CN105024073A - Cathode material Fe<2.95>(PO4)2(OH)2 of lithium ion battery and preparation method thereof - Google Patents

Cathode material Fe<2.95>(PO4)2(OH)2 of lithium ion battery and preparation method thereof Download PDF

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Publication number
CN105024073A
CN105024073A CN201510482624.6A CN201510482624A CN105024073A CN 105024073 A CN105024073 A CN 105024073A CN 201510482624 A CN201510482624 A CN 201510482624A CN 105024073 A CN105024073 A CN 105024073A
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Prior art keywords
lithium
anode material
ion batteries
preparation
iron
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CN201510482624.6A
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CN105024073B (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 invention relates to a cathode material Fe<2.95>(PO4)2(OH)2 of a lithium ion battery and a preparation method thereof. The formula of the cathode material of the lithium ion battery is Fe<2.95>(PO4)2(OH)2. The preparation method comprises the following steps of: adding H3PO4 solution and FeCl3 solid powder to water and uniformly mixing; adding methyl triethyl ammonium chloride, adjusting pH to be 2.0-3.5, controlling a temperature to be 150-200 DEG C, and carrying out hydrothermal synthesis for 30 hours to obtain a reaction liquid; and centrifugally separating, cleaning and drying the reaction liquid to obtain Fe<2.95>(PO4)2(OH)2. The cathode material and the preparation method have the characteristics of process simplicity, safety, low cost and the like, and are suitable for production at a large scale, ferric ion is taken as a reactant, a protective atmosphere or reducing atmosphere is unnecessarily added, cost is reduced, and the product is dried in the air without adding the protective atmosphere.

