CN105024073B - Anode material for lithium-ion batteries di iron and preparation method thereof - Google Patents

Anode material for lithium-ion batteries di iron and preparation method thereof Download PDF

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Publication number
CN105024073B
CN105024073B CN201510482624.6A CN201510482624A CN105024073B CN 105024073 B CN105024073 B CN 105024073B CN 201510482624 A CN201510482624 A CN 201510482624A CN 105024073 B CN105024073 B CN 105024073B
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Prior art keywords
lithium
anode material
ion batteries
iron
preparation
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CN105024073A (en
Inventor
陈泽华
麻鹏程
孙广
曹建亮
王晓冬
孟哈日巴拉
张传祥
张战营
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Henan University of Technology
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Henan University of Technology
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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
    • H01M4/58—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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 present invention relates to a kind of anode material for lithium-ion batteries di iron and preparation method thereof, the molecular formula of described anode material for lithium-ion batteries is Fe2.95(PO4)2(OH)2；Its preparation method is by by H3PO4Solution, FeCl3After solid powder is mixed with water, methyl triethyl ammonium chloride regulation pH is added to 2.0 ~ 3.5, is controlled temperature to carry out hydrothermal synthesis reaction 30h for 150~200 DEG C and is obtained reaction solution, reaction solution is by centrifuging, cleaning, dry obtained Fe2.95(PO4)2(OH)2；The present invention has process simple, safety, cost low, the features such as suitable for large-scale production；Using ferric iron as reactant, without adding protective atmosphere or reducing atmosphere, cost is reduced, product need not add protective atmosphere, when drying under air.

