CN101118963A - Method for preparing anode material iron phosphate lithium of lithium ion battery - Google Patents
Method for preparing anode material iron phosphate lithium of lithium ion battery Download PDFInfo
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- CN101118963A CN101118963A CNA2007100410171A CN200710041017A CN101118963A CN 101118963 A CN101118963 A CN 101118963A CN A2007100410171 A CNA2007100410171 A CN A2007100410171A CN 200710041017 A CN200710041017 A CN 200710041017A CN 101118963 A CN101118963 A CN 101118963A
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Abstract
The present invention relates to a method for producing LiFePO4 of positive pole of lithium ion battery. The invention is prominently characterized in that the method comprises three steps as follows: mixing the iron material, the lithium material and the phosphorus material uniformly to compound highly crystallized LiFePO4 in a high temperature first; adding a little diluted acid in the LiFePO4, after mixing and drying the processed LiFePO4 and conductive agent or pre-conductive agent, conducting ball mill for the mixture using a heavy ball; processing the mixture at a lower temperature and then the positive material LiFePO4 with excellent electrochemical performance can be gained. The gained LiFePO4 has favorable crystallinity and the electronic and the lithium ion conducting net is unique with excellent performance. The present invention uses cheap chemical product as raw material and the compounding art is simple thus is easy for producing on scale. The electrochemical character is favorable.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, particularly adopt pyroreaction, trace acid molten, be the method that the technology of medium ball milling and the reparation of low temperature lattice prepares lithium ion battery anode material lithium iron phosphate with the heavy ball.
Background technology
Energy density height, long service life, light weight, self discharge are little because lithium ion battery has, memory-less effect and advantage such as environmentally friendly, development is very rapid since it comes out, become the first-selected power supply of portable type electronic products such as mobile communication, notebook computer and camera, and progressively be developed as the power supply of electric motor car, defence equipment etc., this also promoted lithium ion battery to high energy, environmental protection, low price and secure side to development.The lifting of lithium ion battery performance and range of application widen the improvement of depending on the positive electrode performance to a great extent.Therefore, develop new synthesis technique and prepare anode material for lithium-ion batteries, the research preparating mechanism and with the relation of material structure, performance, have important significance for theories and practical value.
Commercial lithium ion battery is many with LiCoO
2Be positive electrode, cobalt costs an arm and a leg, poor safety performance, resource-constrained and harm environment, has limited further developing of lithium ion battery.The LiFePO of Goodenough research group [1] discovery olivine-type in 1997
4Under little charging and discharging currents, can obtain the specific capacity of 100-110mAh/g, and charge and discharge platform is very smooth.This discovery has caused the very big concern of battery circle.Because LiFePO
4Raw material sources are wide, price is low, the Heat stability is good of material, and the fail safe of prepared battery is outstanding, so be considered to have most a kind of anode material for lithium-ion batteries of application prospect, particularly in large-sized power field of batteries such as electric automobile to cost, life-span, safety requirements harshness.
Method preparing phosphate iron lithium mainly contains high-temperature solid phase reaction method (US6528033, US 2004/0151649, CN200410017382.5), liquid phase co-electrodeposition method (WO02/083555A2), sol-gel process (CN1410349A), high-energy ball milling method (CN1255888C; Z.Liao, Z.F.Ma, L.Wang, Electrochem Solid State Lett 7 (2004) A522) etc.High temperature solid-state method is with ferrous salt, mixes roasting synthesizing iron lithium phosphate under inert atmosphere protection with phosphate and lithium salts or lithium hydroxide.The advantage of high temperature method is that technology is simple, easily realizes industrialization, but the common mixing of reactant is inhomogeneous, and product particle, crystal grain are easily grown up, and purity is not high, and the excessive lithium ion stroke that causes of primary particle is long, and the lithium ion conducting performance is poor, so chemical property is not high.Liquid phase co-electrodeposition method technology more complicated, Fe
2+Easily be oxidized to Fe
3+, needing reducing agent addings such as ascorbic acid, cost is higher, is unfavorable for industrialization.Sol-gel process can make iron, phosphate radical and lithium realize that molecular level mixes, and also realizes easily mixing, and the gained material property is also more satisfactory, but technology is comparatively complicated, unsuitable large-scale production.High-energy ball milling method (CN1255888C, Electrochem Solid State Lett 7 (2004) A522) with metal iron powder, ferric phosphate, lithium phosphate, mix up element phosphor hydrochlorate, conductive agent or conductive agent presoma and mix in proportion, place the ball mill container of filling inert atmosphere, high-energy ball milling 18-36 hour; Gained ball milling product is put into high temperature furnace, in inert atmospheres such as nitrogen or argon gas in 450-750 ℃ of constant temperature roast 10-60min, the iron phosphate powder that makes or mix up iron phosphate powder, the crystallinity of this positive electrode is not fine, the lithium ion conducting performance is not good during high power charging-discharging, can't realize large batch of production in addition.
