CN101388459B - Preparation of ferric phosphate composite positive pole - Google Patents
Preparation of ferric phosphate composite positive pole Download PDFInfo
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- CN101388459B CN101388459B CN2007100770340A CN200710077034A CN101388459B CN 101388459 B CN101388459 B CN 101388459B CN 2007100770340 A CN2007100770340 A CN 2007100770340A CN 200710077034 A CN200710077034 A CN 200710077034A CN 101388459 B CN101388459 B CN 101388459B
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- lithium
- iron phosphate
- anode material
- preparation
- phosphate compound
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- 238000002360 preparation method Methods 0.000 title claims description 13
- 239000002131 composite material Substances 0.000 title abstract description 4
- 239000005955 Ferric phosphate Substances 0.000 title 1
- 229940032958 ferric phosphate Drugs 0.000 title 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title 1
- 239000010405 anode material Substances 0.000 claims abstract description 36
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 28
- 238000009818 secondary granulation Methods 0.000 claims abstract description 21
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 17
- 238000012545 processing Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 38
- 229910052744 lithium Inorganic materials 0.000 claims description 38
- -1 iron phosphate compound Chemical class 0.000 claims description 27
- 238000000498 ball milling Methods 0.000 claims description 23
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 16
- 230000004907 flux Effects 0.000 claims description 8
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 7
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 229910012258 LiPO Inorganic materials 0.000 claims description 4
- 241001460678 Napo <wasp> Species 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 21
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 229910012274 LiPO3F Inorganic materials 0.000 abstract 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 abstract 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 abstract 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 abstract 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 abstract 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 abstract 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 abstract 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 27
- 238000001816 cooling Methods 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Classifications
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for manufacturing composite anode material of lithium iron phosphate, which comprises doing secondary granulation treatment for lithium iron phosphate which is got through high-temperature solid phase synthesis method after mixing with additional anode material and fluxing agent, wherein the weight ratio of lithium iron phosphate and additional anode material is 90:10-95:5, and the addition of fluxing agent is 0.5%-2.0% of the sum of the weight of additional anode material, and additional anode material is at least one of lithium cobalt oxide, lithium manganeseoxide, lithium nickel oxide or nickel-cobalt lithium manganese oxide, and fluxing agent is at least one of NaPO3F and LiPO3F. The method can lead lithium iron phosphate particles to secondarily grow,which improves the tap density, and composite anode material of lithium iron phosphate which is got not only has better rate capability, but also has higher specific volumetric capacity, and the processing property is effectively improved. The invention has the advantages of simple step and easy execution.
Description
Technical field
The present invention relates to the preparation method of lithium ion secondary battery anode material, especially a kind of preparation method who makes oarse-grained iron phosphate compound anode material of lithium.
Background technology
LiFePO4 (LiFePO
4) theoretical capacity up to 170mAh/g, reversible capacity is high, structure is firm before and after discharging and recharging, and all has voltage platform stably.LiFePO4 has received extensive concern as the research of positive electrode.The synthetic method of lithium ion battery anode material lithium iron phosphate mainly contains high temperature solid phase synthesis, coprecipitation, sol-gel process, Pechini method etc. at present; Wherein soft chemical method complex process such as coprecipitation, sol-gel method, Pechini method are difficult for realizing industrialization.What generally adopt in the conventional production practices mainly is high temperature solid phase synthesis.
High temperature solid phase synthesis is that lithium salts and ferrous salt are mixed according to a certain percentage, and a period of time of calcination at high temperature becomes.Reason salt commonly used has lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate etc., and source of iron then is a ferrous oxalate, and calcination temperature is 600 ℃～950 ℃ even higher temperature, and calcination time is about 20h～60h.High temperature solid phase synthesis operation and Process Route are simple, and technological parameter is easy to control, less demanding to equipment, and the material property of preparation is stable, is easy to realize large-scale industrialization production.But; Also there is following defective in conventional high temperature solid phase synthesis: adopted a large amount of presoma carbon as preventing the protective agent that ferrous ion is oxidized; The residual carbon that contains high-load in the synthetic like this lithium iron phosphate positive material product; The existence of carbon has suppressed growing up of LiFePO4 crystal grain; Though synthetic granule lithium iron phosphate positive material has rate charge-discharge performance preferably because the particle of material little (being nanometer or submicron order) thereby, specific area caused its processing characteristics relatively poor greatly, the anode sizing agent of particularly processing is difficult to cover paper tinsel.In addition, because the particle of material is little, tap density is lower, thereby the volume and capacity ratio of material is also seriously influenced.Therefore, the research of large-particle lithium iron phosphate method for preparing anode material is the important directions of lithium iron phosphate positive material research and development.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method who makes oarse-grained iron phosphate compound anode material of lithium.
