CN105244481A - Lithium iron phosphate cathode material with carbon coating in situ and preparation method thereof - Google Patents
Lithium iron phosphate cathode material with carbon coating in situ and preparation method thereof Download PDFInfo
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- CN105244481A CN105244481A CN201510555704.XA CN201510555704A CN105244481A CN 105244481 A CN105244481 A CN 105244481A CN 201510555704 A CN201510555704 A CN 201510555704A CN 105244481 A CN105244481 A CN 105244481A
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- lithium ion
- positive electrode
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- ion batteries
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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
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title claims abstract description 11
- 238000000576 coating method Methods 0.000 title claims abstract description 11
- 239000010406 cathode material Substances 0.000 title abstract 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title abstract 5
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 41
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 33
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000006183 anode active material Substances 0.000 claims description 4
- 229910013553 LiNO Inorganic materials 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000006258 conductive agent Substances 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000013543 active substance Substances 0.000 abstract 2
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 230000004087 circulation Effects 0.000 description 8
- 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
- 239000011149 active material Substances 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 235000019837 monoammonium phosphate Nutrition 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
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 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
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 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
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 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
- 230000015572 biosynthetic process Effects 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
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material 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
- 238000011835 investigation Methods 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
- 239000002086 nanomaterial Substances 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
- 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
- 238000003786 synthesis reaction Methods 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium iron phosphate cathode material with carbon coating in situ and a preparation method thereof. A product is prepared by a liquid phase ball milling method, the particle surface of the product is coated with a uniform carbon layer, particles are connected to one another by an amorphous carbon net, and the grain size of the particles is 100 to 200 nanometers. The preparation method mainly comprises preparation of precursor powder and the preparation of the product. The lithium iron phosphate cathode material is synthesized by the liquid phase ball milling method, the particle grain size of the product is nano scale, the particles are uniformly distributed, and the lithium iron phosphate cathode material has the obvious advantages of high specific surface area, low charge mass transfer resistance and improvement on electron and ion conductivity. By carbon coating in situ, bulk conductivity among active substance particles and between an active substance and a conductive agent is improved, the impedance among the particles is reduced, the electrochemical performance is excellent, market promotion at a large scale is facilitated, and the lithium iron phosphate cathode material can serve as a positive material of a lithium ion battery.
Description
Technical field
The present invention relates to nano material and technical field of electrochemistry, be specifically related to a kind of in-situ carbon coated LiFePO 4 for lithium ion batteries (LiFePO
4/ C) positive electrode and preparation method thereof.
Background technology
Along with the traditional fuels such as oil are day by day exhausted, development green novel energy source industry has become the prioritizing selection of various countries.Wherein new-energy automobile has become Global Auto industrial development direction, and current urgent task determines technology path and market Advancing Measures as early as possible, promotes the spanning development of new-energy automobile industry.Electrokinetic cell is as the supportive product of new-energy automobile industry, and various countries try to be the first and study its correlation technique, carry forward vigorously the industrialization process of electrokinetic cell.Electrokinetic cell needs to possess that capacity is high, power is high simultaneously, have extended cycle life and the feature of low cost.LiFePO4 (LiFePO
4) be olivine structural, as anode material for lithium-ion batteries, have that security performance is high, the high (170mAhg of theoretical capacity
-1), have extended cycle life, the advantage such as good environmental adaptability.But, LiFePO
4electronic conductivity (10
-7-10
-9scm
-1) and ionic conductivity (~ 10
-16em
2s
-1) all lower, simultaneously in charge and discharge process due to LiFePO
4/ FePO
4there is phase in version and produce structural stress, therefore pure LiFePO
4electrode material exists that capacity is low, polarize high, that high rate capability is poor and cycle life is short problem.
