CN102054978A - Method for preparing cathode electrode material of nanometer sheet microspheric lithium ion cell - Google Patents
Method for preparing cathode electrode material of nanometer sheet microspheric lithium ion cell Download PDFInfo
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- CN102054978A CN102054978A CN2010105588261A CN201010558826A CN102054978A CN 102054978 A CN102054978 A CN 102054978A CN 2010105588261 A CN2010105588261 A CN 2010105588261A CN 201010558826 A CN201010558826 A CN 201010558826A CN 102054978 A CN102054978 A CN 102054978A
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- microballoon
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- fepo
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- 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 discloses a method for preparing a cathode electrode material of a nanometer sheet microspheric lithium ion cell, belonging to the field of energy sources. The method comprises the following steps of: firstly alternatively carrying out the heat treatment and the acid washing treatment on NH4FePO4 to prepare FePO4.H2O nanometer sheet microspheres with a porous structure, and reducing with an acetonitrile solution of LiI at room temperature, finally mixing with cane sugar and sintering in vacuum at high temperature to obtain carbon-coated olivine-type LiFePO4 multilevel nanometer sheet microspheres. The method has simple process and is easy for operation, and the synthesized material has high purity, high activity, small particle diameter, narrow and small distribution; meanwhile, the high temperature treatment is short so that the shortages of larger particle diameter and wider distribution due to high temperature incineration are overcome, and the electrical conductivity and the lithium intercalation and de-intercalation stability of the LiFePO4 are effectively improved; in addition, the prepared material has the characteristics of high specific capacity, good cyclical stability and high conservation rate of high-rate discharge capacity, and is suitable to be used as the cathode electrode material of high-power lithium ion cell.
Description
Technical field
The invention belongs to energy field, particularly a kind of preparation method of nanometer sheet microspheroidal lithium ion battery cathode electrode material is that carbon coats olivine-type LiFePO specifically
4The preparation method of multilevel hierarchy nanometer sheet microballoon.
Background technology
Strong energy safeguard has become the important leverage of the sustained and rapid development of human society.In the modern society, production, life and transport services have become the main field of power consumption.At present, the non-renewable mineral matter energy is supporting the operation in the world, and it is non-renewable, finiteness, and serious environmental problem makes people more and more urgent to the requirement of the novel high-energy energy.And be widely used in the lithium ion battery of portable electronic products, because of advantages such as its energy density height, security performance is good, the storage time is long, operating temperature range is wide, environmental friendliness, become the direction of the development novel high-energy energy.Wherein, development high performance lithium ion battery cathode material becomes the important channel of development high power lithium ion cell.The LiFePO of report such as Goodenough
4With its high theoretical capacity (170mAh/g), stable structure makes it become optimal candidate material [A.K.Padhi, the K.S.Nanjundaswarmy of high power power lithium-ion battery cathode material, J.B.Goodenough, J.Electrochem.Soc., 1997,144,1188].But because of LiFePO
4Poorly conductive has limited the application of this cathode material in electrokinetic cell greatly.Improve LiFePO
4The common means of conductivity generally are the LiFePO of and narrowly distributing little by the preparation particle diameter
4Nanocrystal and carbon coated material, but the LiFePO of high-crystallinity
4Often need be under higher temperature (＞600 ℃) heat treatment (＞8 hours) for a long time, this often makes LiFePO
4Crystal grain is bigger, wider distribution, and structural collapse, reunion simultaneously seriously reduced its chemical property.Simultaneously, the nano particle of single structure or nanosphere specific area are very big, coat a large amount of carbon of process need, have reduced the discharge capacity of material, and low-density carbon has also reduced the energy density of material simultaneously.
