CN108565459A - A kind of method that iron oxide modified prepares LiFePO4 - Google Patents
A kind of method that iron oxide modified prepares LiFePO4 Download PDFInfo
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- CN108565459A CN108565459A CN201810331996.2A CN201810331996A CN108565459A CN 108565459 A CN108565459 A CN 108565459A CN 201810331996 A CN201810331996 A CN 201810331996A CN 108565459 A CN108565459 A CN 108565459A
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- Prior art keywords
- modified oxidized
- iron
- oxidized iron
- fepo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052493 LiFePO4 Inorganic materials 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 20
- 239000000284 extract Substances 0.000 claims abstract description 19
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 6
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940063953 ammonium lauryl sulfate Drugs 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 150000004698 iron complex Chemical class 0.000 claims abstract description 3
- 244000166124 Eucalyptus globulus Species 0.000 claims abstract 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 229910010710 LiFePO Inorganic materials 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000005374 membrane filtration Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical group [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 229910011140 Li2C2 Inorganic materials 0.000 claims description 3
- 239000008236 heating water Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 3
- 241000219927 Eucalyptus Species 0.000 description 22
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 235000000396 iron Nutrition 0.000 description 6
- 235000005979 Citrus limon Nutrition 0.000 description 5
- 244000131522 Citrus pyriformis Species 0.000 description 5
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical class OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 3
- 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 description 3
- 239000007788 liquid Substances 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- -1 phosphate anion Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005720 sucrose Substances 0.000 description 3
- 241000040710 Chela Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical compound [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012913 prioritisation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000002163 immunogen Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of method that iron oxide modified prepares LiFePO4, step includes：(1) prepared by pretreatment fluid；(1) it takes iron chloride, ammonium lauryl sulfate and eucalyptus leaf extract in being mixed in reaction kettle, reacts, modified oxidized iron is made；(2) modified oxidized iron is added in enveloping agent solution, and stirring stands to obtain modified oxidized iron complex；(3) H is added into step (2)3PO4, adjust pH, stirring, be aged, be filtered, washed, dry obtain pre-process FePO4·2H2O presomas；(4) pretreatment FePO is weighed4·2H2O presomas, lithium source, carbon source, dispersant in ball mill mixing, and are transferred in sintering furnace, 200~300 DEG C of sintering under inert atmosphere protection；(5) 650~750 DEG C are continuously heating to, 6~10h is kept the temperature, is cooled to room temperature, obtains carbon coating LiFePO4.50 DEG C of positive electrode made from this method, 10C charge/discharge capacities reach 153mAh/g.
Description
Technical field
The present invention is patent of invention《A kind of method that modified oxidized iron prepares carbon-coated LiFePO 4 for lithium ion batteries》(application number：
2016101583764) divisional application is related to a kind of battery material, and especially a kind of iron oxide modified prepares LiFePO4
Method.
Background technology
Lithium ion battery is high-energy battery of new generation, with energy density is big, voltage is high, cycle compared with cobalt acid lithium battery
The advantages that performance is good, battery quality is light, memory-less effect, wide environmentally protective and operating temperature range and be widely used.From
Padhi in 1997 et al. is for the first time by the LiFePO of orthogonal olivine structural4For anode material for lithium-ion batteries, to the material
Research has been increasingly becoming the research hotspot of various countries' Scientific Research Workers.But LiFePO4Material electronics electrical conductivity and lithium ion
Diffusion coefficient is relatively low, causes its rate charge-discharge performance very poor, limits the application of the material.Effectively in LiFePO4
The surface coating conducting substance of particle, and by LiFePO4 particle miniaturization (about 100nm or less) to increase reaction table
Area is the research emphasis of current lithium iron phosphate positive material.
It needs to select source of iron, phosphorus source and lithium source, source of iron in LiFePO4 preparation process to be usually molysite, also there is part preparation
Extensive, the cheap iron oxide of process selection raw material sources, but iron oxide and H3PO4It is swift in response, presoma FePO4
Grain growth, which is reunited, to be precipitated, and 3 times of excessive lithium source (lithium sources are resulted in the need for：Source of iron：Phosphorus source is 3:1:It 1) can forward reaction generation phosphorus
Sour iron lithium causes reaction impurities content high, expensive, complicated for operation.So utilizing the LiFePO4 system that iron oxide is raw material
Standby technique multiselect lithium dihydrogen phosphate is as phosphorus source and lithium source, such as《A kind of preparation method of LiFePO 4 of anode material》(application number：
200910140333.3), but lithium dihydrogen phosphate cost is apparently higher than H3PO4And LiOH, cause production cost to remain high.