Description

Anode material for lithium-ion batteries di iron and preparation method thereof
Technical field
The present invention relates to electrochemical field, specifically a kind of anode material for lithium-ion batteries di iron and its system Preparation Method.
Background technology
LiFePO4 is cheap, environment-friendly, with good structural stability and heat endurance, with overwhelming majority electricity Solve liquid compatible, remain to keep stable under overcharging state.Its theoretical capacity is 170mAh/g, and operating voltage is 3.45V or so, into For the lithium ion anode material of new generation of most development and application potentiality, it is expected to apply in electrokinetic cell and energy-storage battery.
LiFePO but then4Resistivity is larger, and electrochemical process controls for diffusion, is allowed to hold in heavy-current discharge Amount decay is larger, its electrical conductivity is typically improved by appropriate synthesis technique, such as：Carbon coated plus carbon are made composite, mixed Miscellaneous metal ion and addition metal dust induction nucleation.
The content of the invention
It is an object of the invention to provide a kind of anode material for lithium-ion batteries di iron and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of anode material for lithium-ion batteries di iron, the molecular formula of described anode material for lithium-ion batteries is Fe2.95(PO4)2(OH)2；
A kind of preparation method of described anode material for lithium-ion batteries di iron, comprises the following steps：
1）Take 2.39mol/L H3PO4Solution is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, then by FeCl3Solid powder It is poured into reactor, then adds water, stirs, Fe in resulting solution3+:PO4Mol ratio be 1:3~1:5, in stirring During be continuously added methyl triethyl ammonium chloride regulation pH value, when pH be 2.0 ~ 3.5 when stop stirring；
2）10 DEG C/min of programming rate is controlled, reactor is warming up to 150~200 DEG C of progress hydrothermal synthesis reaction 30h, obtained To reaction solution；
3）By step 2）The reaction solution of gained is by centrifuging and adding washes of absolute alcohol, by the filter cake of gained in sky Compression ring is dried in border, obtains anode material for lithium-ion batteries Fe2.95(PO4)2(OH)2；
The step 1）Reactant in Fe3+:PO4Mol ratio be 1:4；
The step 3）In drying temperature be 80 ~ 100 DEG C；
A kind of application of anode material for lithium-ion batteries di iron as described above, described Fe2.95(PO4)2 (OH)2It can be used as lithium ion battery material.
Beneficial effects of the present invention：
（1）The present invention has the advantages that preparation technology is simple and convenient to operate, suitable for large-scale production；
（2）The present invention, without adding protective atmosphere or reducing atmosphere, reduces cost using ferric iron as reactant；
（3）Product of the present invention need not add protective atmosphere, when drying in air ambient；
（4）Reaction raw materials of the present invention are ferric trichloride, prepare cost low；
（5）Preparation technology of the present invention is succinct, and application process is simple.
Brief description of the drawings
Lithium ion battery electrode material Fe prepared by Fig. 1 embodiments 12.95(PO4)2(OH)2Morphology analysis figure one；
Lithium ion battery electrode material Fe prepared by Fig. 2 embodiments 12.95(PO4)2(OH)2Morphology analysis figure two；
Lithium ion battery electrode material Fe prepared by Fig. 3 embodiments 12.95(PO4)2(OH)2Thermal gravimetric analysis curve；
Lithium ion battery electrode material Fe prepared by Fig. 4 embodiments 12.95(PO4)2(OH)2X-ray diffractogram.
Embodiment
With reference to embodiment, the present invention is further elaborated.
A kind of anode material for lithium-ion batteries di iron, the molecular formula of described anode material for lithium-ion batteries is Fe2.95(PO4)2(OH)2。
A kind of preparation method of anode material for lithium-ion batteries di iron as described above, comprises the following steps：
1）Take 2.39mol/L H3PO4Solution is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, then by FeCl3Solid powder It is poured into reactor, then adds water, stirs, Fe in resulting solution3+:PO4Mol ratio be 1:3~1:5, in stirring During be continuously added methyl triethyl ammonium chloride regulation pH value, when pH be 2.0 ~ 3.5 when stop stirring；
2）10 DEG C/min of programming rate is controlled, reactor is warming up to 150~200 DEG C of progress hydrothermal synthesis reaction 30h, obtained To reaction solution；
3）By step 2）The reaction solution of gained is by centrifuging and adding washes of absolute alcohol, by the filter cake of gained in sky Compression ring is dried in border, obtains anode material for lithium-ion batteries Fe2.95(PO4)2(OH)2。
A kind of application of anode material for lithium-ion batteries di iron as described above, described Fe2.95(PO4)2 (OH)2It can be used as lithium ion battery material.
Embodiment 1
A kind of preparation method of anode material for lithium-ion batteries di iron, comprises the following steps：
1）Take 2.39mol/L H3PO4Solution 16.7ml is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, then is weighed 1.703g FeCl3Solid powder is poured into reactor, then adds 20ml water, resulting solution stirs, in the mistake of stirring Methyl triethyl ammonium chloride regulation pH value is continuously added in journey, stirring is stopped when pH is 2.5；
2）10 DEG C/min of programming rate is controlled, reactor is warming up to 150 DEG C of progress hydrothermal synthesis reaction 30h, obtains anti- Answer liquid；
3）By step 2）The reaction solution of gained is by centrifuging and adding washes of absolute alcohol, by the filter cake of gained in sky It is dried in compression ring border under the conditions of 90 DEG C, obtains anode material for lithium-ion batteries Fe2.95(PO4)2(OH)2。
Gained Fe2.95(PO4)2(OH)2Sample is pure, is octahedra particle, as shown in Figure 1 and Figure 2；Heat is carried out to sample 1 Weight analysis, 400 DEG C begin with gas effusion, and 520 DEG C reach capacity, and weight-loss ratio is about that 5%, Fig. 3 is gained Fe2.95(PO4)2 (OH)2The thermal gravimetric analysis curve of sample；Fig. 4 is the X-ray diffractogram of sample 1, and as can be seen from the figure its main component is Fe2.95(PO4)2(OH)2, and product is single.
Embodiment 2
A kind of preparation method of anode material for lithium-ion batteries di iron, comprises the following steps：
1）Take 2.39mol/L H3PO4Solution is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, then by FeCl3Solid powder It is poured into reactor, then adds water, stirs, Fe in resulting solution3+:PO4Mol ratio be 1:3, in the mistake of stirring Methyl triethyl ammonium chloride regulation pH value is continuously added in journey, stirring is stopped when pH is 2.0；
2）10 DEG C/min of programming rate is controlled, reactor is warming up to 200 DEG C of progress hydrothermal synthesis reaction 30h, obtains anti- Answer liquid；
3）By step 2）The reaction solution of gained is by centrifuging and adding washes of absolute alcohol, by the filter cake of gained in sky It is dried in compression ring border under the conditions of 80 DEG C, obtains anode material for lithium-ion batteries Fe2.95(PO4)2(OH)2。
Embodiment 3
A kind of preparation method of anode material for lithium-ion batteries di iron, comprises the following steps：
1）Take 2.39mol/L H3PO4Solution is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, then by FeCl3Solid powder It is poured into reactor, then adds water, stirs, Fe in resulting solution3+:PO4Mol ratio be 1:5, in the mistake of stirring Methyl triethyl ammonium chloride regulation pH value is continuously added in journey, stirring is stopped when pH is 3.5；
2）10 DEG C/min of programming rate is controlled, reactor is warming up to 180 DEG C of progress hydrothermal synthesis reaction 30h, obtains anti- Answer liquid；
3）By step 2）The reaction solution of gained is by centrifuging and adding washes of absolute alcohol, by the filter cake of gained in sky It is dried in compression ring border under the conditions of 100 DEG C, obtains anode material for lithium-ion batteries Fe2.95(PO4)2(OH)2。

