CN105244481B - A kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ and preparation method thereof - Google Patents
A kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ and preparation method thereof Download PDFInfo
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- CN105244481B CN105244481B CN201510555704.XA CN201510555704A CN105244481B CN 105244481 B CN105244481 B CN 105244481B CN 201510555704 A CN201510555704 A CN 201510555704A CN 105244481 B CN105244481 B CN 105244481B
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- lithium ion
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 229910010707 LiFePO 4 Inorganic materials 0.000 title claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 41
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229940062993 ferrous oxalate Drugs 0.000 claims description 9
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 9
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical group OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 235000008429 bread Nutrition 0.000 claims 1
- 239000011149 active material Substances 0.000 abstract description 7
- 239000006258 conductive agent Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical class [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 description 7
- 230000004087 circulation Effects 0.000 description 7
- 229910000904 FeC2O4 Inorganic materials 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 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 6
- 229930006000 Sucrose Natural products 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000005720 sucrose Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010025 steaming Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 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 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical class [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003319 supportive effect Effects 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/5825—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
- H01M4/62—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)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ and preparation method thereof, product is prepared by liquid phase ball-milling method, product particle Surface coating has uniform carbon-coating, it is connected with each other between particle by agraphitic carbon net, the particle diameter of particle is 100 200nm, and preparation method mainly includes the preparation of precursor powder and the preparation of product.The present invention is synthesized using liquid phase ball-milling method, product particle particle diameter is nanoscale, and it is evenly distributed, with specific surface area is big, electric charge mass transfer resistance is low and electronics, ionic conductivity improve obvious advantage, carbon coating in situ improves between people's active material particle and the electrical contact between active material and conductive agent, reduces the impedance between particle, electrochemical performance, be advantageous to mass market popularization, can be as the positive electrode of lithium ion battery.
Description
Technical field
The present invention relates to nanometer material and electrochemical technology field, and in particular to a kind of carbon-coated LiFePO 4 for lithium ion batteries in situ
(LiFePO4/ C) positive electrode and preparation method thereof.
Background technology
As the traditional fuels such as oil are increasingly exhausted, development green novel energy source industry has become the prioritizing selection of various countries.
Wherein new-energy automobile turns into Global Auto industrial development direction, and current urgent task is to determine technology path and city as early as possible
Field Advancing Measures, promote the spanning development of new-energy automobile industry.Electrokinetic cell produces as the supportive of new-energy automobile industry
Product, various countries, which try to be the first, studies its correlation technique, carries forward vigorously the industrialization process of electrokinetic cell.Electrokinetic cell needs to be provided simultaneously with holding
The characteristics of measuring high, power height, having extended cycle life and be inexpensive.LiFePO4 (LiFePO4) it is olivine structural, as lithium ion
Cell positive material, there is security performance height, theoretical capacity height (170mA h g-1), have extended cycle life, good environmental adaptability etc.
Advantage.However, LiFePO4Electronic conductivity (10-7-10-9S cm-1) and ionic conductivity (~10-16em2s-1) relatively low,
Simultaneously due to LiFePO in charge and discharge process4/FePO4Phase in version be present and produce structural stress, therefore pure LiFePO4Electrode
The problem of capacity is low, polarization is high, high rate capability difference and cycle life is short be present in material.
In order to preferably play LiFePO4Chemical property, by the further investigation in 10 She's years, researchers use carbon
The methods of cladding, metal ion mixing, metallic cover, nanosizing the chemical property for improving LiFePO4.And numerous
In method of modifying, carbon coating in situ is considered as to improve LiFePO4 electronic conductivity, improves the cyclical stability of LiFePO4
And high rate performance is most direct, maximally effective approach.Research think carbon coating in situ can improve between active material particle and
Electrical contact (bulk conductivity) between active material and conductive agent, reduce the impedance between particle, while can be with
Atoms permeating is hindered, suppresses LiFePO4The growth of crystal grain, shorten the diffusion path of lithium ion, improve its chemical property.Especially
It is that Goodenough etc. takes the lead in LiFePO4Surface coating conductive layer, it is modified after the chemical property for improving the material
LiFePO4Academic and business circles upsurges are even more started.
The content of the invention
It is an object of the invention to provide a kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ and its preparation method and application, adopt
Carbon-coated LiFePO 4 for lithium ion batteries (LiFePO in situ is synthesized with liquid phase-ball-milling method4/ C) positive electrode, the particle surface of product is coated with
Even carbon-coating, it is connected with each other by agraphitic carbon net between particle, and particle diameter distribution is uniform, electrochemical performance, is advantageous to big
The scale marketization is promoted, can be as the positive electrode of lithium ion battery.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ, is prepared, product particle Surface coating has by liquid phase ball-milling method
Uniform carbon-coating, it is connected with each other by agraphitic carbon net between particle, the particle diameter of the particle is 100-200nm.
