CN101327921A - Preparation of ferric phosphate lithium composite material - Google Patents
Preparation of ferric phosphate lithium composite material Download PDFInfo
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- CN101327921A CN101327921A CNA2007100351756A CN200710035175A CN101327921A CN 101327921 A CN101327921 A CN 101327921A CN A2007100351756 A CNA2007100351756 A CN A2007100351756A CN 200710035175 A CN200710035175 A CN 200710035175A CN 101327921 A CN101327921 A CN 101327921A
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Abstract
The invention discloses a preparation method of lithium iron phosphate composite material which is characterized by adopting ferric hydrogen phosphate as iron source and phosphor source, mixing lithium source (lithium hydroxide, lithium carbonate, lithium oxalate or the like), ferric hydrogen phosphate with doping source materials, replacing the hydrogen in the FeHPO4 with lithium during the mechanochemical reaction in the ball mill, calcining the milled materials under protective atmosphere for several hours and crystallizing to obtain lithium iron phosphate (LiFePO4) composite material. The preparation method of the invention simplifies the synthesis technology and reduces the cost of material. The lithium iron phosphate composite material obtained has advantages of high specific capacity and good circulation performance, which is suitable for industrial application.
Description
Technical field
The invention belongs to the preparation method of energy and material positive electrode material for secondary battery, be specifically related to the preparation method of anode material for lithium-ion batteries.
Background technology
LiFePO
4As the lithium-ion secondary cell novel anode material, have high theoretical specific storage (170mAh/g) and moderate voltage platform (about 3.4V), and good cycle, low price, security are good, caused that people greatly pay close attention to, be considered to the particularly positive electrode material of power lithium-ion battery of lithium ion battery that the utmost point has an application potential.
Usually, preparation LiFePO
4Method have:
(1) high temperature solid-state method.Use the synthetic LiFePO of high temperature solid-state method
4, be raw material with Ferrox, ammonium phosphate and Quilonum Retard, fully grind the back and under inert atmosphere, calcine a few hours to drive the gas of decomposition in 200-300 ℃.Grind again after the cooling, promptly obtain LiFePO to room temperature in 600-800 ℃ of insulation for some time postcooling
4Equipment and technology that it is required are simple, and synthesis condition is easy to control, is convenient to suitability for industrialized production.But owing to reactant is difficult for mixing, coarse size, skewness, pattern is irregular, causes the chemical property variation of synthetic product;
(2) solution method.Adopt the method for reduction system electromotive force reduction embedding lithium also can prepare LiFePO
4But because Li
+Too slow with the solid phase diffusion speed of reductive agent, adopt this method to need long reaction times or higher hydrothermal temperature.This reduction embedding lithium process is often at high temperature implemented by the pyrogenic process roasting in the practical study, whole process complexity, and production cost is also higher.As people such as Silvera Scaccia with Fe
2+Oxidation obtains FePO
42H
2O is with FePO
42H
2After O sloughs crystal water, in organic solvent such as acetonitrile, add LiI again and carry out lithiumation.Filter then, wash, be deposited in air drying after, at Ar+H
2High-temperature calcination obtains LiFePO under the atmosphere
4
As mentioned above, existing preparation LiFePO
4Technology all exist certain defective.
Summary of the invention
The object of the invention is to provide a kind of manufacture method of simple synthesizing iron lithium phosphate composite material, and this method technical process is short, and energy consumption is low, and safety performance is good, is easy to realize industrialization, and the conductive agent in the product is evenly distributed stable electrochemical property.
Technical scheme of the present invention is: the preparation method of ferric phosphate lithium composite material is divided into the presoma preparation and two steps are handled in high-temperature calcination:
(1) presoma preparation: lithium source, phosphoric acid hydrogen iron and doped source material are mixed in proportion, wherein Li: Fe: the P mol ratio is 0.9～1.2: 1: 1; Doped source material addition is 5～15% of a reaction product weight percent; Mixture ball milling mill was obtained presoma in 1～10 hour.
(2) high-temperature calcination is handled: presoma under protective atmosphere, was warming up to 500～800 ℃ of temperature lower calcinations 2～20 hours, is cooled to room temperature then, promptly obtain product; Heat-up rate is 5～50 ℃/min, and cooling rate is 1～10 ℃/min.
Among the present invention, a kind of in Quilonum Retard, lithium hydroxide or the lithium oxalate adopts in the lithium source; Phosphoric acid hydrogen iron is all adopted in source of iron and phosphorus source; Doping element compound is one or more the mixture in acetylene black, sucrose, glucose, metal oxide, the metal-powder; Metal oxide is magnesium oxide, aluminum oxide, titanium dioxide or nickel oxide; Metal-powder is copper powder, silver powder or aluminium powder.
