CN102390824A - Preparation method of lithium ion phosphate - Google Patents

Preparation method of lithium ion phosphate Download PDF

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CN102390824A
CN102390824A CN201110231947XA CN201110231947A CN102390824A CN 102390824 A CN102390824 A CN 102390824A CN 201110231947X A CN201110231947X A CN 201110231947XA CN 201110231947 A CN201110231947 A CN 201110231947A CN 102390824 A CN102390824 A CN 102390824A
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phosphate
iron
salt
lithium
soluble
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CN102390824B (en
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朱叙国
罗昔贤
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Nanjing Hongyi Botai Digital Technology Co ltd
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Abstract

The invention relates to a preparation method of lithium ion phosphate. The method comprises the following steps of: preparing an iron phosphate salt precursor by utilizing reverse precipitation of soluble iron salts and phosphate; cladding the ion phosphate salt precursor by using a surfactant; and then mixing with a lithium source and roasting together to prepare a carbon-doped LiFePO4 powder material with evenly distributed particles and small particle size. The preparation method disclosed by the invention has the advantages of low reaction temperature, mild reaction conditions, short technological flow, simple equipment requirement, environment friendliness and the like.

Description

Method preparing phosphate iron lithium
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of method for preparing iron lithium phosphate.
Background technology
Iron lithium phosphate has specific storage height, good cycle, stable electrochemical property, lower-price characteristic, is first-selected dynamic lithium battery material of new generation.
Since nineteen nineties had reported that the iron lithium phosphate with olivine structural can reversible ground doff lithium, the research of iron lithium phosphate was more and more.
At present, the main preparation method of iron lithium phosphate has following several kinds:
1, high temperature solid-state method, promptly the compound of molysite, lithium and phosphoric acid salt mix, and under hot environment, react to obtain.The product of this method preparation is because poorly conductive causes performance not good, and particle diameter is thick, and size distribution is inhomogeneous.Of following document:
1) Padhi A K, Nanjundaswamy K S, Masquelier C etc.; Phospho-olivines as positive-elect rode materials for rechargeable lithiumbatteries.Electro-chemical Soc.; 1997,144 (4), 1188-94.
2) Wang G X, Bewlaya S L, Konstantinov K etc., Physical andelectrochemical properties of doped lithium iron phosphate electrodes.Electrochimica Acta, 2004,50:443-7.
3) Prosini P P, Lisi M, Zane D etc., Determination of the chemicaldiffusion coeficient of lithium in LiFePO 4.Solid State lonics, 2002,148:3517-23.
4) Li Faxi, Chou Weihua, Hu Huanyu etc., microwave synthesizes anode material of lithium battery LiFePO chemical property, research and design, 2005,29 (6): 346-8.
5) Iriyama Y, Yokoyama M, Yada C etc., Preparation of LiFePO 4Thinfilms by pulsed laser deposition and their electrochemical properties [J] .Electrochem.SolidState Lett., 2004,7 (10): A340-2.
6) Sauvage F, Baudrin E, Gengembre L etc., Efect oftexture on theelectrochemical properties of LiFePO 4Thin films.Solid State lonics, 2005,176:1869-76.
2, carbothermic method, promptly the ferric iron source to cheapness carries out high temperature reduction.Though this method has overcome the expensive shortcoming of the molysite prices of raw and semifnished materials, but still exists regional area carbon deposit storage bigger, the problem of unstable product quality.Of following document:
7) Mich H, Cao G S, Zhao X B etc., Low-cost, one-step process forsynthesis of carbon-coated LiFePO 4Cathode.Materials Letters, 2005,59:127-30.
8) open treasured, Li Xinhai, Zhu Ping Quan, etc. deposition carbothermic reduction integrated process prepares the peridotites iron lithium phosphate. China YouSe Acta Metallurgica Sinica, 2006,16 (8): 1445-9.
3, sol-gel method is a raw material with ferric acetate or nitrate salt, mixes Lithium Hydroxide MonoHydrate, Hydrocerol A, phosphoric acid, reacts down at 60 ℃ to make.Though this method temperature of reaction is lower, the product shrinkability is big when drying, only is suitable for the short run experiment, and large batch of suitability for industrialized production difficulty is bigger, and synthesis cycle is longer.Of following document:
