CN102593447B - A kind of metal-doped method of lithium iron phosphate positive material - Google Patents
A kind of metal-doped method of lithium iron phosphate positive material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 48
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 34
- 238000005245 sintering Methods 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000000227 grinding Methods 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 25
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 12
- 229930006000 Sucrose Natural products 0.000 claims description 12
- 239000005720 sucrose Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229940062993 ferrous oxalate Drugs 0.000 claims description 5
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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 discloses a kind of metal-doped method of lithium iron phosphate positive material, one, for the first time ground and mixed; Two, first sintering: rear obtained material dry in step one is carried out first sintering, and the temperature of sintering is 300 DEG C-600 DEG C; Three, second time ground and mixed: material obtained after first sintering in step 2 is joined purity and is more than or equal in 85% alcohol dispersant, and second time ground and mixed is carried out in grinder, carbon-source cpd is added according to 21% of Li source compound quality in step one, proceed grinding after 2 hours, then under 100 DEG C of-120 DEG C of oxygen free conditions, carry out drying, complete adding of second time carbon-source cpd; Four, second time sintering: material dried in step 3 is carried out second time sintering; Five, third time sintering: material obtained after sintering in step 4 is carried out third time sintering again, obtains having the lithium iron phosphate positive material that Zn and Ti adulterates.
Description
Technical field
The present invention relates to a kind of metal-doped method of lithium iron phosphate positive material.
Background technology
Along with the aggravation of mankind's environmental pollution pressure, the finiteness of primary energy, urgently needs high-energy at present, low stain, continuable green novel energy source.
Since the eighties lithium ion battery commercialization in last century, it has been observed that its potential quality as a kind of new forms of energy of sustainable development, but the prices of raw and semifnished materials main due to lithium ion battery are originally expensive, and manufacture craft is immature, limit its development.Meanwhile, city automobile tail gas becomes the first principal element of city environmental pollution, becomes as free of contamination new forms of energy power electric motor car the main method instantly solving auto-pollution.The power source mainly lithium ion battery of electric automobile, and as the LiFePO4 (LiFePO of positive electrode
4) become one of preferred material.LiFePO4 (LiFePO
4) positive electrode is orthorhombic system olivine structural, belongs to polyanionic compound.Its space group is PZnb.LiFePO
4crystal is by FeO
6octahedron and PO
4the spatial skeleton that tetrahedron is formed.With the LiCoO of stratiform and spinelle
2, LiNiO
2, LiMn
2o
4compare Deng positive electrode, it is good that polyanionic compound positive electrode has security performance, and crystal structure is stablized, the advantages such as thermal stability.
At present, LiFePO4 (LiFePO
4) the poor conductivity of material itself and lower lithium ion diffusion coefficient be hinder its practical main reason always, thus impels Chinese scholars at raising LiFePO
4the aspect of conductive capability expand research.For this reason, domestic and international expert can through method that is coated, that replace, be prepared into the upgradings such as nanometer materials to overcome this shortcoming.Add conductive materials to improve the LiFePO after de-lithium
4electron conduction, can at LiFePO
4introduce the conductive agent of good dispersion property between powder, such as carbon black or the precious metal such as gold, silver, copper, can significantly improve interparticle electric conductivity, make LiFePO
4utilization ratio improve, reversible capacitance amount can reach 95% of theoretical value, even under the high current charge-discharge condition of 5C cycle performance performance also very good.But LiFePO
4still there is poorly conductive and the low shortcoming of lithium ion diffusion coefficient in material itself.
Summary of the invention
The present invention proposes a kind of metal-doped method of lithium iron phosphate positive material, and it can at LiFePO
4anode material for lithium-ion batteries codope different proportion Zn and Ti replaces Fe ionic vacancies, improves the lithium ion diffusion coefficient in lithium ion charge and discharge process, makes LiFePO
4charge-discharge performance improve, cycle-index increase.