Invention content
The technical assignment of the present invention is to be directed to the above the deficiencies in the prior art, provides that a kind of step is simple, and production cost is low
The modified oxidized iron method for preparing carbon-coated LiFePO 4 for lithium ion batteries.
The present invention the technical solution to solve the technical problem is that：A kind of method that iron oxide modified prepares LiFePO4,
It is characterized in that：Step includes：
(1) prepared by pretreatment fluid：It weighs eucalyptus leaves to shred, be added in distilled water, heating water bath, membrane filtration, gained filter
Liquid is eucalyptus leaf extract, is stored in Brown Glass Brown glass bottles and jars only and continues to employ.
(2) prepared by modified oxidized iron：Take iron chloride, ammonium lauryl sulfate and eucalyptus leaf extract in mixed in reaction kettle
It closes, 2~4h is stirred to react at 60~80 DEG C, reaction product is cleaned, filtered, is dry, and modified oxidized iron is obtained；
(3) preparation of modified oxidized iron complex：It weighs modified oxidized iron to be added in enveloping agent solution, stir, stand
30min；
(4)FePO4·2H2It is prepared by O presomas：68ml H are added into the solution of step (3)3PO4(mass fraction
85%) it is 2.0~3.0, to adjust pH with 1mol/L ammonium hydroxide, stirs 1h, is aged, is filtered, washed, drying and pre-processed
FePO4·2H2O presomas；
(5) according to Fe：Li=1:1 weighs pretreatment FePO4·2H2O presomas lithium source and carbon source and dispersant, Yu Hang
Planetary ball mill ball milling 10min is uniformly mixed, and mixed material is transferred to lower 200~300 DEG C of burnings of nitrogen atmosphere protection in sintering furnace
1.5~2h of knot；
(6) mixed material is continuously heating to 650~750 DEG C after step (5) sintering, keeps the temperature 6~10h, naturally cools to room
Temperature obtains particle fine uniform, the complete carbon coating LiFePO of crystal form4。
In prioritization scheme, eucalyptus leaves are 300g, distilled water 5L, 80 DEG C of waters bath with thermostatic control 1.5h, 0.50um in step (1)
Membrane filtration.
The wherein described complexing agent is one kind in citric acid, polyethylene glycol, ethylenediamine tetra-acetic acid；Lithium source is
CH3COOLi·2H2O、LiOH、Li2C2O4One or more of dispersant be ethyl alcohol, methanol, one kind in acetone.
Compared with prior art, the present invention has advantageous effect following prominent：
1, intermediate product FePO can be improved by doing raw material with iron oxide4·2H2O granular precursors bond degree of aggregation, make
FePO4·2H2O granular precursor good dispersions；
2, using citric acid as chelating agent, citric acid orients chelates ferric ions, one layer of uniform lemon is formd on surface
Lemon acid film effectively prevents presoma FePO4The citric acid macromolecular of the fast-growth of particle, chelating is made with steric hindrance
With restrained effectively FePO4Reunion between crystal grain is decomposed to form carbon shell in subsequent low-temperature sintering and inhibits LiFePO4It is brilliant
The growth of grain；
3, segmented sintering can inhibit LiFePO4The growth of crystal grain obtains purity height, the uniform carbon coating of granule-morphology
LiFePO4；
4, secondary clacining addition mixed carbon source sucrose, starch, glucose etc., make carbon coating LiFePO4Good dispersion, carbon source
The big coordination aromatic rings of generation is decomposed under high temperature can improve the degree of graphitization of carbon residue, and electric conductivity and specific capacity ratio are once sintered
It wants high, makes battery material polarization in application process and impedance smaller.
5, the organic matter for using eucalyptus leaf extract in order to obtain more stable effect, in prioritization scheme and there are lone pair electrons
Act synergistically modified oxidized iron, so that iron oxide surface is organised, antioxidant present in eucalyptus leaf extract such as polyphenol, lemon
Alkene, reduced sugar, amino acid etc. can be used as reducing agent, on the one hand modified oxidized iron can utilize going back in eucalyptus leaf extract
Immunogenic substance further restores iron oxide, and the reunion growth of ferric oxide particles on the one hand can be also reduced as stabilizer.
Description of the drawings
Fig. 1 is the charge/discharge capacity figure of 1 product of the embodiment of the present invention.
Fig. 2 is the charge/discharge capacity figure of 2 product of the embodiment of the present invention.
Fig. 3 is the charge/discharge capacity figure of 3 product of the embodiment of the present invention.
Fig. 4 is the charge/discharge capacity figure of 4 product of the embodiment of the present invention.