In order to better play LiFePO
4chemical property, through the further investigation in 10 She's years, researchers adopt the methods such as carbon is coated, metal ion mixing, metallic cover, nanometer for improving the chemical property of LiFePO4.And in numerous method of modifying, in-situ carbon is coated is considered to improve LiFePO4 electronic conductivity, improve the cyclical stability of LiFePO4 and high rate performance the most directly, the most effective approach.The coated electrical contact (bulkconductivity) that can improve between active material particle and between active material and conductive agent of in-situ carbon is thought in research, reduces the impedance between particle, can also hinder atoms permeating simultaneously, suppresses LiFePO
4the growth of crystal grain, shortens the evolving path of lithium ion, improves its chemical property.Particularly Goodenough etc. take the lead at LiFePO
4surface coating conductive layer, after improving the chemical property of this material, modification LiFePO
4start the upsurge of science and business circles especially.
Summary of the invention
The object of this invention is to provide a kind of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode and its preparation method and application, adopt liquid phase-ball-milling method synthesis in-situ carbon coated LiFePO 4 for lithium ion batteries (LiFePO
4/ C) positive electrode, the particle surface of product is coated with even carbon-coating, is interconnected between particle by agraphitic carbon net, and even particle size distribution, electrochemical performance, is conducive to mass market and promotes, can as the positive electrode of lithium ion battery.
To achieve these goals, the technical solution used in the present invention is as follows:
A kind of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode, prepared by liquid phase ball-milling method, product particle Surface coating has even carbon-coating, is interconnected between particle by agraphitic carbon net, and the particle diameter of described particle is 100-200nm.
According to above scheme, as anode active material of lithium ion battery.
A preparation method for in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode, comprises the steps:
1) preparation of precursor powder: by source of iron and oxalic acid (C
2h
2o
4) join in distilled water and stir, obtain yellow suspension; 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 adding thermal agitation; Obtain yellow sol after stirring and drying, yellow sol is placed in drying in oven and carries out solid-phase ball milling and obtain precursor powder;
2) preparation of product: by precursor powder pre-burning under protective gas atmosphere, pre-burning product is calcined after liquid phase ball milling, oven dry under protective gas atmosphere again, obtains black product.
According to above scheme, described source of iron is ferrous oxalate (FeC
2o
42H
2o), the mol ratio of described ferrous oxalate and oxalic acid is 1: 1 ~ 1: 6.
According to above scheme, described lithium source is LiOHH
2o, CH
3cOOLi2H
2o, LiNO
3in any one or more than one mixture.
According to above scheme, described phosphorus source is H
3pO
4, NH
4h
2pO
4or both mixtures.
According to above scheme, described carbon source is C
6h
12o
6h
2o, C
12h
22o
11or both mixtures.
According to above scheme, described in add thermal agitation temperature be 80-95 DEG C, heating mixing time is 12-36 hour; The time of described solid-phase ball milling is 1-24 hour.
According to above scheme, described protective gas is nitrogen, and the temperature of described pre-burning is 300-400 DEG C, and the time is 3-7 hour.
According to above scheme, the liquid of described liquid phase ball milling is alcohol, isopropyl alcohol or both mixtures, and the time of ball milling is 1-12 hour; The temperature of described calcining is 550-700 DEG C, and the time is 10-15 hour.
Product particle Surface coating of the present invention has even carbon-coating, is interconnected between particle by agraphitic carbon net; LiFePO simultaneously
4/ C granular size is 100-200nm, and particle size distribution is comparatively even, has that specific area is large, electric charge mass transfer resistance is low and electronics, ionic conductivity improve obvious advantage.Electrical contact between the coated raising active material particle of in-situ carbon and between active material and conductive agent, reduces the impedance between particle.Can also atoms permeating be hindered simultaneously, suppress the growth of crystal grain, and nano particle shorten the evolving path of lithium ion especially, improves LiFePO
4chemical property.
The liquid phase ball milling that the present invention adopts is simple, and by changing the concentration of reactant, iron and oxalic acid than the pattern of controlled prepared material and size, and obtained material yield is high, purity is high, good dispersion.
The invention has the beneficial effects as follows:
1) the present invention has prepared the coated LiFePO of in-situ carbon by simple liquid phase ball-milling method
4/ C positive electrode material, when it is as anode active material of lithium ion battery, shows that discharge capacity is high, high rate performance is excellent, the feature of good cycling stability;
2) technique of the present invention is simple, namely obtains precursor powder, then can obtain product through pre-burning, liquid phase ball milling, calcination by simple solid-phase ball milling.
