CN101924204A - Method for preparing conducting film LiFePO4 cladding material containing nitrogen - Google Patents
Method for preparing conducting film LiFePO4 cladding material containing nitrogen Download PDFInfo
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- CN101924204A CN101924204A CN2010100398222A CN201010039822A CN101924204A CN 101924204 A CN101924204 A CN 101924204A CN 2010100398222 A CN2010100398222 A CN 2010100398222A CN 201010039822 A CN201010039822 A CN 201010039822A CN 101924204 A CN101924204 A CN 101924204A
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- lifepo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 27
- 229910052493 LiFePO4 Inorganic materials 0.000 title abstract description 3
- 238000005253 cladding Methods 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 56
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 45
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000010453 quartz Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 7
- 229910010710 LiFePO Inorganic materials 0.000 claims description 43
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 32
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 24
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 239000000376 reactant Substances 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 7
- 230000033228 biological regulation Effects 0.000 claims description 2
- 238000005255 carburizing Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 24
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 238000010438 heat treatment Methods 0.000 abstract description 17
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000010287 polarization Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 2
- RTOYJIFECJCKIK-UHFFFAOYSA-K iron(3+) phosphate tetrahydrate Chemical compound O.O.O.O.[Fe+3].[O-]P([O-])([O-])=O RTOYJIFECJCKIK-UHFFFAOYSA-K 0.000 abstract 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 56
- 239000002245 particle Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 17
- 230000006641 stabilisation Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 238000011105 stabilization Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 238000007363 ring formation reaction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007888 film coating Substances 0.000 description 4
- 238000009501 film coating Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000010450 olivine Substances 0.000 description 4
- 229910052609 olivine Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- -1 aromatic hydrocarbon Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 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 1
- 241000826860 Trapezium Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 102000057593 human F8 Human genes 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 239000006210 lotion Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229940047431 recombinate Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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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 relates to a preparation method of a lithium ion battery anode material, aiming to provide a method for preparing a conducting film LiFePO4 cladding material containing nitrogen. The method comprises the following steps of: ball milling and mixing FePO4.4H2O, LiOH.H2O and a polyacrylonitrile emulsion, blending into a paste and putting the paste into a quartz reactor; regulating and controlling the microwave output power and controlling the reaction temperature to be at 150 DEG C; raising the microwave output power in an oxygen atmosphere and heating up to 300 DEG C from 150 DEG C; switching to a highly pure nitrogen atmosphere, raising the microwave output power and heating up to 600 DEG C from 300 DEG C; and continuously raising the microwave output power under the highly pure nitrogen atmosphere and annealing at 700-800 DEG C for denitrifying. Nitrogen atoms remain on the conducting carbon film formed by the invention, and lone pair electrons of the nitrogen atoms can effectively improve the conductivity of the carbon film so as to improve electrochemical and dynamic properties of the anode, reduce the electrode polarization and improve the velocity volume of the lithium cell, thus the invention can be applied to power cells of electric vehicles.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, particularly nitrogenous conducting polymer coats LiFePO
4Material, the LiFePO that utilizes the nitrogenous conductive carbon film of temperature control microwave prepared in reaction to coat
4Method.
Background technology
In light weight, advantages such as capacity big, memory-less effect that lithium ion battery has, thereby obtained widespread usage.Present many digital equipments have all adopted lithium ion battery to make power supply.The energy density of lithium ion battery is very high, and its capacity is 1.5~2 times with the Ni-MH battery of weight, and to have very low self-discharge rate, do not contain advantages such as Toxic matter be the major reason of its extensive use.Lithium ion battery is owing to use LiCoO at present
2As positive electrode, relatively more expensive comparatively speaking.
Since initiative proposition anode material for lithium-ion batteries LiFePO such as Padhi in 1997
4Since, LiFePO
4Become one of research focus of rechargeable lithium ion batteries positive electrode.With respect to other lithium ion cell positive alternative materials, LiFePO
4Advantage with self: (1) is high theoretical capacity (170mAh/g) relatively, and the charging/discharging voltage platform makes organic bath safer in battery applications stably; (2) good electrode reaction invertibity; (3) good chemical stability and thermal stability; (4) cheap and be easy to preparation; (5) pollution-free; Safer when (6) handling with operation.
