CN101330141B - Method for preparing lithium ionic battery anode material spherical LiFePO4 /C - Google Patents

Method for preparing lithium ionic battery anode material spherical LiFePO4 /C Download PDF

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CN101330141B
CN101330141B CN2008101168216A CN200810116821A CN101330141B CN 101330141 B CN101330141 B CN 101330141B CN 2008101168216 A CN2008101168216 A CN 2008101168216A CN 200810116821 A CN200810116821 A CN 200810116821A CN 101330141 B CN101330141 B CN 101330141B
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spherical
weighing
lifepo
anode
density
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CN101330141A (en
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高剑
应皆荣
姜长印
万春荣
李建军
陈克勤
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清华大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

A process for preparing the high-density spherical LiFePO4/C anode material of lithium ion batteries belongs to the technical field of the energy material. The process comprises the following steps: weighing Fe2O3, a phosphate compound and a lithium-source compound by a stoichiometric ratio; slowly adding to one or more aqueous solutions of hexane diacid, polyethylene glycol, polyacrylic acid or polyvinyl alcohol, and adding one or more of conductive carbon black, sucrose and glucose in a certain amount as well as the doping ions, heating, ball-milling and stirring to form an uniform suspension; spray-drying the obtained suspension to obtain the spherical mixed powder precursor; and carrying out the heat treatment of the precursor under the protection of the inert gas to obtain the high-density high-conductivity LiFePO4/C anode material. The prepared LiFePO4/C anode material granule is spherical, has a tap density as high as 1.35-1.45g*cm<-3>, a larger specific surface area and good conductivity, and has high application value in the field of the power-type lithium ion batteries.