3) feasibility of the present invention is strong, is easy to amplificationization, meets the feature of Green Chemistry, is beneficial to the marketization and promotes.
Accompanying drawing explanation
Fig. 1 is preparation technology's schematic flow sheet of the embodiment of the present invention 1;
Fig. 2 is the XRD figure of the embodiment of the present invention 1 product;
Fig. 3 is the SEM figure of the embodiment of the present invention 1 product;
Fig. 4 is the low current density cycle performance of the embodiment of the present invention 1 product and different cycle-index charging and discharging curve figure;
Fig. 5 is the cycle performance of battery figure of the embodiment of the present invention 1 product.
Embodiment
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is described.
Embodiment 1, see shown in Fig. 1 to Fig. 5:
The invention provides a kind of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode and preparation method thereof, comprise the steps (as shown in Figure 1):
1) by 1.26g ferrous oxalate dihydrate (FeC
2o
42H
2o), 2.56g oxalic acid (C
2h
2o
42H
2o) join in 20mL distilled water, form yellow suspension solution;
2) by 0.75g lithium acetate (CH
3cOOLi2H
2o) be dissolved in 10mL distilled water, form settled solution; By 0.3g glucose (C
6h
12o
6h
2o) be dissolved in 10mL distilled water, form settled solution; Respectively lithium acetate solution, 480 μ L phosphoric acid, glucose solution are added (lithium source and phosphorus source mol ratio are 1.05: 1, and lithium source actual amount is 1.05 times of required reacting dose) in above-mentioned yellow suspension;
3) by after stirring 24h at above-mentioned yellow suspension 80 DEG C, yellow suspension becomes yellow solution; Yellow sol is obtained by after yellow solution stirring and drying; The solid obtained after yellow sol being dried at 120 DEG C is placed in ball mill ball milling 12 hours, obtains bronzing precursor powder;
4) by precursor powder pre-burning 5h under 350 DEG C of nitrogen atmospheres, be placed in ball mill by pre-burning product, and add alcohol as ball-milling medium, ball milling 5h post-drying, obtains Red-brown powder, then calcines 12h under 600 DEG C of nitrogen atmospheres, obtains product.
The structure of the present embodiment product is determined by X-ray diffractometer, and its X ray diffracting spectrum (XRD) (see Fig. 2) shows, product is LiFePO
4(JCPDSNo.01-081-1173), without other dephasign peaks, carbon is agraphitic carbon.
ESEM (SEM) image (see Fig. 3) of the present embodiment product shows, product is nanometer spherical particle, and granular size is 100-200nm, and particle size distribution is comparatively even.
The product of the present embodiment gained is as follows as the application of anode active material of lithium ion battery: the preparation process of positive plate adopts the present embodiment product as active material, acetylene black is as conductive agent, polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, polytetrafluoroethylene is 70: 20: 10; After they fully being mixed in proportion, add a small amount of isopropyl alcohol, grinding evenly, twin rollers is pressed the electrode slice that about 0.5mm is thick; It is for subsequent use after 24 hours that the positive plate pressed is placed in the oven drying of 80 DEG C.With the LiPF of 1M
6be dissolved in as electrolyte in vinyl carbonate (EC) and dimethyl carbonate (DMC), lithium sheet is negative pole, and Celgard2325 is barrier film, and CR2025 type stainless steel is that battery case is assembled into fastening lithium ionic cell.All the other steps of the preparation method of lithium ion battery are identical with common preparation method.
Carry out performance test to application the present embodiment product of above-mentioned making as the lithium ion battery of positive electrode active materials, wherein as shown in Figure 4, cycle performance of battery as shown in Figure 5 for the low current density cycle performance of the present embodiment product and charging and discharging curve figure.From Fig. 4 A, the first discharge specific capacity of the present embodiment product under 0.5C (1C=170mA/g) current density can reach 154mAh/g, and after 800 circulations, capacity still can reach 146mAh/g.Fig. 4 B shows, the present embodiment product has highly stable stable platform in charge and discharge process, and after from the 1st time to circulation 800 times, discharge voltage is still stabilized in 3.4V, and charging/discharging voltage difference maintains below 0.05V all the time, and ripple disable.This shows that the present embodiment product polarizes very little and has very excellent cyclical stability.