Traditional viewpoint is thought, LiFePO
4Be two phase reaction when in battery, discharging and recharging:
Charging (taking off lithium): LiFePO
4-xLi
+-xe
-→ xFePO
4+ (1-x) LiFePO
4
Discharge (embedding lithium): FePO
4+ xe+xLi
+→ xLiFePO
4+ (1-x) FePO
4
During electricity, Li
+From FeO
6Layer moves out, enters negative pole, Fe through electrolyte
2+Be oxidized to Fe
3+, electronics then arrives negative pole through conductive agent and the collector that is in contact with one another from external circuit; Discharge process then in contrast.
Lithium ion battery is in charge and discharge process, and lithium ion takes off/the embedding process is at LiFePO
4/ FePO
4Taking off/the embedding process of two-phase interface.During charging, two-phase interface is inwardly nuclear propulsion constantly, outer field LiFePO
4Constantly change FePO into
4, constantly the two-phase interface by new formation is keeping effective current for lithium ion and electronics, but the diffusion rate of lithium ion is constant under certain condition, along with dwindling of two-phase interface, the diffusing capacity of lithium ion is not enough to keep effective current the most at last, like this, and the LiFePO of bulky grain kernel portion
4Can not be fully utilized, thereby cause capacitance loss.
There is report to utilize acrylic resin and LiOH and FePO
4The synthetic carbon of reaction coats LiFePO
4Synthetic method (JournalofThe Electrochemical Society, 152 (2005) A483-A487), can improve LiFePO
4The electrochemical reaction dynamics of electrode improves LiFePO
4Electrode life.But this method is with LiOH and FePO
4Mix and needed ball milling 2 hours, and need heat treatment at high temperature 10 hours, and inapplicable suitability for industrialized production LiFePO
4
The capacity of lithium ion battery is that positive electrode capacity limits, and the capacity of lithium ion battery depends on positive electrode capacity.Traditional LiFePO
4Preparation technology adopts dry powder blend, heat treatment at high temperature 10 hours.Because dry powder blend causes uneven components easily, and heat inhomogeneous or heat conduction inhomogeneous, finally all can cause product quality problem, thereby influence the capacity and the cycle life of lithium ion battery, and LiFePO
4The traditional handicraft production cycle also longer.Traditional electrical heating relies on outer heating by heat exchange pattern the material bed tempertaure to be raise heat, because FePO4 and LiOH poor thermal conductivity, the temperature distributing disproportionation that is easy to generate reaction bed is even and reaction speed that cause is unbalanced, causes LiFePO
4The rate of crystalline growth disunity is difficult to control LiFePO
4The shape of crystal and size.
Microwave heating is to heat by " dielectric loss ".Molecule with permanent dipole produces resonance frequency up to 4.9x10 in the electromagnetic field of 2450MHz
9Inferior/s, the ultrahigh speed rotation increases sharply (temperature rising) the molecule mean kinetic energy, and perhaps Ionized material because of friction produces thermal effect, is interior mode of heating in hyperfrequency electromagnetic field high speed vibration (conduction).The thermal effect that is produced depend on ionic size, electric charge what, conductive performance and with the interaction of solvent.Have the compound of big dielectric constant such as water, ethanol, LiOH, FePO
4, polyacrylonitrile, can be heated rapidly under microwave action; And little compound such as aromatic hydrocarbon, the aliphatic hydrocarbon of polarity or do not have compound such as carbon dioxide, dioxane, carbon tetrachloride and the highly crystalline carbon of clean dipole is poor to microwave energy absorption, is difficult for being heated.
In order to shorten LiFePO
4Generated time, reduce reaction temperature, control LiFePO
4The shape of crystal and size, the quality of raising product improves LiFePO
4The electrochemical reaction dynamics of electrode improves LiFePO
4Electrode life, there is Chinese invention patent " a kind of microwave synthesis method of carbon-coated LiFePO 4 for lithium ion batteries " (CN200510086594.3) to report: to press stoichiometry with lithium carbonate, ferrous oxalate and ammonium dihydrogen phosphate, an amount of thermal conducting agent and the organic substance that is used to carry out the carbon coating: the saccharide compound of poly-hydrocarbon compound such as polyethylene or sucrose, starch, make the abundant ground and mixed of dispersant with absolute ethyl alcohol, be pressed into bulk after drying, put into the crucible that active carbon is housed, crucible is placed the microwave field radiation heating, can make mutually the evenly LiFePO4 of carbon coating.