Protective atmosphere during the presoma high-temperature calcination is handled is meant nitrogen, argon gas, hydrogen or carbon monoxide atmosphere.
The present invention by adopt alkaline matters such as lithium hydroxide or Quilonum Retard go in and hydrogen in the acid salt phosphoric acid hydrogen iron, use positive 1 valency ion lithium mutually and come the balance anion electric charge.Consider that from the thermodynamics angle trend that reaction is carried out is very big.The present invention mixes lithium source, phosphoric acid hydrogen iron and doped source material by stoichiometric ratio according to this thinking, by the mechanochemical treatment of high energy milling, and fast reaction speed, optimization reaction conditions; Utilize mechanochemistry to handle and make doped source material disperseization, so in calcination process equably disperse at LiFePO
4Among form bulk phase-dopedly, comprise LiFePO
4/ C, Li
xMe
1-xFePO
4And Li
xMe
1- xFePO
4/ C, wherein Me represents one or more metallic elements of Ti, Co, Ni, Mg, Al, Cu etc.
In preparation process, do not need loaded down with trivial details operation such as dry presoma etc., presoma can directly obtain from the component of mixture of stoichiometric ratio, be a kind of very practical preparation method under the technical scale, and before mechanical ball milling, will join in the component by metal oxide and the metal-powder that thermolysis forms the material of conductive carbon or forms sosoloid.Therefore, with respect to existing industrial preparation LiFePO
4Method, it is extensive, cheap that the present invention has material source; Method is simple, and technical process is short, and easy to operate, energy consumption is low, and safety performance is good, is easy to realize industrialization; The positive electrode material of preparation is realized mixing easily; Conductive agent in the product is evenly distributed, advantages such as stable electrochemical property.
Description of drawings
The LiFePO of Fig. 1: embodiment 1 preparation
4The x-ray diffraction pattern of matrix material;
The LiFePO of Fig. 2: embodiment 2 preparations
4The x-ray diffraction pattern of matrix material;
The LiFePO of Fig. 3: embodiment 3 preparations
4The first charge-discharge graphic representation of matrix material;
The LiFePO of Fig. 4: embodiment 3 preparations
4The cycle performance figure of matrix material;
The LiFePO of Fig. 5: embodiment 4 preparations
4The first charge-discharge graphic representation of matrix material;
The LiFePO of Fig. 6: embodiment 4 preparations
4The cycle performance figure of matrix material.
Embodiment
In order to explain the present invention in more detail, enumerate following examples and describe, but the present invention is not limited to these embodiment.
Embodiment 1
With lithium hydroxide: phosphoric acid hydrogen iron is by 1.2: 1 mixed in molar ratio, and adds 5% carbon black by the reaction product weight ratio, places vibration ball mill mixed grinding 1 hour; Take out grinding product, the porcelain boat of packing into places electric furnace, at flow velocity is under 5 liters/minute the nitrogen protection, to be warming up to 500 ℃ with 20 ℃/minute speed, is incubated 20 hours, cools to room temperature then with the furnace, and the product of gained is a product A.Accompanying drawing 1 is the XRD figure of product A, and the result shows that product is LiFePO
4, crystalline structure is complete.
Take by weighing 0.75 gram product A, add 0.15 gram carbon black and 0.1 gram tetrafluoroethylene, after the grinding evenly, prepare electrode with coating method.Choose suitable positive plate, make counter electrode with the lithium sheet, the foam nickel screen is made negative current collector, is 1.0molL with the concentration that is dissolved in ethyl-carbonate+methylcarbonate+diethyl carbonate (volume ratio is 1: 1: 1) mixed solvent
-1LiPF
6Be electrolytic solution, polyethylene micropore film microseptum is assembled into battery.With its charging and discharging capacity of constant current charge-discharge technical measurement and cycle performance, the electrochemical property test result is as follows: discharge and recharge under the current density of room temperature, 0.1C, charging platform is about 3.5V, and discharge platform is about 3.4V.In the voltage range of 2.3～4.1V, its first discharge specific capacity is 128.2mAh/g, and the specific storage that circulates after 10 times is 114.7mAh/g.