Utilize reducing agent low temperature reduction Fe
3+Presoma, the amorphous Fe that the mixing sucrose protection is also original
2+Product, quick high-temp crystallization under the vacuum can be to LiFePO
4The structure of crystal grain designs synthetic, prepares narrow diameter distribution, and structural collapse is few, and the reunion rate is low, and the carbon with multilevel hierarchy coats LiFePO
4Crystal grain makes full use of the advantage of its Nanosurface then, improves chemical property, the effective way that addresses the above problem just.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nanometer sheet microspheroidal lithium ion battery cathode electrode material is characterized in that described nanometer sheet microspheroidal lithium ion battery cathode electrode material is the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon is earlier to NH
4FePO
4Hocket heat treatment and pickling processes, preparation has the FePO of loose structure
4H
2O nanometer sheet microballoon, the acetonitrile solution with LiI reduces under the room temperature then, last mixing sucrose, high temperature sintering obtains in a vacuum, and concrete preparation process comprises:
(1) iron phosphate nano sheet microballoon preparation technology: at first with 20-30g FePO
44H
2O, 5-8g (NH
4)
2SO
3H
2O and 1.5-3mL concentration be 25wt% ammoniacal liquor in the 100mL deionized water, fully mix, reflux down at 45-70 ℃ then and stirred 5-8 hour, by suction filtration deionized water cyclic washing, 50-60 ℃ of dry 8-12 hour acquisition product (NH down
4)
xFePO
40＜x＜1 wherein; Pass through 180-210 ℃ of heat treatment after 2 hours, ammonia that discharges and steam, the passivation of overflowing the ammonium radical ion by the surface makes FePO
4Nano microcrystalline is grown to serve as the nanometer disk, and the hydrogen bond that ammonium root, hydrone and phosphate radical form then links these nanometer disks with different angles, has obtained the nanometer sheet microballoon of ferric phosphate; Mix stirring after 4 hours with the nanometer sheet microballoon of 0.5-1g ferric phosphate and the watery hydrochloric acid 100mL of 0.1mol/L, be incubated 24 hours down, obtain having the iron phosphate nano sheet microballoon of loose structure at 380-500 ℃;
(2) the olivine-type LiFePO of carbon coating
4Multilevel hierarchy nanometer sheet microballoon preparation technology: 3-4g LiI and 0.08-0.2g iron phosphate nano sheet microballoon are dissolved in the 10mL acetonitrile solution, stirred 24 hours under the room temperature, under 6000 rev/mins of rotating speeds, centrifugal, with acetonitrile solution cyclic washing sediment, 40 ℃ of vacuumizes 2 hours; Sediment and the sucrose ground and mixed that accounts for sediment quality 15-25wt% with drying, place corundum to burn boat, heat treatment under vacuum condition, programming rate with 10 ℃/minute, reacted 1 hour down at 500-600 ℃ earlier, reacted 1 hour down at 600-800 ℃ again, can obtain the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon.
Beneficial effect of the present invention is:
(1) utilize simple alternately heat treatment and weak acid scrubbing to handle, obtained having the nanometer sheet assembling microballoon of loose structure, the raw material sources cost is low, method simple controllable, easy operating;
(2) utilize the reduction of the excessive LiI acetonitrile solution room temperature of high concentration to have the FePO of loose structure
4, do not destroy the material grains structure, reduce very thoroughly, inserted elemental lithium simultaneously, formed amorphous LiFePO
4Excessive LiI acetonitrile solution can also recycle, and has reduced cost.
(3) sucrose can not only be protected amorphous LiFePO
4, reduced requirement to vacuum condition, formed the coating carbon-coating simultaneously, reduced interface resistance, improve the mobility of lithium ion, and then improved the reversible capacity and the cycle performance of material.
(4) LiFePO of this multilevel hierarchy
4Material, its cavernous structure has improved the wettability of material and electrolyte, for the transmission of electronics and particle provides more reaction site; Laminated structure provides lithium ion migrating channels fast; Carbon coats provides electron propagation ducts; Assembling morphology has been stablized the overall structure of material, has improved stability, and the size that assembly is bigger has prevented to be dissolved in the material of electrolyte and crossed over the self-discharge phenomenon that barrier film causes, and makes it safer, and superior performance is in common nanometer LiFePO
4Material.
In addition, preparation method provided by the invention, flow process is simple, and energy consumption is little, is beneficial to mass preparation production.
Description of drawings
Fig. 1 is the olivine-type LiFePO that carbon coats
4The crystallogram (XRD) of multilevel hierarchy nanometer sheet microballoon adopts Bruker D8-Advance type X ray polycrystalline diffractometer (Cu target K
aBeam wavelength λ=0.15418nm).
Fig. 2 is the olivine-type LiFePO that carbon coats
4Electronic scanner microscope (SEM) picture of multilevel hierarchy nanometer sheet microballoon adopts JSM 7401F type field emission microscope.
Fig. 3 is that the employing metal lithium sheet is an anode material, the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon is the charging and discharging curve of battery under different discharge-rates that cathode material is assembled into.