According to above scheme, as anode active material of lithium ion battery.
A kind of preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ, comprises the following steps：
1) preparation of precursor powder：By source of iron and oxalic acid (C2H2O4) be added in distilled water and stir, it is suspended to obtain yellow
Liquid；By lithium source, phosphorus source, carbon source is added dropwise in yellow suspension after being made into the aqueous solution respectively；Yellow solution is obtained after heating stirring；
Yellow sol is obtained after stirring and drying, yellow sol is placed in drying in oven and carries out solid-phase ball milling obtains precursor powder；
2) preparation of product：By precursor powder pre-burning under protective gas atmosphere, pre-burning product is through liquid phase ball milling, drying
Calcined again under protective gas atmosphere afterwards, obtain black product.
According to above scheme, the source of iron is ferrous oxalate (FeC2O4·2H2O), mole of the ferrous oxalate and oxalic acid
Than for 1: 1~1: 6.
According to above scheme, the lithium source is LiOHH2O、CH3COOLi·2H2O、LiNO3In any one or one
The mixture of the kind above.
According to above scheme, phosphorus source H3PO4、NH4H2PO4Or both mixture.
According to above scheme, the carbon source is C6H12O6·H2O、C12H22O11Or both mixture.
According to above scheme, the temperature of the heating stirring is 80-95 DEG C, the heating stirring time is 12-36 hours；It is described
The time of solid-phase ball milling is 1-24 hours.
According to above scheme, the protective gas is nitrogen, and the temperature of the pre-burning is 300-400 DEG C, and the time is that 3-7 is small
When.
According to above scheme, the liquid of the liquid phase ball milling is alcohol, the mixture of isopropanol or both, the time of ball milling
For 1-12 hours；The temperature of the calcining is 550-700 DEG C, and the time is 10-15 hours.
The product particle Surface coating of the present invention has uniform carbon-coating, is connected with each other between particle by agraphitic carbon net；Together
When LiFePO4/ C granular sizes are 100-200nm, and particle size distribution is more uniform, have that specific surface area is big, electric charge mass transfer
Resistance is low and electronics, ionic conductivity improve obvious advantage.It is between carbon coating raising active material particle in situ and active
Electrical contact between material and conductive agent, reduce the impedance between particle.Atoms permeating can also be hindered simultaneously, suppresses crystal grain
Growth, and nano particle is even more the diffusion path for shortening lithium ion, improves LiFePO4Chemical property.
The liquid phase ball milling that the present invention uses is simple and easy, by changing concentration, iron and the oxalic acid of reactant than controllable saw lumber
The pattern and size of material, and obtained material yield is high, purity is high, good dispersion.
The beneficial effects of the invention are as follows：
1) present invention is prepared for carbon coating LiFePO in situ by simple and easy liquid phase ball-milling method4/ C positive electrode material, its
During as anode active material of lithium ion battery, show that discharge capacity is high, high rate performance is excellent, good cycling stability spy
Point；
2) technique of the invention is simple, and precursor powder is obtained by simple and easy solid-phase ball milling, then through pre-burning, liquid phase
Ball milling, calcination can obtain product.
3) feasibility of the present invention is strong, is easy to amplificationization, the characteristics of meeting Green Chemistry, is promoted beneficial to the marketization.
Brief description of the drawings
Fig. 1 is the preparation technology schematic flow sheet of the embodiment of the present invention 1；
Fig. 2 is the XRD of the product of the embodiment of the present invention 1；
Fig. 3 is the SEM figures of the product of the embodiment of the present invention 1；
Fig. 4 is the low current density cycle performance of the product of the embodiment of the present invention 1 and different cycle-index charging and discharging curve figures；
Fig. 5 is the cycle performance of battery figure of the product of the embodiment of the present invention 1.