With lithium hydroxide: phosphoric acid hydrogen iron is by 1: 1 mixed in molar ratio, and adds 5% sucrose by the reaction product weight ratio, places roller ball grinding machine mixed grinding 10 hours; Taking out grinding product, in the porcelain boat of packing into, place electric furnace, is under 1 liter/minute the argon shield, to be warming up to 800 ℃ with 15 ℃/minute speed at flow velocity, and insulation is 2 hours under this temperature, cools to room temperature then with the furnace, and the product of gained is a product B.Accompanying drawing 2 is the XRD figure of product B, and the result shows that product is olivine-type LiFePO
4
Comprise the battery of the electrode of being made by product B and test according to the assembling of the method for embodiment 1, the result shows that its first discharge specific capacity is 147.4mAh/g, and the specific storage that circulates after 10 times is 142.8mAh/g.
With Quilonum Retard: phosphoric acid hydrogen iron is by 0.5: 1 mixed in molar ratio, and adds 10% glucose by the reaction product weight ratio, places the planetary ball mill mixed grinding 2 hours; Taking out grinding product, is under 10 liters/minute the nitrogen protection, to be warming up to 600 ℃ with 20 ℃/minute speed at flow velocity, is incubated 12 hours, is cooled to room temperature with 3 ℃/minute speed of cooling then, and the product of gained is a products C, and the result shows that product is LiFePO
4
Comprise the battery of the electrode of being made by products C according to the assembling of the method for embodiment 1, test under room temperature, 1C current density, the result shows that its first discharge specific capacity is 143.6mAh/g, and the specific storage that circulates after 20 times is 142.8mAh/g; Its first charge-discharge graphic representation, cycle performance figure are respectively shown in accompanying drawing 3, accompanying drawing 4.
With Quilonum Retard: phosphoric acid hydrogen iron is by 0.55: 1 mixed in molar ratio, and adds 10% metal A g powder by the reaction product weight ratio, places the agitating ball mill mixed grinding 4 hours; Taking out grinding product, is under 5 liters/minute the nitrogen protection, to be warming up to 600 ℃ with 20 ℃/minute speed at flow velocity, and insulation is 4 hours under this temperature, cools to room temperature then with the furnace, and the product of gained is product D, and the result shows that product is LiFePO
4
Method according to embodiment 1 is assembled the battery that comprises the electrode of being made by product D, carries out charge-discharge test under the electric current of room temperature, 3C.The result shows that its first discharge specific capacity is 138mAh/g, and the specific discharge capacity that circulates after 50 times is 141.3mAh/g.Its first charge-discharge graphic representation, cycle performance figure are respectively shown in accompanying drawing 5, accompanying drawing 6.
Embodiment 5
With lithium hydroxide: phosphoric acid hydrogen iron is by 0.9: 1 mixed in molar ratio, and adds 15% doped source material by the reaction product weight ratio, wherein is 5% magnesium oxide and 10% glucose, places the agitating ball mill mixed grinding 5 hours; Taking out grinding product, is under 5 liters/minute the nitrogen protection, to be warming up to 650 ℃ with 20 ℃/minute speed at flow velocity, and insulation is 8 hours under this temperature, cools to room temperature then with the furnace, and the product of gained is a product E, and the result shows that product is LiFePO
4
Method according to embodiment 1 is assembled the battery that comprises the electrode of being made by product E, tests under room temperature, 5C electric current.The result shows that its first discharge specific capacity is 128.2mAh/g, and the specific discharge capacity that circulates after 40 times is 122.3mAh/g.
Claims (5)
1. the preparation method of ferric phosphate lithium composite material is characterized in that may further comprise the steps:
(1) presoma preparation: lithium source, phosphoric acid hydrogen iron and doped source material are proportionally mixed, wherein mol ratio Li: Fe: P=0.9～1.2: 1: 1; Doped source material addition is 5～15% of a reaction product weight percent; The mixture ball milling was promptly obtained presoma in 1～10 hour;
(2) high-temperature calcination is handled: presoma under protective atmosphere, was warming up to 500～800 ℃ of temperature lower calcinations 2～20 hours, is cooled to room temperature then and promptly obtains product; Heat-up rate is 5～50 ℃/min, and cooling rate is 1～10 ℃/min.
2. the method for claim 1 is characterized in that: described lithium source is a kind of in Quilonum Retard, lithium hydroxide or the lithium oxalate.
3. the method for claim 1, it is characterized in that: described doped source material is one or more in acetylene black, sucrose, glucose, metal-powder, the metal oxide.
4. method as claimed in claim 3 is characterized in that: described metal-powder is a copper powder, silver powder or aluminium powder; Metal oxide is an aluminum oxide, magnesium oxide, titanium dioxide or nickel oxide.