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 preparation method thereof.
Background technology
LiFePO4 is cheap, environmental friendliness, have good structural stability and thermal stability, compatible with most electrolyte, still can keep stable overcharging under state.Its theoretical capacity is 170mAh/g, and operating voltage is about 3.45V, becomes the lithium ion anode material of new generation of most development and application potentiality, is expected to apply in electrokinetic cell and energy-storage battery.
LiFePO but then 4resistivity is larger, electrochemical process is diffusion control, to make it when heavy-current discharge capacity attenuation comparatively large, generally improve its conductivity by suitable synthesis technique, as: carbon coated, add carbon and make composite material, doped metal ion and add metal dust induction nucleation.
Summary of the invention
The object of this invention is to provide a kind of anode material for lithium-ion batteries di iron and preparation method thereof.
For solving the problems of the technologies described above, the technical solution used in 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 Fe 2.95(PO 4) 2(OH) 2;
A preparation method for upper described anode material for lithium-ion batteries di iron, comprises the following steps:
1) H of 2.39mol/L is got 3pO 4solution is put in polytetrafluoroethylene hydrothermal reaction kettle, then by FeCl 3pressed powder is poured in reactor, then adds water, stirs, Fe in gained solution 3+: PO 4mol ratio be 1:3 ~ 1:5, stir process in constantly add methyl triethyl ammonium chloride adjust ph, when pH is 2.0 ~ 3.5 stop stir;
2) control programming rate 10 DEG C/min, reactor is warming up to 150 ~ 200 DEG C and carries out hydrothermal synthesis reaction 30h, obtain reactant liquor;
3) by step 2) reactant liquor of gained is by centrifugation and add washes of absolute alcohol, and the filter cake of gained is carried out drying in air ambient, obtains anode material for lithium-ion batteries Fe 2.95(PO4) 2(OH) 2;
Fe in the reactant of described step 1) 3+: PO 4mol ratio be 1:4;
Baking temperature in described step 3) is 80 ~ 100 DEG C;
An application for anode material for lithium-ion batteries di iron as above, described Fe 2.95(PO 4) 2(OH) 2can be used as lithium ion battery material to use.
Beneficial effect of the present invention:
(1) the present invention has simple, the easy to operate advantage of preparation technology, is suitable for large-scale production;
(2) the present invention take ferric iron as reactant, without the need to adding protective atmosphere or reducing atmosphere, reduces cost;
(3) product of the present invention is without the need to adding protective atmosphere, time dry in air ambient;
(4) reaction raw materials of the present invention is ferric trichloride, and preparation cost is low;
(5) preparation technology of the present invention is succinct, and application process is simple.
Accompanying drawing explanation
Lithium ion battery electrode material Fe prepared by Fig. 1 embodiment 1 2.95(PO 4) 2(OH) 2morphology analysis figure mono-;
Lithium ion battery electrode material Fe prepared by Fig. 2 embodiment 1 2.95(PO 4) 2(OH) 2morphology analysis figure bis-;
Lithium ion battery electrode material Fe prepared by Fig. 3 embodiment 1 2.95(PO 4) 2(OH) 2thermal gravimetric analysis curve;
Lithium ion battery electrode material Fe prepared by Fig. 4 embodiment 1 2.95(PO 4) 2(OH) 2x-ray diffractogram.
Embodiment
Below in conjunction with 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 Fe 2.95(PO 4) 2(OH) 2.
A preparation method for anode material for lithium-ion batteries di iron described above, comprises the following steps:
1) H of 2.39mol/L is got 3pO 4solution is put in polytetrafluoroethylene hydrothermal reaction kettle, then by FeCl 3pressed powder is poured in reactor, then adds water, stirs, Fe in gained solution 3+: PO 4mol ratio be 1:3 ~ 1:5, stir process in constantly add methyl triethyl ammonium chloride adjust ph, when pH is 2.0 ~ 3.5 stop stir;
2) control programming rate 10 DEG C/min, reactor is warming up to 150 ~ 200 DEG C and carries out hydrothermal synthesis reaction 30h, obtain reactant liquor;
3) by step 2) reactant liquor of gained is by centrifugation and add washes of absolute alcohol, and the filter cake of gained is carried out drying in air ambient, obtains anode material for lithium-ion batteries Fe 2.95(PO4) 2(OH) 2.
An application for anode material for lithium-ion batteries di iron as above, described Fe 2.95(PO 4) 2(OH) 2can be used as lithium ion battery material to use.
Embodiment 1
A preparation method for anode material for lithium-ion batteries di iron, comprises the following steps:
1) H of 2.39mol/L is got 3pO 4solution 16.7ml puts in polytetrafluoroethylene hydrothermal reaction kettle, then takes 1.703g FeCl 3pressed powder is poured in reactor, then adds 20ml water, and gained solution stirs, in the process stirred, constantly add methyl triethyl ammonium chloride adjust ph, stops stirring when pH is 2.5;
2) control programming rate 10 DEG C/min, reactor is warming up to 150 DEG C and carries out hydrothermal synthesis reaction 30h, obtain reactant liquor;
3) by step 2) reactant liquor of gained is by centrifugation and add washes of absolute alcohol, and the filter cake of gained is carried out drying in air ambient under 90 DEG C of conditions, obtains anode material for lithium-ion batteries Fe 2.95(PO4) 2(OH) 2.
Gained Fe 2.95(PO4) 2(OH) 2sample is pure, is octahedra particle, as shown in Figure 1 and Figure 2; Carry out thermogravimetric analysis to sample 1,400 DEG C start have gas to overflow, and 520 DEG C reach capacity, and it is gained Fe that weight-loss ratio is about 5%, Fig. 3 2.95(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 Fe 2.95(PO 4) 2(OH) 2, and product is single.
Embodiment 2
A preparation method for anode material for lithium-ion batteries di iron, comprises the following steps:
1) H of 2.39mol/L is got 3pO 4solution is put in polytetrafluoroethylene hydrothermal reaction kettle, then by FeCl 3pressed powder is poured in reactor, then adds water, stirs, Fe in gained solution 3+: PO 4mol ratio be 1:3, stir process in constantly add methyl triethyl ammonium chloride adjust ph, when pH is 2.0 stop stir;
2) control programming rate 10 DEG C/min, reactor is warming up to 200 DEG C and carries out hydrothermal synthesis reaction 30h, obtain reactant liquor;
3) by step 2) reactant liquor of gained is by centrifugation and add washes of absolute alcohol, and the filter cake of gained is carried out drying in air ambient under 80 DEG C of conditions, obtains anode material for lithium-ion batteries Fe 2.95(PO4) 2(OH) 2.
Embodiment 3
A preparation method for anode material for lithium-ion batteries di iron, comprises the following steps:
1) H of 2.39mol/L is got 3pO 4solution is put in polytetrafluoroethylene hydrothermal reaction kettle, then by FeCl 3pressed powder is poured in reactor, then adds water, stirs, Fe in gained solution 3+: PO 4mol ratio be 1:5, stir process in constantly add methyl triethyl ammonium chloride adjust ph, when pH is 3.5 stop stir;
2) control programming rate 10 DEG C/min, reactor is warming up to 180 DEG C and carries out hydrothermal synthesis reaction 30h, obtain reactant liquor;
3) by step 2) reactant liquor of gained is by centrifugation and add washes of absolute alcohol, and the filter cake of gained is carried out drying in air ambient under 100 DEG C of conditions, obtains anode material for lithium-ion batteries Fe 2.95(PO4) 2(OH) 2.