Summary of the invention
The present invention discloses a kind of preparation method of lithium ion battery anode material lithium iron phosphate: at first will evenly mix good source of iron, lithium source and phosphorus source material synthesize highly crystallineization under higher temperature LiFePO4; Then will add the LiFePO4 that drips a little diluted acid and conductive agent or conductive agent presoma and mix also after the drying, be that medium carries out ball milling with the heavy ball; Heat treatment at a lower temperature at last can obtain the LiFePO 4 of anode material of chemical property excellence.Specifically be to implement like this:
A kind of preparation method of lithium ion battery anode material lithium iron phosphate is characterized in that:
(1) iron, lithium and phosphorus source material is mixed, the mol ratio of wherein phosphorous, iron and lithium is 1.0: 0.85-1.00: 0.95-1.05, in the 800-950 ℃ of stove that nitrogen, argon gas or hydrogen argon hybrid protection atmosphere are arranged insulation reaction 1-10 hour, be cooled to room temperature then, the LiFePO4 pure phase that obtains;
(2) interpolation is pressed LiFePO4 weight ratio 2-20% conductive agent conductive agent or conductive agent presoma and dropping and is pressed LiFePO4 weight ratio 1-5% diluted acid in the LiFePO4 pure phase, after the fully mixed also drying, is that medium carried out ball milling 2-48 hour again with the heavy ball;
(3) be insulation 0.5-2 hour in 550-750 ℃ the inert atmosphere protection stove in temperature, discharging is LiFePO 4 of anode material.
The lithium source that the present invention adopts is lithia, lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium dihydrogen phosphate.
The source of iron that the present invention adopts is iron, ferrous oxide, tri-iron tetroxide, di-iron trioxide, ferrous sulfate, iron ammonium sulfate, ferric phosphate, ferrous phosphate, ferrous ammonium phosphate, ferrous citrate and mixture.
The phosphorus source that the present invention adopts is phosphorus pentoxide, phosphoric acid, ammonium di-hydrogen phosphate, lithium dihydrogen phosphate, DAP, ferrous ammonium phosphate, phosphoric acid hydrogen ammonia salt.
The diluted acid that the present invention adopts is concentration 10-30% sulfuric acid phosphoric acid, nitric acid, hydrochloric acid.
The conductive agent that the present invention adopts is a conductive carbon black, and the conductive agent presoma is sucrose, glucose, starch.
The heavy medium that the present invention adopts is to be made up of iron and steel, zirconia, agate or the corundum ball of the φ 1-50mm of 2-3 kind size.
The distinguishing feature of method that the present invention prepares lithium ion battery anode material lithium iron phosphate is that the preparation method comprises three step main technique: the reaction of (1) higher temperature, resulting LiFePO4 have that thing is simple mutually, degree of crystallinity is high and lattice defect is few; (2) drip a small amount of diluted acid and dense media ball milling, diluted acid can dissolving phosphoric acid iron lithium, dissolved matter and conductive agent or the conduction presoma coated LiFePO 4 for lithium ion batteries particle that can wet, and the dense media ball milling is refinement LiFePO4 particle further; (3) lower temperature reaction, wet coating and LiFePO4 particle is compound with the tap density that improves material with form the good electron conductive network, and repair in thinning process ruined LiFePO4 lattice to improve the lithium ion conducting performance.The innovative point that the present invention prepares the method for lithium ion battery anode material lithium iron phosphate is included in that preparation can obtain the high and good LiFePO4 (helping lithium ion conducting) of crystallization of thing phase purity under the higher temperature (800-950 ℃), and generally openly method in the material for preparing below 800 ℃, comprise dephasign and lattice defect; That utilizes diluted acid to be partly dissolved to carry out dissolved matter and conductive agent or conduction presoma wetly is coated with the refinement particle and cloth is built conduction forerunner network, (helping electron conduction); The dense media ball milling is refinement LiFePO4 particle (helping lithium ion conducting) further; Reaction will realize the compound tap density and the formation good electron conductive network to improve material of wet coating and LiFePO4 particle under lower temperature (550-750 ℃), and reparation ruined LiFePO4 lattice (helping lithium ion and electron conduction) in thinning process.The raw material that the present invention adopts can be cheap chemical products, and synthesis technique is simple, and product is highly suitable for battery and makes, and is easy to large-scale production.
Description of drawings
Figure below is respectively the X-ray diffracting spectrum of the LiFePO4 of Comparative Examples of the present invention and embodiment 1 on Fig. 1.
Fig. 2 is the stereoscan photograph of the LiFePO4 of the embodiment of the invention 1.