Fig. 5 is the loop attenuation figure of 1~4 product of the embodiment of the present invention.
Specific implementation mode
The present invention is further described with specific implementation mode with reference to the accompanying drawings of the specification.
Embodiment 1
(1) prepared by modified oxidized iron：Mixing in 1mol iron chloride, 20gSDS (ammonium lauryl sulfate) reaction kettle is weighed,
3h is stirred to react at 80 DEG C, reaction product is cleaned, filtered, being dried to obtain SDS modified oxidized irons；
(2) it weighs 1mol modified oxidized irons to be added in the citric acid solution of 1L3mol/L, stirring stands 30min；
(3) 68ml H are added into the solution of step (2)3PO4(mass fraction 85%), adjusting pH with 1mol/L ammonium hydroxide is
2.0, stir 1h, be aged, be filtered, washed, dry obtain pre-process FePO4·2H2O presomas；SDS is anion surface active
Agent, the surface energy that can reduce ferric oxide particles hinder its reunion, reduce iron oxide grain size, increase specific surface area, but due to molten
Electronegative group C is ionized out in liquid12H25SO4 2-Replace the OH of iron oxide surface-, reduce iron oxide surface and carry out ligand friendship
The surface of the adsorption site changed, modified oxidized iron and phosphate anion is negatively charged, enhances electrostatic repulsion, reduces iron and phosphoric acid
The coagulation of root is reunited；
(4) it weighs and pre-processes FePO obtained by 1mol steps (3)4·2H2O presomas, 1.2mol CH3COOLi·2H2O,
20g sucrose, wherein iron lithium molar ratio are Fe:Li=1:1.2,100g ethyl alcohol is added, is mixed in planetary ball mill ball milling 10min
Uniformly, mixed material is transferred to the lower 200 DEG C of sintering 2h of nitrogen atmosphere protection in sintering furnace；
(5) mixed material is continuously heating to 650 DEG C after step (4) sintering, keeps the temperature 10h, cooled to room temperature, obtains
Grain fine uniform, the complete carbon coating LiFePO of crystal form4。
Embodiment 2
(1) prepared by pretreatment fluid：It weighs 300g eucalyptus leaves to shred, be added in 5L distilled water, 80 DEG C of water bath with thermostatic control 1.5h,
0.50um membrane filtrations, gained filtrate are eucalyptus leaf extract, are stored in Brown Glass Brown glass bottles and jars only and continue to employ.
(2) prepared by modified oxidized iron：Weigh 1mol iron chloride, 20gSDS (ammonium lauryl sulfate) and 1.0L eucalyptus leaves
It is mixed in extracting solution reaction kettle, is stirred to react 3h at 80 DEG C, reaction product is cleaned, filtered, being dried to obtain SDS modified oxidized irons；
Antioxidant present in eucalyptus leaf extract such as polyphenol, limonene, reduced sugar, amino acid etc. has reduction, by chlorination
Iron is added to eucalyptus leaf extract, and simultaneously heating water bath for a period of time, the reunion growth of ferric oxide particles can be reduced as stabilizer, is obtained
To the iron oxide that organises of favorable dispersibility；
(3) it weighs 1mol modified oxidized irons to be added in the citric acid solution of 1L1.1mol/L, stirring stands 30min；
(4) 68mlH is added into the solution of step (3)3PO4(mass fraction 85%), adjusting pH with 1mol/L ammonium hydroxide is
2.0, stir 1h, be aged, be filtered, washed, dry obtain pre-process FePO4·2H2O presomas；Contain in eucalyptus leaf extract
Atom has the polar group of lone pair electrons centered on oxygen-containing, and forming coordinate bond with the empty d tracks of iron atom passes through polycondensation, chela
The effects that conjunction, forms protective film and protects iron atom, and the part high polymer in eucalyptus leaf extract has the characteristic of electric charge transfer,
A large amount of charge-exchanges occur with iron ion in solution, and are effectively enriched in iron oxide surface, it can after the alcohol radical compounding in extracting solution
To be largely complexed with citrate, FePO is prevented4Particle aggregation；
(5) it weighs and pre-processes FePO obtained by 1mol steps (4)4·2H2O presomas, 1mol CH3COOLi·2H2O, 20g
Sucrose, wherein iron lithium molar ratio are Fe:Li=1:1,100g ethyl alcohol is added, is uniformly mixed in planetary ball mill ball milling 10min,
Mixed material is transferred to the lower 200 DEG C of sintering 2h of nitrogen atmosphere protection in sintering furnace；
(6) mixed material is continuously heating to 650 DEG C after step (5) sintering, keeps the temperature 10h, cooled to room temperature, obtains
Grain fine uniform, the complete carbon coating LiFePO of crystal form4.Polymer polyphenol, lemon during low-temperature sintering in folium eucalypti extracting solution
The dehydrations polycondensation such as lemon alkene, reducing sugar is coated on LiFePO4 surface, forms network-like carbon coating in situ, effectively inhibits high temperature
LiFePO4 particle is grown up in sintering process, so as to shorten the diffusion length of Li ions in charge and discharge process.Two under high temperature
Secondary cladding carbon source is decomposed is formed with conductive network on LiFePO4 surface, can not only prevent the reunion of particle, can also be quickly
Electronics, lithium ion to each carbon coating particle surface are conveyed, the cycle life of LiFePO 4 material charge and discharge is extended.