In electrode, add the conductivity that nitrogenous conducting polymer composite can significantly improve electrode material, have the carbon based cobaltous hydroxide of patent report (CN200910098410.3) polypyrrole modifying to have good electro catalytic activity.Compare with graphite, the nitrogen in polypyrrole, polyaniline or the polyacrylonitrile can increase the concentration of conjugated pi electron owing to the existence of its lone pair electrons, thereby can obtain surpassing the conductivity of graphite.
The present invention proposes the wet-mixed raw material, the LiFePO that utilizes synthetic nitrogenous conductive carbon film with high conductivity of one step of temperature control microwave heating to coat
4Material.Be with the difference of patent (CN200510086594.3): the conducting film of formation is different, and synthesis step is different with conducting film formation mechanism, and the unreal trip temperature control of patent (CN200510086594.3) is difficult to guarantee product quality.And temperature is controlled at LiFePO
4Synthesis technique in, no matter be at control LiFePO
4Granularity, vpg connection, still aspect control of product quality, all play decisive action.Use polyacrylonitrile to carry out temperature control microwave and add the LiFePO that the nitrogenous conductive carbon film of thermal synthesis coats as raw material
4Material does not still have successful precedent, does not see the LiFePO that has nitrogenous conductive carbon film to coat yet
4The report of material.
Summary of the invention
The technical problem to be solved in the present invention is, a kind of efficient energy-saving is provided, and synthetic have a LiFePO that high-performance, high-quality nitrogenous conductive carbon film coat
4Preparation methods.
For the technical solution problem, the preparation method in the technical scheme provided by the invention comprises step:
(1) getting purity is 99.99% FePO
44H
2O and purity are 99.99% LiOH H
2O and polyacrylonitrile emulsion (40wt%) are pressed mass ratio 9.31: 1: 5~20, and ball milling mixed 10~30 minutes, was modulated into paste, put into quartz reactor, and the regulation and control microwave output power makes temperature of charge be controlled at 150 ℃.Partial melting takes place in this moment, begins to take place dehydration, forms anhydrous FePO
4With the LiOH mixture, polyacrylonitrile emulsion dehydration back forms polyacrylonitrile film and covers FePO
4On LiOH mixture particle.By adjusting FePO
44H
2O, LiOHH
2O and polyacrylonitrile emulsion blending ratio and ball milling speed (200~800rpm) and time may command dehydration back form FePO
4Shape and size with LiOH mixture particle.
(2) strengthen microwave output power gradually under oxygen atmosphere, the temperature rise control that makes reactant is heated to 300 ℃ at 1~2 ℃/min from 150 ℃, and cyclization, dehydrogenation reaction and the oxidation reaction of polyacrylonitrile takes place this moment, and the stabilization procedures of polyacrylonitrile film takes place.Molecular structure changes carbon-to-nitrogen double bon (C=N) ring structure that contracts, promptly so-called trapezium structure into by polyene structure.In stabilization procedures, the attached cyano group group of polyacrylonitrile, commissure macromolecular structure in echelon at first, this process can add a small amount of 2-methylene-succinic acid and carry out catalysis.In stabilization procedures, oxygen molecule also participates in the ladderlike polymer reaction, thereby several trapezoidal molecular structures may occur.Polyacrylonitrile film causes film to shrink after process cyclization and stabilisation, because polyacrylonitrile film coats FePO
4On LiOH mixture particle, stoped the contraction of film on area to take place, but therefore the thickness of film reduce.
