CN101817515B - High-volume and capacity ratio spherical lithium ferric phosphate and preparation method thereof - Google Patents

High-volume and capacity ratio spherical lithium ferric phosphate and preparation method thereof Download PDF

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CN101817515B
CN101817515B CN2010101544353A CN201010154435A CN101817515B CN 101817515 B CN101817515 B CN 101817515B CN 2010101544353 A CN2010101544353 A CN 2010101544353A CN 201010154435 A CN201010154435 A CN 201010154435A CN 101817515 B CN101817515 B CN 101817515B
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yellow powder
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CN101817515A (en
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沈培康
邹红丽
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Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The invention discloses high-volume and capacity ratio spherical lithium ferric phosphate and a preparation method thereof. The method comprises the following steps of: preparing a spherical precursor by combining with an alternative microwave/solvent hot method, then heating at high temperature under the protection of inert gas to obtain regularly spherical lithium ferric phosphate, wherein the tap density of the prepared lithium ferric phosphate reaches 2g/cm3. The method of the invention can be used for controlling the degree of crystallization and the granule size of the heated material. Meanwhile, the method also can control the structure and the composition of a phase through regulating the proportions of raw materials, thereby ensuring that the combined product has the quality meeting requirements.

Description

High-volume and capacity ratio spherical lithium ferric phosphate and preparation method thereof
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, particularly a kind of preparation method of high volume density spherical LiFePO 4.
Background technology
Lithium ion battery has obtained increasing application as a kind of chargeable battery of environment-friendly type high performance in various electronic products and communication tool.Be the electromobile of power and be that the hybrid-electric car of power has received increasing attention with the high energy secondary cell with fuel oil and battery; This has proposed requirements such as high-performance, low cost to lithium ion battery, and then has also promoted the research to various novel electrode materials.In novel anode material for lithium-ion batteries, rhombic system olivine-type LiFePO 4Has the capacity height, characteristics such as charging/discharging voltage is steady.Advantages such as particularly it is cheap, security good, Heat stability is good, environmentally safe more make it become one of the most potential positive electrode material.But LiFePO 4There are two significant disadvantages: the one, electronic conductivity is low, causes high-rate charge-discharge capability poor, and actual specific capacity is low; The 2nd, tap density is low, causes volume and capacity ratio low.These two shortcomings have hindered the practical application of this material.At present, investigators are solving LiFePO 4Specific conductivity is hanged down this field, makes substantial progress.Yet the shortcoming that tap density is low can not get fine solution, LiFePO always 4Theoretical density is merely 3.6g/cm 3, well below LiCoO 2(5.1g/cm 3), LiNiO 2(4.8g/cm 3) and LiMn 2O 4(4.2g/cm 3).For improving LiFePO 4Electroconductibility, people mix conductive carbon material, have significantly reduced the tap density of material again, make the LiFePO of general carbon dope 4Tap density have only 0.8-1.2g/cm 3So low tap density makes LiFePO 4Volume and capacity ratio is little, and the battery volume of processing is big.Therefore, improve LiFePO 4Tap density and volume and capacity ratio to LiFePO 4Practicability have the decision meaning.
The tap density of powder body material and the pattern of powder granule, particle diameter and distribution thereof are closely related.The LiFePO that has reported both at home and abroad at present 4All be made up of random sheet or granular particle, tap density is low.The material of being made up of the spheroidal particle of rule will have higher tap density, and moreover, spherical product also has excellent flowability and dispersiveness.Very help making the coating of positive electrode material slurry and electrode slice, improve electrode quality.In disclosed patent CN1635648 and CN101508431A, invention is per capita with liquid phase sluggish precipitation elder generation synthesizing spherical tertiary iron phosphate presoma, and high-temperature calcination obtains spherical LiFePO 4 again, and tap density can reach 2-2.2g/cm 3In patent CN101112979, with raw material and doping metals and nucleus growth agent mixing and ball milling, high-temperature calcination obtains spherical LiFePO 4, and tap density can reach 1.55-1.75g/cm 3Yet in these disclosed patents, the method for preparing spherical LiFePO 4 is very high to processing requirement control, and process is complicated, difficult realization industriallization.
