CN101913589A - Preparation method of positive electrode material LiFePO4 of lithium ion battery - Google Patents
Preparation method of positive electrode material LiFePO4 of lithium ion battery Download PDFInfo
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- CN101913589A CN101913589A CN2010102528979A CN201010252897A CN101913589A CN 101913589 A CN101913589 A CN 101913589A CN 2010102528979 A CN2010102528979 A CN 2010102528979A CN 201010252897 A CN201010252897 A CN 201010252897A CN 101913589 A CN101913589 A CN 101913589A
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- lithium
- iron
- lifepo4
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- phosphate
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a positive electrode material LiFePO4 of a lithium ion battery. The preparation method comprises the following steps of: mixing a trivalent iron-source compound, a phosphorus-source compound and lithium metal in a molar ratio of 1:1:1.1-1.9, putting the mixture into a closed container, and adding water into the closed container and controlling the molar ratio of the water to the lithium in aqueous solution to be 1:1-10:1; stirring the mixture for 0.1 to 20 hours at room temperature to ensure that the lithium metal reacts with the water in the mixture to generate lithium ions, release hydrogen gas and simultaneously generate a great deal of heat energy, the hydrogen gas reduces trivalent iron ions into ferrous ions, and the ferrous ions react with the lithium ions and the phosphorus-source compound to generate amorphous LiFePO4; and drying the LiFePO4, and calcining the LiFePO4 for 2 to 20 hours at the temperature of between 400 and 700 DEG C to obtain a LiFePO4 finished product. The preparation method has the advantages of low synthesis temperature, short synthesis period, simple and convenient condition control and low synthesis cost, the synthesized LiFePO4 particles are fine and have uniform particle size distribution, the ionic conductivity and the electronic conductivity are obviously improved, and the LiFePO4 particles have good high-current (1C) discharge performance.
Description
The present invention relates to a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery.
Background technology
LiFePO
4It is a kind of new type lithium ion battery positive electrode material.It has good charge and discharge platform, excellent cycle performance, and cheap, the theoretical capacity height, advantages of environment protection is considered to the most promising anode material for lithium-ion batteries, and to be expected to be used in the lithium ion battery be on the electromobile of power, and its prospect is immeasurable.The preparation of ferrous phosphate doping lithium anode material can be divided into solid phase method and liquid phase method simply.Existing solid phase method mainly contains following several: high temperature solid-phase sintering method, carbothermic method, the former generally is to be raw material with ferrous iron, makes finished product through oversintering; The latter generally adopts ferric iron as raw material, by the reduction of the material in the reaction process, ferric iron at high temperature by carbothermic reduction reaction, is reduced to ferrous iron, makes the LiFePO 4 finished product.Yet all there are some inherent shortcomings in these methods, and as: synthesis temperature height, synthesis cycle is long, control condition is harsh, cost is high and the shortcomings such as large current discharging capability difference of synthetic materials, these are all limiting the extensive industrialization of LiFePO 4.Along with the fast development of China's new forms of energy industry, iron lithium phosphate is as the preferred material of power cell, because its preparation cost height has become one of most important reason of restriction electromobile shiploads of merchandiseization.
Summary of the invention
The objective of the invention is to overcome the deficiency of traditional preparation process LiFePO 4 method, a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery is provided.To realize that synthesis temperature is low, synthesis cycle is short, and condition control is easy, and the synthetic cost of reduction, product have good big electric current (1C) discharge performance.
Technical scheme of the present invention is to adopt in encloses container, utilizes a large amount of heat of metallic lithium and water reaction generation and discharges hydrogen, and be energy with the heat that discharges, be reducing gas with the hydrogen that discharges, the reduction ferric iron.
Technical scheme of the present invention may further comprise the steps:
(1) with ferric iron source compound, P source compound and metallic lithium by iron: phosphorus: the mol ratio=1:1:1.1 of elemental lithium～1.9 are mixed and are placed in the encloses container, add a certain amount of water then, the mol ratio of water and lithium is 1:1～10:1 in the control aqueous solution; At room temperature violent stirring is 0.1～20 hour, water reaction in metallic lithium and the mixture generates lithium ion and releasing hydrogen gas produces a large amount of heat energy simultaneously, hydrogen is reduced into ferrous ion with ferric ion, and ferrous ion and lithium ion and P source compound generate the amorphous phosphorus ferrous silicate lithium;
(2) oven dry back makes the LiFePO 4 finished product 400～700 ℃ temperature lower calcination 2～20 hours.
