CN103208626A - Method for preparing lithium iron phosphate/carbon composite material by using aniline - Google Patents
Method for preparing lithium iron phosphate/carbon composite material by using aniline Download PDFInfo
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- CN103208626A CN103208626A CN2012100137842A CN201210013784A CN103208626A CN 103208626 A CN103208626 A CN 103208626A CN 2012100137842 A CN2012100137842 A CN 2012100137842A CN 201210013784 A CN201210013784 A CN 201210013784A CN 103208626 A CN103208626 A CN 103208626A
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- China
- Prior art keywords
- aniline
- phosphate
- lithium iron
- fepo4
- iron phosphate
- Prior art date
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 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 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 47
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 47
- 229920000767 polyaniline Polymers 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 17
- 239000011574 phosphorus Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 22
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 20
- 239000005955 Ferric phosphate Substances 0.000 claims description 17
- 229940032958 ferric phosphate Drugs 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 10
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 10
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 235000019628 coolness Nutrition 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 23
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 3
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 230000002687 intercalation Effects 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 16
- 229910010710 LiFePO Inorganic materials 0.000 description 10
- 229910052493 LiFePO4 Inorganic materials 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 241000143437 Aciculosporium take Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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 method for preparing a lithium iron phosphate/carbon composite material by using aniline. The method comprises the steps that: trivalent iron salt and a phosphorus-containing compound are respectively dissolved in a certain amount of deionized water, such that solutions are prepared; a proper amount of aniline is dropped into the phosphorus-containing compound solution, and the mixture is stirred, such that the mixture is uniformly dispersed; the trivalent iron salt solution is slowly dropped into the water-soluble phosphorus-containing compound solution comprising aniline; the mixture is stirred for 3-5h under room temperature, such that a FePO4/PANI precursor is synthesized. During the process, when Fe<3+> enters the water solution comprising PO4<3-> and aniline, FePO4 precipitate is first precipitated; simultaneously, Fe<3+> serves as a catalyst for promoting an oxidative polymerization reaction of aniline on the surface of FePO4 particles, such that polyaniline is produced and coated on the surface of FePO4. Therefore, FePO4 particle growth is effectively limited, and the FePO4/PANI precursor with relatively small particle size is obtained. Lithium intercalation is carried out upon the FePO4/PANI precursor, such that lithium iron phosphate/carbon is obtained. With the method, prepared lithium iron phosphate/carbon has the advantages of small particles and excellent electrochemical properties.
Description
Technical field
The invention belongs to technical field of lithium ion, particularly relate to the preparation method of a kind of LiFePO4/carbon for lithium ion cell positive (LiFePO4/C) composite material.
Background technology
LiFePO4 (LiFePO
4) and cobalt-lithium oxide (LiCoO
2) and other positive electrodes compare the advantages that have long service life, abundant raw material, cost are low, specific capacity is higher, thermal stability is high, cyclical stability is good, environmental friendliness etc. is outstanding.First the LiFePO4 of quadrature olivine structural is used for anode material for lithium-ion batteries from people such as Padhi in 19997, the research of this material has been become various countries research work personnel's research focus gradually, is a kind of anode material for lithium-ion batteries that has application potential.But LiFePO
4The electronic conductivity (10 that material is low
-9～10
-10S/cm) and lithium ion diffusion coefficient (1.8x10
-14Cm
2/ S), cause its rate charge-discharge performance extreme difference, limited the application of this material.
Existing research report (Fisher, C.A.J.; Prieto, V.M.H.; Islam, M.S.Chem.Master.2008,20,5907-5915), at LiFePO
4In the crystal, Li
+Transmission be to carry out in the mode of antistructure defect, therefore, the number of defective has determined Li
+Transmission rate, adopt the method for nanometer usually, reduce particle size, namely reduce Li
+The evolving path in LiFePO4 inside, thus Li improved
+Diffusion rate.
Refinement particle over-borrowing at present helps liquid phase process such as coprecipitation, hydro thermal method and realizes, but simple LiFePO by the littler nanoscale of synthetic particle diameter
4Material though can shorten the evolving path of Li+, makes Li
+At LiFePO
4It is convenient that the surface embeds/take off embedding, but can't effectively improve LiFePO
4The electronic conductivity of material.