Embodiment
Technical scheme is illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment 1, as shown in Fig. 1 to Fig. 5：
The present invention provides a kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ and preparation method thereof, comprises the following steps (such as
Shown in Fig. 1)：
1) by 1.26g ferrous oxalate dihydrates (FeC2O4·2H2O), 2.56g oxalic acid (C2H2O4·2H2O 20mL steamings) are added to
In distilled water, yellow suspension solution is formed；
2) by 0.75g lithium acetates (CH3COOLi·2H2O) it is dissolved in 10mL distilled water, forms settled solution；By 0.3g
Glucose (C6H12O6·H2O) it is dissolved in 10mL distilled water, forms settled solution；Respectively by lithium acetate solution, 480 μ L phosphoric acid,
Glucose solution adds in above-mentioned yellow suspension that (lithium source is 1.05: 1 with phosphorus source mol ratio, and lithium source actual amount is required anti-
Should measure 1.05 times)；
3) after stirring 24h at above-mentioned 80 DEG C of yellow suspension, yellow suspension is changed into yellow solution；Yellow solution is stirred
Yellow sol is obtained after mixing drying；The solid obtained after yellow sol is dried at 120 DEG C is placed in ball mill ball milling 12 hours,
Obtain bronzing precursor powder；
4) by precursor powder under 350 DEG C of nitrogen atmospheres pre-burning 5h, pre-burning product is placed in ball mill, and add wine
Essence is used as ball-milling medium, is dried after ball milling 5h, obtains Red-brown powder, then calcines 12h under 600 DEG C of nitrogen atmospheres, is produced
Product.
The structure of the present embodiment product is determined that its X ray diffracting spectrum (XRD) shows (see Fig. 2) by X-ray diffractometer,
Product is LiFePO4(JCPDS No.01-081-1173), without other dephasign peaks, carbon is agraphitic carbon.
ESEM (SEM) image of the present embodiment product shows that product is nanometer spherical particle (see Fig. 3), and particle is big
Small is 100-200nm, and particle size distribution is more uniform.
Product obtained by the present embodiment is as follows as the application of anode active material of lithium ion battery：The preparation of positive plate
Cheng Caiyong the present embodiment product is as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene (PTFE) is as binding agent, active material
Material, acetylene black, the mass ratio of polytetrafluoroethylene (PTFE) are 70: 20: 10；After they are sufficiently mixed in proportion, a small amount of isopropanol is added,
Grinding is uniform, and the thick electrode slices of about 0.5mm are pressed on twin rollers；The positive plate pressed was placed in 80 DEG C of oven drying after 24 hours
It is standby.With 1M LiPF6It is dissolved in vinyl carbonate (EC) and dimethyl carbonate (DMC) and is used as electrolyte, lithium piece is negative pole,
Celgard2325 is barrier film, and CR2025 types stainless steel is that battery case is assembled into fastening lithium ionic cell.The system of lithium ion battery
Remaining step of Preparation Method is identical with common preparation method.
Performance test is carried out using lithium ion battery of the present embodiment product as positive electrode active materials to above-mentioned making,
Wherein the low current density cycle performance of the present embodiment product and charging and discharging curve figure are as shown in figure 4, cycle performance of battery such as Fig. 5
It is shown.From Fig. 4 A, first discharge specific capacity of the present embodiment product under 0.5C (1C=170mA/g) current density can be with
Reach 154mAh/g, capacity still can reach 146mAh/g after 800 circulations.Fig. 4 B show that the present embodiment product is in discharge and recharge
There is highly stable stable platform, from the 1st time to after circulating 800 times, discharge voltage is still stablized in 3.4V, discharge and recharge in journey
Voltage difference maintains below 0.05V all the time, has no fluctuation.This shows that the polarization of the present embodiment product is very small and has very excellent
Cyclical stability.
Fig. 5 A show, under 2C (1C=170mA/g) current density, the first discharge specific capacity of the present embodiment product can be with
Reach 140mAh/g, capacity still can reach 127mAh/g after 800 circulations, and capability retention reaches 90.7%.In addition, from Fig. 5 B
In as can be seen that the cyclical stability of the present embodiment product is also very prominent, under 5C current density, material circulation 1000 times
Specific capacity afterwards is still 118mAh/g, capability retention 93.7%.Above-mentioned performance shows that the present embodiment product has capacity
High, high rate performance is excellent and is a kind of preferable anode material for lithium-ion batteries the advantages of good cycling stability.