Described ferric iron source is in iron carbonate, ferric oxide, tertiary iron phosphate, iron(ic) chloride, iron nitrate and the ironic oxalate one or more.
Described phosphorus source is in ammonium di-hydrogen phosphate, DAP, tricresyl phosphate ammonia, phosphoric acid, Vanadium Pentoxide in FLAKES, tertiary iron phosphate and the phosphorus trioxide one or more.
Advantage of the present invention: (1) selects the ferric iron source compound, greatly reduces synthesis condition and raw-material cost; (2) utilize metallic lithium and water to react in encloses container, producing a large amount of hotworks is energy, is reducing gas with the hydrogen of its generation, ferric iron is reduced, both solve ferrous ion oxidized problem easily, do not needed to feed reducing atmosphere again, greatly reduced the synthetic cost of material; (3) adopt low-temperature heat treatment to greatly reduce material synthetic energy consumption, thereby reduced synthetic cost.(4) synthetic LiFePO 4 particle is tiny and size distribution is even, and ionic conductivity and electron conduction are significantly improved, and have good big electric current (1C) discharge performance.
Description of drawings
The X ray diffracting spectrum of No. 3 samples among Fig. 1: the embodiment 1;
The electron-microscope scanning figure of No. 3 samples among Fig. 2: the embodiment 1.
Embodiment
Embodiment 1:
With 0.1mol tertiary iron phosphate (FePO
4) and the 0.11mol metallic lithium be raw material, mix and be placed in the encloses container, add 2.2mol water then and stirred 2 hours; Water reaction in metallic lithium and the mixture generates lithium ion and releasing hydrogen gas produces a large amount of heat energy simultaneously, and hydrogen is reduced into ferrous ion with ferric ion, and ferrous ion and lithium ion and phosphate radical generate the amorphous phosphorus ferrous silicate lithium; The amorphous phosphorus ferrous silicate lithium respectively under temperature is 300 ℃, 400 ℃, 500 ℃ condition, was calcined respectively 10 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Can obtain the particle diameter of product about 150nm by SEM.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, their loading capacity first and the circulation 50 times after loading capacity see Table 1
Embodiment 2:
With 0.2mol iron carbonate (Fe
2(CO
3)
3), 0.5mol metallic lithium, 0.2mol DAP (NH
4H
2PO
4), 0.2mol Secondary ammonium phosphate ((NH
4)
2HPO
4) be raw material, mix and be placed in the encloses container, add 1.5mol water, and mixed 8 hours; Be under 500 ℃ in temperature then, constant temperature 15 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 154 mAhg
-1, loading capacity 150 mAhg after 50 times circulate
-1
Embodiment 3:
With 1mol iron(ic) chloride (FeCl
3), 1.2mol metallic lithium, 0.5mol ammonium di-hydrogen phosphate, 0.5mol ammonium phosphate be raw material, mixes to be placed in the encloses container, add 12mol water then, and mixed 10 hours; Then under 600 ℃ temperature, calcining at constant temperature 18 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 160mAhg
-1, loading capacity 153.8 mAhg after 50 times circulate
-1
Embodiment 4:
With 2mol ironic oxalate (Fe
2(C
2O
4)
3), 4.6mol metallic lithium, 4mol phosphoric acid be raw material, mixes being placed in the encloses container, add 4.6mol water then, and mixed 15 hours; Then under temperature is 600 ℃ temperature, calcining at constant temperature 18 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 158mAhg
-1, loading capacity 152 mAhg after 50 times circulate
-1
Embodiment 5:
With 1mol iron nitrate (Fe (NO--
3)
3), 0.5mol ferric oxide (Fe
2O
3), 2.4mol metallic lithium, 2mol ammonium di-hydrogen phosphate be raw material, mixes to be placed in the encloses container, add 11mol water then, and mixed 5 hours; Then under 600 ℃ temperature, calcining at constant temperature 18 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 163mAhg
-1, loading capacity 154.8 mAhg after 50 times circulate
-1
Embodiment 6:
With 0.5mol ironic oxalate (Fe
2(C
2O
4)
3), 1mol iron nitrate (Fe (NO
3)
3), 2.4mol metallic lithium, 2mol phosphoric acid be raw material, mixes being placed in the encloses container, add 5mol water then, and mixed 13 hours; Then under temperature is 600 ℃ temperature, calcining at constant temperature 18 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 153mAhg