9) Sang Junli, Wang Qiaojuan, Guo Xifeng. the synthetic and characterization techniques of lithium iron phosphate positive material. inorganic chemicals industry, 2008,40 (2): 13-6.
10) Croce F, Ep ifanio A D etc., A novel concept for the synthesis ofan improved LiFePO 4Lithium battery cathode.Electrochem Solid StateLett., 2002,5 (3): A47-50.
4, the precipitator method prepare phosphoric acid molysite precursor earlier, roasting at a certain temperature again.This method is more a kind of method of using at present.But the problem that exists is because the electroconductibility of iron lithium phosphate own is relatively poor, need when post-processed, mixes conductive carbon material, thereby significantly reduce the tap density of material.Therefore the battery volume of processing will be very huge, be difficult to obtain practical application.Of following document:
11) Han Enshan, Feng Zhihui, Wei Zihai etc., coprecipitation method synthesizing iron lithium phosphate carbon dope composite positive pole. inorganic chemicals industry, 2008,40 (1): 22-5.
12) Li Jun, Zheng Yuying, Li Daguang etc., the preparation of novel high-energy-density iron lithium phosphate and chemical property. material Leader, 2008,22 (4): 138-9.
Except above-mentioned shortcoming, also there is following deficiency in existing method: at LiFePO 4In the structure, because the PO between the octahedron 4Tetrahedron has limited the variation of lattice volume, influence the Li atom in charge and discharge process embedding and deviate from, make LiFePO 4Ion diffusion speed lower; Owing to there is not successive FeO 6The octahedra network in limit can not form electronic conductor altogether, and the conduction of electronics can only be carried out through Fe-O-Fe, makes LiFePO 4Electronic conductivity lower.
Summary of the invention
The technical problem that the present invention will solve is how to improve the specific conductivity of iron lithium phosphate.
In order to solve the problems of the technologies described above, the present invention provides a kind of method for preparing iron lithium phosphate.
The method that the present invention prepares iron lithium phosphate may further comprise the steps: soluble ferric iron salt and soluble phosphate reverse precipitation are prepared tertiary iron phosphate salt precursor body; Coat gained tertiary iron phosphate salt precursor body with the carbon containing tensio-active agent; Be blended in roasting in the atmosphere of shielding gas with the lithium source then, obtain the LiFePO of carbon dope 4Powder.
Wherein, said soluble ferric iron salt is selected from FeSO 4, FeCl 2, Fe 2(SO 4) 3, Fe (NO 3) 3, Fe (NO 3) 2And FeCl 3In one or more; Preferred FeSO 4
In the raw material soluble ferric iron salt of the present invention, can add divalence or trivalent iron salt separately, but when adopt adding the mixture of divalence and trivalent iron salt, can make product property better.
Said soluble phosphate is selected from NH 4H 2PO 4, (NH 4) 2HPO 4, (NH 4) 3PO 4, LiH 2PO 4, Li 2HPO 4, Li 3PO 4, KH 2PO 4, K 2HPO 4, K 3PO 4, NaH 2PO 4, Na 2HPO 4And Na 3PO 4In one or more; Preferably phosphoric acid ammonium salt and phosphoric acid lithium salts, because of its technological process is simpler, lithium salts particularly, effect is best; More preferably NH 4H 2PO 4Also can adopt sylvite or sodium salt, but washing process is complicated slightly.
Said soluble ferric iron salt needs slowly to add in the soluble phosphoric acid salts solution, can improve combination rate; If add excessive velocities, then can cause reacting insufficient.
The said carbon surface active agent that contains is selected from C 10～C 20In carboxylic acid or the carboxylate salt one or more; Preferred C 14～C 18In the carboxylic acid one or more are like oleic acid, linolic acid etc.; The more preferably C of better effects if 14～C 18The solubility carboxylate salt is like C 14～C 18Carboxylic acid lithium or carboxylic acid ammonium.
Said carbon containing influence of surfactant is that uniform particles is distributed, and as carbon source.In addition, when soluble ferric iron salt adopted trivalent iron salt, in reaction process, containing carbon surface active agent can also be reduced to ferrous iron with ferric iron, made it can be evenly attached to the product surface, thereby improved the electroconductibility of product, avoided carbon deposit to deposit, and promoted Li +Deviate from and embed, improve electronic conductivity.