Present invention employs following technical scheme: a kind of metal-doped method of lithium iron phosphate positive material, it comprises the following steps: step one, for the first time ground and mixed: first by Li source compound, Fe source compound, PO
4source compound adds purity according to mol ratio 1.000: 0.854: 0.954 and is more than or equal in the alcohol dispersant of 95%, and ground and mixed process in addition, after mixing, add Ti source compound and Zn source compound, Li source compound: Ti source compound: the mol ratio of Zn source compound is 1: 0.02-0.04: 0.02, then add carbon-source cpd according to 7% of lithium source quality, then carry out grinding after 1 hour, then under 100 DEG C of-120 DEG C of oxygen free conditions, carry out drying; Step 2, first sintering: rear obtained material dry in step one is carried out first sintering, and the temperature of sintering is 300 DEG C-600 DEG C; Step 3, second time ground and mixed: material obtained after first sintering in step 2 is joined purity and is more than or equal in 85% alcohol dispersant, and second time ground and mixed is carried out in grinder, carbon-source cpd is added according to 21% of Li source compound quality in step one, proceed grinding after 2 hours, then under 100 DEG C of-120 DEG C of oxygen free conditions, carry out drying, complete adding of second time carbon-source cpd; Step 4, second time sintering: material dried in step 3 is carried out second time sintering, sintering temperature is set in 300 DEG C-350 DEG C; Step 5, third time sintering: material obtained after sintering in step 4 is carried out again third time sintering, sintering temperature is set in 650-730 DEG C, obtains having the lithium iron phosphate positive material that Zn and Ti adulterates.
A kind of Li source compound of step of the present invention is lithium carbonate, lithium hydroxide or lithium acetate, and Fe source compound is ferrous oxalate, PO
4source compound is ammonium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate or sodium phosphate, and Zn source compound is zinc acetate, and Ti source compound is TiO
2.Step one of the present invention and the carbon-source cpd described in step 3 are sucrose, and in the carbon-source cpd added in step one and step 3, the carbon-source cpd mass ratio that adds is 1: 3.In step 2 of the present invention, the process of first sintering refers to be placed on by material dried in step 2 in iron crucible and at the temperature of 300 DEG C-600 DEG C, sinters 2 hours with chamber type sintering stove, and processes passing under nitrogen protection.In step 4 of the present invention, the process of second time sintering refers to be placed on by material dried in step 3 in iron crucible and at the temperature of 300 DEG C-350 DEG C, sinters 2 hours with chamber type sintering stove, and processes passing under nitrogen protection.In step 5 of the present invention third time sintering process refer to that the material after by second time sintering in step 4 to be placed in oxidation aluminum cup and to sinter 10 hours-15 hours at the temperature of 650-730 DEG C in tunnel cave, and to process passing under nitrogen protection.
The present invention has following beneficial effect: the raw material lithium carbonate that the present invention adopts, lithium hydroxide, lithium acetate, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium phosphate and sucrose are all raw material rich and easy to get, not containing any rare precious metal, it is convenient to buy, cheap, production cost is low, and is conducive to large-scale industrial production.The present invention adopts twice material by wet type mixing and three solid-phase sintering synthesizing iron lithium phosphates, and process is simple, low for equipment requirements, and production cost is also low.. the lithium iron phosphate positive material prepared by the present invention adopts Zn, Ti ion doping, and it has extended cycle life, particle size distribution is controlled, conducts electricity very well, and tap density is high, and specific capacity can reach 160mAh/g.The present invention is played preferably to realize the performance of lithium iron phosphate positive material in lithium ion battery, this lithium iron phosphate positive material can regulate the doping ratio of metal ion according to its preparation technology, namely by the ground and mixed time, the doping ratio of metal ion, drying means, sintering temperatures etc. control the granule-morphology of phosphoric acid iron crystalline lithium structured forerunner, make its particle size distribution controlled, , greatly can improve the degree of crystallinity of lithium iron phosphate positive material, Lithium-ion embeding and the invertibity of deviating from, dispersed homogeneous degree, and when becoming ferric ion after ferrous ion can be suppressed to deviate from, the impact of trip path change is produced after cell volume diminishes, and then improve the chemical property of lithium iron phosphate positive material, degree of crystallinity is better simultaneously, the lithium iron phosphate positive material of superior electrical property is mainly through control Zn, Ti is compound doped and obtain control, namely Zn is added by a batch mixing, Ti compound, then through high temperature sintering, obtain that there is Zn, the lithium iron phosphate positive material of Ti doping, Zn, Ti ion doping acid iron lithium, by in high―temperature nuclei process, Zn ion, Ti ionic compartmentation Fe ionic lattice room, obtain Zn ion, the high-performance iron phosphate lithium of Ti ion co-doped.
