CN102583296A - Method for preparing nanometer lithium iron phosphate in liquid phase - Google Patents
Method for preparing nanometer lithium iron phosphate in liquid phase Download PDFInfo
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- CN102583296A CN102583296A CN2011100014763A CN201110001476A CN102583296A CN 102583296 A CN102583296 A CN 102583296A CN 2011100014763 A CN2011100014763 A CN 2011100014763A CN 201110001476 A CN201110001476 A CN 201110001476A CN 102583296 A CN102583296 A CN 102583296A
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Abstract
The invention discloses a method for preparing nanometer lithium iron phosphate in liquid phase, which is characterized in that: reaction can be quickly completed in normal-pressure liquid phase, the synthesized lithium iron phosphate powder has small and homogenous particle size, and the particle size is 50nm to 400nm. The invention adopts a technical scheme that: ferrite and phosphoric acid mixed aqueous solution with a given concentration is prepared according to an equivalent mol ratio, the mixed aqueous solution is placed into a reactor, polarity organic solvent with a high boiling point such as dimethylsulfoxide with a volume ratio to the aqueous solution of 0.5 to 2:1 and 0.5 to 3 percent of crystal growth inhibitors such as polyacrylamide are added, lithium hydroxide solution is slowly added during the blending until the pH value of the reaction solution is 6 to 7, then the mixed solution is heated to the boiling point to have refluxing reaction for 0.5 to 3 hours, and products are conventionally filtered, washed and vacuum dried to obtain the nanometer lithium iron phosphate. The product is used as an anode material of a lithium-ion battery.
Description
Technical field
The invention belongs to a kind of preparation method of anode material for lithium-ion batteries, particularly under the normal pressure liquid-phase condition, directly prepare the method for nano-scale lithium iron phosphate.
Background technology
Iron lithium phosphate theoretical capacity 170mAh/g, sparking voltage 3.4V has superior safety ability and cycle performance; And the raw material sources of this material are extensive, and are cheap, environmentally safe; Be considered to have the power lithium-ion battery material of potentiality, become the focus of development research in recent years.Yet iron lithium phosphate itself also exists some defectives, the firstth, and what its particular structural had hindered lithium ion takes off embedding speed; The secondth, electronic conductivity is poor, causes high-rate discharge ability relatively poor.According to above-mentioned defective, people adopt particulates such as doping C, Ag, Cu to improve intergranular conductivity usually, through doped with Mg, Mn, Cu, Ti plasma with reduce the conductive performance that the iron lithium phosphate particle diameter improves the lithium ion of material.Nearest research shows, the reducing of iron lithium phosphate particle diameter can directly shorten the conduction distance of lithium ion in solid phase, thus improve lithium ion take off embedding fast, can significantly improve high rate performance.For homogeneity and the trickle property of improving material particle size, people often adopt methods such as sol-gel, spraying drying, but these methods only are the degree of mixing of having improved the presoma material, and finally still will pass through the high temperature sintering of long period.Some researchists have also proposed hydrothermal synthesis method; Publication number is the patent of invention " the synthetic preparation of hydrothermal method all disperses the brilliant method of lithium iron phosphate nano " of CN101047242A; Adopt ferrous salt, phosphoric acid and lithium hydroxide aqueous solution reaction 5-10h, the reaction precursor body that obtains is inserted at autoclave, reaction 5-24h under 150-200 ℃ hydrothermal condition; 600-700 ℃ of sintering 5-10h under inert atmosphere then, all dispersions lithium iron phosphate nano that obtains 0.2-0.5 μ m is brilliant.Publication number is that the patent of invention of CN10101650A adopts overcritical continuous hydro-thermal synthetic technology under the high pressure of 374 ℃ of high temperature and 22.1MPa, to synthesize LiFePO 4 powder.The patent of invention of publication number CN101659407A adopts the ethanol place of water to disclose supercritical solvent heat synthetic technology continuously as solvent, and this technology still needs 245-300 ℃ high temperature and the high pressure of 7-20MPa.Though, can synthesize the uniform submicron order iron lithium phosphate of particle diameter particle it is thus clear that hydrothermal synthesis method is in liquid phase, to carry out, need carry out at high-temperature and high-pressure conditions, higher to equipment requirements, be difficult in industry, using.People such as Yang Rong are at document " the synthetic and Mn of the co-precipitation of LiFePO 4 of anode material
2+Mix and study " [J] Xi'an University of Technology journal 2006,22 (1): 82-84 has proposed a kind of liquid phase coprecipitation method, with (NH
4)
2FeSO
4With (NH
4)
2HPO
4Solution mixes and adds xitix by the metering ratio; With ageing 4-6h behind the LiOH solution reaction; Throw out is washed drying to be placed in the High Temperature Furnaces Heating Apparatus; 550 ℃ of sintering 12h under inert atmosphere protection, the throw out that this method liquid phase generates not is the LiFePO 4 powder of olivine structural, still needs the high temperature sintering reaction long period.
