CN100385713C - Method for preparing ferrous lithium phosphate - Google Patents
Method for preparing ferrous lithium phosphate Download PDFInfo
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- CN100385713C CN100385713C CNB2005100574115A CN200510057411A CN100385713C CN 100385713 C CN100385713 C CN 100385713C CN B2005100574115 A CNB2005100574115 A CN B2005100574115A CN 200510057411 A CN200510057411 A CN 200510057411A CN 100385713 C CN100385713 C CN 100385713C
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Abstract
The present invention discloses a method for directly preparing lithium iron phosphate (LiFePO4) used as anode materials of a lithium ion battery by using a solid phase reducing method. A compound containing lithium, a ferric iron compound and a phosphorus compound are mixed with an organic additive and are balled and milled for 1 to 8 hours in a ball mill after a proper quantity of organic solvent are added, and a sample is dried at the temperature of 100 to 120 DEG C; the sample is burnt for 4 to 24 hours at the constant temperature of 500 to 800 DEG C under a sealing condition without protective gases, the sample is then naturally cooled, and a manufactured lithium iron phosphate solid is pulverized in the ball mill. Because the present invention adopts ferric iron, material cost is reduced; the protective gases are not used in the process of preparation, and the atmosphere condition of the additive is fully used when thermal decomposition is carried out. Synthetical technology is simplified by the method, and the LiFePo 4 is easy to produce industrially.
Description
Technical field
The invention belongs to a kind of preparation method of anode material for lithium-ion batteries, particularly a kind ofly directly prepare lithium ferrous phosphate as anode material of lithium ion battery (LiFePO with the solid phase reduction method
4) synthetic method.
Background technology
The performance of battery and the performance of electrode material are closely related, and the progress of battery material is depended in the progress of battery to a great extent.It is relatively low that the positive electrode of lithium rechargeable battery in contrast to the negative material energy density, and cost is higher.The new type lithium ion battery positive electrode can be by a relatively large margin the raising entire cell energy density and reduce cost.Goodenoungh research group found olivine structural LiFePO 4 (LiFePO in 1997
4)) can be used as lithium ion secondary battery anode material.This material has high theoretical specific capacity 170mAh/g, and discharge platform is stably arranged about 3.4V; Advantages such as wherein required iron, phosphor resource are abundant, low price, environmental protection, security performance are good cause that industry pays close attention to widely.LiFePO 4 (LiFePO
4) synthetic method mainly contain high temperature solid-state method, liquid phase reduction, hydro thermal method etc.High temperature solid-state method is a raw material with ferrous oxalate, ferric acetate, DAP, lithium carbonate, in blanket of nitrogen in 500-800 ℃ of prepared in reaction LiFePO
4In a word, in existing synthetic method, need use expensive acetate or oxalates, in roasting process, need to use protective gas (nitrogen or argon gas etc.), certainly will increase the preparation cost of material, and realize industrial production cost.
Summary of the invention
There is the deficiency of cost of material height, complex process at existing production method, the purpose of this invention is to provide a kind of reduction material cost, simplify synthesis technique, make it the LiFePO 4 (LiFePO that is easy in industrial enforcement
4) the preparation method.
The technical measures that the present invention adopts are: the present invention mixes containing Li source compound, ferric iron source compound, P source compound and organic additive, adds appropriate amount of organic, and ball milling is 1～8 hour in ball mill, and sample is in 80～120 ℃ of oven dry; Under the condition of sealing, in 500～800 ℃ of constant temperature calcinings 4～24 hours, natural cooling got final product the LiFePO 4 solid pulverize in ball mill that makes then.
Key of the present invention is to use ferric iron source, relies on the organic additive that adds, and is not using the good LiFePO 4 of direct preparation chemical property under the inert atmosphere conditions.The present invention mainly prevents that ferric iron is not reduced and by oxidized once more after over reduction and the reduction, reaches the conductive capability that improves LiFePO 4 by following measure: (1) selects suitable organic additive and suitable consumption; (2) in building-up process, select best roasting time, adopted the sealing roasting, and utilized organic catabolite to carry out the carbon coating; (3) by in building-up process, introducing the electric conductivity that element doping improves material.
