CN102299320A - Preparation method for lithium iron phosphate material applicable to power batteries - Google Patents
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- CN102299320A CN102299320A CN2011102041619A CN201110204161A CN102299320A CN 102299320 A CN102299320 A CN 102299320A CN 2011102041619 A CN2011102041619 A CN 2011102041619A CN 201110204161 A CN201110204161 A CN 201110204161A CN 102299320 A CN102299320 A CN 102299320A
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- lithium
- lifepo
- lifepo4
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- 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 preparation method for a lithium iron phosphate material applicable to power batteries. The method comprises the following steps: (1) preparing nanometer primary particles of lithium iron phosphate, that is, weighing phosphate, a ferric salt and a lithium salt according to the molar ration of P to Fe to Li being 1:1:3, respectively dissolving phosphate, the ferric salt and the lithium salt in water, stirring the mixtures until the three above-mentioned substances are completely dissolved so as to form three uniform solutions, pouring the three uniform solutions into a flask with a large round bottom for oil bath heating, adding an organic solvent and sodium hydrosulphite simultaneously, adjusting the pH value of obtained mixture to be 7 to 8, and repeatedly filtering flocculent precipitates at the bottom of the flask so as to obtain nanometer primary particles of lithium iron phosphate; (2) carrying out spraying to form secondary particles; (3) roasting the secondary particles at high temperature to obtain a lithium iron phosphate material in a spherical shape. According to the invention, raw materials used in the method are widely available and cheap; a synthetic process is simple, practicable, safe and reliable; production cost is low while yield is high; no environmental pollution is produced; the obtained product has good electrochemical performance.
Description
Technical field
The invention belongs to the anode material for lithium-ion batteries technical field, particularly relate to a kind of preparation method of LiFePO 4 material.
Background technology
Since phase at the end of the nineties in last century, olivine-type LiFePO
4The research of positive electrode causes numerous researchers' concern.LiFePO4 has high theoretical capacity (170mAh/g), high working voltage (voltage platform about 3.5V), suitable mass density (3.64g/cm
3), self discharge is little, LiFePO under low current density
4In Li
+Almost can 100% embed/take off embedding, have extended cycle life, good cycle, memory-less effect, cheap, Heat stability is good, advantage such as environmentally friendly, be expected to become anode material for lithium-ion batteries of new generation.
The lithium ion battery quilt widely should be in making various electronic equipments, as notebook computer, in machine battery, digital camera, portable lighting equipment etc.Simultaneously, it also is used to electric tool, electric bicycle and electric automobile.Along with the consumption gradually of world petroleum resource, and the society requirement on environmental protection is improved gradually, electric motor car has obtained unprecedented opportunity to develop.As electric vehicle power sources, is the direction of electric motor car development with lithium ion battery.
In lithium ion battery, positive electrode occupies important status, also is the emphasis of current lithium ion battery development.Traditional positive electrode is to bore sour lithium, and its advantage is that energy height, good cycle, preparation are simple, technology maturation, Technological adaptability are good, and shortcoming is that price is too high, poor safety performance.The LiMn2O4 low price, but cycle performance and high-temperature behavior have much room for improvement./ 2nd materials that partly substitute cobalt with manganese and nickel are materials of acid energy of LiMn2O4 and cobalt and price compromise, and its cobalt content can not fall very lowly, and the price of nickel is also very high, so its cost performance is undesirable.And ferric phosphate this is low hammer out, aboundresources, good cycle, be desirable anode material for lithium-ion batteries.
LiFePO
4Positive electrode also has very big defective, and its ion and electronic conductivity are not good, causes the charge-discharge magnification performance not good.This shortcoming has greatly influenced LiFePO
4Replace LiCoO
2Become anode material for lithium-ion batteries of new generation.LiFePO
4This defective of positive electrode can overcome by the preparation ultra-fine grain.By increasing the material specific area, promote being in contact with one another or the coated with conductive charcoal between the particle, can improve LiFePO
4The electric conductivity of positive electrode.But thereupon a new problem arose again.Along with the increase of specific area, the amount that is coated with required bonding agent and solvent also increases greatly, has brought very big difficulty for the coating of pole piece, and after pole piece is prepared into electric core or battery, is easy to occur falling the material phenomenon.At present, LiFePO 4 material ubiquity coating difficult problem.