Description

A kind of lithium ion battery anode material spherical LiFePO 4The preparation method of/C
Technical field
The present invention relates to a kind of preparation technology of lithium ion battery high-density spherical ferric lithium phosphate positive electrode, belong to the energy and material technical field.
Background technology
Lithium ion battery is the green high-capacity battery of a new generation, is widely used in fields such as mobile phone, notebook computer.Yet at present lithium ion battery is still based on low capacity, low battery power, in big capacity, in the not large-scale production as yet of high-power lithium ion battery, make lithium ion battery not be used widely as yet in the motive-power battery field.The popularization and application of motive-power battery need obtain important breakthrough on electrode material.
Positive electrode is the important component part of lithium ion battery.Studying maximum positive electrodes so far is lithium-compound transition metal oxide positive electrode and polyanion type positive electrode, mainly comprises LiCoO 2, LiNiO 2, LiMn 2O 4, LiNi 0.8Co 0.2O 2, LiNi 1/3Co 1/3Mn 1/3O 2, LiFePO 4And Li 3V 2(PO 4) 3Deng.Concerning power-type lithium ion battery, the cost of positive electrode, cycle performance, fail safe are very important.The LiFePO of quadrature olivine structural 4Positive electrode has become new research focus both at home and abroad with its outstanding performance.Primary Study shows, LiFePO 4Positive electrode raw material cheapness; Stability Analysis of Structures, security performance is splendid; Cycle performance and thermal stability obviously are better than other positive electrode; Bulk effect when cooperating with carbon negative pole material during charging is good; Good with most of electrolyte system compatibilities, storge quality is good; Nontoxic.LiFePO 4Positive electrode is expected to become the desirable positive electrode of power-type lithium ion battery because have outstanding advantage aspect cost, cycle performance, the fail safe.
The advantage of LiFePO4 is very outstanding, but also exists some shortcomings, and the one, the intrinsic electronic conductivity that it is extremely low, this has had a strong impact on the large-current electric chemical property of this material; The 2nd, the product bulk density that adopts conventional synthetic method to synthesize is lower, has limited the practical application of this material in high power high energy density lithium ion field of batteries.Current, people are improving LiFePO 4The research aspect of conductivity and bulk density has obtained many progress.The measure of the raising conductivity of taking usually has: granule interior is mixed conductive carbon material or conductive metal particle; Particle surface coated with conductive material with carbon element; The doping of metal ion; Reduce LiFePO 4The size of crystal grain, even the powder particle of synthesis of nano size.The measure of the raising bulk density of taking usually is the powder particle of synthesizing spherical pattern, and the control particle size distribution.
Synthetic LiFePO 4Method have a variety ofly, the source of iron raw material of employing is also varied.Wherein the synthetic method of cheap and simple is a high-temperature solid phase reaction method the most, a kind of method is for after adopting comparatively expensive ferrous oxalate of price or ferrous acetate divalence source of iron raw material and phosphate and lithium salt compound and mixing, and pyroreaction makes under inert gas shielding; Another kind method is for after adopting di-iron trioxide or ferric phosphate ferric iron source raw material and phosphate and lithium salt compound and mixing; add carbon-source cpd or metal iron powder again, pyrocarbon thermal reduction reaction or high temperature iron thermal reduction reaction make under inert gas shielding.Though the high-temperature solid phase reaction method synthesis process is simple, the cost of material height that has can not effectively reduce LiFePO 4Cost; The more important thing is synthetic LiFePO 4Product particle is random pattern, and bulk density is lower.The applicant had once invented " crystallization control " technology, was the synthesizing spherical FePO of raw material elder generation with ferric nitrate or iron chloride 4Presoma is again by pyrocarbon thermal reduction reaction synthesizing spherical LiFePO 4Method, the product particle that this method obtains has higher bulk density for spherical; And by reduce crystallite dimension, granule interior is mixed conductive materials, coated with carbon material and is carried out ion doping, has improved the large-current electric chemical property of material largely.Though this method has solved LiFePO simultaneously 4The problem of material bulk density and conductivity, but preparation technology or more complicated, LiFePO 4The cost of product is still higher.
Summary of the invention
The objective of the invention is to propose a kind of lithium ion battery anode material spherical LiFePO 4The preparation method of/C makes the product particle of its preparation not only spherical in shape, has higher tap density and large-current electric chemical property preferably; And technology is simpler, and synthetic cost is cheaper, thereby further reduces LiFePO 4The cost of material.
Technical scheme of the present invention is as follows:
A kind of anode material for lithium-ion batteries high-density spherical LiFePO 4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion 2O 3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO 4Product quality percentage is 1~5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd;
2) slowly to join mass concentration be in 5%~30% the organic compound aqueous thickener solution, under the heating and ball-milling stirring condition, to make mixed solution form uniform suspension-turbid liquid to the compound that step 1) is taken by weighing;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical powder;
4) with the spherical powder of step 3) gained under inert gas shielding in 700 ℃~900 ℃ following heat treatments 8~20 hours, promptly obtain spherical LiFePO 4/ C product.
The present invention also provides a kind of anode material for lithium-ion batteries high-density spherical Li doped FePO 4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion 2O 3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO 4Product quality percentage is 1~5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd is nitrate or the acetate that M/Li=0.5%~2% takes by weighing doped metal ion M more in molar ratio; A kind of among doped metal ion M=Mg, Mn, Zr, Mo or the Cr;
2) slowly to join mass concentration be in 5%~30% the organic compound aqueous thickener solution to the compound that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical adulterated powder;
4) with the spherical adulterated powder of step 3) gained under inert gas shielding in 700 ℃~900 ℃ following heat treatments 8~20 hours, promptly obtain spherical Li doped FePO 4/ C product.
In the technique scheme, described phosphate compounds is LiH 2PO 4, NH 4H 2PO 4With (NH 4) 2HPO 4In a kind of, Li source compound is CH 3COOLi2H 2O, LiCO 3Or LiOHH 2A kind of among the O, carbon-source cpd is sucrose or glucose; The organic compound thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more.