Select for use suitable carbon source to LiFePO
4Carry out carbon and coat, can improve the electronic conductivity of material effectively.Therefore at nanometer LiFePO
4In the building-up process of material, must could fundamentally improve LiFePO in conjunction with the carbon cladding process
4The chemical property of material.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts aniline to prepare lithium iron phosphate, the less and chemical property of the lithium iron phosphate particle that makes by this method significantly improves.
To achieve these goals, the present invention takes following technical scheme: adopt aniline to prepare the method for lithium iron phosphate, comprise the steps: that a. is dissolved in wiring solution-forming in the deionized water with trivalent iron salt and phosphorus-containing compound respectively by element mol ratio 1～1.1: 1, aniline is added drop-wise in the phosphorus-containing compound solution and stirs according to the ratio of the corresponding 1 moles iron element of 25～100ml make it even dispersion; Again ferric salt solution is added in the phosphorus-containing compound solution that contains aniline and stir very first time section and generate ferric phosphate/polyaniline, clean ferric phosphate/polyaniline several all over also centrifugation with deionized water, gained ferric phosphate/polyaniline precipitation is put into convection oven, dry second time period under 80 ℃ of conditions.B. dried ferric phosphate/polyaniline is ground to form powdery, place tube furnace with first heating rate, under the condition of protective atmosphere, 300～600 ℃ of annealing coolings naturally after 4～6 hours obtain removing the crystallization water and polyaniline by the FePO of pyrolysis carbonization
4/ C.C. get mass ratio and be 2～4: 1 lithium iodide and FePO
4/ C is dissolved in the acetonitrile, and the concentration of LiI in acetonitrile is 0.2～1.0mol/L; Stirred under the room temperature 10～24 hours, centrifugal and clean several times with acetonitrile, the gained precipitation places in the vacuum drying chamber 60 ℃ of the 3rd time periods of drying.D. place tube furnace with second heating rate above-mentioned dry gained material, under protective atmosphere, 500～800 ℃ of calcining coolings naturally after 2～4 hours obtain LiFePO
4/ C composite material.
Compared with prior art, the present invention adopts aniline to prepare lithium iron phosphate, works as Fe
3+Enter into and contain PO
4 3-During with the aqueous solution of aniline, at first generate FePO
4Precipitation is separated out, simultaneously Fe
3+Impel aniline at FePO again as catalyst
4Oxidative polymerization takes place in the surface of particle, generates polyaniline (PANI) and is coated on FePO
4The surface, effectively limited FePO
4The growth of particle, thus the less FePO of particle diameter obtained
4/ PANI presoma.Therefore it is littler to adopt aniline to synthesize particle diameter than general liquid phase method; And this LiFePO
4/ C composite material coats so chemical property significantly improves because skin has carbon.
Description of drawings
Fig. 1 is that the present invention adopts aniline to prepare the LiFePO that makes among the embodiment 1 of lithium iron phosphate
4The X ray diffracting spectrum of/C composite material;
Fig. 2 is that the present invention adopts aniline to prepare the LiFePO that makes among the embodiment 1 of lithium iron phosphate
4The stereoscan photograph of/C composite material;
Fig. 3 is that the present invention adopts aniline to prepare the LiFePO that makes among the embodiment 1 of lithium iron phosphate
4The transmission electron microscope photo of/C composite material;
Fig. 4 is that the present invention adopts aniline to prepare the LiFePO that makes among the embodiment 2 of lithium iron phosphate
4The stereoscan photograph of/C composite material;
Fig. 5 is that the present invention adopts aniline to prepare the LiFePO that makes among the embodiment 3 of lithium iron phosphate
4The stereoscan photograph of/C composite material;
Fig. 6 obtains LiFePO with the embodiment 1 that the present invention adopts aniline to prepare lithium iron phosphate
4The discharge curve of button cell under different charge-discharge magnifications that/C composite material is prepared;
Fig. 7 obtains LiFePO with the embodiment 1 that the present invention adopts aniline to prepare lithium iron phosphate
4The cycle performance of button cell under the 0.1C multiplying power that/C composite material is prepared.