Summary of the invention
The purpose of this invention is to provide high-volume and capacity ratio spherical lithium ferric phosphate and preparation method thereof; Adopt this method processing parameter easy to control; Production cost is low, and prepared spherical LiFePO 4 product has regular shape and very high tap density, and concrete technical scheme is following.
The preparation method of high-volume and capacity ratio spherical lithium ferric phosphate, comprising the steps: that (1) adds lithium salts in the container that acid solution is housed dissolves, and mixes, and adds molysite and organic acid reduction agent again, mix solution, and regulator solution pH value is 6-7; The container that (2) mixing solutions will be housed is put into microwave oven, with intermittent microwave heating evaporate to dryness acid solution, obtains yellow powder, grinds to form the yellow powder of fine particle; (3) with the yellow powder that the obtains porcelain boat of packing into, put into High Temperature Furnaces Heating Apparatus, in protective atmosphere, the heating that heats up obtains the black sample.
Among the above-mentioned preparation method, said acid solution is a kind of in nitric acid, hydrochloric acid and the phosphoric acid, and concentration is 0.5-1mol/L.
Among the above-mentioned preparation method, said molysite is FePO 4, FeCl 3In one or more mixtures; Said lithium salts is LiOH, Li 2CO 3And Li (CH 3COO) one or more mixtures in.
Among the above-mentioned preparation method, said organic acid reduction agent is one or more mixtures in Hydrocerol A, the vitamins C.
Among the above-mentioned preparation method, said lithium salts, molysite and organic acid mol ratio are 0.95-1: 0.95-1: 0.5-1.
Among the above-mentioned preparation method, described intermittent microwave is heated to be microwave heating and alternately opens and close by setting-up time.
Among the above-mentioned preparation method, described intermittent microwave is heated to be heating 5-30 second, stops 5-60 second, alternately heats for several times, and microwave power is 1000W.
Among the above-mentioned preparation method, the speed that heats up described in the step (3) is 1-5 ℃/min, is warming up to 500-800 ℃.
Among the above-mentioned preparation method, the protective atmosphere in the described step (3) is one or more mixtures in nitrogen, hydrogen or the argon gas.
Among the above-mentioned preparation method, said volume and capacity ratio is 250-350mAh/cm 3
Among the above-mentioned preparation method, step (1) pH value of solution value can be regulated by ammoniacal liquor.
Among the above-mentioned preparation method, said microwave heating program to heat 5-30 second, is stopped alternately heating completion for several times 5-60 second for alternately heating.Be that microwave heating is alternately opened and closed by certain hour, can repeat multipass.Depend on material-to-be-heated amount and the temperature of required control with (relaxation) time of closing heat-up time.
Among the above-mentioned preparation method, the Heating temperature in the described step (3) is 500-800 ℃, and better temperature is 600-700 ℃.
Among the above-mentioned preparation method, the protective atmosphere in the described step (3) is one or more mixtures in nitrogen, hydrogen or the argon gas, and temperature rise rate is 1-5 ℃/min.
Compare the temperature that method may command of the present invention is material-to-be-heated and the structure of thing phase with existing wet method synthesizing spherical iron lithium phosphate.In evaporating solvent; The mode that adopts microwave alternately to heat has following characteristics: on the one hand; Intermittent microwave adds thermal utilization microwave heating, and microwave is by absorbed and be transformed into heat energy, can heat its integral body from the inside of material; Sample evenly heating apace at short notice, and the reaction of generation homogeneous; On the other hand; Intermittent microwave adds the existence of thermal utilization relaxation time; The better rapid rising of controlled temperature; Can make particle that a process of growth of nucleation-crystallization-grow up takes place in solution again, thereby prevent that particle from growing up rapidly along with the rising of temperature, guarantee that again particle has intact crystallization and has regular appearance.For example obtain highdensity spheroidal particle, their tap density can reach 1.5-2g/cm3, and volume and capacity ratio is at 250-350mAh/cm3.Thereby make the synthetic product have satisfactory quality.
Description of drawings
Fig. 1 is the shape appearance figure of spherical LiFePO 4.
Fig. 2 is the first charge-discharge curve of spherical LiFePO 4 at 0.1C.
Embodiment
Pass through embodiment below, and combine accompanying drawing, technical scheme of the present invention is described further, but the present invention is not limited to these embodiment.
Embodiment 1