For solving the problems of the technologies described above, the present invention provides a kind of preparation method of iron phosphate compound anode material of lithium, and the LiFePO4 that high temperature solid phase synthesis is obtained mixes with additional positive electrode, flux, then mixture heating carrying out secondary granulation is handled; Additional positive electrode is at least a in cobalt acid lithium, LiMn2O4, lithium nickelate or the nickle cobalt lithium manganate, and flux is NaPO
3F and LiPO
3At least a among the F.
The LiFePO4 that is adopted in the inventive method is the LiFePO4 that the high temperature solid phase synthesis that generally adopts in the present conventional production practices makes.LiFePO4 mixes back mixture is heated and carries out secondary granulation with additional positive electrode, flux, additional positive electrode can improve the tap density of the iron phosphate compound anode material of lithium of final gained; Flux helps LiFePO4 particle secondary and grows up.
Secondary granulation is handled and can under 100 ℃～900 ℃ protective atmosphere, be carried out.Can select nitrogen atmosphere, inert gas atmosphere or vacuum is the protective atmosphere in the roasting process.
The secondary granulation processing time may be selected to be 12h～48h.
Secondary granulation can be selected when handling: the weight ratio of LiFePO4 and additional positive electrode is 90: 10～95: 5, the addition of flux account for LiFePO4 and additional positive electrode the weight sum 0.5%～2.0%.
For obtaining uniform iron phosphate compound anode material of lithium, being convenient to prepare slurry, after the roasting process end, product of roasting is carried out ball milling.
The invention has the beneficial effects as follows: adopt the inventive method that the high temperature solid phase synthesis gained LiFePO4 of routine is handled, LiFePO4 particle secondary is grown up, improve the tap density of iron phosphate compound anode material of lithium; The grain diameter of the iron phosphate compound anode material of lithium that obtains promptly has high rate performance preferably obviously greater than the high temperature solid phase synthesis gained LiFePO4 of routine, has higher volume and capacity ratio again, and processing characteristics has also obtained effective improvement.The inventive method step is simple, and is easy to implement, makes to adopt the conventional less scarce limit of high temperature solid phase synthesis gained lithium iron phosphate positive material particle diameter to be improved.
Description of drawings
Through embodiment and combine accompanying drawing, the present invention is done further detailed description below:
Fig. 1 is 2000 times of stereoscan photographs of embodiment 1 sample;
Fig. 2 is the particle size distribution test figure of embodiment 1 sample;
Fig. 3 is the half-cell that adopts embodiment 2 gained iron phosphate compound anode material of lithium and make cyclical voltage-specific capacity curve first;
Fig. 4 is the full battery that adopts embodiment 3 gained iron phosphate compound anode material of lithium and the make cyclic curve of (0.2C, 0.5C and 1C) under different multiplying.
Embodiment
With mol ratio Li: Fe: P=1: take by weighing raw material Li OHH at 1: 1
2O, FeC
2O
4And NH
4H
2PO
4, place the rotating speed ball milling 6h of ball grinder with 400 commentaries on classics/min～600 commentaries on classics/min, then the mixed material behind the ball milling is sent in the box type furnace at 350 ℃ of preliminary treatment 6h.Pretreated sample is carried out sending into N again behind the ball milling
2With 700 ℃ of roasting 24h, take out again the ball milling screening in the stove of protection, will sieve products obtained therefrom and nickle cobalt lithium manganate positive electrode, NaPO with the furnace temperature cooling
3F mixing and ball milling after sends into N according to mass ratio at 95: 5: 1
2Carry out secondary granulation in the stove of protection, the secondary granulation temperature is controlled at 900 ℃, and the secondary granulation time is 12h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate compound anode material of lithium of larger particles.