(3) oxygen atmosphere is switched to continuation increasing microwave output power under the high pure nitrogen atmosphere, the temperature rise control that makes reactant is heated to 600 ℃, the carbonisation of generation polyacrylonitrile film, formation graphite-like structure at 3~5 ℃/min from 300 ℃.High purity nitrogen among the present invention is meant that purity is 99.99% nitrogen.At the carburizing reagent initial stage, temperature is 400~500 ℃ of scopes, and the hydroxy that is present in the already oxidised polyacrylonitrile begins to carry out the commissure condensation reaction, helps cyclisation partly to recombinate and engage, this cross-linking reaction is fixed the macromolecular structure of silicon carbide/polypropylene nitrile film, as shown in Figure 1.Remaining linear structure partly becomes cyclisation or carries out chain splitting and discharge reducibility gas such as hydrogen.These cyclized structure carry out dehydrogenation reaction, and begin to connect in side surface direction, produce three hexagons that side surface direction forms by the nitrogen-atoms bond and form and so on graphite-structure, the conductive carbon film coating layer, as shown in Figure 2.Meanwhile, FePO
4In being reduced property of ferric iron gas such as the hydrogen reducing LiFePO that forms ferrous iron and LiOH reaction generation olivine structural
4:
2FePO
4+2LiOH+H
2→2LiFePO
4+2H
2O
(4) under the high pure nitrogen atmosphere, continue to strengthen microwave output power, make temperature of charge reach 700~800 ℃ of denitrogenations of annealing, make the conductive carbon film growth more complete, as shown in Figure 3, eliminate the stress in the conductive carbon film coating layer, finally form the LiFePO that conductive carbon film coats
4Material.
Among the present invention, in the conductive carbon film that forms, nitrogen content depends on the time of 700~800 ℃ of denitrogenations of annealing, and the time, long more nitrogen content was low more.Because nitrogen has lone pair electrons, it has facilitation for the conduction of the conjugated pi electron of graphite-like structure.But nitrogen content is too high, will cause the incomplete of conductive carbon film growth, and is unfavorable to the conductivity of electrode.Therefore for the positive electrode of different purposes, the time that should control corresponding denitrogenation is 1~5 hour.Among the present invention, the percentage by weight of nitrogen in conducting film is 0.1~1wt.%.
Among the present invention, adopt temperature control microwave to add thermal synthesis, effectively controlled the LiFePO that conductive carbon film coats
4Shape and size, can obtain the LiFePO of particle diameter less than 100nm
4Spheroidal particle, residual LiFePO in the time of can avoiding charging
4The appearance of phase improves charge/discharge capacity.
Among the present invention, adopt accurate infrared measurement of temperature method, by infrared signal controlled microwave power output, to arrive the purpose of accurate control programming rate and reaction temperature.
Among the present invention, because at LiFePO
4Particle shape has become the nitrogenous carbon film of high conductivity, because the lone pair electrons of nitrogen have been strengthened the flowability of conjugated pi electron in the carbon film graphite-like structure, improve the conductivity of carbon film, played the function of current collection effectively, anodal conductivity is greatly improved, need not in the preparation process of electrode, to add conductive agent in addition, thereby improved anodal capacity.Limit because the capacity of lithium ion battery is a positive electrode capacity, therefore also just improved the capacity of lithium ion battery.
Among the present invention, the LiFePO that conductive carbon film coats
4During as the positive electrode of lithium ion battery, because LiFePO
4Particle is among the coating of conductive carbon film, and lithium ion battery is LiFePO in charge and discharge process
4The change in volume that the taking off of lithium ion/embedding caused all coats in the capsule at conductive carbon film and takes place, and can not cause coming off of positive electrode, stable anodal structure, thereby the life-span of improving lithium ion battery.This point is showing particularly outstandingly aspect the high power charging-discharging cycle life that improves lithium ion battery.
The beneficial effect that the present invention has:
The present invention utilizes microwave can only heat the characteristics of polar molecule, carries out FePO
4With the individuality heating of LiOH mixture particle, eliminate FePO
4The even reaction speed that causes of temperature distributing disproportionation of the reaction bed that produces because of poor thermal conductivity with LiOH is unbalanced, LiFePO
4The skimble-scamble problem of rate of crystalline growth accurately and fast control reaction temperature and reaction time, forms LiFePO thereby control effectively
4Shape and size.And in the conductive carbon film forming process, in case form nonpolar complete carbon film, microwave heating is just ineffective, and therefore, microwave heating always forms the forward position at carbon film and plays heat effect.And microwave action causes resonance on oxygen, hydrogen and the nitrogen-atoms of polar binding, helps the cyclization of polyacrylonitrile and dehydrogenation subsequently and denitrification reaction, helps the formation of conductive carbon film.Can not occur because the inhomogeneous or incomplete defective that causes of the inhomogeneous reaction that occurs of heat conduction of heating.