Fig. 4 is that the employing metal lithium sheet is an anode material, the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon is 80 circle cycle performances and the enclosed pasture efficient of battery under constantly change situation of multiplying power that cathode material is assembled into.
Embodiment
The invention provides a kind of preparation method of nanometer sheet microspheroidal lithium ion battery cathode electrode material, this nanometer sheet microspheroidal lithium ion battery cathode electrode material is the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon, the present invention will be further described with implementing embodiment below in conjunction with accompanying drawing.Concrete preparation process comprises:
(1) iron phosphate nano sheet microballoon preparation technology: at first with 22.3g FePO
44H
2O, 6.7g (NH
4)
2SO
3H
2O and 2mL concentration be 25wt% ammoniacal liquor in the 100mL deionized water, fully mix, reflux down at 60 ℃ then and stirred 5-8 hour, by suction filtration deionized water cyclic washing, 50 ℃ of dry 8-12 hour acquisition product (NH down
4)
xFePO
4(0＜x＜1); Through 196 ℃ of heat treatments after 2 hours, ammonia that discharges and steam, the passivation of overflowing the ammonium radical ion by the surface makes FePO
4Nano microcrystalline is grown to serve as the nanometer disk, and the hydrogen bond that ammonium root, hydrone and phosphate radical form then links these nanometer disks with different angles, has obtained the nanometer sheet microballoon of ferric phosphate; Mix stirring after 4 hours with the nanometer sheet microballoon of 0.5g ferric phosphate and the watery hydrochloric acid 100mL of 0.1mol/L, be incubated 24 hours down, obtain having the iron phosphate nano sheet microballoon of loose structure at 400 ℃;
(2) the olivine-type LiFePO of carbon coating
4Multilevel hierarchy nanometer sheet microballoon preparation technology: 3.34g LiI and 0.1g iron phosphate nano sheet microballoon are dissolved in the 10mL acetonitrile solution, stirred 24 hours under the room temperature, under 6000 rev/mins of rotating speeds, centrifugal, with acetonitrile solution cyclic washing sediment, 40 ℃ of vacuumizes 2 hours; Sediment and the sucrose ground and mixed that accounts for sediment quality 20wt% with drying place corundum to burn boat, heat treatment under vacuum condition, programming rate with 10 ℃/minute, reacted 1 hour down at 550 ℃ earlier, reacted 1 hour down at 700 ℃ again, can obtain the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon.
Fig. 1 is its XRD figure, conformance with standard card (JCPDS No.40-1499; Pmnb (62);
), do not observe impurity peaks.Fig. 2 is its SEM picture, can observe about 1 micron of nanometer sheet diameter, nanometer sheet assembling microballoon distribution of sizes homogeneous.
Olivine-type LiFePO with the carbon coating
4Multilevel hierarchy nanometer sheet microballoon is made cathode material, and metal lithium sheet is assembled into lithium ion battery as anode material, carries out the constant current charge-discharge test.With the electrode active material of 78wt%, the acetylene black of 12wt% and the polyvinylidene fluoride powder of 10wt%, dissolve with N-methyl-pyrrolidones (NMP), in mortar, fully grind, after thing to be mixed becomes glue, with scraper it evenly is coated on copper sheet (diameter 10mm) collector electrode, drying is 10 hours under 110 ℃, is pressed into electrode (10MPa) then.Electro-chemical test adopts two electrode systems to carry out, and is to electrode with the pour lithium slice of same diameter, and capillary polypropylene (Ceigard-2402) is as barrier film, 1.0M LiPF
6/ EC+DMC+DEC (volume ratio is 1: 1: 1) is an electrolyte, is assembled into simulated battery in being full of the glove box of nitrogen.Adopt the Roofer battery test system at room temperature to carry out the constant current charge-discharge test, to the charge/discharge capacity of sample, cycle life and capability retention are tested in the 4.2-2.0V scope.The PARSTAT 2273Potentiostat/Galvanostat electrochemical analyser of employing United States advanced measuring technology company writes down the impedance spectrum of battery, and bias voltage is 5mV, and frequency range is 100KHz-100mHz.
Fig. 3 is the olivine-type LiFePO that coats with carbon
4Multilevel hierarchy nanometer sheet microballoon is a negative electrode, and metal lithium sheet is the battery charging and discharging curve of anode, show the battery of surveying under different multiplying, discharge platform is stable, and the platform capacity is bigger, and under 5C (1C=170mA/g) discharging current, the platform capacity has still surpassed 50mAh/g.