With Li: Fe: P=1: 1: 1 ratio takes by weighing raw material Li OHH
2O, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400 commentaries on classics/min～600 commentaries on classics/min speed ball milling 6h, after finishing the mixed material behind the ball milling is sent in the box type furnace with 350 ℃ of left and right sides preliminary treatment 6h.Pretreated sample is carried out sending into N again behind the ball milling
2With 700 ℃ of roasting 24h, take out the ball milling screening in the stove of protection, will sieve products obtained therefrom and lithium cobaltate cathode material, LiPO with the furnace temperature cooling
3F mixed ball milling after once more sends into according to mass ratio in the stove of protective atmosphere and carries out secondary granulation at 90.0: 10.0: 0.5, and the secondary granulation temperature is controlled at 100 ℃, and the secondary granulation time is 48h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate compound anode material of lithium of larger particles.
Gained iron phosphate compound anode material of lithium and SP, polyvinylidene fluoride (PVDF) are prepared anode sizing agent according to 80: 15: 5 (mass ratio); After mixing with machine,massing; Slurry on small-sized tensile pulp machine, using the thickness of aluminium foil is 16 μ m, the slurry surface density is 8mg/cm
2～9mg/cm
2As to electrode, adopt EC: DMC=1 with metal Li: 1 (volume ratio), 1M lithium hexafluoro phosphate electrolyte, in being full of the glove box of argon shield, assemble half-cell, H in the glove box
2O and O
2All less than 1ppm.Carry out the constant current charge and discharge with 0.1C, charging is by voltage 3.8V, and discharge is by voltage 2.0V.This half-cell cyclical voltage-specific capacity curve first is as shown in Figure 3.
With Li: Fe: P=1: 1: 1 ratio takes by weighing raw material Li OHH
2O, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400 commentaries on classics/min～600 commentaries on classics/min speed ball milling 6h, after finishing the mixed material behind the ball milling is sent in the box type furnace with 350 ℃ of left and right sides preliminary treatment 6h.Pretreated sample is carried out sending into N again behind the ball milling
2With 700 ℃ of roasting 24h, take out the ball milling screening in the stove of protection, will sieve products obtained therefrom and manganate cathode material for lithium, composite fluxing agent NaPO with the furnace temperature cooling
3F+LiPO
3F mixed ball milling after once more sends into according to mass ratio and carries out secondary granulation in the vacuum furnace at 92: 8: 2, and secondary granulation temperature temperature is controlled at 700 ℃, and the secondary granulation time is 20h.After the furnace temperature cooling, take out ball milling, finally obtain the iron phosphate compound anode material of lithium of larger particles.
Technological process according to slurrying → coating → compressing tablet → cut → reel → go into shell → weldering cover plate → fluid injection → seal; Adopting present embodiment gained iron phosphate compound anode material of lithium to make model is 18650 full battery, between 2.0v-3.6v voltage under different multiplying (0.2C, 0.5C and 1C) carry out the rate charge-discharge circulation experiment.The rate charge-discharge cycle performance of this full battery is as shown in Figure 4.
Embodiment 4
With embodiment 1, just wherein nickle cobalt lithium manganate replaces with the mixture of cobalt acid lithium and LiMn2O4.
With embodiment 1, just wherein nickle cobalt lithium manganate replaces with LiMn2O4.
With embodiment 2, just wherein cobalt acid lithium replaces with nickle cobalt lithium manganate.
With embodiment 2, just wherein cobalt acid lithium replaces with LiMn2O4.
With embodiment 3, just wherein LiMn2O4 replaces with nickle cobalt lithium manganate.
Embodiment 9
With embodiment 3, just wherein LiMn2O4 replaces with cobalt acid lithium.