Fig. 5 A shows, under 2C (1C=170mA/g) current density, the first discharge specific capacity of the present embodiment product can reach 140mAh/g, and after 800 circulations, capacity still can reach 127mAh/g, and capability retention reaches 90.7%.In addition, as can be seen from Fig. 5 B, the cyclical stability of the present embodiment product is also very outstanding, and under the current density of 5C, the specific capacity after material circulation 1000 times is still 118mAh/g, and capability retention is 93.7%.Above-mentioned performance shows, the present embodiment product has that capacity is high, high rate performance is excellent and the advantage of good cycling stability, is a kind of desirable anode material for lithium-ion batteries.
Embodiment 2:
1) by 1.26g ferrous oxalate dihydrate (FeC
2o
42H
2o), 1.28g oxalic acid (C
2h
2o
42H
2o) join in 20mL distilled water, form yellow suspension solution;
2) by 0.3084g Lithium hydroxide monohydrate (LiOHH
2o) be dissolved in 10mL distilled water, form settled solution; By 0.3g sucrose (C
12h
22o
11) be dissolved in 10mL distilled water, form settled solution; Respectively lithium hydroxide solution, 480 μ L phosphoric acid, sucrose solution are added (lithium source and phosphorus source mol ratio are 1.05: 1, and lithium source actual amount is 1.05 times of required reacting dose) in above-mentioned yellow suspension;
3) by after stirring 36h at above-mentioned yellow suspension 90 DEG C, yellow suspension becomes yellow solution; Yellow sol is obtained by after yellow solution stirring and drying; The solid obtained after yellow sol being dried at 120 DEG C is placed in ball mill ball milling 6 hours, obtains bronzing precursor powder;
4) by precursor powder pre-burning 6h under 375 DEG C of nitrogen atmospheres, be placed in ball mill by pre-burning product, and add isopropyl alcohol as ball-milling medium, ball milling 1h post-drying, obtains Red-brown powder, then calcines 12h under 625 DEG C of nitrogen atmospheres, obtains product.
After becoming lithium ion battery with the production of the present embodiment gained, carry out performance test, under 5C current density, LiFePO
4the first discharge specific capacity of/C can reach 125mAh/g, and after 1000 circulations, specific discharge capacity is 115mAh/g, and capability retention is 92%.
Embodiment 3:
1) by 1.26g ferrous oxalate dihydrate (FeC
2o
42H
2o), 5.12g oxalic acid (C
2h
2o
42H
2o) join in 20mL distilled water, form yellow suspension solution;
2) by 0.75g lithium acetate (CH
3cOOLi2H
2o) be dissolved in 10mL distilled water, form settled solution; By 0.8051g ammonium dihydrogen phosphate (NH
4h
2pO
4) be dissolved in 10mL distilled water, form settled solution; By 0.3g glucose (C
6h
12o
6h
2o) be dissolved in 10mL distilled water, form settled solution; Respectively lithium acetate solution, ammonium dihydrogen phosphate, glucose solution are added (lithium source and phosphorus source mol ratio are 1.05: 1, and lithium source actual amount is 1.05 times of required reacting dose) in above-mentioned yellow suspension;
3) by after stirring 12h at above-mentioned yellow suspension 95 DEG C, yellow suspension becomes yellow solution; Yellow sol is obtained by after yellow solution stirring and drying; The solid obtained after yellow sol being dried at 120 DEG C is placed in ball mill ball milling 24 hours, obtains bronzing precursor powder;
4) by precursor powder pre-burning 7h under 300 DEG C of nitrogen atmospheres, pre-burning product is placed in ball mill, and add 1: 1 alcohol and isopropyl alcohol mixed liquor as ball-milling medium, ball milling 5h post-drying, obtain Red-brown powder, then calcine 15h under 550 DEG C of nitrogen atmospheres, obtain product.