Accompanying drawing explanation
The LiFePO4 SEM of Fig. 1 prepared by the embodiment of the present invention one schemes.
The LiFePO4 X-ray diffracting spectrum of Fig. 2 prepared by the embodiment of the present invention two.
Discharge curve result after the LiFePO4 composition experimental cell of Fig. 3 prepared by the embodiment of the present invention three.
Embodiment
Embodiment one:
Step one, ground and mixed for the first time: first lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate are added purity according to mol ratio 1.000: 0.854: 0.954 and be more than or equal in the alcohol dispersant of 95%, and in addition ground and mixed process, grind grinding after 1 hour and evenly, add TiO after grinding
2with Zn (C
2h
3o
2)
2, lithium carbonate: TiO
2: Zn (C
2h
3o
2)
2mol ratio is 1: 0.02: 0.02, then adds the sucrose of 7% of lithium carbonate quality, continues grinding after 1 hour, under 100 DEG C of-120 DEG C of oxygen free conditions, carries out drying;
Step 2, first sintering: by material obtained for step one drying, carry out first sintering, the method of first sintering is placed in iron crucible by material obtained for step one drying at 300 DEG C-600 DEG C, to sinter 2 hours with chamber type sintering stove, and process passing under the condition under nitrogen protection;
Step 3, second time ground and mixed: the material of first sintering in step 2 is joined purity and to be more than or equal in 85% alcohol dispersant in grinding machine for grinding after 1 hour, then the sucrose of lithium carbonate quality 21% in cloth rapid one is added, continue grinding again after 2 hours, under 100 DEG C of-120 DEG C of oxygen free conditions, carry out drying, complete adding of second time sucrose;
Step 4, second time sintering: dried for step 3 material is carried out second time sintering, the method of second time sintering is placed by dried material in iron crucible at 300 DEG C-350 DEG C, to sinter 2 hours with chamber type sintering stove, and process passing under the condition under nitrogen protection;
Step 5, third time sinters; Obtained material after second time sintering in step 4 is carried out third time sintering; third time sintering process refer to by step 4 second time sintering after material be placed on oxidation aluminum cup in and in tunnel cave with at the temperature of 650-730 DEG C sinter 10 hours; and process passing under nitrogen protection, finally obtain the lithium iron phosphate positive material of Zn and Ti doping.
Detect lithium iron phosphate positive material prepared by this case method, in FIG, the lithium iron phosphate positive material of detection, records tap density and reaches 1.52g/cm
3, sem analysis shows, even particle distribution.In fig. 2, X-ray diffraction test shows, this lithium iron phosphate battery positive material purity is high, free from foreign meter, has intact degree of crystallinity.In figure 3, this lithium iron phosphate positive material is made experimental cell in the glove box being filled with argon gas, carry out charge-discharge test at about 25 DEG C, charging/discharging voltage scope is 2.0V-3.7V, and the 0.5C first discharge specific capacity of this material can reach 160mAh/g.