Claims (5)

1. an anode material for lithium-ion batteries di iron, is characterized in that: the molecular formula of described anode material for lithium-ion batteries is Fe 2.95(PO 4) 2(OH) 2.
2. a preparation method for anode material for lithium-ion batteries di iron as claimed in claim 1, is characterized in that, comprise the following steps:
1) H of 2.39mol/L is got 3pO 4solution is put in polytetrafluoroethylene hydrothermal reaction kettle, then by FeCl 3pressed powder is poured in reactor, then adds water, stirs, Fe in gained solution 3+: PO 4mol ratio be 1:3 ~ 1:5, stir process in constantly add methyl triethyl ammonium chloride adjust ph, when pH is 2.0 ~ 3.5 stop stir;
2) control programming rate 10 DEG C/min, reactor is warming up to 150 ~ 200 DEG C and carries out hydrothermal synthesis reaction 30h, obtain reactant liquor;
3) by step 2) reactant liquor of gained is by centrifugation and add washes of absolute alcohol, and the filter cake of gained is carried out drying in air ambient, obtains anode material for lithium-ion batteries Fe 2.95(PO4) 2(OH) 2.
3. the preparation method of anode material for lithium-ion batteries di iron as claimed in claim 2, is characterized in that: Fe in the reactant of described step 1) 3+: PO 4mol ratio be 1:4.
4. the preparation method of anode material for lithium-ion batteries di iron as claimed in claim 2, is characterized in that: the baking temperature in described step 3) is 80 ~ 100 DEG C.
5. an application for anode material for lithium-ion batteries di iron as claimed in claim 1, is characterized in that: described Fe 2.95(PO 4) 2(OH) 2can be used as lithium ion battery material to use.
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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107910552A (en) * 2017-11-14 2018-04-13 山东黄蓝伟业新能源科技有限公司 A kind of preparation method of di iron ammonium

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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
US20130244100A1 (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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CN101276910A (en) * 2008-05-16 2008-10-01 北京工业大学 Preparation of Fe5(PO4)4(OH)3 and application thereof
US20130244100A1 (en) * 2012-03-15 2013-09-19 Imra America, Inc. Iron phosphates: negative electrode materials for aqueous rechargeable sodium ion energy storage devices
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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN107910552A (en) * 2017-11-14 2018-04-13 山东黄蓝伟业新能源科技有限公司 A kind of preparation method of di iron ammonium
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

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