Comparative Examples
Adopt conventional high temperature solid phase synthesis to prepare lithium iron phosphate positive material: with Li: Fe: P=1: 1: 1 ratio takes by weighing LiOHH
2O, FeC
2O
4And NH
4H
2PO
4, place ball grinder with 400 commentaries on classics/min～600 commentaries on classics/min speed ball milling 6h, after finishing mixture sent in the box type furnace and with about 350 ℃, handle 6h.Pretreated sample is carried out sending into N again behind the ball milling
2With 700 ℃ of roasting 24h, take out the ball milling screening with the furnace temperature cooling and obtain lithium iron phosphate positive material in the stove of protection.
Fig. 1 is 2000 times of stereoscan photographs of embodiment 1 sample.Can know by Fig. 1, compare, adopt the particle diameter of the iron phosphate compound anode material of lithium of the inventive method gained obviously to grow up with the nanometer or the submicron order lithium iron phosphate positive material that adopt conventional high temperature solid phase synthesis to make.
Can know from Fig. 2, adopt the particle diameter of the iron phosphate compound anode material of lithium of the inventive method gained to concentrate on about 10 μ m, and the D of the lithium iron phosphate positive material agglomerated particle that the conventional high temperature solid phase synthesis of employing makes
50Below 2 μ m.
Can know that from Fig. 3 the half-cell that the iron phosphate compound anode material of lithium of employing the inventive method gained is made is functional, battery capacity reaches 150mAhg.
Fig. 4 is the rate charge-discharge cycle performance curve of the full battery among the embodiment 3; Curve group 1 is that charging curve, the curve group 6 under the 1C condition is the discharge curve under the 1C condition; Curve group 2 is that charging curve, the curve group 5 under the 0.5C condition is the discharge curve under the 0.5C condition, and curve group 3 is that charging curve, the curve group 4 under the 0.2C condition is the discharge curve under the 0.2C condition.Can know from Fig. 4, adopt full battery that the iron phosphate compound anode material of lithium of the inventive method gained makes respectively under different multiplying (0.2C, 0.5C and 1C) carry out circulation experiment, show good rate charge-discharge performance.
Measure the tap density of Comparative Examples and each embodiment gained positive electrode respectively with JZ-1 type powder tapping density appearance, the result is as shown in table 1.Can know from table 1; Compare with the lithium iron phosphate positive material that adopts conventional high temperature solid phase synthesis to make; Adopt the tap density of each embodiment iron phosphate compound anode material of lithium of the inventive method gained to be largely increased, this will improve the volume and capacity ratio of material greatly.
Adopt Comparative Examples and each embodiment gained positive electrode respectively; Positive electrode and SP, polyvinylidene fluoride (PVDF) are prepared anode sizing agent according to 95: 3: 2 (mass ratio); After mixing with machine,massing; On coating machine, be coated with, using the thickness of aluminium foil is 16 μ m, and coated face density is 39mg/cm
2～40mg/cm
2Be rolled into positive plate after the drying.The foil-covering effect of each positive plate is as shown in table 2.Can know from table 2, compare with the lithium iron phosphate positive material that adopts conventional high temperature solid phase synthesis to make, adopt the inventive method gained iron phosphate compound anode material of lithium positive plate have a good foil-covering effect, processing characteristics be improved significantly.
Table 1 tap density test result
| Sample | Tap density g/cm 3 |
| Comparative Examples | 0.90～1.10 |
| |
1.69 |
| |
1.72 |
| |
1.60 |
| Embodiment 4 | 1.75 |
| |
1.67 |
| |
1.72 |
| |
1.65 |
| |
1..73 |
| Embodiment 9 | 1.70 |
Table 2 Comparative Examples is described with each embodiment sample foil-covering effect
| Sample | Foil-covering effect |
| Comparative Examples | Surface density is 36mg/cm
2, exist and seriously fall to expect |
| Embodiment | |
| 1 | Surface density is 40mg/cm 2, do not have the material of falling |
| |
Surface density is 40mg/cm 2, do not have the material of falling |
| |
Surface density is 40mg/cm 2, do not have the material of falling |
| Embodiment 4 | Surface density is 40mg/cm 2, do not have the material of falling |
| |
Surface density is 40mg/cm 2, do not have the material of falling |
| |
Surface density is 40mg/cm 2, do not have the material of falling |
| |
Surface density is 40mg/cm 2, do not have the material of falling |
| |
Surface density is 40mg/cm 2, do not have the material of falling |
| Embodiment 9 | Surface density is 40mg/cm 2, do not have the material of falling |
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For the those of ordinary skill of technical field under the present invention, under the prerequisite that does not break away from the present invention's design, can also make some simple deduction or replace, all should be regarded as belonging to protection scope of the present invention.