5. the method for claim 1, it is characterized in that: the described protective atmosphere of step (2) is nitrogen, argon gas, hydrogen or carbon monoxide atmosphere.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101826618A (en) * | 2010-05-14 | 2010-09-08 | 成都联禾化工医药有限责任公司 | Method for preparing superfine and high-dispersibility lithium iron phosphate |
| WO2010148638A1 (en) * | 2009-06-21 | 2010-12-29 | 海特电子集团有限公司 | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced thereby |
| CN101966986A (en) * | 2010-11-19 | 2011-02-09 | 中南大学 | Preparation method of lithium iron phosphate cathode material for lithium ion battery |
| CN102299331A (en) * | 2011-07-19 | 2011-12-28 | 彩虹集团公司 | Carbon-coated lithium iron phosphate-doped lithium ion battery anode material and preparation method thereof |
| CN102299321A (en) * | 2011-07-23 | 2011-12-28 | 蔡道国 | Phosphatic anode material, its preparation method, and lithium ion power battery |
| CN102623697A (en) * | 2012-03-30 | 2012-08-01 | 天津巴莫科技股份有限公司 | Lithium iron phosphate/titanium diboride composite cathode material for lithium ion battery and preparation method of lithium iron phosphate/titanium diboride composite cathode material |
| CN103165882A (en) * | 2011-12-15 | 2013-06-19 | 河南科隆集团有限公司 | Preparation method for positive electrode material--lithium iron phosphate |
| CN103647076A (en) * | 2013-11-15 | 2014-03-19 | 成都兴能新材料有限公司 | Magnesium and aluminum activated lithium iron phosphate cathode material |
| CN110980681A (en) * | 2019-11-07 | 2020-04-10 | 河北科技大学 | Na3Mg3(PO4)3MgO photocatalytic material, preparation method and application |
Family Cites Families (3)
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| CN1280185C (en) * | 2004-02-20 | 2006-10-18 | 北大先行科技产业有限公司 | Preparation process of lithium ferrous phosphate for positive pole of lithium ion cell |
| CN1585168A (en) * | 2004-05-21 | 2005-02-23 | 河南金龙精密铜管股份有限公司 | Modified ferrous phosphate anode material for lithium ion battery and production method thereof |
| CN100428542C (en) * | 2006-09-30 | 2008-10-22 | 天津大学 | Anode material for lithium ion battery and method for making same |
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2007
- 2007-06-20 CN CN200710035175A patent/CN101327921B/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010148638A1 (en) * | 2009-06-21 | 2010-12-29 | 海特电子集团有限公司 | Method for producing composite lithium iron phosphate material and composite lithium iron phosphate material produced thereby |
| CN101826618A (en) * | 2010-05-14 | 2010-09-08 | 成都联禾化工医药有限责任公司 | Method for preparing superfine and high-dispersibility lithium iron phosphate |
| CN101826618B (en) * | 2010-05-14 | 2012-11-07 | 成都联禾化工医药有限责任公司 | Method for preparing superfine and high-dispersibility lithium iron phosphate |
| CN101966986A (en) * | 2010-11-19 | 2011-02-09 | 中南大学 | Preparation method of lithium iron phosphate cathode material for lithium ion battery |
| CN102299331A (en) * | 2011-07-19 | 2011-12-28 | 彩虹集团公司 | Carbon-coated lithium iron phosphate-doped lithium ion battery anode material and preparation method thereof |
| CN102299321A (en) * | 2011-07-23 | 2011-12-28 | 蔡道国 | Phosphatic anode material, its preparation method, and lithium ion power battery |
| CN102299321B (en) * | 2011-07-23 | 2014-04-30 | 路华电子科技（汕尾）有限公司 | Phosphatic anode material, its preparation method, and lithium ion power battery |
| CN103165882A (en) * | 2011-12-15 | 2013-06-19 | 河南科隆集团有限公司 | Preparation method for positive electrode material--lithium iron phosphate |
| CN102623697A (en) * | 2012-03-30 | 2012-08-01 | 天津巴莫科技股份有限公司 | Lithium iron phosphate/titanium diboride composite cathode material for lithium ion battery and preparation method of lithium iron phosphate/titanium diboride composite cathode material |
| CN103647076A (en) * | 2013-11-15 | 2014-03-19 | 成都兴能新材料有限公司 | Magnesium and aluminum activated lithium iron phosphate cathode material |
| CN103647076B (en) * | 2013-11-15 | 2015-12-30 | 成都兴能新材料有限公司 | Magnesium, aluminium activation lithium iron phosphate positive material |
| CN110980681A (en) * | 2019-11-07 | 2020-04-10 | 河北科技大学 | Na3Mg3(PO4)3MgO photocatalytic material, preparation method and application |
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| CN101327921B (en) | 2010-05-26 |
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