Adopt accurate infrared measurement of temperature method,, can accurately control programming rate and reaction temperature, thereby avoid causing LiFePO when reacting by infrared signal controlled microwave power output
4The crystal forming core is inhomogeneous, avoids non-spherical LiFePO
4The formation of crystal, the LiFePO of formation
4The crystalline size consistency is better.Accurately the control programming rate can make carbon film grow up fully, forms and coats LiFePO fully
4The carbon film of particle makes the nitrogen content in the carbon film controlled, and the carbon film conductivity that obtains is better.Use the synthetic LiFePO of temperature control microwave heating of the present invention
4, form and coat LiFePO fully
4The carbon film of particle, LiFePO
4The LiFePO that the size of crystal more consistent (as shown in Figure 4), its capacity and speed capabilities are all synthetic than traditional heating or common microwave is synthetic
4Want high (as shown in Figure 5).
Remaining on the conductive carbon film that forms among the present invention have a nitrogen-atoms, its lone pair electrons can effectively improve the conductivity of carbon film, thereby improve anodal electrochemical kinetics performance, reduce electrode polarization, improve the speed capabilities of lithium battery, can be applicable to the electrokinetic cell of electric automobile.
Description of drawings
Fig. 1 is the film stabilization procedures of polyacrylonitrile film through generation dehydration behind the cyclization.
Fig. 2 is the dehydrogenation carbonisation of polyacrylonitrile film through film stabilization procedures caudacoria.
Fig. 3 is the denitrogenation growth course of polyacrylonitrile film through film stabilization procedures, dehydrogenation carbonisation caudacoria.
The ball shaped nano LiFePO that Fig. 4 coats for the nitrogenous conductive carbon film for preparing among the embodiment
4The material transmission electron microscope photo.
The ball shaped nano LiFePO that Fig. 5 coats for the nitrogenous conductive carbon film for preparing among the embodiment
4Synthesize LiFePO for the capacity result of positive electrode and with common microwave
4And the synthetic LiFePO of traditional heating
4Capacity Ratio.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail:
Embodiment one: Paste Preparation
Getting 222.9 gram purity is 99.99% FePO
44H
2O and purity are 99.99% LiOH H
2O, polyacrylonitrile emulsion (40wt%) were pressed mass ratio 9.31: 1: 5, placed ball grinder to mix 10 minutes with the 800rpm ball milling, were modulated into paste.
Embodiment two: the lotion dehydration
Getting 222.9 gram purity is 99.99% FePO
44H
2O and purity are 99.99% LiOH H
2O and polyacrylonitrile emulsion (40wt%) were pressed mass ratio 9.31: 1: 15, placed ball grinder to mix 20 minutes with the rotating speed ball milling of 600rpm, were modulated into paste, put into quartz reactor, and the adjustment microwave output power is 1KW, makes temperature of charge be controlled at 150 ℃.FePO takes place
44H
2O and LiOHH
2The emulsion polymerisation of O and polyacrylonitrile and dehydration form the spherical FePO that polyacrylonitrile film coats
4With the LiOH mixture.FePO
4With the particle diameter of LiOH less than 100nm.
Embodiment three: the formation blank of carbonized film
Getting 222.9 gram purity is 99.99% FePO
44H
2O and purity are 99.99% LiOH H
2O and polyacrylonitrile emulsion (40wt%) were pressed mass ratio 9.31: 1: 20, placed ball grinder to mix 30 minutes with the rotating speed ball milling of 200rpm, were modulated into paste, put into quartz reactor, and the adjustment microwave output power is 1KW, makes temperature of charge be controlled at 150 ℃.FePO takes place
44H
2O and LiOHH
2The emulsion polymerisation of O and polyacrylonitrile and dehydration form the FePO that polyacrylonitrile film coats
4With the LiOH mixture.With the speed aerating oxygen of 10mL/min, strengthen microwave output power in the reactor, the temperature rise control that makes reactant is heated to 300 ℃ at 1 ℃/min from 150 ℃, and this moment is at spherical FePO
4Cyclization and stabilization procedures with polyacrylonitrile film takes place on the LiOH mixture particle form incomplete carbonized film.