The present invention adopts the Fe that is dirt cheap 2O 3Be raw material; with P source compound, Li source compound, carbon-source cpd and thickener mixed uniform suspension-turbid liquid; adopt spray-dired method to obtain spherical mixed powder presoma again, the heat treatment presoma is promptly prepared the spherical LiFePO of high density high conductivity under inert gas shielding 4/ C positive electrode.And this method can also realize the even carbon dope of metal ion mixing and spheric granules inside with comparalive ease, further improves the conductivity of material.This method is than " crystallization control " technology, and product has the feature of high density high conductivity equally, but technological process is simpler, and product cost is cheaper; The LiFePO for preparing 4/ C and Li doped FePO 4/ C powder particle is spherical in shape, has higher tap density and large-current electric chemical property preferably simultaneously; Has very big using value in the power-type lithium ion battery field.
Embodiment
A kind of anode material for lithium-ion batteries high-density spherical LiFePO provided by the invention 4The preparation method of/C, its concrete preparation technology is as follows:
1) takes by weighing Fe respectively by stoichiometric proportion 2O 3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO 4Product quality percentage is 1~5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd, phosphate compounds are LiH 2PO 4, NH 4H 2PO 4With (NH 4) 2HPO 4In a kind of, Li source compound is CH 3COOLi2H 2O, LiCO 3Or LiOHH 2A kind of among the O, carbon-source cpd is sucrose or glucose;
2) slowly to join mass concentration be in 5%~30% the organic compound aqueous thickener solution to the compound that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid carries out spray drying, obtains spherical powder;
4) with the spherical powder of step 3) gained under inert gas shielding in 700 ℃~900 ℃ following heat treatments 8~20 hours, promptly obtain spherical LiFePO 4/ C product.
The present invention also provides a kind of anode material for lithium-ion batteries high-density spherical Li doped FePO 4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion 2O 3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO 4Product quality percentage is 1~5% ultrafine electricity conductive carbon black, and mol ratio C: Fe=1: 1 carbon-source cpd is nitrate or the acetate that M/Li=0.5%~2% takes by weighing doped metal ion M more in molar ratio; Described phosphate compounds is LiH 2PO 4, NH 4H 2PO 4With (NH 4) 2HPO 4In a kind of, described Li source compound is CH 3COOLi2H 2O, LiCO 3Or LiOHH 2A kind of among the O, carbon-source cpd is sucrose or glucose; A kind of among doped metal ion M=Mg, Mn, Zr, Mo or the Cr;
2) slowly to join mass concentration be in 5%~30% the organic compound aqueous thickener solution to the compound that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid employing pneumatic spray drying, obtain spherical adulterated powder;
4) with the spherical adulterated powder of step 3) gained under inert gas shielding in 700 ℃~900 ℃ following heat treatments 8~20 hours, promptly obtain spherical Li doped FePO 4/ C product.
Introduce embodiments of the invention below:
Embodiment 1. takes by weighing 400g Fe 2O 3, 660.3g (NH 4) 2HPO 4, 185.93g LiCO 3, 39.25g conductive carbon black and 142.6g sucrose, slowly add mass concentration and be in 20% the Polyacrylate thickeners aqueous solution, heating and ball-milling mixes solution, form uniform suspension-turbid liquid, resulting suspension-turbid liquid pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1Mpa, and the control temperature of inlet air is 300 ℃, and outlet is 100 ℃, and outlet air separates emptying through the one-level vortex.Spray drying gained powder promptly obtains spherical LiFePO in 800 ℃ of following heat treatments after 15 hours under inert gas shielding 4/ C product.Recording this product tap density is 1.41gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 151mAh/g.
Embodiment 2. takes by weighing 400g Fe 2O 3, 519.8g LiH 2PO 4, 23.55g conductive carbon black and 150g glucose, slowly add mass concentration and be in 30% the polyethylene glycol aqueous thickener solution, heating and ball-milling mixes solution, form uniform suspension-turbid liquid, resulting suspension-turbid liquid pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1Mpa, and the control temperature of inlet air is 300 ℃, and outlet is 100 ℃, and outlet air separates emptying through the one-level vortex.Spray drying gained powder promptly obtains spherical LiFePO in 700 ℃ of following heat treatments after 20 hours under inert gas shielding 4/ C product.Recording this product tap density is 1.42gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 150mAh/g.
Embodiment 3. takes by weighing 400g Fe 2O 3, 575.2g NH 4H 2PO 4, 510gCH 3COOLi2H 2O, 7.85g conductive carbon black and 142.6g sucrose, slowly add mass concentration and be in 5% the adipic acid and polyvinyl alcohol mixing aqueous thickener solution, heating and ball-milling mixes solution, form uniform suspension-turbid liquid, resulting suspension-turbid liquid pneumatic spray drying device drying, adopt and the fluidized drying mode, atomising device adopts the double-current method nozzle.Use the peristaltic pump charging, speed is 10-20mL/min, and the orifice gas flow is controlled by compressed-air actuated pressure, produces atomizing under about 0.1Mpa, and the control temperature of inlet air is 300 ℃, and outlet is 100 ℃, and outlet air separates emptying through the one-level vortex.Spray drying gained powder promptly obtains spherical LiFePO in 900 ℃ of following heat treatments after 8 hours under inert gas shielding 4/ C product.Recording this product tap density is 1.43gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 148mAh/g.
Embodiment 4. and embodiment 1 identical method takes by weighing 400g Fe earlier 2O 3, 660.3g (NH 4) 2HPO 4, 185.93g LiCO 3, 39.25g conductive carbon black and 142.6g sucrose, be the amount weighing magnesium nitrate of Mg/Li=0.5% more in molar ratio, slowly add mass concentration and be in 20% the Polyacrylate thickeners aqueous solution, make the spherical LiFePO that mixes 0.5%Mg by the step identical again with embodiment 1 4/ C product.Recording this product tap density is 1.38gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 152mAh/g.
Embodiment 5. makes the spherical LiFePO that mixes 1%Mn by the method for embodiment 4 4/ C product.Recording this product tap density is 1.39gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 150mAh/g.
Embodiment 6. makes the spherical LiFePO that mixes 2%Zr by the method for embodiment 4 4/ C product.Recording this product tap density is 1.37gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 146mAh/g.
Embodiment 7. makes the spherical LiFePO that mixes 1%Mo by the method for embodiment 4 4/ C product.Recording this product tap density is 1.39gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 149mAh/g.
Embodiment 8. makes the spherical LiFePO that mixes 2%Cr by the method for embodiment 4 4/ C product.Recording this product tap density is 1.38gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 147mAh/g.
Comparing embodiment 1. takes by weighing 16.2g Fe (NO 3) 39H 2O, 1.48g Li 2CO 3, 4.6g NH 4H 2PO 4With 1.36g sucrose ground and mixed evenly after, in nitrogen atmosphere, make LiFePO after 16 hours in 800 ℃ of heat treatments 4/ C product.Recording this product tap density is 1.08gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 132mAh/g.
Do not add carbon black in comparing embodiment 2. raw materials, other is identical with embodiment 1, makes LiFePO 4/ C product.Recording this product tap density is 1.46gcm -3Make negative pole with the pure metal lithium sheet, recording this sample is 0.8mA/cm in room temperature and current density 2Specific discharge capacity when discharging and recharging is 122mAh/g.