The weight that contains carbon surface active agent that the present invention is used is 10%～60% of said tertiary iron phosphate salt precursor body; Preferred 10～25%; More preferably 25%.But optimal addn also depends on washing process.If the raw material that adopts is a nitrate salt, the add-on of tensio-active agent can be lacked, and when adopting vitriol or muriate raw material, the add-on of tensio-active agent is more slightly.
But this optimal addn also depends on washing process.If the raw material that adopts is the nitrate salt of iron, the add-on that contains carbon surface active agent can be lacked, as 10～20%; And the vitriol or the muriate that adopt iron be when being raw material, and the add-on that contains carbon surface active agent can be more more, as 40～60%.
Said lithium source is selected from Li 3PO 4, Li 2CO 3, LiOH and CH 3Among the COOLi one or more; Preferred Li 2CO 3More preferably Li 3PO 4As adopt when precipitating Trilithium phosphate as precipitation agent, and it can be simultaneously as lithium source and precipitation agent use, and technological process is easy, can also reduce the add-on of tensio-active agent.
Said shielding gas is nitrogen or argon gas.
The temperature of said roasting is 400～1200 ℃, preferred 800～1000 ℃, and more preferably 800 ℃.
The time of said roasting is 2～20h, preferred 12～15h, more preferably 15h.
Maturing temperature and time are then depended on the product cut size of needs, and required particle diameter hour can adopt the long-time sinter process of low temperature; And when requiring size distribution narrower, can adopt sinter process between high temperature, short time.Maturing temperature and time are also depended on the amount of each calcination product, and amount is many, and temperature is higher, and the time is correspondingly longer.
The mol ratio in soluble ferric iron salt, soluble phosphate, lithium source is very crucial to product performance, and their molar ratio range is (1～3): (2～6): 1; Preferred mol ratio is 2: 4: 1.Based on producing actual needs, the mol ratio of these three kinds of raw materials can also be regulated according to the raw material type that adopts, the factors such as technological parameter of preparation.
To the different application field of iron lithium phosphate, for example fields such as battery of mobile phone, power cell, energy-accumulating power station on the basis of the inventive method, in scope disclosed by the invention, through changing various parameters, can obtain the product of different electro-chemical properties; In the raw material soluble ferric iron salt, can add divalence or trivalent iron salt separately, but performance is better when adopt adding the mixture of divalence and trivalent iron salt.Influence is not very big to the anion species of raw material source of iron to performance of products, but production process is had certain influence, and is as simpler with nitrate salt technology, complicated slightly during with vitriol and muriate.But from the raw materials cost angle, vitriol and muriate have more advantage undoubtedly.
Beneficial effect of the present invention is following.
1. the present invention adopts soluble ferric iron salt to be equipped with phosphoric acid molysite, post precipitation are prepared the small particle size of even particle distribution, surface coating one deck carbon nanometer layer through the three-step approach of carbon containing tensio-active agent parcel, the source roasting of remix lithium LiFePO with soluble phosphate reverse precipitation legal system 4Powdered material.
2. method of the present invention has whole advantages of reverse precipitation method, prepared LiFePO 4Powdered material good dispersivity, even particle size distribution.
3. parcel contains carbon surface active agent in the preparation process, and it mainly acts on as follows: (1) has promoted the particulate uniform distribution better; (2), in roasting process, do not need to add again carbon source as carbon source; (3) when soluble ferric iron salt adopts trivalent iron salt, in reaction process, ferric iron is reduced to ferrous iron, and can improves product electric conductivity, promote Li +Deviate from and embed; (4) the nanometer carbon-coating that evenly coats can greatly improve LiFePO 4The chemical property of positive electrode material causes the inhomogeneous reduction with the material tap density of carbon dope when simultaneously having avoided the ordinary method carbon dope again.