Fig. 4 by 80 cyclic curves and the enclosed pasture efficient of survey battery under discharging current constantly changes, circulation is at least 5 times under different electric currents, its corresponding average specific capacity is respectively as can be seen: 158mAh/g (0.1C), 147mAh/g (0.2C), 134mAh/g (0.5C), 117mAh/g (1C), 109mAh/g (2C) and 85mAh/g (5C), 80 almost not losses of circulation back specific capacity, enclosed pasture efficient is all the time more than 96%.
Experimental result shows: the olivine-type LiFePO that this carbon coats
4Multilevel hierarchy nanometer sheet microballoon has improved the wettability of material and electrolyte by utilizing its cavernous structure, for electronics and particle transmission provide more reaction site; Laminated structure provides lithium ion migrating channels fast; Carbon coating layer provides electron propagation ducts; Made full use of its Nanosurface, obtained higher specific capacity, simultaneously, assembling morphology has been stablized the nanostructure of material, improved stability, the size that assembly is bigger has prevented to be dissolved in the material of electrolyte and has crossed over the self-discharge phenomenon that barrier film causes, and makes it safer, and superior performance is in common nanometer LiFePO
4Material.
Claims (2)
1. the preparation method of a nanometer sheet microspheroidal lithium ion battery cathode electrode material is characterized in that described nanometer sheet microspheroidal lithium ion battery cathode electrode material is the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon is earlier to NH
4FePO
4Hocket heat treatment and pickling processes, preparation has the FePO of loose structure
4H
2O nanometer sheet microballoon, the acetonitrile solution with LiI reduces under the room temperature then, last mixing sucrose, high temperature sintering obtains in a vacuum, and concrete preparation process comprises:
(1) iron phosphate nano sheet microballoon preparation technology: at first with 20-30g FePO
44H
2O, 5-8g (NH
4)
2SO
3H
2O and 1.5-3mL concentration be 25wt% ammoniacal liquor in the 100mL deionized water, fully mix, reflux down at 45-70 ℃ then and stirred 5-8 hour, by suction filtration deionized water cyclic washing, 50-60 ℃ of dry 8-12 hour acquisition product (NH down
4)
xFePO
40＜x＜1 wherein; Pass through 180-210 ℃ of heat treatment after 2 hours, ammonia that discharges and steam, the passivation of overflowing the ammonium radical ion by the surface makes FePO
4Nano microcrystalline is grown to serve as the nanometer disk, and the hydrogen bond that ammonium root, hydrone and phosphate radical form then links these nanometer disks with different angles, has obtained the nanometer sheet microballoon of ferric phosphate; Mix stirring after 4 hours with the nanometer sheet microballoon of 0.5-1g ferric phosphate and the watery hydrochloric acid 100mL of 0.1mol/L, be incubated 24 hours down, obtain having the iron phosphate nano sheet microballoon of loose structure at 380-500 ℃;
(2) the olivine-type LiFePO of carbon coating
4Multilevel hierarchy nanometer sheet microballoon preparation technology: 3-4g LiI and 0.08-0.2g iron phosphate nano sheet microballoon are dissolved in the 10mL acetonitrile solution, stirred 24 hours under the room temperature, under 6000 rev/mins of rotating speeds, centrifugal, with acetonitrile solution cyclic washing sediment, 40 ℃ of vacuumizes 2 hours; Sediment and the sucrose ground and mixed that accounts for sediment quality 15-25wt% with drying, place corundum to burn boat, heat treatment under vacuum condition, programming rate with 10 ℃/minute, reacted 1 hour down at 500-600 ℃ earlier, reacted 1 hour down at 600-800 ℃, cooling naturally can obtain the olivine-type LiFePO that carbon coats again
4Multilevel hierarchy nanometer sheet microballoon.