Claims (2)

1. a kind of preparation method of anode material for lithium-ion batteries di iron, point of described anode material for lithium-ion batteries Minor is Fe2.95(PO4)2(OH)2, it is characterised in that comprise the following steps：
1）Take 2.39mol/L H3PO4Solution is put into polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, then by FeCl3Solid powder is poured into Into reactor, water is then added, is stirred, Fe in resulting solution3+:PO4Mol ratio be 1:3~1:5, in the mistake of stirring Methyl triethyl ammonium chloride regulation pH value is continuously added in journey, stirring is stopped when pH is 2.0 ~ 3.5；
2）10 DEG C/min of programming rate is controlled, reactor is warming up to 150~200 DEG C of progress hydrothermal synthesis reaction 30h, obtains anti- Answer liquid；
3）By step 2）The reaction solution of gained is by centrifuging and adding washes of absolute alcohol, by the filter cake of gained in air ring It is dried in border, drying temperature is 80 ~ 100 DEG C, obtains anode material for lithium-ion batteries Fe2.95(PO4)2(OH)2。
2. the preparation method of anode material for lithium-ion batteries di iron as claimed in claim 1, it is characterised in that：It is described Step 1）Reactant in Fe3+:PO4Mol ratio be 1:4.
CN201510482624.6A 2015-08-10 2015-08-10 Anode material for lithium-ion batteries di iron and preparation method thereof Expired - Fee Related CN105024073B (en)

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CN106340645A (en) * 2016-09-08 2017-01-18 西北工业大学 Preparation method of hydroxyl iron phosphate-based battery material with novel morphology
CN107910552B (en) * 2017-11-14 2020-06-09 山东黄蓝伟业新能源科技有限公司 Preparation method of hydroxyl ammonium ferric phosphate

Citations (2)

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CN101276910A (en) * 2008-05-16 2008-10-01 北京工业大学 Preparation of Fe5(PO4)4(OH)3 and application thereof
CN103311543A (en) * 2012-12-10 2013-09-18 上海电力学院 Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof

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WO2013138541A1 (en) * 2012-03-15 2013-09-19 Imra America, Inc. Iron phosphates: negative electrode materials for aqueous rechargeable sodium ion energy storage devices

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Publication number Priority date Publication date Assignee Title
CN101276910A (en) * 2008-05-16 2008-10-01 北京工业大学 Preparation of Fe5(PO4)4(OH)3 and application thereof
CN103311543A (en) * 2012-12-10 2013-09-18 上海电力学院 Anode material hydroxyl iron phosphate for lithium ion batteries and preparation method thereof

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"新型锂离子电池正极材料研究与探索";张世明;《中国优秀硕士学位论文全文数据库-工程科技Ⅱ辑》;20140615(第06期);第77页第13行至第78页倒数第7行,第78页第13行至第84页第1行 *

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