4. characteristics such as it is low that method of the present invention has temperature of reaction, and reaction conditions is gentle, and the short and equipment requirements of technical process is simple.In the preparation process, do not adopt toxic substance, environmental protection, the little and homogeneous of the product granularity of preparation.
5. the LiFePO of method preparation of the present invention 4Because particle diameter is little, particle surface is even, Li +The diffusion distance shorten, promoted Li +Embedding and deviate from, improved LiFePO 4Ion diffusion speed, make product have better electrochemical performance, can improve LiFePO 4Electronic conductivity 10～50%.This material has specific storage height, good cycle, stable electrochemical property, lower-price characteristic.The prepared iron lithium phosphate product that goes out of the present invention can be used as power lithium-ion battery positive electrode material of new generation.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
Embodiment 1
With ferrous sulfate (FeSO 47H 2O, analytical pure) be source of iron, ammonium di-hydrogen phosphate (NH 4H 2PO 4) be the phosphorus source, Li 2CO 3Be the lithium source.Get FeSO 47H 2O 5.558g is dissolved in 20ml deionized water, NH 4H 2PO 44.6g be dissolved in the 20ml deionized water, filter, copperas solution is slowly splashed in the biphosphate ammonia solution, generate NH 4FePO 4The presoma deposition is filtered, washing, dry 24h under 80 ℃; Then presoma is dissolved under ultrasound condition in the ethanolic soln of oil-containing acid surfaces promoting agent, the oleic acid consumption is 25% of a presoma quality, filters drying; Get Li 2CO 30.74g ball milling descends and the tertiary iron phosphate salt precursor body constant temperature calcining 15h (N that is coated by tensio-active agent at 800 ℃ 2Atmosphere), cooling promptly obtains LiFePO 4Positive electrode material.FeSO in the present embodiment 47H 2O: NH 4H 2PO 4: Li 2CO 3Between mol ratio be 2: 4: 1.
Embodiment 2
With iron nitrate and Iron nitrate (Fe (NO 3) 39H 2O and Fe (NO 3) 26H 2O, analytical pure) be source of iron, potassium primary phosphate (KH 2PO 4) be the phosphorus source, LiOH is the lithium source.Get Fe (NO respectively 3) 3And Fe (NO 3) 26.06g be dissolved in 30ml deionized water, KH with 2.70g 2PO 48.16g be dissolved in the 30ml deionized water, filter, iron nitrate and ferrous nitrate solution are slowly splashed in the potassium dihydrogen phosphate, generate KFePO 4The presoma deposition is filtered, washing, dry 24h under 80 ℃; Then presoma is dissolved under ultrasound condition in the ethanolic soln that contains ammonium oleate, the ammonium oleate consumption is 10% of a presoma quality, filters drying; Get LiOH 0.24g, ball milling descends and the tertiary iron phosphate salt precursor body constant temperature calcining 7h (N that is coated by tensio-active agent at 1200 ℃ 2Atmosphere), cooling promptly obtains LiFePO 4Positive electrode material.Fe (NO in the present embodiment 3) 3: Fe (NO 3) 2: KH 2PO 4: the mol ratio between LiOH is 1.5: 1.5: 6: 1.
Embodiment 3
With iron(ic)chloride (FeCl 3, analytical pure) and be source of iron, Trilithium phosphate (Li 3PO 4) be the phosphorus source, LiOH is the lithium source.Get FeCl 31.62g be dissolved in the 20ml deionized water, Li 3PO 42.32g be dissolved in the 20ml deionized water, filter, ferric chloride Solution(38 is slowly splashed in the Trilithium phosphate solution, generate LiFePO 4The presoma deposition is filtered, washing, dry 20h under 90 ℃; Then presoma is dissolved under ultrasound condition and contains in the linoleic ethanolic soln, the linolic acid consumption is 40% of a presoma quality, filters drying; Get LiOH 0.24g, ball milling, with the tertiary iron phosphate salt precursor body constant temperature calcining 20h (argon gas atmosphere) that is coated by tensio-active agent, cooling promptly obtains LiFePO under 400 ℃ 4Positive electrode material.FeCl in the present embodiment 3: Li 3PO 4: the mol ratio between LiOH is 1: 2: 1.
The product that present method obtains is compared with ordinary method, and granule-morphology is subglobular more, and good fluidity, processability are good; Grain diameter can reduce more than 20%, and size distribution is narrower.When the products obtained therefrom powder was made battery, tap density improved 5～15% than ordinary method.As with the 1.3-1.5g/cm of ordinary method 3Compare, the product tap density of present method preparation can reach 1.6-1.8g/cm 3
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.