LiOHH with 0.21 gram 2O adds the 0.5mol/L HNO of preparation 3Dissolve in the solution, add 1.11 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 5 seconds, intermittently 5 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 5 ℃/min is warmed up to 700 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 2g/cm 3The XRD test is the iron lithium phosphate of purified olive shape structure.The shape appearance figure of this sample and be presented at respectively among Fig. 1 and Fig. 2 at the first charge-discharge curve of 0.1C.As shown in Figure 1, the sample that obtains is that size is even, dispersed well highly regular spherical LiFePO4, and the diameter of ball is about 600 nanometers.According to literature survey, the present spherical LiFePO4 that reports is that only part is spherical in shape or seemingly spherical mostly, and regular spherical LiFePO4 of uniform size like this does not but appear in the newspapers as yet.Up to 2g/cm3, this also is the high tap density of the LiFePO4 of report at present through the tap density of measuring regular spherical LiFePO4.In the charging and discharging curve of Fig. 2, can see a voltage platform, the charging voltage platform is about 3.4V, and discharge voltage plateau is about 3.3V.Loading capacity is 154mAh/g, and being scaled volume and capacity ratio is 325mAh/cm3.
Embodiment 2
Take by weighing the CH of 0.52 gram 3COOLi2H 2O adds the 0.5mol/L HNO of preparation 3Dissolve in the solution, add 1.11 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 5 seconds, intermittently 30 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 5 ℃/min is warmed up to 700 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.7g/cm 3
Embodiment 3
Li with 0.19 gram 2CO 3The 0.5mol/L HNO that adds preparation 3Dissolve in the solution, add 1.11 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 10 seconds, intermittently 30 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 5 ℃/min is warmed up to 700 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.7g/cm 3
Embodiment 4
Take by weighing the LiOHH of 0.20 gram 2Dissolve in the 0.5mol/L HCl solution of O adding preparation, add 1.09 gram FePO more successively 44H 2O and 0.54 gram Hydrocerol A, stirred solution mixes.With NH3 water be adjusted to just occur the deposition (pH=7).Then solution is put into microwave oven, to heat 30 seconds, intermittently 60 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 2 ℃/min is warmed up to 700 ℃ with speed, is incubated 8 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.8g/cm 3
Embodiment 5
Take by weighing the LiOHH of 0.21 gram 2O adds the 0.5mol/L H of preparation 3PO 4Dissolve in the solution, add 1.35 gram FeCl more successively 36H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 5 seconds, intermittently 5 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 1 ℃/min is warmed up to 500 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.7g/cm 3
Embodiment 6
With the LiOHH that takes by weighing 0.21 gram 2Dissolve in the 0.5mol/L HCl solution of O adding preparation, add 1.11 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 10 seconds, intermittently 10 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 5 ℃/min is warmed up to 600 ℃ with speed, is incubated 8 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.8g/cm 3
Embodiment 7
LiOHH with 0.20 gram 2Dissolve in the 1mol/LHCl solution of O adding preparation, add 1.11 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.With NH3 water be adjusted to just occur the deposition (pH=7).Then solution is put into microwave oven, to heat 5 seconds, intermittently 5 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high-purity argon gas atmosphere, is that 5 ℃/min is warmed up to 650 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.8g/cm 3
Embodiment 8
LiOHH with 0.20 gram 2O adds the 0.5mol/L H of preparation 3PO 4Dissolve in the solution, add 1.06 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 5 seconds, intermittently 5 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high-purity hydrogen atmosphere, is that 5 ℃/min is warmed up to 800 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 2g/cm 3
Embodiment 9
LiOHH with 0.21 gram 2O adds the 1mol/L H of preparation 3PO 4Dissolve in the solution, add 1.11 gram FePO more successively 44H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 5 seconds, intermittently 5 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 3 ℃/min is warmed up to 600 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.8g/cm 3
Embodiment 10
Take by weighing the LiOHH of 0.21 gram 2O adds the 1mol/L HNO of preparation 3Dissolve in the solution, add 1.28 gram FeCl more successively 36H 2O and 0.44 gram vitamins C, stirred solution mixes.Use NH 3Water is adjusted to and deposition (pH=7) just occurs.Then solution is put into microwave oven, to heat 5 seconds, intermittently 5 seconds intermittent microwave solvent evaporated obtains yellow powder.Grind the gained yellow powder and become fine particle, the porcelain boat of packing into is put into High Temperature Furnaces Heating Apparatus, in high pure nitrogen atmosphere, is that 5 ℃/min is warmed up to 750 ℃ with speed, is incubated 6 hours, obtains the spherical LiFePO 4 sample.Tap density is 1.9g/cm 3