Claims (4)

1. anode material for lithium-ion batteries high-density spherical LiFePO 4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion 2O 3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO 4Product quality percentage is 1~5% ultrafine electricity conductive carbon black and mol ratio C: Fe=1: 1 carbon-source cpd;
2) slowly to join mass concentration be in 5%~30% the organic compound aqueous thickener solution, under the heating and ball-milling stirring condition, to make mixed solution form uniform suspension-turbid liquid to the material that step 1) is taken by weighing;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical powder;
4) with the spherical powder of step 3) gained under inert gas shielding in 700 ℃~900 ℃ following heat treatments 8~20 hours, promptly obtain spherical LiFePO 4/ C product.
2. according to the described a kind of anode material for lithium-ion batteries high-density spherical LiFePO of claim 1 4The preparation method of/C is characterized in that: described phosphate compounds is LiH 2PO 4, NH 4H 2PO 4With (NH 4) 2HPO 4In a kind of, Li source compound is CH 3COOLi2H 2O, LiCO 3Or LiOHH 2A kind of among the O, carbon-source cpd is sucrose or glucose; The organic compound thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more.
3. anode material for lithium-ion batteries high-density spherical Li doped FePO 4The preparation method of/C is characterized in that this method carries out according to the following steps:
1) takes by weighing Fe respectively by stoichiometric proportion 2O 3, phosphoric acid or phosphate compounds and Li source compound, and take by weighing and account for LiFePO 4Product quality percentage is 1~5% ultrafine electricity conductive carbon black and mol ratio C: Fe=1: 1 carbon-source cpd is nitrate or the acetate that M/Li=0.5%~2% takes by weighing doped metal ion M more in molar ratio; A kind of among doped metal ion M=Mg, Mn, Zr, Mo or the Cr;
2) slowly to join mass concentration be in 5%~30% the organic compound aqueous thickener solution to the material that step 1) is taken by weighing, under the heating and ball-milling stirring condition, make mixed solution form uniform suspension-turbid liquid, thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more;
3) to step 2) prepared suspension-turbid liquid pneumatic spray drying device drying, obtain spherical adulterated powder;
4) with the spherical adulterated powder of step 3) gained under inert gas shielding in 700 ℃~900 ℃ following heat treatments 8~20 hours, promptly obtain spherical Li doped FePO 4/ C product.
4. according to the described a kind of anode material for lithium-ion batteries high-density spherical LiFePO of claim 3 4The preparation method of/C is characterized in that: described phosphate compounds is LiH 2PO 4, NH 4H 2PO 4With (NH 4) 2HPO 4In a kind of, Li source compound is CH 3COOLi2H 2O, LiCO 3Or LiOHH 2A kind of among the O, carbon-source cpd is sucrose or glucose; The organic compound thickener be in adipic acid, polyethylene glycol, polyacrylic acid or the polyvinyl alcohol one or more.
CN2008101168216A 2008-07-18 2008-07-18 Method for preparing lithium ionic battery anode material spherical LiFePO4 /C CN101330141B (en)

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