The people such as J.B.Goodenough of U.S. Texas university in 1999 obtain the patent right of US Patent No.591382de lithium battery anode LiFePO 4 material, low discharging current with 0.05mA/cm2, capacity is 110mAh/g, reach the theoretical capacity of 170mAh/g far away, reason is that LiFePO4 electronics and ionic conductivity are low.Be head it off, people such as N.Ravet and M.Armand adopt charcoal coating, method metal-doped and that phosphate potential substitutes to improve the LiFePO4 conductivity greatly.The Yet-Ming Chiang of Massachusetts Institute Technology in 2002 etc. applies for a patent US2004/005265A1, and+2 above metal ions that mix in the lithium position can increase substantially electronic conductivity, thereby have improved the multiplying power property of LiFePO4.More than provide fundamental basis for the application in the power lithium-ion battery.
Sony company adopts Li
3PO and Fe
3(PO)
2-8H
20 is raw material, adds amorphous carbon black or carbon precursor ball milling together, prepares LiFePO4 below 6000C.This method biggest advantage is to have only water to discharge in the tail gas, the productive rate height, but need preparation ferrous phosphate presoma earlier, and also if other elements that mix need to add in addition in proportion the balance that phosphoric acid could keep each element metering ratio.
Based on pyrocarbon thermal reduction synthetic technology, the cheap ferric iron sources such as di-iron trioxide of U.S. Valence Technology Inc. company, it is excessive to add weight ratio 100% when raw material mix, and is prepared LiFePO4 in ferric iron by the amorphous carbon black that carbon black is reduced to ferrous consumption.
Prior art generally adopts solid phase method or wet chemical method to prepare positive active material LiFeP04, and for example CN 1401559A discloses a kind of LiFePO4 (LiFePO
4) the preparation method, this method is the even back high-temperature calcination of lithium salts, ferrous salt and phosphate ground and mixed, the calcining back that finishes adds the conductive agent ground and mixed and makes LiFePO4.But when adopting solid phase method, various solid constituents are difficult to fully mix, therefore in the iron phosphate lithium positive pole active material that obtains various compositions especially conductive agent disperse inhomogeneously, directly influence the conductivity of positive active material.
Summary of the invention
It is abundant, cheap to the purpose of this invention is to provide a kind of raw material sources, synthesis technique is simple, safe and reliable, production cost is low, productive rate is high, non-environmental-pollution, product have the preparation method of the LiFePO 4 material that is applicable to electrokinetic cell of better chemical property.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of preparation method who is applicable to the LiFePO 4 material of electrokinetic cell may further comprise the steps:
(1) preparation nano-scale lithium iron phosphate primary particle:
According to P: Fe: Li=1: 1: 3 molar ratio, it is soluble in water respectively to take by weighing phosphate, molysite and lithium salts, is stirred to dissolving fully, forms three kinds of homogeneous solutions; Pour three kinds of homogeneous solutions into big round bottom flask and mix the formation mixed solution, add organic solvent and sodium sulfite simultaneously and form mixed reaction solution, the pH value of regulating mixed reaction solution is 7-8; 100-140 ℃ of oil bath agitating heating is 1-5 hour then; Filter drag and form flocculent deposit and cleaning, obtain the nano-scale lithium iron phosphate primary particle; Adding volume of organic solvent is 2/3rds of mixed liquor volume; The molal quantity of the sodium sulfite that adds is 0.046: 1 with the ratio of the molal quantity of taking by weighing molysite;
(2) spraying forms offspring:
Step (1) is made the LiFePO4 primary particle add water to be mixed with LiFePO4 primary particle mass percent concentration be 10% suspension-turbid liquid, in suspension-turbid liquid, add surfactant, use spraying machine to carry out spray drying then, obtain the LiFePO4 second particle;
(3) LiFePO4 sintering:
The LiFePO4 second particle is placed in the nitrogen environment,, obtains being shaped as spherical LiFePO 4 material through high-temperature roasting.