Embodiment
In the aqueous solution, aniline is at Fe
3+Catalytic action under, can polymerization reaction take place generate and contain phenyl ring alternately and the high molecular polymer polyaniline (PANI) of nitrogen-atoms on the main chain.Make aniline polymerization reaction can with generate FePO
4The two carries out the reaction of precipitation simultaneously, just can synthesize the FePO of surface parcel one deck organic polymer
4Particle.So not only can limit FePO effectively
4Particle is grown up, and is conducive to the synthetic more FePO of small particle diameter
4Presoma; And FePO
4The organic polymer of particle surface annealing carbonization after again to FePO
4Particle carries out effective carbon and coats, and is conducive to prepare the LiFePO of Nano grade
4/ C composite material.
After now specific embodiments of the invention being described in.
Take by weighing 2.62 gram ammonium dihydrogen phosphate (NH
4H
2PO
4) and 3.73 gram iron chloride (FeCl
3) and be dissolved in respectively in the deionized water of 250mL and 125mL, 1.0 milliliters of (mL) aniline are added drop-wise to NH
4H
2PO
4Also stir in the solution and make it even dispersion; Then, FeCl3 solution slowly is added drop-wise in the NH4H2PO4 solution that contains aniline.Above-mentioned mixed solution is at room temperature stirred 5 hours generation ferric phosphate/polyaniline presomas, ferric phosphate/polyaniline is cleaned several times and all centrifugations at every turn with deionized water, gained ferric phosphate/polyaniline precipitation is put into convection oven, 80 ℃ (degree centigrade) dry 4 hours down.Dried material is ground to form powdery, place tube furnace with the heating rate of 5 ℃/min (degrees celsius/minute), under protective atmosphere, 400 ℃ of annealing coolings naturally after 6 hours obtain removing the crystallization water and polyaniline by the FePO4/C of pyrolysis carbonization.
Get 2.01g lithium iodide (LiI) and be dissolved in the 30mL acetonitrile, add the FePO4/C after 0.75g anneals again; Stir under the room temperature and generated amorphous LiFePO4 precursor/carbon in 12 hours; this ferric lithium phosphate precursor/carbon is cleaned 3 times with acetonitrile and all carry out centrifugation at every turn; the amorphous LiFePO4 precursor/carbon deposition of gained places in the vacuum drying chamber; 60 ℃ of dryings were placed in the tube furnace in 2 hours; under protective atmosphere; heating rate with 5 ℃/min is warming up to 600 ℃, calcines cooling naturally after 2 hours, obtains the LiFePO4/C composite material.
Wherein, protective atmosphere can be N2 (nitrogen) or Ar (argon) inert gas, and perhaps the ratio of inert gas and H2 (hydrogen) reducing gas is 95: 5 mist.
Utilize the X ray diffracting spectrum (XRD) of the product LiFePO4/C composite material that the method for embodiment 1 makes to see shown in Fig. 1, contrast JCPDS card (No.40-1499), be the intact olivine-type LiFePO4 of crystal formation (belonging to the Pnma space group), and fail to observe the diffraction maximum of carbon, illustrate that residual carbon mainly exists with the form of amorphous carbon.Fig. 2 and Fig. 3 are respectively stereoscan photograph and the transmission electron microscope photos that makes end product LiFePO4/C composite material with the method for embodiment 1, the gained material is that average grain diameter is the equally distributed nano particle about 30nm as we can see from the figure, and does not significantly reunite.
LiFePO4/C composite material with the method gained of embodiment 1 is positive pole, be negative pole with the metal lithium sheet, LiPF6 with 1.0mol/L is electrolyte, polypropylene microporous film is diaphragm material, in being full of the glove box of argon gas, be assembled into CR2016 type button cell, carry out charge-discharge test at the LAND battery test system.Voltage range is 2.5～4.2V, and the measurement temperature is room temperature.Fig. 6 is the prepared discharge curve of button cell under different charge-discharge magnifications of LiFePO4/C composite material with the method gained of embodiment 1.When charge-discharge magnification was 0.1C, the discharge capacity first of battery reached 151.8mAh/g; The high-rate charge-discharge capability excellence, 1C, 2C and 5C specific discharge capacity reach 130.7mAh/g, 120.1mAh/g and 105.8mAh/g.Fig. 7 is the prepared cycle performance of button cell under the 0.1C multiplying power of LiFePO4/C composite material that the method with embodiment 1 makes.Under the 0.1C multiplying power, the capacity attenuation of 50 charge and discharge cycles is 9.15%.