Embodiment four: LiFePO
4Formation and the growth of carbonized film
Getting 222.9 gram purity is 99.99% FePO
44H
2O and purity are 99.99% LiOHH
2O and polyacrylonitrile emulsion (40wt%) were pressed mass ratio 9.31: 1: 20, placed ball grinder to mix 30 minutes with the rotating speed ball milling of 400rpm, were modulated into paste, put into quartz reactor, and the adjustment microwave output power is 1KW, makes temperature of charge be controlled at 150 ℃.FePO takes place
44H
2O and LiOHH
2The emulsion polymerisation of O and polyacrylonitrile and dehydration form FePO4 and LiOH mixture that polyacrylonitrile film coats.With the speed aerating oxygen of 10mL/min, strengthen microwave output power to 1.5KW in the reactor, the temperature rise control that makes reactant is heated to 300 ℃ at 2 ℃/min from 150 ℃, and this moment is at FePO
4With cyclization and stabilization procedures that polyacrylonitrile film takes place on the LiOH mixture particle.Oxygen atmosphere is switched to (10mL/min) continuation increasing microwave output power (1.6KW) under the high pure nitrogen atmosphere, the temperature rise control that makes reactant is at 4 ℃/min, be heated to 600 ℃, the carbonisation of generation polyacrylonitrile film, formation graphite-like structure release reducibility gas hydrogen from 300 ℃.FePO
4In ferric iron formed the LiFePO of ferrous iron and LiOH reaction generation olivine structural by hydrogen reducing
4, particle diameter is less than 100nm.Begin to take shape the spherical LiFePO that nitrogenous carbonized film coats
4
Embodiment five: the ball shaped nano LiFePO that nitrogenous carbonized film coats
4Preparation
Getting 222.9 gram purity is 99.99% FePO
44H
2O and purity are 99.99% LiOHH
2O and polyacrylonitrile emulsion (40wt%) were pressed mass ratio 9.31: 1: 20, placed ball grinder to mix 30 minutes with the rotating speed ball milling of 400rpm, were modulated into paste, put into quartz reactor, and the adjustment microwave output power is 1KW, makes temperature of charge be controlled at 150 ℃.FePO takes place
44H
2O and LiOHH
2The emulsion polymerisation of O and polyacrylonitrile and dehydration form the FePO that polyacrylonitrile film coats
4With the LiOH mixture.With the speed aerating oxygen of 10mL/min, strengthen microwave output power to 1.5KW in the reactor, the temperature rise control that makes reactant is heated to 300 ℃ at 2 ℃/min from 150 ℃, and this moment is at FePO
4With cyclization and stabilization procedures that polyacrylonitrile film takes place on the LiOH mixture particle.Oxygen atmosphere is switched to (10mL/min) continuation increasing microwave output power (1.6KW) under the high pure nitrogen atmosphere, the temperature rise control that makes reactant is at 5 ℃/min, be heated to 600 ℃, the carbonisation of generation polyacrylonitrile film, formation graphite-like structure release reducibility gas hydrogen from 300 ℃.FePO
4In ferric iron formed the LiFePO of ferrous iron and LiOH reaction generation olivine structural by hydrogen reducing
4, particle diameter is less than 100nm.Under the high pure nitrogen atmosphere, continue to strengthen microwave output power (2KW), make temperature of charge reach 800 ℃ of denitrogenations 1 hour of annealing, make the conductive carbon film growth more complete, form the ball shaped nano LiFePO that nitrogenous conductive carbon film coats
4Material, as shown in Figure 4.Detect through XPS, the content of nitrogen in the nitrogenous film of conduction is 0.1wt.%.