Embodiment two:
Step one, ground and mixed for the first time: first lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate are added purity according to mol ratio 1.000: 0.854: 0.954 and be more than or equal in the alcohol dispersant of 95%, and in addition ground and mixed process, grind grinding after 1 hour and evenly, add TiO after grinding
2with Zn (C
2h
3o
2)
2, lithium carbonate: TiO
2: Zn (C
2h
3o
2)
2mol ratio is 1: 0.03: 0.02, then adds the sucrose of 7% of lithium carbonate quality, continues grinding after 1 hour, under 100 DEG C of-120 DEG C of oxygen free conditions, carries out drying;
Step 2, first sintering: by material obtained for step one drying, carry out first sintering, the method of first sintering is placed in iron crucible by material obtained for step one drying at 300 DEG C-600 DEG C, to sinter 2 hours with chamber type sintering stove, and process passing under the condition under nitrogen protection;
Step 3, second time ground and mixed: the material of first sintering in step 2 is joined purity and to be more than or equal in 85% alcohol dispersant in grinding machine for grinding after 1 hour, then the sucrose of lithium carbonate quality 21% in cloth rapid one is added, continue grinding again after 2 hours, under 100 DEG C of-120 DEG C of oxygen free conditions, carry out drying, complete adding of second time sucrose;
Step 4, second time sintering: dried for step 3 material is carried out second time sintering, the method of second time sintering is placed by dried material in iron crucible at 300 DEG C-350 DEG C, to sinter 2 hours with chamber type sintering stove, and process passing under the condition under nitrogen protection;
Step 5, third time sinters; Obtained material after second time sintering in step 4 is carried out third time sintering; third time sintering process refer to by step 4 second time sintering after material be placed on oxidation aluminum cup in and in tunnel cave with at the temperature of 650-730 DEG C sinter 10 hours; and process passing under nitrogen protection, finally obtain the lithium iron phosphate positive material of Zn and Ti doping.
Detect lithium iron phosphate positive material prepared by this case method, the lithium iron phosphate positive material of detection, record tap density and reach 1.50g/cm
3, sem analysis shows, even particle distribution, and X-ray diffraction test shows, this lithium iron phosphate battery positive material purity is high, free from foreign meter, has intact degree of crystallinity.This lithium iron phosphate positive material is made experimental cell in the glove box being filled with argon gas, carries out charge-discharge test at about 25 DEG C, charging/discharging voltage scope is 2.0V-3.7V, and the 0.5C first discharge specific capacity of this material can reach 155mAh/g;
Embodiment three:
Step one, ground and mixed for the first time: first lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate are added purity according to mol ratio 1.000: 0.854: 0.954 and be more than or equal in the alcohol dispersant of 95%, and in addition ground and mixed process, grind grinding after 1 hour and evenly, add TiO after grinding
2with Zn (C
2h
3o
2)
2, lithium carbonate: TiO
2: Zn (C
2h
3o
2)
2mol ratio is 1: 0.04: 0.02, then adds the sucrose of 7% of lithium carbonate quality, continues grinding after 1 hour, under 100 DEG C of-120 DEG C of oxygen free conditions, carries out drying;
Step 2, first sintering: by material obtained for step one drying, carry out first sintering, the method of first sintering is placed in iron crucible by material obtained for step one drying at 300 DEG C-600 DEG C, to sinter 2 hours with chamber type sintering stove, and process passing under the condition under nitrogen protection;
Step 3, second time ground and mixed: the material of first sintering in step 2 is joined purity and to be more than or equal in 85% alcohol dispersant in grinding machine for grinding after 1 hour, then the sucrose of lithium carbonate quality 21% in cloth rapid one is added, continue grinding again after 2 hours, under 100 DEG C of-120 DEG C of oxygen free conditions, carry out drying, complete adding of second time sucrose;
Step 4, second time sintering: dried for step 3 material is carried out second time sintering, the method of second time sintering is placed by dried material in iron crucible at 300 DEG C-350 DEG C, to sinter 2 hours with chamber type sintering stove, and process passing under the condition under nitrogen protection;
Step 5, third time sinters; Obtained material after second time sintering in step 4 is carried out third time sintering; third time sintering process refer to by step 4 second time sintering after material be placed on oxidation aluminum cup in and in tunnel cave with at the temperature of 650-730 DEG C sinter 10 hours; and process passing under nitrogen protection, finally obtain the lithium iron phosphate positive material of Zn and Ti doping.