Embodiment 2：
1) by 1.26g ferrous oxalate dihydrates (FeC2O4·2H2O), 1.28g oxalic acid (C2H2O4·2H2O 20mL steamings) are added to
In distilled water, yellow suspension solution is formed；
2) by 0.3084g Lithium hydroxide monohydrates (LiOHH2O) it is dissolved in 10mL distilled water, forms settled solution；Will
0.3g sucrose (C12H22O11) be dissolved in 10mL distilled water, form settled solution；Respectively by lithium hydroxide solution, 480 μ L phosphorus
Acid, sucrose solution add in above-mentioned yellow suspension (lithium source is 1.05: 1 with phosphorus source mol ratio, lithium source actual amount for it is required instead
Should measure 1.05 times)；
3) after stirring 36h at above-mentioned 90 DEG C of yellow suspension, yellow suspension is changed into yellow solution；Yellow solution is stirred
Yellow sol is obtained after mixing drying；The solid obtained after yellow sol is dried at 120 DEG C is placed in ball mill ball milling 6 hours,
Obtain bronzing precursor powder；
4) by precursor powder under 375 DEG C of nitrogen atmospheres pre-burning 6h, pre-burning product is placed in ball mill, and is added different
Propyl alcohol is dried after ball milling 1h, obtains Red-brown powder as ball-milling medium, then calcines 12h under 625 DEG C of nitrogen atmospheres, is obtained
Product.
With the production obtained by the present embodiment into after lithium ion battery, performance test is carried out, under 5C current densities,
LiFePO4/ C first discharge specific capacity can reach 125mAh/g, and specific discharge capacity is 115mAh/g after 1000 circulations, is held
It is 92% to measure conservation rate.
Embodiment 3：
1) by 1.26g ferrous oxalate dihydrates (FeC2O4·2H2O), 5.12g oxalic acid (C2H2O4·2H2O 20mL steamings) are added to
In distilled water, yellow suspension solution is formed；
2) by 0.75g lithium acetates (CH3COOLi·2H2O) it is dissolved in 10mL distilled water, forms settled solution；Will
0.8051g ammonium dihydrogen phosphates (NH4H2PO4) be dissolved in 10mL distilled water, form settled solution；By 0.3g glucose
(C6H12O6·H2O) it is dissolved in 10mL distilled water, forms settled solution；Respectively by lithium acetate solution, ammonium dihydrogen phosphate,
Glucose solution adds in above-mentioned yellow suspension that (lithium source is 1.05: 1 with phosphorus source mol ratio, and lithium source actual amount is required anti-
Should measure 1.05 times)；
3) after stirring 12h at above-mentioned 95 DEG C of yellow suspension, yellow suspension is changed into yellow solution；Yellow solution is stirred
Yellow sol is obtained after mixing drying；The solid obtained after yellow sol is dried at 120 DEG C is placed in ball mill ball milling 24 hours,
Obtain bronzing precursor powder；
4) by precursor powder under 300 DEG C of nitrogen atmospheres pre-burning 7h, pre-burning product is placed in ball mill, and add 1:
1 alcohol and isopropanol mixed liquor are dried after ball milling 5h, obtain Red-brown powder as ball-milling medium, then in 550 DEG C of nitrogen gas
15h is calcined under atmosphere, obtains product.
With the production obtained by the present embodiment into after lithium ion battery, performance test is carried out, under 5C current densities,
LiFePO4/ C first discharge specific capacity can reach 124mAh/g, and specific discharge capacity is 117mAh/g after 1000 circulations, is held
It is 94.4% to measure conservation rate.
Embodiment 4：
1) by 1.26g ferrous oxalate dihydrates (FeC2O4·2H2O), 1.75g oxalic acid (C2H2O4·2H2O 20mL steamings) are added to
In distilled water, yellow suspension solution is formed；
2) by 0.5067g lithium nitrates (LiNO3) be dissolved in 10mL distilled water, form settled solution；By 0.8051g phosphoric acid
Ammonium dihydrogen (NH4H2PO4) be dissolved in 10mL distilled water, form settled solution；By 0.3g sucrose (C12H22O11) it is dissolved in 10mL
In distilled water, settled solution is formed；Lithium nitrate solution, ammonium dihydrogen phosphate, sucrose solution are added into above-mentioned yellow respectively to hang
In turbid (lithium source is 1.05: 1 with phosphorus source mol ratio, and lithium source actual amount is 1.05 times of required reacting dose)；
3) after stirring 30h at above-mentioned 85 DEG C of yellow suspension, yellow suspension is changed into yellow solution；Yellow solution is stirred
Yellow sol is obtained after mixing drying；The solid obtained after yellow sol is dried at 120 DEG C is placed in ball mill ball milling 24 hours,
Obtain bronzing precursor powder；
4) by precursor powder under 350 DEG C of nitrogen atmospheres pre-burning 6h, pre-burning product is placed in ball mill, and add 1:
2 alcohol and isopropanol mixed liquor are dried after ball milling 1h, obtain Red-brown powder as ball-milling medium, then in 700 DEG C of nitrogen gas
15h is calcined under atmosphere, obtains product.