After becoming lithium ion battery with the production of the present embodiment gained, carry out performance test, under 5C current density, LiFePO
4the first discharge specific capacity of/C can reach 124mAh/g, and after 1000 circulations, specific discharge capacity is 117mAh/g, and capability retention is 94.4%.
Embodiment 4:
1) by 1.26g ferrous oxalate dihydrate (FeC
2o
42H
2o), 1.75g oxalic acid (C
2h
2o
42H
2o) join in 20mL distilled water, form yellow suspension solution;
2) by 0.5067g lithium nitrate (LiNO
3) be dissolved in 10mL distilled water, form settled solution; By 0.8051g ammonium dihydrogen phosphate (NH
4h
2pO
4) be dissolved in 10mL distilled water, form settled solution; By 0.3g sucrose (C
12h
22o
11) be dissolved in 10mL distilled water, form settled solution; Respectively lithium nitrate solution, ammonium dihydrogen phosphate, sucrose solution are added (lithium source and phosphorus source mol ratio are 1.05: 1, and lithium source actual amount is 1.05 times of required reacting dose) in above-mentioned yellow suspension;
3) by after stirring 30h at above-mentioned yellow suspension 85 DEG C, yellow suspension becomes yellow solution; Yellow sol is obtained by after yellow solution stirring and drying; The solid obtained after yellow sol being dried at 120 DEG C is placed in ball mill ball milling 24 hours, obtains bronzing precursor powder;
4) by precursor powder pre-burning 6h under 350 DEG C of nitrogen atmospheres, pre-burning product is placed in ball mill, and add 1: 2 alcohol and isopropyl alcohol mixed liquor as ball-milling medium, ball milling 1h post-drying, obtain Red-brown powder, then calcine 15h under 700 DEG C of nitrogen atmospheres, obtain product.
After becoming lithium ion battery with the production of the present embodiment gained, carry out performance test, under 5C current density, LiFePO
4the first discharge specific capacity of/C can reach 118mAh/g, and after 1000 circulations, specific discharge capacity is 110mAh/g, and capability retention is 93.2%.
Embodiment 5:
1) by 1.26g ferrous oxalate dihydrate (FeC
2o
42H
2o), 3.85g oxalic acid (C
2h
2o
42H
2o) join in 20mL distilled water, form yellow suspension solution;
2) by 0.3084g Lithium hydroxide monohydrate (LiOHH
2o) be dissolved in 10mL distilled water and be dissolved in 10mL distilled water, form settled solution; By 0.8051g ammonium dihydrogen phosphate (NH
4h
2pO
4) be dissolved in 10mL distilled water, form settled solution.By 0.3g sucrose (C
12h
22o
11) be dissolved in 10mL distilled water, form settled solution.Respectively lithium hydroxide solution, ammonium dihydrogen phosphate, sucrose solution are added (lithium source and phosphorus source mol ratio are 1.05: 1, and lithium source actual amount is 1.05 times of required reacting dose) in above-mentioned yellow suspension;
3) by after stirring 18h at above-mentioned yellow suspension 80 DEG C, yellow suspension becomes yellow solution; Yellow sol is obtained by after yellow solution stirring and drying; The solid obtained after yellow sol being dried at 120 DEG C is placed in ball mill ball milling 1 hour, obtains bronzing precursor powder;
4) by precursor powder pre-burning 4h under 375 DEG C of nitrogen atmospheres, pre-burning product is placed in ball mill, and add 2: 1 alcohol and isopropyl alcohol mixed liquor as ball-milling medium, ball milling 12h post-drying, obtain Red-brown powder, then calcine 10h under 650 DEG C of nitrogen atmospheres, obtain product.
After becoming lithium ion battery with the production of the present embodiment gained, carry out performance test, under 5C current density, LiFePO
4the first discharge specific capacity of/C can reach 115mAh/g, and after 1000 circulations, specific discharge capacity is 111mAh/g, and capability retention is 96.5%.
Above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although above-described embodiment is to invention has been detailed description, the person skilled of this area is to be understood that: can modify to the present invention or replace on an equal basis, but any amendment not departing from spirit and scope of the invention all should be encompassed in right of the present invention with local replacement.