Detect lithium iron phosphate positive material prepared by this case method, the lithium iron phosphate positive material of detection, record tap density and reach 1.45g/cm
3, sem analysis shows, even particle distribution, and X-ray diffraction test shows, this lithium iron phosphate battery positive material purity is high, free from foreign meter, has intact degree of crystallinity.This lithium iron phosphate positive material is made experimental cell in the glove box being filled with argon gas, carries out charge-discharge test at about 25 DEG C, charging/discharging voltage scope is 2.0V-3.7V, and the 0.5C first discharge specific capacity of this material can reach 154mAh/g.
Claims (1)
1. a metal-doped method for lithium iron phosphate positive material, it comprises the following steps:
Step one, for the first time ground and mixed: first by Li source compound, Fe source compound, PO
4source compound adds purity according to mol ratio 1.000: 0.854: 0.954 and is more than or equal in the alcohol dispersant of 95%, and ground and mixed process in addition, after mixing, add Ti source compound and Zn source compound, Li source compound: Ti source compound: the mol ratio of Zn source compound is 1: 0.02-0.04: 0.02, then carbon-source cpd is added according to 7% of Li source compound, carry out grinding again after 1 hour, then under 100 DEG C of-120 DEG C of oxygen free conditions, drying is carried out, in step one, Li source compound is lithium carbonate, lithium hydroxide or lithium acetate, Fe source compound is ferrous oxalate, PO
4source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or sodium phosphate, and Zn source compound is zinc acetate, and Ti source compound is TiO
2,
Step 2, first sintering: obtained material after dry in step one is placed in iron crucible and sinters 2 hours with chamber type sintering stove at the temperature of 300 DEG C-600 DEG C, and process passing under nitrogen protection;
Step 3, second time ground and mixed: material obtained after first sintering in step 2 is joined purity and is more than or equal in 85% alcohol dispersant, and second time ground and mixed is carried out in grinder, carbon-source cpd is added according to 21% of Li source compound quality in step one, proceed grinding after 2 hours, then under 100 DEG C of-120 DEG C of oxygen free conditions, drying is carried out, complete adding of second time carbon-source cpd, step one and the carbon-source cpd described in step 3 are sucrose, in the carbon-source cpd added in step one and step 3, the carbon-source cpd mass ratio that adds is 1: 3,
Step 4, second time sintering: material dried in step 3 is placed in iron crucible and sinters 2 hours with chamber type sintering stove at the temperature of 300 DEG C-350 DEG C, and process passing under nitrogen protection;
Step 5; third time sinters: material obtained after sintering in step 4 is carried out again third time sintering; sintering temperature is set in 650-730 DEG C; obtain the lithium iron phosphate positive material with Zn and Ti doping; in step 5 third time sintering process refer to that the material after by second time sintering in step 4 to be placed in oxidation aluminum cup and to sinter 10 hours-15 hours at the temperature of 650-730 DEG C in tunnel cave, and to process passing under nitrogen protection.
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Effective date of registration: 20171127 Address after: 225300 Taizhou medical high tech Zone, Taizhou, Jiangsu Province, Binjiang Industrial Park, Hong Kong City Road No. 12 Patentee after: Jiangsu East lithium Co., Ltd. Address before: 225300 No. 1, east side of foreshore Road, Binjiang Industrial Park, Taizhou Economic Development Zone, Jiangsu, Taizhou Patentee before: Jiangsu First New Energy Co., Ltd. |
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