With the production obtained by the present embodiment into after lithium ion battery, performance test is carried out, under 5C current densities,
LiFePO4/ C first discharge specific capacity can reach 118mAh/g, and specific discharge capacity is 110mAh/g after 1000 circulations, is held
It is 93.2% to measure conservation rate.
Embodiment 5：
1) by 1.26g ferrous oxalate dihydrates (FeC2O4·2H2O), 3.85g oxalic acid (C2H2O4·2H2O 20mL steamings) are added to
In distilled water, yellow suspension solution is formed；
2) by 0.3084g Lithium hydroxide monohydrates (LiOHH2O) it is dissolved in 10mL distilled water and is dissolved in 10mL distilled water
In, form settled solution；By 0.8051g ammonium dihydrogen phosphates (NH4H2PO4) be dissolved in 10mL distilled water, form settled solution.
By 0.3g sucrose (C12H22O11) be dissolved in 10mL distilled water, form settled solution.Respectively by lithium hydroxide solution, di(2-ethylhexyl)phosphate
Hydrogen ammonium salt solution, sucrose solution add in above-mentioned yellow suspension that (lithium source is 1.05: 1 with phosphorus source mol ratio, and lithium source actual amount is
1.05 times of required reacting dose)；
3) after stirring 18h at above-mentioned 80 DEG C of yellow suspension, yellow suspension is changed into yellow solution；Yellow solution is stirred
Yellow sol is obtained after mixing drying；The solid obtained after yellow sol is dried at 120 DEG C is placed in ball mill ball milling 1 hour,
Obtain bronzing precursor powder；
4) by precursor powder under 375 DEG C of nitrogen atmospheres pre-burning 4h, pre-burning product is placed in ball mill, and add 2:
1 alcohol and isopropanol mixed liquor are dried after ball milling 12h, obtain Red-brown powder as ball-milling medium, then in 650 DEG C of nitrogen
10h is calcined under atmosphere, obtains product.
With the production obtained by the present embodiment into after lithium ion battery, performance test is carried out, under 5C current densities,
LiFePO4/ C first discharge specific capacity can reach 115mAh/g, and specific discharge capacity is 111mAh/g after 1000 circulations, is held
It is 96.5% to measure conservation rate.
Above example is only to illustrative and not limiting technical scheme, although above-described embodiment enters to the present invention
Detailed description is gone, the person skilled of this area should be understood：The present invention can be modified or replaced on an equal basis, but
Any modification and local replacement for not departing from spirit and scope of the invention all should be covered in scope of the presently claimed invention.
Claims (9)
1. a kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ, it is characterised in that prepared by liquid phase ball-milling method, product particle table
Bread is covered with uniform carbon-coating, is connected with each other between particle by agraphitic carbon net, and the particle diameter of the particle is 100-200nm；
The preparation method of one of the above original position carbon-coated LiFePO 4 for lithium ion batteries positive electrode is as follows：
1）The preparation of precursor powder：Source of iron is added in distilled water with oxalic acid and stirred, obtains yellow suspension；By lithium source,
Phosphorus source, carbon source are added dropwise in yellow suspension after being made into the aqueous solution respectively；Yellow solution is obtained after heating stirring；After stirring and drying
Yellow sol is obtained, yellow sol is placed in drying in oven and carries out solid-phase ball milling obtains precursor powder；
2）The preparation of product：By precursor powder pre-burning under protective gas atmosphere, pre-burning product after liquid phase ball milling, drying again
Calcined under protective gas atmosphere, obtain black product.
2. carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that as lithium ion battery
Positive electrode active materials.
3. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
Source of iron is ferrous oxalate, and the mol ratio of the ferrous oxalate and oxalic acid is 1:1~1:6.
4. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
Lithium source is LiOHH2O、CH3COOLi·2H2O、LiNO3In any one or more than one mixture.
5. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
Phosphorus source is H3PO4、NH4H2PO4Or both mixture.
6. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
Carbon source is C6H12O6·H2O、C12H22O11Or both mixture.
7. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
The temperature of heating stirring is 80-95 DEG C, the heating stirring time is 12-36 hours；The time of the solid-phase ball milling is 1-24 hours.
8. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
Protective gas is nitrogen, and the temperature of the pre-burning is 300-400 DEG C, and the time is 3-7 hours.
9. the preparation method of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ according to claim 1, it is characterised in that described
The liquid of liquid phase ball milling is the mixture of alcohol, isopropanol or both, and the time of ball milling is 1-12 hours；The temperature of the calcining
For 550-700 DEG C, the time is 10-15 hours.
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