Claims (10)
1. an in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode, is characterized in that, is prepared by liquid phase ball-milling method, and product particle Surface coating has even carbon-coating, is interconnected between particle by agraphitic carbon net, and the particle diameter of described particle is 100-200nm.
2. in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 1, is characterized in that, as anode active material of lithium ion battery.
3. a preparation method for in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode, is characterized in that, comprises the steps:
1) preparation of precursor powder: source of iron and oxalic acid are joined in distilled water and stirs, obtain yellow suspension; 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 adding thermal agitation; Obtain yellow sol after stirring and drying, yellow sol is placed in drying in oven and carries out solid-phase ball milling and obtain precursor powder;
2) preparation of product: by precursor powder pre-burning under protective gas atmosphere, pre-burning product is calcined after liquid phase ball milling, oven dry under protective gas atmosphere again, obtains black product.
4. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, described source of iron is ferrous oxalate, and the mol ratio of described ferrous oxalate and oxalic acid is 1: 1 ~ 1: 6.
5. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, described lithium source is LiOHH
2o, CH
3cOOLi2H
2o, LiNO
3in any one or more than one mixture.
6. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, described phosphorus source is H
3pO
4, NH
4h
2pO
4or both mixtures.
7. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, described carbon source is C
6h
12o
6h
2o, C
12h
22o
11or both mixtures.
8. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, described in add thermal agitation temperature be 80-95 DEG C, heating mixing time is 12-36 hour; The time of described solid-phase ball milling is 1-24 hour.
9. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, described protective gas is nitrogen, and the temperature of described pre-burning is 300-400 DEG C, and the time is 3-7 hour.
10. the preparation method of in-situ carbon coated LiFePO 4 for lithium ion batteries positive electrode according to claim 3, is characterized in that, the liquid of described liquid phase ball milling is alcohol, isopropyl alcohol or both mixtures, and the time of ball milling is 1-12 hour; The temperature of described calcining is 550-700 DEG C, and the time is 10-15 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359336A (en) * | 2017-07-12 | 2017-11-17 | 北方奥钛纳米技术有限公司 | The preparation method and LiFePO4 and lithium ion battery of LiFePO4 |
| CN108172813A (en) * | 2018-02-01 | 2018-06-15 | 广东工业大学 | A kind of composite positive pole and preparation method thereof |
| CN112794301A (en) * | 2021-01-06 | 2021-05-14 | 中国地质大学（武汉） | Grid-structured carbon-coated lithium iron phosphate nano-particles and preparation method and application thereof |
| CN113540410A (en) * | 2021-07-12 | 2021-10-22 | 天津大学 | Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method |
Citations (1)
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| CN104409688A (en) * | 2014-10-29 | 2015-03-11 | 中航锂电（洛阳）有限公司 | Lithium iron phosphate material for lithium ion power battery, and preparation method thereof |
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| CN104409688A (en) * | 2014-10-29 | 2015-03-11 | 中航锂电（洛阳）有限公司 | Lithium iron phosphate material for lithium ion power battery, and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107359336A (en) * | 2017-07-12 | 2017-11-17 | 北方奥钛纳米技术有限公司 | The preparation method and LiFePO4 and lithium ion battery of LiFePO4 |
| CN108172813A (en) * | 2018-02-01 | 2018-06-15 | 广东工业大学 | A kind of composite positive pole and preparation method thereof |
| CN108172813B (en) * | 2018-02-01 | 2020-12-08 | 广东工业大学 | Composite cathode material and preparation method thereof |
| CN112794301A (en) * | 2021-01-06 | 2021-05-14 | 中国地质大学（武汉） | Grid-structured carbon-coated lithium iron phosphate nano-particles and preparation method and application thereof |
| CN112794301B (en) * | 2021-01-06 | 2022-08-09 | 中国地质大学（武汉） | Grid-structured carbon-coated lithium iron phosphate nano-particles and preparation method and application thereof |
| CN113540410A (en) * | 2021-07-12 | 2021-10-22 | 天津大学 | Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method |
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