Claims (6)
1. the preparation method of an iron phosphate compound anode material of lithium, it is characterized in that: the LiFePO4 that high temperature solid phase synthesis is obtained mixes with additional positive electrode, flux, then mixture heating carrying out secondary granulation is handled; Said additional positive electrode is at least a in cobalt acid lithium, LiMn2O4, lithium nickelate or the nickle cobalt lithium manganate, and said flux is NaPO
3F and LiPO
3At least a among the F.
2. the preparation method of iron phosphate compound anode material of lithium according to claim 1 is characterized in that: secondary granulation is handled and under 100 ℃～900 ℃ protective atmosphere, is carried out.
3. the preparation method of iron phosphate compound anode material of lithium according to claim 1 and 2, it is characterized in that: the secondary granulation processing time is 12h～48h.
4. the preparation method of iron phosphate compound anode material of lithium according to claim 3; It is characterized in that: the weight ratio of said LiFePO4 and additional positive electrode is 90: 10～95: 5, the addition of said flux account for said LiFePO4 and additional positive electrode the weight sum 0.5%～2.0%.
5. the preparation method of iron phosphate compound anode material of lithium according to claim 4 is characterized in that: the protective atmosphere that said secondary granulation is handled is nitrogen atmosphere or vacuum.
6. the preparation method of iron phosphate compound anode material of lithium according to claim 5 is characterized in that: after said secondary granulation processing finished, the product that secondary granulation is handled carried out ball milling.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100770340A CN101388459B (en) | 2007-09-11 | 2007-09-11 | Preparation of ferric phosphate composite positive pole |
| HK09108273.2A HK1128556A1 (en) | 2007-09-11 | 2009-09-09 | Method for preparing lithium ferric phosphate composite anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100770340A CN101388459B (en) | 2007-09-11 | 2007-09-11 | Preparation of ferric phosphate composite positive pole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101388459A CN101388459A (en) | 2009-03-18 |
| CN101388459B true CN101388459B (en) | 2012-07-25 |
Family
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102148367A (en) * | 2010-02-08 | 2011-08-10 | 江西省金锂科技有限公司 | Method for preparing lithium-ion battery anode material of lithium iron phosphate |
| CN102306790A (en) * | 2011-08-15 | 2012-01-04 | 青岛乾运高科新材料有限公司 | Method for manufacturing LiFePO (lithium iron phosphate)/lithium cobaltate composite anode |
| US9306214B2 (en) | 2012-02-29 | 2016-04-05 | Hitachi Chemical Company, Ltd. | Lithium ion battery |
| CN103715417B (en) * | 2014-01-09 | 2016-05-25 | 合肥恒能新能源科技有限公司 | The preparation method of a kind of lithium battery anode active material and coating sizing-agent thereof |
| CN105185987B (en) * | 2014-05-29 | 2017-09-12 | 宁德新能源科技有限公司 | Positive electrode and lithium rechargeable battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1659728A (en) * | 2001-10-26 | 2005-08-24 | 化合价技术股份有限公司 | Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials |
| CN1874047A (en) * | 2005-03-18 | 2006-12-06 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1659728A (en) * | 2001-10-26 | 2005-08-24 | 化合价技术股份有限公司 | Alkali/transition metal halo-and hydroxy-phosphates and related electrode active materials |
| CN1874047A (en) * | 2005-03-18 | 2006-12-06 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
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| CN101388459A (en) | 2009-03-18 |
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