Described lithium salts is lithium carbonate, lithium hydroxide, lithium fluoride; Described molysite is ferrous acetate, ferrous nitrate, frerrous chloride; Described phosphate is lithium dihydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, phosphoric acid.
In the step (2) inlet temperature 130-180 ℃ of spraying machine, outlet temperature 50-100 ℃.
The temperature of high-temperature roasting is 400-800 ℃ in the step (3), and roasting time is 6-25 hour.
The organic solvent that adds in the step (1) is an ethylene glycol.
The surfactant that adds in the step (2) is a neopelex, and the ratio of the molal quantity of the molal quantity of adding and step (1) molysite that takes by weighing is 0.01: 1.
During the oil bath agitating heating, mixing speed is 200～400 rev/mins in the step (1).
Advantage of the present invention is: the inventive method is simple, safe and reliable, production cost is low, productive rate is high, and non-environmental-pollution, product have better chemical property; Prepared LiFePO 4 material carries out SEM and detects, and particle diameter is even, and segmentation is few, and particle is spherical, can effectively increase tap density; It is fine as antioxidant effect to add sodium sulfite in the reaction, and product purity has very big lifting; The present invention adds surfactant during dissolving phosphoric acid iron lithium primary particle when carrying out spray drying, reduce the reunion of particle, helps improving spray effect.
Description of drawings
Fig. 1 is sem photograph (SEM) figure of the LiFePO4 of example 1 preparation;
Fig. 2 is sem photograph (SEM) figure of the LiFePO4 of example 2 preparations;
Fig. 3 is sem photograph (SEM) figure of the LiFePO4 of example 3 preparations
Fig. 4 is X-ray diffraction (XRD) figure of the LiFePO4 of example 1 preparation;
Fig. 5 is X-ray diffraction (XRD) figure of the LiFePO4 of example 2 preparations;
Fig. 6 is X-ray diffraction (XRD) figure of the LiFePO4 of example 3 preparations.
Embodiment
Further specify preparation process of the present invention below in conjunction with concrete embodiment:
Embodiment 1
Utilize assay balance accurately to take by weighing (NH respectively
4)
3PO
4Be 149g, FeCl
2Be 126.9g, LiF is 78g, is dissolved in respectively in the 500ml water, utilizes magnetic agitation to stir and fully dissolving, approximately stirs 20 minutes, and medicine dissolves fully, and solution becomes homogeneous solution, and does not have visible crystals particle vision as seen.At this moment, under mechanical agitation slurry (rotating speed=400 rev/min) effect, successively three kinds of solution that prepare are poured into big round bottom flask while stirring and formed mixed solution, the boiling point that adds organic solvent ethylene glycol raising reactant liquor simultaneously, add sodium sulfite 6.54g as antioxidant, utilize the Ph=7.5 of nitric acid and ammoniacal liquor regulator solution.Utilize oil bath (silicone oil is used in this laboratory) to heat 1h down for 100 ℃, in heating, utilize mechanical agitator (rotating speed=400 rev/min) to stir simultaneously, the solid of drag is cleaned repeatedly and filters, finally obtain the nano-scale lithium iron phosphate primary particle.The volume that adds ethylene glycol is 2/3rds of a mixed liquor volume.
The water that filtration obtains and the mixed solution of diethanol are poured Rotary Evaporators into, and vacuum degree is-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, and keeps temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salts, the pure diethanol that obtains utilizes refractometer to carry out purity test, makes the coprecipitation reaction of LiFePO4 in next time and reuses as organic solvent.
The LiFePO4 primary particle is added water, and to be mixed with LiFePO4 primary particle mass percent concentration be 10% suspension-turbid liquid, in suspension-turbid liquid, add surfactant neopelex 3.49g, spray and obtain second particle, spraying machine is set spray parameters, 160 ℃ of inlet temperatures, 50 ℃ of outlet temperatures obtain the LiFePO4 second particle.