Embodiment 2
Take by weighing 5.52 gram concentration and be 38% phosphoric acid (H3PO4) with 5.31 gram ferric nitrates (Fe (NO3) 3) and be dissolved in respectively in the deionized water of 400mL and 200mL, be added drop-wise to 0.5mL aniline in the H3PO4 solution and stirring makes it even dispersion; Then, Fe (NO3) 3 solution slowly are added drop-wise in the H3PO4 solution that contains aniline.Above-mentioned mixed solution is at room temperature stirred 3 hours generation ferric phosphate/polyaniline presomas, ferric phosphate/polyaniline is cleaned several times and all centrifugations at every turn with deionized water, gained ferric phosphate/polyaniline precipitation is put into convection oven, and drying is 5 hours under 80 ℃.Dried material is ground to form powdery, place tube furnace with the heating rate of 10 ℃/min, under the nitrogen atmosphere protection, 300 ℃ of annealing coolings naturally after 5 hours obtain removing the crystallization water and polyaniline by the FePO4/C of pyrolysis carbonization.
Get 1.51g LiI and be dissolved in the 23mL acetonitrile, add the FePO4/C after 0.84g anneals again; Stir under the room temperature and generated amorphous ferric lithium phosphate precursor/carbon in 24 hours; this ferric lithium phosphate precursor/carbon is cleaned 3 times with acetonitrile and all carry out centrifugation at every turn; amorphous ferric lithium phosphate precursor/the carbon deposition of gained places in the vacuum drying chamber; 60 ℃ of dryings were placed in the tube furnace in 4 hours; under protective atmosphere (the Ar/H2 volume ratio is 95: 5); heating rate with 10 ℃/min is warming up to 500 ℃, calcines cooling naturally after 4 hours, obtains the LiFePO4/C composite material.
Fig. 4 is the stereoscan photograph that utilizes the end product LiFePO4/C composite material that the method for embodiment 2 makes, and the gained material is that average grain diameter is the equally distributed nano particle about 40nm as we can see from the figure.When charge-discharge magnification was 0.1C, the discharge capacity first of battery reached 146.3mAh/g.
Embodiment 3
Take by weighing 2.17 gram diammonium hydrogen phosphates ((NH4) 2HPO4) and 4.38 gram ironic citrates and being dissolved in respectively in the deionized water of 200mL and 100mL, be added drop-wise to 1.5mL aniline in the H3PO4 solution and stirring makes it even dispersion; Then, ironic citrate solution slowly is added drop-wise in (NH4) 2HPO4 solution that contains aniline.Above-mentioned mixed solution is at room temperature stirred 4 hours generation ferric phosphate/polyaniline presomas, ferric phosphate/polyaniline presoma is cleaned several times and all centrifugations at every turn with deionized water, gained ferric phosphate/polyaniline precipitation is put into convection oven, and drying is 3 hours under 80 ℃.Dried material is ground to form powdery, place tube furnace with the heating rate of 15 ℃/min, under the nitrogen atmosphere protection, 500 ℃ of annealing coolings naturally after 4 hours obtain removing the crystallization water and polyaniline by the FePO4/C of pyrolysis carbonization.
Get 3.02g LiI and be dissolved in the 45mL acetonitrile, add the FePO4/C after 1.13g anneals again; Stir under the room temperature and generated amorphous LiFePO4 precursor/carbon in 18 hours; this ferric lithium phosphate precursor/carbon is cleaned 3 times with acetonitrile and all carry out centrifugal treating at every turn; the amorphous LiFePO4 precursor/carbon deposition of gained places in the vacuum drying chamber; 60 ℃ of dryings were placed in the tube furnace in 3 hours; under protective atmosphere (the Ar/H2 volume ratio is 95: 5); heating rate with 15 ℃/min is warming up to 700 ℃, calcines cooling naturally after 3 hours, obtains the LiFePO4/C composite material.