Summary of the invention
The present invention is directed to the weak point that aforesaid method exists, propose a kind of liquid-phase synthesis process, this method can be in the normal pressure liquid phase rapid reaction generate the LiFePO 4 powder of olivine structural, and particle diameter is tiny and even, particle diameter is " grain of rice greatly " shape pattern.The technical scheme that the present invention adopts is: a kind of method of liquid phase production LiFePO 4 powder is characterized in that:
1, a kind of method of liquid phase production nano-scale lithium iron phosphate is characterized in that: include following operation:
(1) solution preparation, by Fe: the P mol ratio is to prepare solubility divalent iron salt and phosphoric acid mixed aqueous solution at 1: 1, and the solubility divalent iron salt is selected from any of nitrate salt, vitriol, hydrochloride and acetate;
(2) chemical reaction; Earlier above-mentioned mixing solutions is put into the reactor drum of reflux; Add the high boiling point polar organic solvent, the water-content volume ratio of add-on and solution is 0.5-2: 1, add crystal growth inhibitor; Add-on is the 0.5-3% of solution quality, stirs slowly to add 0.5-3.0mol.L down
-1Lithium hydroxide solution, to the pH value of reaction solution at 6-7, be heated to solution boiling point reaction 0.5-3h then, resultant through filtration, washing and the vacuum-drying of routine get final product product of the present invention.
2, the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the concentration of divalent iron salt described in the step (1) and phosphoric acid mixed aqueous solution is 0.1-3.0mol.L
-1
3, the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the high boiling organic solvent described in the step (2) is methyl-sulphoxide, terepthaloyl moietie, glycol ether, Tetraglycol 99, N a kind of.
4, the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the crystal formation inhibitor described in the step (2) can be selected a kind of of sucrose, SEPIGEL 305, CMC 99.5, sodium lauryl sulphate, X 2073, cetyl trimethylammonium bromide for use.
5, the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the solution boiling point that is heated to described in the step (2) is 104-120 ℃
Technology of the present invention need not adopt high-temperature high pressure water thermal reaction device and follow-up high temperature sintering; Reaction only needs 0.5-3h can generate the nano ferric phosphate powder for lithium under 105-120 ℃ the liquid phase environment under normal pressure; Owing to be that liquid phase is synthetic, and again owing to the effect of grain growth inhibitor, institute's synthetic LiFePO 4 powder particle reaches nano-scale; And particle diameter is even, controlled amount.
Description of drawings
Fig. 1 is the XRD figure spectrum of instance 1 synthetic nano-scale lithium iron phosphate of the present invention
Fig. 2 is the SEM photo of instance 1 synthetic nano-scale lithium iron phosphate of the present invention
Embodiment:
In conjunction with following instance the present invention is elaborated
Instance 1
By Fe: the P mol ratio is 1: 1 preparation 1mol.L
-1Ferrous sulfate and phosphoric acid mixed aqueous solution 100ml, mixing solutions is placed the 500ml reaction vessel that has the reflux condensation mode pipe unit, successively add the polyacrylamide solution 15ml of methyl-sulphoxide 100ml and 0.6%, stir and slowly to add 3mol.L down
-1The pH of lithium hydroxide solution to reaction solution be 7, be heated to solution boiling point (108 ℃) reaction 2h then, resultant is through filtering, using deionized water and absolute ethanol washing respectively, 100 ℃ of vacuum-drying 10h promptly obtain product of the present invention.Product detects through the XRD powdery diffractometry and is the pure phase LiFePO of olivine structural
4(Fig. 1), particle diameter is 40-400nm (Fig. 2).