Place tube furnace to carry out roasting second particle, feed the mist of 90% nitrogen and 10% hydrogen in tube furnace, be warmed up to 800 ℃ with the speed of 2 ℃/min, keep temperature 6h, stove naturally cools to room temperature, obtains the ball shape ferric phosphate lithium material.
See also shown in Figure 1ly, LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle be a sphere, can effectively increase tap density.The X-ray diffractogram of this ball shape ferric phosphate lithium material as shown in Figure 4.
Embodiment 2
Utilize assay balance accurately to take by weighing (NH respectively
4)
3PO
4Be 14.9g, FeCl
2Be 12.7g, LiF is 7.8g, is dissolved in respectively in the 50ml water, utilizes magnetic agitation to stir and fully dissolving, approximately stirs 10 minutes, and medicine dissolves fully, and solution becomes homogeneous solution, and does not have visible crystals particle vision as seen.At this moment, under mechanical agitation slurry (rotating speed=300 rev/min) effect, successively three kinds of solution that prepare are poured into big round bottom flask while stirring and mixed the formation mixed solution, the boiling point that adds organic solvent ethylene glycol raising reactant liquor simultaneously, add sodium sulfite 0.65g as antioxidant, utilize the Ph=7.0 of nitric acid and ammoniacal liquor regulator solution.Utilize oil bath (silicone oil is used in this laboratory) to heat 10h down for 110 ℃, in heating, utilize mechanical agitator (rotating speed=300 rev/min) to stir simultaneously, the solid of drag is cleaned repeatedly and filters, finally obtain the LiFePO4 primary particle.The volume that adds ethylene glycol is 2/3rds of a mixed liquor volume.
The water that filtration obtains and the mixed solution of diethanol are poured Rotary Evaporators into, and vacuum degree is-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, and keeps temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salts, the pure diethanol that obtains utilizes refractometer to carry out purity test, makes the coprecipitation reaction of LiFePO4 in next time and reuses as organic solvent.
The LiFePO4 primary particle is added water, and to be mixed with LiFePO4 primary particle mass percent concentration be 10% suspension-turbid liquid, in suspension-turbid liquid, add surfactant neopelex 0.35g, spray and obtain second particle, spraying machine is set spray parameters, 180 ℃ of inlet temperatures, 100 ℃ of outlet temperatures obtain the LiFePO4 second particle.
Place tube furnace to carry out roasting second particle, feed the mist of 95% nitrogen and 5% hydrogen in tube furnace, be warmed up to 700 ℃ with the speed of 10 ℃/min, keep temperature 12h, stove naturally cools to room temperature, obtains the ball shape ferric phosphate lithium material.
See also shown in Figure 2ly, LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle be a sphere, can effectively increase tap density.The X-ray diffractogram of this ball shape ferric phosphate lithium material as shown in Figure 5.
Embodiment 3
Utilize assay balance accurately to take by weighing (NH respectively
4)
3PO
4Be 1490g, FeCl
2Be 1269g, LiF is 780g, is dissolved in respectively in the 5000ml water, utilizes magnetic agitation to stir and fully dissolving, approximately stirs 20 minutes, and medicine dissolves fully, and solution becomes homogeneous solution, and does not have visible crystals particle vision as seen.At this moment, under mechanical agitation slurry (rotating speed=300 rev/min) effect, successively three kinds of solution that prepare are poured into big round bottom flask while stirring and mixed the formation mixed solution, the boiling point that adds organic solvent ethylene glycol raising reactant liquor simultaneously, add sodium sulfite 65.4g as antioxidant, utilize the Ph=8.0 of nitric acid and ammoniacal liquor regulator solution.Utilize 140 ℃ of oil baths (this laboratory use silicone oil) heating 5h down, in heating, utilize mechanical agitator (rotating speed=200 rev/min) to stir simultaneously, the solid of drag is cleaned repeatedly and filters, finally obtain the LiFePO4 primary particle.The volume that adds ethylene glycol is 2/3rds of a mixed liquor volume.