-1, loading capacity 147 mAhg after 50 times circulate
-1
Embodiment 7:
With 0.5mol ironic oxalate (Fe
2(C
2O
4)
3), 0.5mol iron nitrate (Fe (NO
3)
3), 0.5 tertiary iron phosphate (FePO
4), 2.6mol metallic lithium, 2mol phosphoric acid be raw material, mixes being placed in the encloses container, add 6mol water then, and mixed 8 hours; Then under temperature is 600 ℃ temperature, calcining at constant temperature 20 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 150mAhg
-1, loading capacity 143 mAhg after 50 times circulate
-1
Embodiment 8:
With 1mol ferric oxide (Fe
2O
3), 2.5mol metallic lithium, 1mol ammonium di-hydrogen phosphate, 0.25mol Vanadium Pentoxide in FLAKES, 0.25mol phosphorus trioxide be raw material, mixes to be placed in the encloses container, add 11mol water then, and mixed 10 hours; Then under 600 ℃ temperature, calcining at constant temperature 18 hours.The material of gained is an olivine structural through X-ray diffraction analysis, and spacer is Pnma, is LiFePO
4Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first loading capacity 161mAhg
-1, loading capacity 155.8 mAhg after 50 times circulate
-1
Claims (3)
1. the preparation method of a lithium ferrous phosphate as anode material of lithium ion battery is characterized in that: may further comprise the steps:
(1) with ferric iron source compound, P source compound and metallic lithium by iron: phosphorus: the mol ratio=1:1:1.1 of elemental lithium～1.9 are mixed and are placed in the encloses container, add a certain amount of water then, the mol ratio of water and lithium is 1:1～10:1 in the control aqueous solution; At room temperature violent stirring is 0.1～20 hour, water reaction in metallic lithium and the mixture generates lithium ion and releasing hydrogen gas produces a large amount of heat energy simultaneously, hydrogen is reduced into ferrous ion with ferric ion, and ferrous ion and lithium ion and P source compound generate the amorphous phosphorus ferrous silicate lithium;
(2) oven dry back makes the LiFePO 4 finished product 400～700 ℃ temperature lower calcination 2～20 hours.
2. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that: described ferric iron source is in iron carbonate, ferric oxide, tertiary iron phosphate, iron(ic) chloride, iron nitrate and the ironic oxalate one or more.
3. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that described phosphorus source, is in ammonium di-hydrogen phosphate, DAP, tricresyl phosphate ammonia, phosphoric acid, Vanadium Pentoxide in FLAKES, tertiary iron phosphate and the phosphorus trioxide one or more.
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| CN2010102528979A CN101913589A (en) | 2010-08-13 | 2010-08-13 | Preparation method of positive electrode material LiFePO4 of lithium ion battery |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060263286A1 (en) * | 2004-11-03 | 2006-11-23 | Tatung Company | Preparation of olivine Li Fe PO4 cathode materials for lithium batteries via a solution method |
| CN101262059A (en) * | 2008-04-15 | 2008-09-10 | 中南大学 | A method for making anode material LiFePO4 of lithium ion battery |
-
2010
- 2010-08-13 CN CN2010102528979A patent/CN101913589A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060263286A1 (en) * | 2004-11-03 | 2006-11-23 | Tatung Company | Preparation of olivine Li Fe PO4 cathode materials for lithium batteries via a solution method |
| CN101262059A (en) * | 2008-04-15 | 2008-09-10 | 中南大学 | A method for making anode material LiFePO4 of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of The Electrochemical Society》 20020520 Pier Paolo Prosini et al A New Synthetic Route for Preparing LiFePO4 with Enhanced Electrochemical Performance A887页Experimental左栏10-30行, A887页Conclusions 1-3 第149卷, 第7期 2 * |
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Assignee: Shandong Jiuli Electronic Technology Co., Ltd. Assignor: Zhang Bao Contract record no.: 2012370000032 Denomination of invention: Preparation method of lithium iron phosphate as cathode material of lithium ion battery License type: Exclusive License Open date: 20101215 Record date: 20120327 |
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Application publication date: 20101215 |