Compared to existing technology, the present invention has following characteristics: (1) uses cheap ferric iron source to replace the organic source of iron of expensive divalence; (2) residual carbon reaches carbon coated or carbon dope; (3) gas of decomposition that utilizes organic additive is as reducing gas, and roasting process can not use inert atmosphere protection; (4) particle diameter of product is controlled easily, can control by the ball milling time; (5) product mixes easily; (6) preparation technology is simple, and is easy to control, easily realizes industrialization.
Description of drawings:
Fig. 1 is by the X-ray diffraction of example 1 prepared LiFePO 4 (XRD), test condition: Cu-K
αRadiation, pipe is pressed 36kV, pipe stream 20mA, 4 °/min of sweep speed, 10～80 ° of sweep limitss (2 θ);
Fig. 2 is the particle size distribution figure by example 1 prepared LiFePO 4;
Fig. 3 is to be positive active material by example 1 obtained sample, and the lithium sheet is a negative pole, and electrolyte is 1mol/l LiPF
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume 1: 1) is assembled into the two-electrode experiment battery.Carry out the charge and discharge cycles test with Shanghai square DC-5 type cell tester, charging and discharging currents density is 0.3mA/cm
2, voltage range 2.0～4.2V measures about 25 ℃ of temperature.
Fig. 4 is respectively 0.3mA/cm by example 5 obtained samples in charging and discharging currents density
2, 0.5mA/cm
2, 3mA/cm
2, 5mA/cm
2Cycle performance figure, voltage range 2.0～4.2V measures about 25 ℃ of temperature.
Embodiment
The present invention will contain Li source compound, ferric iron source compound, P source compound and reduction additive and mix, and add appropriate amount of organic, and ball milling is 1～8 hour in ball mill, and sample is in 100～120 ℃ of oven dry; Under the condition of sealing without protective gas, in 500～800 ℃ of constant temperature calcinings 4～24 hours, natural cooling then was with the LiFePO 4 solid pulverize in ball mill that makes; The mol ratio of Li source compound, Fe source compound and P source compound consumption is a lithium in the reaction: iron: phosphorus=0.95～1.05 (mol ratio): 1: 1; The consumption of reduction additive is (phosphorus content is calculated 0.5～3 mole in the reducing agent consumption).
Li source compound is selected from lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate, any in lithium phosphate or the lithium oxalate;
Fe source compound is selected from any in di-iron trioxide, tri-iron tetroxide, iron hydroxide or the ferric phosphate;
P source compound is selected from any in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate;
The reduction additive is selected from any in carbohydrate, polyhydroxy-alcohol, polyhydroxy-acid, nylon, the amino acid.
Doped chemical Li source compound, ferric iron source compound, P source compound and conductive additive mix, add appropriate amount of organic, be selected from aluminium, magnesium, vanadium, chromium, copper, manganese, cobalt, nickel, zinc or the rare earth any, consumption is 0.1～5% (molar fraction) of lithium or iron in the LiFePO 4.
The invention will be further described below by embodiment.
Embodiment 1: with the 0.05mol lithium carbonate, 0.05mol di-iron trioxide, 0.1mol ammonium dihydrogen phosphate mix (molal quantity * molecular weight can be calculated the weight that needs), add the nylon-66s of 1.25 grams, and nylon-66 adds after with 15ml glacial acetic acid heating for dissolving.Add the 10ml absolute ethyl alcohol again, with sample on ball mill in 300/ fen ball milling of rotating speed 8 hours, oven dry obtains sample.Sample under air-proof condition, was warmed up to 650 ℃ of constant temperature calcinings 8 hours in 30-60 minute fast, naturally cools to room temperature, the LiFePO that makes
4In ball mill, be ground into powder.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, crystalline structure is complete.
Powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, and by sample: conductive agent (acetylene black): bonding agent is that 85%: 10%: 5% mixed is ground in the alms bowl at agate and milled, and the gained slurry is applied on the aluminium foil.Behind the air dry 8h, be cut into 1cm
2Disk with the Small diaphragm-piece weighing, is put into vacuum drying chamber, more than 80 ~ 100 ℃ of dry 8h.Dry good sample thin slice is put into the glove box that is full of Ar.In glove box, to do electrode with the lithium sheet, electrolyte is for being dissolved in the lithium hexafluoro phosphate (LiPF of ethylene carbonate (EC) and carbonic acid diethyl ester (DEC) mixed solution (its volume ratio is 1: 1)
b, 1mol/l), use the polypropylene porous septum, stainless steel gasket (or anodal aluminium backing, the negative pole copper backing), assemble two electrode Experimental cells.Sealing.Measure charging and discharging capacity with the constant current discharge instrument, with 0.3mA/cm
2Constant-current discharge, specific volume 152.6mAh/g first discharges.
Embodiment 2: with the 0.15mol lithium nitrate, and the 0.05mol tri-iron tetroxide, 0.15mol ammonium dihydrogen phosphate and 4.00 gram lactose mix, and add 30ml95% ethanol, and in 300/ fen ball milling of rotating speed 2 hours, oven dry obtained sample on ball mill.Sample under air-proof condition, was warmed up to 650 ℃ of constant temperature calcinings 6 hours in 30-60 minute fast, naturally cools to room temperature, the LiFePO that makes
4In ball mill, be ground into powder.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, crystalline structure is complete.
Powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.Measure charging and discharging capacity with the constant current discharge instrument, with 0.3mA/cm
2Constant-current discharge, first discharge specific capacity are 150mAh/g.
Embodiment 3: with the 0.05mol lithium carbonate, and the 0.05mol di-iron trioxide, the 0.1mol ammonium dihydrogen phosphate, 3.00 gram lactose, the weight ratio of pressing iron adds 1%Dy
2O
3Mix, add the 20ml absolute ethyl alcohol, in 300/ fen ball milling of rotating speed 4 hours, oven dry obtained sample on ball mill.Sample under air-proof condition, was warmed up to 650 ℃ of constant temperature calcinings 12 hours in 30-60 minute fast, naturally cools to room temperature, the LiFePO that makes
4The pure one-tenth of powder powder in ball mill.
The product of gained shows to be olivine LiFePO through X-ray diffraction analysis
4, crystalline structure is complete.Powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.Measure charging and discharging capacity with the constant current discharge instrument, with 0.3mA/cm
2Constant-current discharge, first discharge specific capacity are 154.5mAh/g.
Embodiment 4: the sucrose of 0.1mol lithium hydroxide, 0.1mol ferric phosphate and 3.Q0 gram is mixed, add the 20ml absolute ethyl alcohol, in 300/ fen ball milling of rotating speed 3 hours, oven dry obtained sample on ball mill.Under air-proof condition, the 650 ℃ of calcining at constant temperature that are rapidly heated 10 hours naturally cool to room temperature, with the LiFePO that makes with sample
4In ball mill, be ground into powder.The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, crystalline structure is complete, and powder is 1 ~ 3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.Measure charging and discharging capacity with the constant current discharge instrument, with 0.3mA/cm
2Constant-current discharge, first discharge specific capacity are 150.4mAh/g.
Embodiment 5: with the 0.05mol lithium acetate, and 0.05mol iron hydroxide, 0.05mol diammonium hydrogen phosphate, 2.50 gram sucrose, the mass ratio of pressing iron adds the 1%mol copper powder and mixes, and adds the 20ml absolute ethyl alcohol, in 300/ fen ball milling of rotating speed 3 hours, oven dry obtained sample on ball mill.Under air-proof condition, the 650 ℃ of calcining at constant temperature that are rapidly heated 8 hours naturally cool to room temperature, with the LiFePO that makes with sample
4In ball mill, be ground into powder.
The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, crystalline structure is complete, and powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.With 0.3mA/cm
2Constant-current discharge, end of charge voltage are 4.2V, and discharge cut-off voltage is 2.0V, and first discharge specific capacity is 151.7mAh/g.