Embodiment
Comparative Examples
A kind of solid phase preparation method of lithium ion battery anode material lithium iron phosphate; lithium dihydrogen phosphate, ferrous oxide are evenly mixed; the mol ratio of controlling phosphorus, iron and lithium in the raw material is 1.0: 1.0: 1.0; make protection atmosphere with argon gas; in 3 hours, be warming up to 650 ℃; insulation reaction 3 hours is cooled to room temperature then, obtains LiFePO4.The last figure of Fig. 1 is the X-ray diffracting spectrum of prepared LiFePO4, wherein contains not pure phase.
Embodiment 1
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, lithium dihydrogen phosphate, ferrous oxide are evenly mixed, the mol ratio of controlling phosphorus, iron and lithium in the raw material is 1.0: 1.0: 1.0, make protection atmosphere with argon gas, in 5 hours, be warming up to 850 ℃, insulation reaction 3 hours is cooled to room temperature then, obtains the LiFePO4 pure phase;
In the LiFePO4 pure phase, add the 9% conductive agent presoma sucrose of pressing the LiFePO4 weight ratio and drip and press the dilute sulfuric acid (30%) of LiFePO4 weight ratio 1%, after the fully mixed and drying, again being that medium carried out ball milling 18 hours by the φ 5mm of LiFePO4 weight ratio 60% and 40% φ 20mm zirconia;
Do protection atmosphere heat treatment 1 hour with argon gas under 580 ℃ of temperature, discharging is LiFePO 4 of anode material.Fig. 1 figure below is an X-ray diffractogram, and the iron phosphate powder of analyzing gained is pure olivine-type rhombic system phase structure; Fig. 2 is the stereoscan photograph of iron phosphate powder, and the product particle size is about 0.5 micron.
Active material iron phosphate powder, conductive agent acetylene black and binding agent Kynoar mixed to be applied to by mass ratio at 8: 1: 1 make positive plate on the aluminium foil.In the argon gas atmosphere dry glove box, be to electrode with metal lithium sheet, the UB3025 film is a barrier film, ethylene carbonate (EC)+dimethyl carbonate (DMC)+1MLiPF6 is an electrolyte, is assembled into the button cell test performance.
Under normal temperature (20 ± 2 ℃), battery is carried out the constant current charge-discharge test in 2.5V～4.2V voltage range.From 0.2C multiplying power (34mAg
-1) charge-discharge test as can be known, gained LiFePO 4 material discharge voltage is about 3.4V, reversible specific capacity is 90% of theoretical specific capacity up to 153mAh/g.Cycle performance of battery is also very superior.
Embodiment 2
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, lithium phosphate and ferrous phosphate are evenly mixed, the mol ratio of controlling phosphorus, iron and lithium in the raw material is 1.0: 0.85: 1.00, in argon gas with 3 hours heat temperature raisings to 950 ℃, constant temperature roast 1.5 hours obtains the grey iron phosphate powder then behind the natural cooling;
Prepared be the fully mixed and drying of the watery hydrochloric acid (20%) of LiFePO4 and 5% conductive carbon black and 4% after, carried out ball milling 30 hours with 30% φ 5mm and 70% φ 50mm agate ball again;
Heat treatment 2 hours in argon gas under 650 ℃ of temperature, discharging is LiFePO 4 of anode material.
Embodiment 3
A kind of preparation method of lithium ion battery anode material lithium iron phosphate, to evenly mix at lithium hydroxide and the ferrous ammonia of ammonium di-hydrogen phosphate, the mol ratio of controlling phosphorus, iron and lithium in the raw material is 1.0: 0.95: 1.00, make protection atmosphere with the hydrogen argon, make protection atmosphere with the hydrogen argon and in 6 hours, be warming up to 800 ℃ and insulation reaction 5 hours, obtain iron phosphate powder;
Prepared be the fully mixed and drying of rare nitric acid (15%) of LiFePO4 and 10% starch and 4% after, carried out ball milling 10 hours with 50% φ 10mm and 50% φ 30mm iron ball again;
Do protection atmosphere heat treatment half an hour with the hydrogen argon under 700 ℃ of temperature, discharging is LiFePO 4 of anode material.
Claims (9)
1. the preparation method of a lithium ion battery anode material lithium iron phosphate is characterized in that:
(1) iron, lithium and phosphorus source material is mixed, the mol ratio of wherein phosphorous, iron and lithium is 1.0: 0.85-1.00: 0.95-1.05, in the 800-950 ℃ of stove that nitrogen, argon gas or hydrogen argon hybrid protection atmosphere are arranged insulation reaction 1-10 hour, be cooled to room temperature then, the LiFePO4 pure phase that obtains;
(2) interpolation is pressed LiFePO4 weight ratio 2-20% conductive agent conductive agent or conductive agent presoma and dropping and is pressed LiFePO4 weight ratio 1-5% diluted acid in the LiFePO4 pure phase, after the fully mixed also drying, is that medium carried out ball milling 2-48 hour again with the heavy ball;
(3) be insulation 0.5-2 hour in 550-750 ℃ the inert atmosphere protection stove in temperature, can obtain LiFePO 4 of anode material.
2. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that the lithium source is lithia, lithium hydroxide, lithium carbonate, lithium acetate, lithium nitrate, lithium phosphate, lithium dihydrogen phosphate.
3. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that source of iron is iron, ferrous oxide, tri-iron tetroxide, di-iron trioxide, ferrous sulfate, iron ammonium sulfate, ferric phosphate, ferrous phosphate, ferrous ammonium phosphate, ferrous citrate and mixture.
4. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that the phosphorus source is phosphorus pentoxide, phosphoric acid, ammonium di-hydrogen phosphate, lithium dihydrogen phosphate, DAP, ferrous ammonium phosphate, phosphoric acid hydrogen ammonia salt.
5. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that diluted acid is concentration 10-30% sulfuric acid phosphoric acid, nitric acid, hydrochloric acid.
6. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that conductive agent is that conductive carbon black or conductive agent presoma are sucrose, glucose, starch.
7. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that dripping by LiFePO4 weight ratio 1-5% diluted acid in LiFePO4, causes the dissolving of part material, and in the particle surface coating of wetting.
8. the preparation method of a kind of lithium ion battery anode material lithium iron phosphate according to claim 1 is characterized in that heavy ball is to be made up of iron and steel, zirconia, agate or the corundum ball of the φ 1-50mm of 2-3 kind size.
9. according to the preparation method of claim 1 and 8 described a kind of lithium ion battery anode material lithium iron phosphates, it is characterized in that heavy ball is 2-48 hour refinement LiFePO4 of a medium ball milling particle.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916860A (en) * | 2010-08-19 | 2010-12-15 | 恒正科技（苏州）有限公司 | Method for manufacturing electrochemical active material |
| CN102208625A (en) * | 2011-05-04 | 2011-10-05 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium iron phosphate of cathode material of lithium ion secondary battery |
| TWI416782B (en) * | 2010-06-15 | 2013-11-21 | Hon Hai Prec Ind Co Ltd | Method for making electrode material of lithium battery |
| US9054380B2 (en) | 2010-06-03 | 2015-06-09 | Tsinghua University | Method for making lithium battery cathode material |
| CN105293458A (en) * | 2014-05-30 | 2016-02-03 | 比亚迪股份有限公司 | Ferrous phosphate, preparation method therefor, lithium iron phosphate positive electrode active material and preparation method therefor |
| CN110121799A (en) * | 2016-12-16 | 2019-08-13 | 株式会社日立制作所 | Electrode for secondary battery, secondary cell, their manufacturing method |
| CN112408489A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Method for refining lithium ion battery anode material |
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2007
- 2007-05-22 CN CN200710041017A patent/CN100576608C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9054380B2 (en) | 2010-06-03 | 2015-06-09 | Tsinghua University | Method for making lithium battery cathode material |
| TWI416782B (en) * | 2010-06-15 | 2013-11-21 | Hon Hai Prec Ind Co Ltd | Method for making electrode material of lithium battery |
| CN101916860A (en) * | 2010-08-19 | 2010-12-15 | 恒正科技（苏州）有限公司 | Method for manufacturing electrochemical active material |
| CN102208625A (en) * | 2011-05-04 | 2011-10-05 | 合肥国轩高科动力能源有限公司 | Preparation method of lithium iron phosphate of cathode material of lithium ion secondary battery |
| CN105293458A (en) * | 2014-05-30 | 2016-02-03 | 比亚迪股份有限公司 | Ferrous phosphate, preparation method therefor, lithium iron phosphate positive electrode active material and preparation method therefor |
| CN105293458B (en) * | 2014-05-30 | 2018-12-21 | 比亚迪股份有限公司 | A kind of ferrous phosphate and preparation method thereof, ferrous lithium phosphate cathode active material and preparation method thereof |
| CN110121799A (en) * | 2016-12-16 | 2019-08-13 | 株式会社日立制作所 | Electrode for secondary battery, secondary cell, their manufacturing method |
| CN110121799B (en) * | 2016-12-16 | 2022-06-10 | 株式会社日立制作所 | Electrode for secondary battery, and methods for producing them |
| CN112408489A (en) * | 2020-11-26 | 2021-02-26 | 中北大学 | Method for refining lithium ion battery anode material |
| CN112408489B (en) * | 2020-11-26 | 2023-01-31 | 中北大学 | Method for refining lithium ion battery anode material |
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