Embodiment 3：
(1) prepared by pretreatment fluid：It weighs 300g eucalyptus leaves to shred, be added in 5L distilled water, 80 DEG C of water bath with thermostatic control 1.5h,
0.50um membrane filtrations, gained filtrate are eucalyptus leaf extract, are stored in Brown Glass Brown glass bottles and jars only and continue to employ.
(2) prepared by modified oxidized iron：Weigh 1mol iron chloride, 30g polyethyleneimines and the reaction of 1.5L eucalyptus leaf extracts
It is mixed in kettle, is stirred to react 2h at 70 DEG C, reaction product is cleaned, filtered, being dried to obtain polyethyleneimine-modified iron oxide；
(3) it weighs 1mol modified oxidized irons to be added in the polyglycol solution of 1L30g/L, stirring stands 30min；
(4) 68mlH is added into the solution of step (3)3PO4(mass fraction 85%), adjusting pH with 1mol/L ammonium hydroxide is
2.0, stir 1h, be aged, be filtered, washed, dry obtain pre-process FePO4·2H2O presomas；Polyethyleneimine (PEI) is to contain
The compound for having poly- azacyclo-, the synergistic effects such as polyphenol, enol in solution and in eucalyptus liquid extract and metal iron ion
Forming complex makes iron oxide surface organise, because PEI contains in polar group amino and adsorpting anion phosphate radical, effectively
Prevent FePO4Reunite；
(5) it weighs and pre-processes FePO obtained by 1mol steps (4)4·2H2O presomas, 1mol LiOH, 25g glucose,
Middle iron lithium molar ratio is Fe:Li=1:1,80g acetone is added, is uniformly mixed in planetary ball mill ball milling 10min, mixture
Material is transferred to the lower 250 DEG C of sintering 1.5h of nitrogen atmosphere protection in sintering furnace；
(6) mixed material is continuously heating to 700 DEG C after step (5) sintering, keeps the temperature 8h, cooled to room temperature, obtains
Grain fine uniform, the complete carbon coating LiFePO of crystal form4。
Embodiment 4：
(1) prepared by pretreatment fluid：It weighs 300g eucalyptus leaves to shred, be added in 5L distilled water, 80 DEG C of water bath with thermostatic control 1.5h,
0.50um membrane filtrations, gained filtrate are eucalyptus leaf extract, are stored in Brown Glass Brown glass bottles and jars only and continue to employ.
(2) prepared by modified oxidized iron：It is anti-to weigh 1mol iron chloride, 40g iminodiacetic acids and 3.0L eucalyptus leaf extracts
Mixing in kettle is answered, is stirred to react 4h at 60 DEG C, reaction product is cleaned, filtered, being dried to obtain iminodiacetic acid modified oxidized iron；
(3) it weighs 1mol modified oxidized irons to be added in 1L40g/L edta solutions, stirring stands 30min；
(4) 68mlH is added into the solution of step (3)3PO4(mass fraction 85%), adjusting pH with 1mol/L ammonium hydroxide is
3.0, stir 1h, be aged, be filtered, washed, dry obtain pre-process FePO4·2H2O presomas；Iminodiacetic acid contains tool
There are N, O coordination atom of lone pair electrons, functional group-N (CH2COOH)2When being metal ion-chelant, N atoms provide lonely right
The empty d tracks of electronics and iron ion form coordinate bond, and carboxylic acid ion forms ionic bond, the two synergistic effect chela with metal ion
Cyclic structure is stablized in synthesis, and iminodiacetic acid is influencing to pre-process with the polymer collective effect in eucalyptus leaf extract
FePO4Presoma.
