquid, and then the solution of 20 min of ultrasound is transferred to training It supports in ware；
(3) culture dish for placing above-mentioned solution is covered with preservative film, is freezed at -80 DEG C, the sample freezed is put into cold Lyophilizer vacuumizes, and dry 10 h, dried sample is put into crucible, and 800 DEG C of 5 h of calcining in Muffle furnace are obtained EuFeO3.Fig. 3 is EuFeO3The SEM of material schemes, and has lesser particle, and the specific surface area of material is larger, is conducive to improve material Chemical property.

Claims (7)

1. a kind of preparation method of electrode material ferrous acid europium, molecular formula EuFeO3, which is characterized in that it is auxiliary using being freeze-dried Microemulsion method is helped to prepare EuFeO3, include the following steps:
(1) n-butanol, cationic surfactant and epoxychloropropane 50g:1.5g:3g in mass ratio are added in beaker, It stirs to mixed solution；
(2) 0.02 mol solubility europium salt and 0.02 mol soluble ferric iron salt are dissolved in deionized water, magnetic agitation 10- 20min obtains uniform salting liquid, which, which is added to, states in step (1) homogeneous solution, and ultrasonic 10-20min's is molten Liquid is transferred in culture dish；
(3) culture dish for placing above-mentioned solution is covered with preservative film, is freezed at -80 DEG C, the sample freezed is put into cold Lyophilizer freeze-drying, is put into crucible for the sample being freeze-dried, 500 ~ 800 DEG C of 5 ~ 10h of calcining in Muffle furnace are obtained EuFeO3。
2. the preparation method of electrode material ferrous acid europium according to claim 1, which is characterized in that the cationic surface is living Property agent be one of cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyldimethylamine oxide Or combinations thereof.
3. the preparation method of electrode material ferrous acid europium according to claim 1, which is characterized in that the soluble europium salt is One of acetic acid europium, europium nitrate or oxalic acid europium or combinations thereof.
4. the preparation method of electrode material ferrous acid europium according to claim 1, it is characterised in that the soluble ferric iron salt is One of ferric acetate, ferric nitrate or ferric oxalate or combinations thereof.
5. the preparation method of electrode material ferrous acid europium according to claim 1, it is characterised in that the freeze-drying condition To vacuumize, freeze-drying 10 ~ for 24 hours.
6. a kind of electrode material ferrous acid europium, it is characterised in that -5 any the methods are prepared according to claim 1.
7. a kind of electrode material ferrous acid europium according to claim 6 is in lithium ion battery as the application of negative electrode material.
CN201811391938.5A 2018-11-21 2018-11-21 Preparation method of electrode material ferrous acid europium and products thereof and application Pending CN109534406A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289228A (en) * 2008-06-03 2008-10-22 浙江理工大学 Method for preparing porous zinc ferrite nano-rods
CN101708423A (en) * 2009-12-10 2010-05-19 大连理工大学 Preparation method for spherical nanometre magnesium ferrite desulfurizer
CN102515096A (en) * 2011-11-22 2012-06-27 中国科学院广州能源研究所 Application of three-dimensional ordered macro-porous perovskite type oxide in preparing hydrogen through carbonic fuel chemical chain
CN102814182A (en) * 2011-06-08 2012-12-12 苏州大学 Preparation method for EuFeO3 nano-photocatalyst
CN103964833A (en) * 2014-05-23 2014-08-06 湖北工程学院 Method for preparing rare-earth magnetic ferrite through in-situ polymerization cracking process
CN105470491A (en) * 2015-11-19 2016-04-06 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing anode material Mn<2>CoO<4> for lithium-ion battery by freeze-drying technology-assisted micro-emulsion method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289228A (en) * 2008-06-03 2008-10-22 浙江理工大学 Method for preparing porous zinc ferrite nano-rods
CN101708423A (en) * 2009-12-10 2010-05-19 大连理工大学 Preparation method for spherical nanometre magnesium ferrite desulfurizer
CN102814182A (en) * 2011-06-08 2012-12-12 苏州大学 Preparation method for EuFeO3 nano-photocatalyst
CN102515096A (en) * 2011-11-22 2012-06-27 中国科学院广州能源研究所 Application of three-dimensional ordered macro-porous perovskite type oxide in preparing hydrogen through carbonic fuel chemical chain
CN103964833A (en) * 2014-05-23 2014-08-06 湖北工程学院 Method for preparing rare-earth magnetic ferrite through in-situ polymerization cracking process
CN105470491A (en) * 2015-11-19 2016-04-06 上海纳米技术及应用国家工程研究中心有限公司 Method for preparing anode material Mn<2>CoO<4> for lithium-ion battery by freeze-drying technology-assisted micro-emulsion method

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Application publication date: 20190329