Embodiment 6: with the 0.05mol lithium oxalate, and the 0.05mol di-iron trioxide, the 0.1mol triammonium phosphate, 2.50 sucrose, the mass ratio of pressing iron adds 1% Dy
2O
3Mix, add the 20ml absolute ethyl alcohol, in 300/ fen ball milling of rotating speed 3 hours, oven dry obtained sample on ball mill; Under air-proof condition, the 650 ℃ of calcining at constant temperature that are rapidly heated 8 hours naturally cool to room temperature, with the LiFePO that makes with sample
4In ball mill, be ground into powder.
The product of gained shows to be olivine LiFePO through X-ray diffraction analysis
4, crystalline structure is complete, and powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.With 0.3mA/cm
2Constant-current discharge, end of charge voltage are 4.2V, and discharge cut-off voltage is 2.0V, and first discharge specific capacity is 154.5mAh/g.
Embodiment 7: with the 0.05mol lithium phosphate, and the 0.025mol di-iron trioxide, 0.1mol ferric phosphate and 2.50 gram sucrose mix, and add the 20ml absolute ethyl alcohol, and in 300/ fen ball milling of rotating speed 6 hours, oven dry obtained sample on ball mill; Sample under air-proof condition, was warmed up to 650 ℃ of constant temperature calcinings 24 hours in 30-60 minute fast, naturally cools to room temperature, the LiFePO that makes
4In ball mill, be ground into powder.
The product of gained shows to be olivine-type LiFePO through X-ray diffraction analysis
4, crystalline structure is complete.Powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.Measure charging and discharging capacity with the constant current discharge instrument, with 0.3mA/cm
2Constant-current discharge, first discharge specific capacity are 148.2mAh/g.
Embodiment 8: with the 0.05mol lithium carbonate, and the 0.05mol di-iron trioxide, the 0.1mol ammonium dihydrogen phosphate, 3.50 gram lysines add the 20ml absolute ethyl alcohol, and in 300/ fen ball milling of rotating speed 4 hours, oven dry obtained sample on ball mill.Sample under air-proof condition, was warmed up to 650 ℃ of constant temperature calcinings 12 hours in 30-60 minute fast, naturally cools to room temperature, the LiFePO that makes
4In ball mill, be ground into powder.
The product of gained shows to be olivine LiFePO through X-ray diffraction analysis
4, crystalline structure is complete.Powder is 1～3 μ m through the grain size analysis average grain diameter.The product of gained is assembled into Experimental cell, with example 1.Measure charging and discharging capacity with the constant current discharge instrument, with the 0.3mA/cm2 constant-current discharge, first discharge specific capacity is 147.5mAh/g.
The present invention controls the chemical analysis and the particle diameter of LiFePO 4 effectively, improves its uniformity and conductivity, improves its chemical property.By adopting ferric iron source to increase the source of iron scope, reduced requirement simultaneously to inert environments, not only reduce material cost, and simplified synthesis technique, make it to be easy in industrial enforcement.
Claims (6)
1. a method for preparing LiFePO 4 is characterized in that mixing containing Li source compound, ferric iron source compound, P source compound and organic additive, adds organic solvent, and ball milling is 1～8 hour in ball mill; Then 100～120 ℃ of oven dry; Roasting 4～24 hours under 500～800 ℃ of constant temperature again; Last natural cooling is with the LiFePO 4 solid pulverize in ball mill that makes;
Described organic additive is selected from any in nylon-66, lactose, sucrose or the lysine, and the mass fraction of organic additive is that consumption is 5～20% of a LiFePO 4.
2. method according to claim 1, the mol ratio that it is characterized in that described Li source compound, ferric iron source compound, P source compound consumption is a lithium: iron: phosphorus=0.95～1.05: 1: 1.
3. method according to claim 1 and 2 is characterized in that described Li source compound is selected from any in lithium carbonate, lithium nitrate, lithium hydroxide, lithium acetate or the lithium oxalate.
4. method according to claim 1 and 2 is characterized in that described Fe source compound is selected from any in di-iron trioxide, tri-iron tetroxide, iron hydroxide or the ferric phosphate.