Instance 2
By Fe: the P mol ratio is 1: 1 preparation 1mol.L
-1Ferrous sulfate and phosphoric acid mixed aqueous solution 100ml, mixing solutions is placed the 500ml reaction vessel that has the reflux condensation mode pipe unit, successively add methyl-sulphoxide 200ml and 1g X 2073, stir and slowly to add 2mol.L down
-1The pH of lithium hydroxide solution to reaction solution be 7, be heated to solution boiling point (115 ℃) reaction 1h then, resultant is through filtering, using deionized water and absolute ethanol washing respectively, 100 ℃ of vacuum-drying 10h promptly obtain product of the present invention.The gained sample detects through the XRD powdery diffractometry and is the pure phase LiFePO of olivine structural
4, particle diameter is 40-350nm.
Instance 3
By Fe: the P mol ratio is 1: 1 preparation 1mol.L
-1Chlorine ferrous salt and phosphoric acid mixed aqueous solution 100ml, mixing solutions is placed the 500ml reaction vessel that has the reflux condensation mode pipe unit, successively add terepthaloyl moietie 100ml and 0.5g cetyl trimethylammonium bromide, stir and slowly to add 1mol.L down
-1The pH of lithium hydroxide solution to reaction solution be 6.5, be heated to solution boiling point (106 ℃) reaction 2h then, resultant is through filtering, using deionized water and absolute ethanol washing respectively, 120 ℃ of vacuum-drying 8h promptly obtain product of the present invention.The gained sample detects through the XRD powdery diffractometry and is the pure phase LiFePO of olivine structural
4, particle diameter is 40-350nm.
Instance 4
By Fe: the P mol ratio is 1: 1 preparation 2mol.L
-1Iron diacetate salt and phosphoric acid mixed aqueous solution 100ml, mixing solutions is placed the 500ml reaction vessel that has the reflux condensation mode pipe unit, successively add glycol ether 100ml and 1.5g sucrose, stir and slowly to add 3mol.L down
-1The pH of lithium hydroxide solution to reaction solution be 7, be heated to solution boiling point (109 ℃) reaction 2h then, resultant is through filtering, using deionized water and absolute ethanol washing respectively, 80 ℃ of vacuum-drying 15h promptly obtain product of the present invention.The gained sample detects through the XRD powdery diffractometry and is the pure phase LiFePO of olivine structural
4, particle diameter is 40-300nm.
Instance 5
By Fe: the P mol ratio is 1: 1 preparation 0.5mol.L
-1Ferrous sulfate and phosphoric acid mixed aqueous solution 100ml, mixing solutions is placed the 500ml reaction vessel that has the reflux condensation mode pipe unit, successively add Tetraglycol 99 100ml and 5% carboxymethyl cellulose aqueous solution 10ml, stir and slowly to add 3mol.L down
-1The pH of lithium hydroxide solution to reaction solution be 7, be heated to solution boiling point (118 ℃) reaction 2h then, resultant is through filtering, using deionized water and absolute ethanol washing respectively, 80 ℃ of vacuum-drying 20h promptly obtain product of the present invention.The gained sample detects through the XRD powdery diffractometry and is the pure phase LiFePO of olivine structural
4, particle diameter is 40-300nm.
Instance 6
By Fe: the P mol ratio is 1: 1 preparation 1mol.L
-1Ferrous sulfate and phosphoric acid mixed aqueous solution 100ml, mixing solutions is placed the 500ml reaction vessel that has the reflux condensation mode pipe unit, successively add N 100ml and 0.5g sodium lauryl sulphate, stir and slowly to add 3mol.L down
-1The pH of lithium hydroxide solution to reaction solution be 7, be heated to solution boiling point (105 ℃) reaction 2h then, resultant is through filtering, using deionized water and absolute ethanol washing respectively, 80 ℃ of vacuum-drying 20h promptly obtain product of the present invention.The gained sample detects through the XRD powdery diffractometry and is the pure phase LiFePO of olivine structural
4, particle diameter is 40-350nm.