Fig. 5 is the stereoscan photograph that utilizes the end product LiFePO4/C composite material that the method for embodiment 3 makes, and the gained material is that average grain diameter is the equally distributed nano particle about 20nm as we can see from the figure.When charge-discharge magnification was 0.1C, the discharge capacity first of battery reached 154.6mAh/g.
In sum, the method that the present invention adopts aniline to prepare lithium iron phosphate adopts " two-step method ", its characterization step is: the first step is the FePO4 presoma that is enclosed with polyaniline (PANI) by polymerization reaction synthetic surface in the aqueous solution of aniline, obtains the FePO4/C that carbon coats after the annealing in process; Second step was adopted lithium iodide liquid phase embedding lithium, and high-temperature calcination obtains the LiFePO4/C composite material of nanoscale under reduction (inertia) atmosphere then.The method that adopts aniline to prepare lithium iron phosphate comprises as follows:
One, the synthetic FePO4/PANI presoma of liquid phase method
A. take by weighing an amount of water-soluble trivalent ferric salt and water-soluble phosphorus-containing compound and be dissolved in a certain amount of deionized water wiring solution-forming respectively, an amount of aniline is added drop-wise in the water-soluble phosphorus-containing compound solution and stirs make it even dispersion; Water-soluble trivalent ferric salt solution slowly is added drop-wise in the water-soluble phosphorus-containing compound solution that contains aniline again.Stir 3～5 hours synthetic FePO4/PANI presomas under the room temperature, FePO4/PANI is cleaned several times and centrifugations at every turn with deionized water, gained FePO4/PANI precipitation is put into convection oven, drying is 3～5 hours under 80 ℃ of conditions.
In said process, when Fe3+ enters into the aqueous solution that contains PO43-and aniline, at first generating the FePO4 precipitation separates out, Fe3+ impels aniline on the surface of FePO4 particle oxidative polymerization to take place again as catalyst simultaneously, generate polyaniline and be coated on the surface of FePO4, effectively limit the growth of FePO4 particle, thereby obtained the less FePO4/PANI presoma of particle diameter.
Wherein, the mol ratio of water-soluble trivalent ferric salt and water-soluble phosphorus-containing compound is 1～1.1: 1; The solution concentration of water-soluble trivalent ferric salt and water-soluble phosphorus-containing compound is 0.05～0.5mol/L; According to the molal quantity of iron in the solution, the aniline of every moles iron correspondence is 25～100ml.
Water-soluble trivalent ferric salt can be any in ferric nitrate, iron chloride, ironic citrate or the ferric acetate.
Water-soluble phosphorus-containing compound can be any in phosphoric acid, ammonium dihydrogen phosphate or the diammonium hydrogen phosphate.
B. dried material is ground to form powdery; place tube furnace with the heating rate of 5～15 ℃/min; under the condition of protective atmosphere, 300～600 ℃ of annealing coolings naturally after 4～6 hours obtain removing the crystallization water and polyaniline by the FePO4/C of pyrolysis carbonization.
Two, the synthetic LiFePO4/C composite material of liquid phase method embedding lithium
C. get a certain amount of lithium iodide and be dissolved in an amount of acetonitrile, add the FePO4/C of respective amount again; The mass ratio of lithium iodide and FePO4/C is 2: 1～4: 1, and the concentration of LiI in acetonitrile is 0.2～1.0mol/L; Stir under the room temperature and generated amorphous ferric lithium phosphate precursor/carbon in 10～24 hours, this ferric lithium phosphate precursor/carbon is cleaned several times and all carries out centrifugation at every turn with acetonitrile, amorphous ferric lithium phosphate precursor/the carbon deposition of gained places in the vacuum drying chamber, 60 ℃ of dryings 2～4 hours;
D. place tube furnace with the heating rate of 5～15 ℃/min above-mentioned dry gained material, under protective atmosphere, 500～800 ℃ of calcinings are cooled off after 2～4 hours naturally, obtain the LiFePO4/C composite material of Nano grade.