5. method according to claim 1 and 2 is characterized in that described P source compound is selected from any in ammonium phosphate, ferric phosphate, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
6. method according to claim 1 and 2, it is characterized in that in copper doped also or the dysprosium any, the molar fraction of its consumption be in the LiFePO 4 lithium or iron 0.1～5%.
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| CNB2005100574115A CN100385713C (en) | 2005-11-30 | 2005-11-30 | Method for preparing ferrous lithium phosphate |
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Families Citing this family (21)
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| CN100491239C (en) * | 2006-11-24 | 2009-05-27 | 横店集团东磁股份有限公司 | Preparation method of lithium iron phosphate as lithium ion battery anode material and product thereof |
| CN101209824B (en) * | 2006-12-31 | 2011-12-14 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
| CN101209823B (en) * | 2006-12-31 | 2011-08-17 | 比亚迪股份有限公司 | Preparation method for lithium ion secondary battery positive pole active substance lithium iron phosphate |
| JP5231535B2 (en) * | 2007-05-28 | 2013-07-10 | ビーワイディー カンパニー リミテッド | Method for preparing lithium iron phosphate as positive electrode active material for lithium ion secondary battery |
| CN101314463B (en) * | 2007-05-28 | 2011-04-06 | 上海比亚迪有限公司 | Method of producing active compound lithium iron phosphate of lithium ion secondary battery anode |
| CN101399343B (en) * | 2007-09-25 | 2011-06-15 | 比亚迪股份有限公司 | Preparing method of anode active material lithium iron phosphate for lithium ionic secondary cell |
| CN101494305B (en) | 2008-01-25 | 2011-05-18 | 比亚迪股份有限公司 | Lithium ion battery electrolyte and battery and battery set containing the same |
| US8088305B2 (en) | 2008-02-22 | 2012-01-03 | Byd Company Limited | Lithium iron phosphate cathode material |
| US8052897B2 (en) | 2008-02-29 | 2011-11-08 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8057711B2 (en) | 2008-02-29 | 2011-11-15 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8062559B2 (en) | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8062560B2 (en) | 2008-02-29 | 2011-11-22 | Byd Company Limited | Composite compound with mixed crystalline structure |
| US8148015B2 (en) | 2008-03-21 | 2012-04-03 | Byd Company Limited | Cathode materials for lithium batteries |
| KR101587671B1 (en) * | 2008-03-31 | 2016-01-21 | 도다 고교 가부시끼가이샤 | Lithium iron phosphate powder manufacturing method, olivine structured lithium iron phosphate powder, cathode sheet using said lithium iron phosphate powder, and non-aqueous solvent secondary battery |
| CN101597089A (en) | 2008-06-06 | 2009-12-09 | 比亚迪股份有限公司 | The preparation method of a kind of transition metal hydroxide and oxide compound thereof and positive electrode material |
| CN101640288B (en) | 2008-07-30 | 2012-03-07 | 比亚迪股份有限公司 | Lithium-ion battery electrolyte and lithium-ion battery containing same |
| US9073760B2 (en) | 2010-12-24 | 2015-07-07 | Shoei Chemical Inc. | Manufacturing method and manufacturing device for multiple oxide |
| CN104332628B (en) * | 2014-09-04 | 2017-09-15 | 北汽福田汽车股份有限公司 | The preparation method and its lithium ion battery of anode material for lithium-ion batteries |
| CN108321383B (en) * | 2016-03-18 | 2020-09-18 | 日照轩宜信息科技有限公司 | Process for preparing lithium iron phosphate from modified iron oxide |
| CN108520947A (en) * | 2018-04-08 | 2018-09-11 | 广州鹏辉能源科技股份有限公司 | Modified phosphate iron lithium material, lithium ion battery, power battery pack and its application |
| CN115513515B (en) * | 2022-09-29 | 2023-12-29 | 欣旺达动力科技股份有限公司 | Secondary battery and preparation method thereof |
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Effective date of registration: 20160824 Address after: Bridge Industrial Park 400085 Dadukou District of Chongqing Road Bridge No. 10 Patentee after: Chongqing Te Rui battery material limited company Address before: 400044 Shapingba street, Shapingba District, Chongqing, No. 174 Patentee before: Chongqing University |
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