Claims (5)
1. the method for a liquid phase production nano-scale lithium iron phosphate is characterized in that: include following operation:
(1) solution preparation, by Fe: the P mol ratio is to prepare solubility divalent iron salt and phosphoric acid mixed aqueous solution at 1: 1, and the solubility divalent iron salt is selected from any of nitrate salt, vitriol, hydrochloride and acetate;
(2) chemical reaction; Earlier above-mentioned mixing solutions is put into the reactor drum of reflux; Add the high boiling point polar organic solvent, the water-content volume ratio of add-on and solution is 0.5-2: 1, add crystal growth inhibitor; Add-on is the 0.5-3% of solution quality, stirs slowly to add 0.5-3.0mol.L down
-1Lithium hydroxide solution, to the pH value of reaction solution at 6-7, be heated to solution boiling point reaction 0.5-3h then, resultant through filtration, washing and the vacuum-drying of routine get final product product of the present invention.
2. the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the concentration of divalent iron salt described in the step (1) and phosphoric acid mixed aqueous solution is 0.1-3.0mol.L
-1
3. the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the high boiling organic solvent described in the step (2) is methyl-sulphoxide, terepthaloyl moietie, glycol ether, Tetraglycol 99, N a kind of.
4. the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the crystal formation inhibitor described in the step (2) can be selected a kind of of sucrose, SEPIGEL 305, CMC 99.5, sodium lauryl sulphate, X 2073, cetyl trimethylammonium bromide for use.
5. the method for a kind of liquid phase production nano-scale lithium iron phosphate according to claim 1 is characterized in that: the solution boiling point that is heated to described in the step (2) is 104-120 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842717A (en) * | 2012-09-26 | 2012-12-26 | 河北工业大学 | Preparation method of self-assembled spindle-shaped nanostructure lithium iron phosphate |
| CN113772697A (en) * | 2021-08-24 | 2021-12-10 | 深圳新宸华科技有限公司 | Nano lithium carbonate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007630A (en) * | 2007-01-16 | 2007-08-01 | 北大先行科技产业有限公司 | Particle appearance regulatory lithium iron phosphate preparation method |
| CN101218172A (en) * | 2005-06-29 | 2008-07-09 | 尤米科尔公司 | Crystalline nanometric lifepo4 |
| CN101519195A (en) * | 2009-03-24 | 2009-09-02 | 河南师范大学 | Preparation method of high-density non-ball shape ferric phosphate powder body |
-
2011
- 2011-01-06 CN CN2011100014763A patent/CN102583296A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101218172A (en) * | 2005-06-29 | 2008-07-09 | 尤米科尔公司 | Crystalline nanometric lifepo4 |
| CN101007630A (en) * | 2007-01-16 | 2007-08-01 | 北大先行科技产业有限公司 | Particle appearance regulatory lithium iron phosphate preparation method |
| CN101519195A (en) * | 2009-03-24 | 2009-09-02 | 河南师范大学 | Preparation method of high-density non-ball shape ferric phosphate powder body |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842717A (en) * | 2012-09-26 | 2012-12-26 | 河北工业大学 | Preparation method of self-assembled spindle-shaped nanostructure lithium iron phosphate |
| CN102842717B (en) * | 2012-09-26 | 2014-09-17 | 河北工业大学 | Preparation method of self-assembled spindle-shaped nanostructure lithium iron phosphate |
| CN113772697A (en) * | 2021-08-24 | 2021-12-10 | 深圳新宸华科技有限公司 | Nano lithium carbonate and preparation method thereof |
| CN113772697B (en) * | 2021-08-24 | 2024-01-09 | 深圳新宸华科技有限公司 | Nanometer lithium carbonate and preparation method thereof |
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Application publication date: 20120718 |