(5) it weighs and pre-processes FePO obtained by 1mol steps (4)4·2H2O presomas, 0.5mol Li2C2O4, 30g conduction charcoals
Black, wherein iron lithium molar ratio is Fe:Li=1:1,120g methanol is added, is uniformly mixed in planetary ball mill ball milling 10min, mixes
It closes material and is transferred to the lower 300 DEG C of sintering 1.5h of nitrogen atmosphere protection in sintering furnace；
(6) mixed material is continuously heating to 750 DEG C after step (5) sintering, keeps the temperature 6h, cooled to room temperature, obtains
Grain fine uniform, the complete carbon coating LiFePO of crystal form4。
1,2,3,4 50 DEG C of gained carbon-coated LiFePO 4 for lithium ion batteries positive electrode of embodiment, 10C charge/discharge capacities test result are as schemed
1, be respectively 144mAh/g, 148mAh/g, 151mAh/g, 153mAh/g shown in 2,3,4,100 efficiency of cycle as shown in figure 5,
1,2,3,4 gained carbon-coated LiFePO 4 for lithium ion batteries positive electrode of embodiment recycles 100 efficiency and is held in 87% or more.
It should be noted that the present invention particular embodiment to the present invention have been described in detail, for ability
For the technical staff in domain, its various of progress is obviously changed without departing from the spirit and scope of the present invention
Become all within protection scope of the present invention.
Claims (5)
1. a kind of method that iron oxide modified prepares LiFePO4, it is characterised in that：Step includes：
(1) prepared by pretreatment fluid：It weighs eucalyptus leaves to shred, be added in distilled water, heating water bath, membrane filtration, gained filtrate is
For eucalyptus leaf extract, it is stored in Brown Glass Brown glass bottles and jars only and continues to employ.
(2) prepared by modified oxidized iron：Take iron chloride, ammonium lauryl sulfate and eucalyptus leaf extract in being mixed in reaction kettle, 60
2~4h is stirred to react at~80 DEG C, reaction product is cleaned, filtered, is dry, and modified oxidized iron is obtained；
(3) preparation of modified oxidized iron complex：It weighs modified oxidized iron to be added in enveloping agent solution, stirring stands 30min；
(4)FePO4·2H2It is prepared by O presomas：68ml H are added into the solution of step (3)3PO4(mass fraction 85%) is used
1mol/L ammonium hydroxide adjust pH be 2.0~3.0, stir 1h, be aged, be filtered, washed, dry obtain pre-process FePO4·2H2O forerunner
Body；
(5) according to Fe：Li=1:1 weighs pretreatment FePO4·2H2O presomas lithium source and carbon source and dispersant, in planetary
Ball mill ball milling 10min is uniformly mixed, and mixed material is transferred to lower 200~300 DEG C of sintering 1.5 of nitrogen atmosphere protection in sintering furnace
~2h；
(6) mixed material is continuously heating to 650~750 DEG C after step (5) sintering, keeps the temperature 6~10h, cooled to room temperature obtains
To particle fine uniform, the complete carbon coating LiFePO of crystal form4。
2. the method that modified oxidized iron according to claim 1 prepares carbon-coated LiFePO 4 for lithium ion batteries, it is characterised in that：Step
(1) eucalyptus leaves are 300g, distilled water 5L, 80 DEG C of water bath with thermostatic control 1.5h, 0.50um membrane filtrations in.
3. the method that modified oxidized iron according to claim 1 prepares carbon-coated LiFePO 4 for lithium ion batteries, it is characterised in that：The network
Mixture is one kind in citric acid, polyethylene glycol, ethylenediamine tetra-acetic acid.
4. the method that modified oxidized iron according to claim 1 prepares carbon-coated LiFePO 4 for lithium ion batteries, it is characterised in that：The lithium
Source is CH3COOLi·2H2O、LiOH、Li2C2O4One or more of.
5. the method that modified oxidized iron according to claim 1 prepares carbon-coated LiFePO 4 for lithium ion batteries, it is characterised in that：Described point
Powder is one kind in ethyl alcohol, methanol, acetone.
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| CN117842956A (en) * | 2024-01-08 | 2024-04-09 | 广东惠云钛业股份有限公司 | High-performance stable ferric phosphate and preparation method thereof |
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| CN107879379B (en) * | 2017-11-07 | 2019-11-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of carbon coating ferric oxide nano pipe and products thereof and application |
| CN110272072B (en) * | 2019-06-20 | 2020-04-28 | 河南大学 | Rivet-shaped nano iron oxide, and preparation method and application thereof |
| CN111908513A (en) * | 2020-07-08 | 2020-11-10 | 傅尚真 | Mesomorphic iron oxide material for dye adsorption and preparation method thereof |
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