The water that filtration obtains and the mixed solution of diethanol are poured Rotary Evaporators into, and vacuum degree is-0.09MPa, and when temperature reaches 70 ℃, water begins violent boiling and steams, and keeps temperature 6 hours, and moisture is separated fully.To not steam liquid filtering and remove precipitation and sl. sol. inorganic salts, the pure diethanol that obtains utilizes refractometer to carry out purity test, makes the coprecipitation reaction of LiFePO4 in next time and reuses as organic solvent.
The LiFePO4 primary particle is added water, and to be mixed with LiFePO4 primary particle mass percent concentration be 10% suspension-turbid liquid, in suspension-turbid liquid, add surfactant neopelex 34.85g, spray and obtain second particle, spraying machine is set spray parameters, 130 ℃ of inlet temperatures, 75 ℃ of outlet temperatures obtain the LiFePO4 second particle.
Place tube furnace to carry out roasting second particle, feed the mist of 97% nitrogen and 3% hydrogen in tube furnace, be warmed up to 750 ℃ with the speed of 5 ℃/min, keep temperature 10h, stove naturally cools to room temperature, obtains the ball shape ferric phosphate lithium material.
See also shown in Figure 3ly, LiFePO 4 material is carried out SEM detect, it is even that pattern can get the offspring particle diameter, and segmentation is few, and particle be a sphere, can effectively increase tap density.The X-ray diffractogram of this ball shape ferric phosphate lithium material as shown in Figure 6.
The raw material of the inventive method adopts ferrous salt, because of its unstable easily characteristic of oxidation, the purity that obtains LiFePO4 is had a significant impact, and carries out ferrous oxidation inhibition by adding antioxidant; The synthetic commonly used antioxidant of LiFePO4 was an ascorbic acid in the past, but by, find that its anti-oxidation characteristics is undesirable, utilize sodium sulfite fine as antioxidant effect, product purity has very big lifting through test; When the present invention mixed three kinds of raw materials, the mixing velocity that liquid shifts was influential to the particle size distribution of product, slowly pours into when pouring into, and the particle size distribution of product is even; Mechanical agitation intensity during oil bath is influential to ultimate size equally, should improve rotating speed and reduces the nanoscale particle diameter; The present invention adds surfactant during dissolving phosphoric acid iron lithium primary particle when carrying out spray drying, reduce the reunion of particle, helps improving spray effect.
Claims (7)
1. a preparation method who is applicable to the LiFePO 4 material of electrokinetic cell is characterized in that, may further comprise the steps:
(1) preparation nano-scale lithium iron phosphate primary particle:
According to P: Fe: Li=1: 1: 3 molar ratio, it is soluble in water respectively to take by weighing phosphate, molysite and lithium salts, is stirred to dissolving fully, forms three kinds of homogeneous solutions; Pour three kinds of homogeneous solutions into big round bottom flask and mix the formation mixed solution, add organic solvent and sodium sulfite simultaneously and form mixed reaction solution, the pH value of regulating mixed reaction solution is 7-8; 100-140 ℃ of oil bath agitating heating is 1-5 hour then; Filter drag and form flocculent deposit and cleaning, obtain the nano-scale lithium iron phosphate primary particle; Adding volume of organic solvent is 2/3rds of mixed liquor volume; The molal quantity of the sodium sulfite that adds is 0.046: 1 with the ratio of the molal quantity of taking by weighing molysite;
(2) spraying forms offspring:
Step (1) is made the LiFePO4 primary particle add water to be mixed with LiFePO4 primary particle mass percent concentration be 10% suspension-turbid liquid, in suspension-turbid liquid, add surfactant, use spraying machine to carry out spray drying then, obtain the LiFePO4 second particle;
(3) LiFePO4 sintering:
The LiFePO4 second particle is placed in the nitrogen environment,, obtains being shaped as spherical LiFePO 4 material through high-temperature roasting.