Claims (7)

1. the preparation method of high-volume and capacity ratio spherical lithium ferric phosphate; It is characterized in that comprising the steps: that (1) adds lithium salts in the container that acid solution is housed dissolves, mix, add molysite and organic acid reduction agent again; Mix solution, and regulator solution pH value is 6-7; Said acid solution is a kind of in nitric acid, hydrochloric acid and the phosphoric acid; Said molysite is FePO 4, FeCl 3In one or both; Said acid solutions is 0.5-1mol/L; The container that (2) mixing solutions will be housed is put into microwave oven, with intermittent microwave heating evaporate to dryness acid solution, obtains yellow powder, grinds to form the yellow powder of fine particle; Described intermittent microwave is heated to be microwave heating and alternately opens and close by setting-up time; (3) with the yellow powder that the obtains porcelain boat of packing into, put into High Temperature Furnaces Heating Apparatus, in protective atmosphere, the heating that heats up obtains the black sample.
2. preparation method according to claim 1 is characterized in that said lithium salts is Li 2CO 3And Li (CH 3COO) a kind of in or replace by LiOH.
3. preparation method according to claim 1 is characterized in that said organic acid reduction agent is one or both in Hydrocerol A, the vitamins C.
4. preparation method according to claim 1 is characterized in that said lithium salts, molysite and organic acid mol ratio are 0.95-1: 0.95-1: 0.5-1.
5. preparation method according to claim 1 is characterized in that described intermittent microwave is heated to be heating 5-30 second, stops 5-60 second, alternately heats for several times, and microwave power is 1000W.
6. preparation method according to claim 1 is characterized in that the speed that heats up described in the step (3) is 1-5 ℃/min, is warming up to 500-800 ℃.
7. preparation method according to claim 1, its characteristics are that the protective atmosphere in the described step (3) is one or more mixtures in nitrogen, hydrogen or the argon gas.
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CN103755111B (en) * 2014-01-08 2015-07-29 中国农业大学 The regulate and control method of phosphorus element high efficiente callback in a kind of livestock and poultry feces
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CN101572304A (en) * 2009-06-16 2009-11-04 上海微纳科技有限公司 LiFePO4/CG compounded anode material prepared by liquid phase synthesis-microwave solid phase sintering method

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CN101555004A (en) * 2009-05-15 2009-10-14 中山大学 Method for rapidly preparing lithium iron phosphate by intermittent microwave
CN101572304A (en) * 2009-06-16 2009-11-04 上海微纳科技有限公司 LiFePO4/CG compounded anode material prepared by liquid phase synthesis-microwave solid phase sintering method

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