Described protective atmosphere can be N2 or Ar inert gas, the perhaps mist of inert gas and H2 reducing gas, and the ratio of H2 is 5vol%.
Described heating rate can be 5～20 ℃/min.
Compared with prior art, the present invention's method of adopting aniline to prepare lithium iron phosphate has following characteristics:
(1) aniline forms the chain high molecular polymer by polymerization reaction on the surface of FePO4 particle, and the effect that has the refinement particle simultaneously and provide carbon to coat the source can other LiFePO4/C composite material of synthesis nano;
(2) FePO4 and LiFePO4 are all synthetic under liquid-phase condition, can effectively control the particle diameter of material, and improve material purity; Technological temperature is low, reduces energy consumption.
(3) earlier synthetic FePO4/PANI presoma, again its embedding lithium is obtained, unique " two-step method " preparation technology can control pattern and the structure of composite material better, significantly improve the chemical property of material, make the LiFePO4/C composite material that finally obtains have bigger specific discharge capacity, the rate charge-discharge performance of excellence and good cyclical stability;
(4) the inventive method preparation technology is simple, does not add any catalyst and chemical initiator, and manufacturing cycle is short; Output is big, the productive rate height, but scale is used.
Claims (10)
1. a method that adopts aniline to prepare lithium iron phosphate is characterized in that, comprises the steps:
A. trivalent iron salt and phosphorus-containing compound are dissolved in wiring solution-forming in the deionized water respectively by element mol ratio 1～1.1: 1, aniline is added drop-wise in the phosphorus-containing compound solution and stirs according to the ratio of the corresponding 1 moles iron element of 25～100ml make it even dispersion; Again ferric salt solution is added in the phosphorus-containing compound solution that contains aniline and stir very first time section and generate ferric phosphate/polyaniline, ferric phosphate/polyaniline is cleaned several times and all centrifugations at every turn with deionized water, then gained ferric phosphate/polyaniline precipitation is put into convection oven, dry second time period under 80 ℃ of conditions;
B. dried ferric phosphate/polyaniline is ground to form powdery, place tube furnace with first heating rate, under the condition of protective atmosphere, 300～600 ℃ of annealing coolings naturally after 4～6 hours obtain removing the crystallization water and polyaniline by the FePO of pyrolysis carbonization
4/ C;
C. get mass ratio and be 2～4: 1 lithium iodide and FePO
4/ C is dissolved in the acetonitrile, and the concentration of LiI in acetonitrile is 0.2～1.0mol/L; Stir 10～24 hours synthetic amorphous ferric lithium phosphate precursor/carbon under the room temperature, this ferric lithium phosphate precursor/carbon is cleaned several times and all carries out centrifugation at every turn with acetonitrile, then the gained precipitation is placed in the vacuum drying chamber 60 ℃ of the 3rd time periods of drying;
D. place tube furnace with second heating rate above-mentioned dry gained material, under protective atmosphere, 500～800 ℃ of calcining coolings naturally after 2～4 hours obtain LiFePO
4/ C composite material.
2. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described trivalent iron salt is ferric nitrate, iron chloride, ironic citrate or ferric acetate.
3. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described phosphorus-containing compound is phosphoric acid, ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
4. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: the solution concentration of trivalent iron salt and phosphorus-containing compound is 0.05～0.5mol/L.
5. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described protective atmosphere is inert gas, and perhaps the ratio of inert gas and hydrogen is 95: 5 mist.
6. employing aniline as claimed in claim 5 prepares the method for lithium iron phosphate, it is characterized in that: described inert gas is argon gas or nitrogen.
7. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described very first time section is 3～5 hours.
8. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described second time period is 3～5 hours.
9. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described the 3rd time period is 2～4 hours.
10. employing aniline as claimed in claim 1 prepares the method for lithium iron phosphate, it is characterized in that: described first, second heating rate is 5～15 ℃/min.
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| CN114715871A (en) * | 2022-04-26 | 2022-07-08 | 张粒新 | Modified lithium iron phosphate cathode material for lithium battery and preparation method |
| CN114715871B (en) * | 2022-04-26 | 2023-09-12 | 四川朗晟新材料科技有限公司 | Modified lithium iron phosphate positive electrode material for lithium battery and preparation method |
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