2. the preparation method of a nanometer sheet microspheroidal lithium ion battery cathode electrode material is characterized in that, this nanometer sheet microspheroidal lithium ion battery cathode electrode material is the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon, concrete preparation process is as follows:
(1) iron phosphate nano sheet microballoon preparation technology: at first with 22.3g FePO
44H
2O, 6.7g (NH
4)
2SO
3H
2O and 2mL concentration be 25wt% ammoniacal liquor in the 100mL deionized water, fully mix, reflux down at 60 ℃ then and stirred 5-8 hour, by suction filtration deionized water cyclic washing, 50 ℃ of dry 8-12 hour acquisition product (NH down
4)
xFePO
4(0＜x＜1); Through 196 ℃ of heat treatments after 2 hours, ammonia that discharges and steam, the passivation of overflowing the ammonium radical ion by the surface makes FePO
4Nano microcrystalline is grown to serve as the nanometer disk, and the hydrogen bond that ammonium root, hydrone and phosphate radical form then links these nanometer disks with different angles, has obtained the nanometer sheet microballoon of ferric phosphate; Mix stirring after 4 hours with the nanometer sheet microballoon of 0.5g ferric phosphate and the watery hydrochloric acid 100mL of 0.1mol/L, be incubated 24 hours down, obtain having the iron phosphate nano sheet microballoon of loose structure at 400 ℃;
(2) the olivine-type LiFePO of carbon coating
4Multilevel hierarchy nanometer sheet microballoon preparation technology: 3.34g LiI and 0.1g iron phosphate nano sheet microballoon are dissolved in the 10mL acetonitrile solution, stirred 24 hours under the room temperature, under 6000 rev/mins of rotating speeds, centrifugal, with acetonitrile solution cyclic washing sediment, 40 ℃ of vacuumizes 2 hours; Sediment and the sucrose ground and mixed that accounts for sediment quality 20wt% with drying place corundum to burn boat, heat treatment under vacuum condition, programming rate with 10 ℃/minute, reacted 1 hour down at 550 ℃ earlier, reacted 1 hour down at 700 ℃ again, can obtain the olivine-type LiFePO that carbon coats
4Multilevel hierarchy nanometer sheet microballoon.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103208627A (en) * | 2013-02-22 | 2013-07-17 | 贵州省开阳安达磷化工有限公司 | Ferric phosphate material and manufacturing method thereof |
| CN107275629A (en) * | 2017-05-08 | 2017-10-20 | 武汉工程大学 | A kind of high power charging-discharging lithium ion battery positive electrode and preparation method thereof |
| WO2021000911A1 (en) * | 2019-07-03 | 2021-01-07 | 重庆特瑞电池材料股份有限公司 | Method for preparing multi-stage pore-forming lithium iron phosphate |
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|---|---|---|---|---|
| CN1469499A (en) * | 2003-06-26 | 2004-01-21 | 清华大学 | Reversed phase lithium inserting process of preparing polycrystal LiFePO4 nano powder material |
| CN101093888A (en) * | 2007-07-20 | 2007-12-26 | 哈尔滨工业大学 | Composite material of round LiFePO4 / C in honeycomb structure, and preparation method |
| CN101859898A (en) * | 2010-06-03 | 2010-10-13 | 清华大学 | Preparation method of electrode materials for lithium batteries |
-
2010
- 2010-11-25 CN CN2010105588261A patent/CN102054978B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1469499A (en) * | 2003-06-26 | 2004-01-21 | 清华大学 | Reversed phase lithium inserting process of preparing polycrystal LiFePO4 nano powder material |
| CN101093888A (en) * | 2007-07-20 | 2007-12-26 | 哈尔滨工业大学 | Composite material of round LiFePO4 / C in honeycomb structure, and preparation method |
| CN101859898A (en) * | 2010-06-03 | 2010-10-13 | 清华大学 | Preparation method of electrode materials for lithium batteries |
Non-Patent Citations (1)
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| 《Journal of Materials Chemistry》 20081208 Kuppan Saravanan,et al Storage performance of LiFePO4 nanoplates 605-610 1-2 第19卷, 第5期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103208627A (en) * | 2013-02-22 | 2013-07-17 | 贵州省开阳安达磷化工有限公司 | Ferric phosphate material and manufacturing method thereof |
| CN103208627B (en) * | 2013-02-22 | 2015-11-25 | 贵州安达科技能源股份有限公司 | A kind of ferric phosphate material and preparation method thereof |
| CN107275629A (en) * | 2017-05-08 | 2017-10-20 | 武汉工程大学 | A kind of high power charging-discharging lithium ion battery positive electrode and preparation method thereof |
| WO2021000911A1 (en) * | 2019-07-03 | 2021-01-07 | 重庆特瑞电池材料股份有限公司 | Method for preparing multi-stage pore-forming lithium iron phosphate |
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