2. according to the described preparation method who is applicable to the LiFePO 4 material of electrokinetic cell of claim 1, it is characterized in that: described lithium salts is lithium carbonate, lithium hydroxide, lithium fluoride; Described molysite is ferrous acetate, ferrous nitrate, frerrous chloride; Described phosphate is lithium dihydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, phosphoric acid.
3. according to the described preparation method who is applicable to the LiFePO 4 material of electrokinetic cell of claim 1, it is characterized in that: in the step (2) inlet temperature 130-180 ℃ of spraying machine, outlet temperature 50-100 ℃.
4. according to the described preparation method who is applicable to the LiFePO 4 material of electrokinetic cell of claim 1, it is characterized in that: the temperature of high-temperature roasting is 400-800 ℃ in the step (3), and roasting time is 6-25 hour.
5. according to the described preparation method who is applicable to the LiFePO 4 material of electrokinetic cell of claim 1, it is characterized in that: the organic solvent that adds in the step (1) is an ethylene glycol.
6. according to the described preparation method who is applicable to the LiFePO 4 material of electrokinetic cell of claim 1, it is characterized in that: the surfactant that adds in the step (2) is a neopelex, and the ratio of the molal quantity of the molal quantity of adding and step (1) molysite that takes by weighing is 0.01: 1.
7. according to the described preparation method who is applicable to the LiFePO 4 material of electrokinetic cell of claim 1, it is characterized in that: during the oil bath agitating heating, mixing speed is 200～400 rev/mins in the step (1).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544490A (en) * | 2012-01-10 | 2012-07-04 | 中南大学 | Method for preparing spherical composite anode material fluorine lithium vanadium phosphate-lithium vanadium phosphate of lithium ion battery |
| CN103915613A (en) * | 2014-04-10 | 2014-07-09 | 山东润昇电源科技有限公司 | Preparation method of hydro-thermal coupling spray pyrolysis MnO2/graphene electrode material |
| CN116404144A (en) * | 2023-06-09 | 2023-07-07 | 华大钠电(北京)科技有限公司 | Sodium ion battery |
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| CN101867042A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Preparation method of nanometer level metallic lithium phosphate salt LiMPO4 |
| CN101877401A (en) * | 2010-06-30 | 2010-11-03 | 彩虹集团公司 | Method for preparing lithium-ion battery anode material LiFePO4 |
| CN102082265A (en) * | 2010-12-27 | 2011-06-01 | 东莞市丰远电器有限公司 | Method for automatically preparing lithium iron phosphate |
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- 2011-07-20 CN CN2011102041619A patent/CN102299320A/en active Pending
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| CN101172594A (en) * | 2007-10-11 | 2008-05-07 | 河北工业大学 | Process for producing iron phosphate for producing iron lithium phosphate material |
| CN101867042A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Preparation method of nanometer level metallic lithium phosphate salt LiMPO4 |
| CN101877401A (en) * | 2010-06-30 | 2010-11-03 | 彩虹集团公司 | Method for preparing lithium-ion battery anode material LiFePO4 |
| CN102082265A (en) * | 2010-12-27 | 2011-06-01 | 东莞市丰远电器有限公司 | Method for automatically preparing lithium iron phosphate |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544490A (en) * | 2012-01-10 | 2012-07-04 | 中南大学 | Method for preparing spherical composite anode material fluorine lithium vanadium phosphate-lithium vanadium phosphate of lithium ion battery |
| CN102544490B (en) * | 2012-01-10 | 2014-08-06 | 中南大学 | Method for preparing spherical composite anode material fluorine lithium vanadium phosphate-lithium vanadium phosphate of lithium ion battery |
| CN103915613A (en) * | 2014-04-10 | 2014-07-09 | 山东润昇电源科技有限公司 | Preparation method of hydro-thermal coupling spray pyrolysis MnO2/graphene electrode material |
| CN116404144A (en) * | 2023-06-09 | 2023-07-07 | 华大钠电(北京)科技有限公司 | Sodium ion battery |
| CN116404144B (en) * | 2023-06-09 | 2023-08-15 | 华大钠电(北京)科技有限公司 | Sodium ion battery |
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Application publication date: 20111228 |