Claims (10)

1. method for preparing iron lithium phosphate; It is characterized in that; May further comprise the steps: soluble ferric iron salt and soluble phosphate reverse precipitation are prepared tertiary iron phosphate salt precursor body; Coat gained tertiary iron phosphate salt precursor body with the carbon containing tensio-active agent, be blended in roasting in the shielding gas atmosphere with the lithium source then, obtain the LiFePO of carbon dope 4Powder.
2. method according to claim 1 is characterized in that said soluble ferric iron salt is selected from FeSO 4, FeCl 2, Fe 2(SO 4) 3, Fe (NO 3) 3, Fe (NO 3) 2And FeCl 3In one or more.
3. method according to claim 1 is characterized in that said soluble phosphate is selected from NH 4H 2PO 4, (NH 4) 2HPO 4, (NH 4) 3PO 4, LiH 2PO 4, Li 2HPO 4, Li 3PO 4, KH 2PO 4, K 2HPO 4, K 3PO 4, NaH 2PO 4, Na 2HPO 4And Na 3PO 4In one or more.
4. method according to claim 1 is characterized in that, the said carbon surface active agent that contains is selected from C 10～C 20In carboxylic acid or the carboxylate salt one or more.
5. method according to claim 4 is characterized in that, the said weight that contains carbon surface active agent is 10%～60% of said tertiary iron phosphate salt precursor body.
6. method according to claim 1 is characterized in that, said lithium source is selected from Li 3PO 4, Li 2CO 3, LiOH and CH 3Among the COOLi one or more.
7. method according to claim 1 is characterized in that, said shielding gas is nitrogen or argon gas.
8. method according to claim 1 is characterized in that, the temperature of said roasting is 400～1200 ℃.
9. method according to claim 1 is characterized in that, the time of said roasting is 2～20h.
10. according to each described method of claim 1-9, it is characterized in that the mol ratio in said soluble ferric iron salt, soluble phosphate, lithium source is 1～3: 2～6: 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ITTO20120709A1 (en) * 2012-08-07 2014-02-08 Fond Istituto Italiano Di Tecnologia PROCEDURE OF COLLOIDAL SYNTHESIS OF LITHIUM FOSFATE IRON
CN104973582A (en) * 2014-04-03 2015-10-14 南京工业大学 Synthesis method of novel ion battery positive pole material iron phosphate
US9954228B2 (en) * 2009-09-18 2018-04-24 A123 Systems, LLC High power electrode materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101546826A (en) * 2009-04-30 2009-09-30 宁波职业技术学院 Preparation method for spherical lithium ferric phosphate used as lithium ion battery anode material
CN101656311A (en) * 2009-09-17 2010-02-24 复旦大学 Preparation method of LiFePO4/C composite material
CN102034964A (en) * 2009-09-24 2011-04-27 复旦大学 Method for preparing lithium ion battery composite material
WO2011057646A1 (en) * 2009-11-10 2011-05-19 Rockwood Italia S.P.A. Hydrothermal process for the production of lifepo4 powder

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101546826A (en) * 2009-04-30 2009-09-30 宁波职业技术学院 Preparation method for spherical lithium ferric phosphate used as lithium ion battery anode material
CN101656311A (en) * 2009-09-17 2010-02-24 复旦大学 Preparation method of LiFePO4/C composite material
CN102034964A (en) * 2009-09-24 2011-04-27 复旦大学 Method for preparing lithium ion battery composite material
WO2011057646A1 (en) * 2009-11-10 2011-05-19 Rockwood Italia S.P.A. Hydrothermal process for the production of lifepo4 powder

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9954228B2 (en) * 2009-09-18 2018-04-24 A123 Systems, LLC High power electrode materials
ITTO20120709A1 (en) * 2012-08-07 2014-02-08 Fond Istituto Italiano Di Tecnologia PROCEDURE OF COLLOIDAL SYNTHESIS OF LITHIUM FOSFATE IRON
WO2014024149A3 (en) * 2012-08-07 2014-04-10 Fondazione Istituto Italiano Di Tecnologia Process for the colloidal synthesis of lithium iron phosphate
US9401507B2 (en) 2012-08-07 2016-07-26 Fondazione Istituto Italiano Di Tecnologia Methods for the colloidal synthesis of lithium iron phosphate
CN104973582A (en) * 2014-04-03 2015-10-14 南京工业大学 Synthesis method of novel ion battery positive pole material iron phosphate

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