Embodiment six: the ball shaped nano LiFePO that nitrogenous carbonized film coats
4Lithium ion battery for positive pole
Getting 222.9 gram purity is 99.99% FePO
44H
2O and purity are 99.99% LiOHH
2O and polyacrylonitrile emulsion (40wt%) were pressed mass ratio 9.31: 1: 20, placed ball grinder to mix 30 minutes with the rotating speed ball milling of 400rpm, were modulated into paste, put into quartz reactor, and the adjustment microwave output power is 1KW, makes temperature of charge be controlled at 150 ℃.FePO takes place
44H
2O and LiOHH
2The emulsion polymerisation of O and polyacrylonitrile and dehydration form the FePO that polyacrylonitrile film coats
4With the LiOH mixture.With the speed aerating oxygen of 10mL/min, strengthen microwave output power to 1.5KW in the reactor, the temperature rise control that makes reactant is heated to 300 ℃ at 2 ℃/min from 150 ℃, and this moment is at FePO
4With cyclization and stabilization procedures that polyacrylonitrile film takes place on the LiOH mixture particle.Oxygen atmosphere is switched to (10mL/min) continuation increasing microwave output power (1.6KW) under the high pure nitrogen atmosphere, the temperature rise control that makes reactant is at 5 ℃/min, be heated to 600 ℃, the carbonisation of generation polyacrylonitrile film, formation graphite-like structure release reducibility gas hydrogen from 300 ℃.FePO
4In ferric iron formed the LiFePO of ferrous iron and LiOH reaction generation olivine structural by hydrogen reducing
4, particle diameter is less than 100nm.Under the high pure nitrogen atmosphere, continue to strengthen microwave output power (1.8KW), make temperature of charge reach 700 ℃ of denitrogenations 5 hours of annealing, make the conductive carbon film growth more complete, form the ball shaped nano LiFePO that nitrogenous conductive carbon film coats
4Material.Detect through XPS, the content of nitrogen in conductive carbon film is 1wt.%.
Getting 1 gram above-mentioned positive electrode and PVDF and ethanol is to mix at 90: 10: 20 to add ethanol and be modulated into slurry according to mass ratio, is coated on the aluminium foil, dries to make electrode after suppressing.With the lithium metal is negative pole, and the PP nonwoven fabrics is a barrier film, and electrolyte is 1mol/L LiPF
6Ethylene carbonate (EC)+dimethyl carbonate (DMC)+methyl ethyl carbonate (EMC) (volume ratio is 1: 1: 1) mixed solution, in glove box, be assembled into button cell, carry out volume test under the electric current of 0.1~10C, Fig. 5 is the ball shaped nano LiFePO of the nitrogenous conductive carbon film coating of preparation
4The volume test result.Coat LiFePO with the synthetic carbon film of common microwave
4And traditional electrical adds thermal synthesis carbon film coating LiFePO
4Compare the ball shaped nano LiFePO that the synthetic nitrogenous conductive carbon film of temperature control microwave coats
4The capacity high-rate discharge ability be improved significantly, be that the synthetic carbon film of common microwave coats LiFePO
41.47 times, be that traditional electrical adds the thermal synthesis carbon film and coats LiFePO
41.36 times.
What more than announce at last, only is specific embodiments of the invention.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (4)
1. a nitrogenous conductive carbon film coats LiFePO
4Preparation methods may further comprise the steps:
(1) with mass ratio is 9.31: 1: 5~20 FePO
44H
2O, LiOHH
2The polyacrylonitrile emulsion of O and 40wt% was mixed 10~30 minutes with the speed ball milling of 200~800rpm, put into quartz reactor after being modulated into paste, and the regulation and control microwave output power makes temperature of charge be controlled at 150 ℃ and dewaters and the polyacrylonitrile emulsion polymerisation;
(2) strengthen microwave output power under oxygen atmosphere, the temperature rise of control reactant is 1~2 ℃/min, is heated to 300 ℃, formation carbonized film blank from 150 ℃;
(3) switch to the high pure nitrogen atmosphere from oxygen atmosphere, continue to strengthen microwave output power, the temperature rise of control reactant is 3~5 ℃/min, be heated to 600 ℃ from 300 ℃, the carbonization that polyacrylonitrile film takes place forms graphite-like structure, at the carburizing reagent initial stage of temperature, begin to take shape the spherical LiFePO that carbonized film coats at 400~500 ℃
4
(4) be to continue under 99.99% the blanket of nitrogen to strengthen microwave output power in purity, make temperature of charge reach 700~800 ℃ of denitrogenations of annealing, form the LiFePO that nitrogenous conductive carbon film coats
4Material product.
2. coat LiFePO according to the described nitrogenous conductive carbon film of claim 1
4Preparation methods is characterized in that, in the step (4), the time of control annealing denitrogenation is 1~5 hour.
3. coat LiFePO according to the described nitrogenous conductive carbon film of claim 1
4Preparation methods is characterized in that, described FePO
44H
2O, LiOHH
2O purity is 99.99%.
4. coat LiFePO according to the described nitrogenous conductive carbon film of claim 1
4Preparation methods is characterized in that, the percentage by weight of nitrogen in conducting film is 0.1~1wt.%.
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