CN106410143B - A kind of foamy graphite alkene-composite ferric lithium phosphate material and preparation method thereof - Google Patents
A kind of foamy graphite alkene-composite ferric lithium phosphate material and preparation method thereof Download PDFInfo
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- CN106410143B CN106410143B CN201610918378.9A CN201610918378A CN106410143B CN 106410143 B CN106410143 B CN 106410143B CN 201610918378 A CN201610918378 A CN 201610918378A CN 106410143 B CN106410143 B CN 106410143B
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- graphite alkene
- foamy graphite
- lithium
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- phosphate material
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- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 82
- 239000010439 graphite Substances 0.000 title claims abstract description 82
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 title claims description 65
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims description 46
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims description 46
- 229910052493 LiFePO4 Inorganic materials 0.000 claims abstract description 46
- -1 graphite alkene Chemical class 0.000 claims abstract description 38
- 239000006260 foam Substances 0.000 claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims abstract description 5
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000011806 microball Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 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 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001282 polysaccharide Polymers 0.000 claims description 4
- 239000005017 polysaccharide Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 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 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 5
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003342 alkenyl group Chemical group 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 27
- 229910001416 lithium ion Inorganic materials 0.000 description 27
- 229910021389 graphene Inorganic materials 0.000 description 17
- 239000010405 anode material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005955 Ferric phosphate Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940032958 ferric phosphate Drugs 0.000 description 2
- 229940116007 ferrous phosphate Drugs 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 2
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 2
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000901 LiFePO4/C Inorganic materials 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010792 warming 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of foamy graphite alkenyl phosphoric acid iron lithium composite material, it is characterized in that LiFePO4 grows synthesis in the network structure of foamy graphite alkene, the spherical foam grapheme lithium iron phosphate composite material of formation regular appearance, good fluidity, foamy graphite alkene not exclusively closely coat LiFePO4.Preparation method is further provided for, using foamy graphite alkene as template and controlling agent, by emulsifying the formation acquisition spherical foam grapheme lithium iron phosphate composite material for promoting with high-speed stirred and controlling spherical LiFePO 4 under the conditions of colloid.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, and it is compound to be related to a kind of foamy graphite alkene-LiFePO4
Material and preparation method thereof.
Background technology
The energy is the important substance basis of human survival and development, is motive power and the society for being engaged in various economic activities
The important symbol of the meeting level of economic development.It is many with petering out and caused by it the problems such as global warming for fossil fuel
More researchers start gradually to pay close attention to New Energy Industry.Wherein, lithium ion battery with its operating voltage it is high, it is bigger than energy, light-weight,
It is small, have extended cycle life, memory-less effect, can fast charging and discharging and non-environmental-pollution etc. it is a series of notable the advantages of and become
The research hotspot of new energy field.
LiFePO4（LiFePO4）It is current the most common type anode material for lithium-ion batteries, there is stable olive
Stone structure, insertion that can be reversible and deintercalate lithium ions.It has higher voltage platform (3.4-3.5V), higher theoretical capacity
(for 170mAh/g), the good cycle (LiFePO synthesized under optimal conditions4, it is 2000 times or more recyclable), stability it is good, high
Warm nature can it is good, have a safety feature, building-up process is simple, environmentally friendly, the features such as nontoxic, abundant raw material, therefore be considered as
Most potential anode material for lithium-ion batteries.But since the uniqueness of LiFePO4 structure has obstructed the conduction of electronics,
So that the electronic conductivity very low (10 of pure phase LiFePO4-9S/cm), ionic diffusion coefficient is low, leads to it in high current charge-discharge
Shi Rongliang is relatively low, i.e., high rate capability is poor, largely constrains application and popularization of the material in power battery field.
In view of such shortcoming, each manufacturer and colleges and universities carry out successively improves LiFePO4The research of performance, including coating, adulterating, being modified skill
Art etc..The mode of generally use is crystal grain thinning, ion doping and carbon coating herein.But ion is excessively refined and can be generated
Agglomeration, and ion doping is then difficult to realize industrialize, while easily generates new impurity, production technology complexity stability
Difference can not meet the needs of volume production, so, carbon coating is one of effective method of modifying.Carbon coating not only can be improved directly
Electronic conductivity promotes the migration of lithium ion, and is taken off in the excessive growth course of limitation crystal and lithium ion to a certain extent
The volume change improvement of embedding process buffers material is apparent.The patent document of carbon coating positive electrode is also disclosed, for example, specially
Sharp document CN101483236A discloses a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery/carbon complex,
It by iron oxide hydroxide, lithium salts, microcosmic salt, is mixed according to stoichiometric ratio, adds in proper amount of carbon source and liquid ball-milling medium, ball milling is done
Mixture after dry reacts at a certain temperature, finally obtains ferrous phosphate lithium/carbon compound.But if LiFePO4Material
Carbon coating layer it is thicker, lithium ion is diffused into LiFePO4, the rate of material internal it is slower, carbon coating layer is closer, lithium ion
Conducting power it is lower.Therefore, a kind of conductivity height and the ultra-thin carbon encapsulated material of structure are selected, to improving LiFePO4Material
The ionic conductivity and electrode power density of material are vital.
Graphene is a kind of new material of carbon family very popular in recent years, and thickness only has 0.335nm, has uniqueness
Electronic structure and electrical properties.Valence band and conduction band intersect on six vertex of fermi level in the band structure of graphene,
In this sense, graphene is a kind of substance without energy gap, shows metallicity.In single-layer graphene, each carbon is former
The electronics of a non-bonding is all contributed, these electronics can move freely in crystal, assign that graphene is extraordinary to lead
Electrically.The Typical conductive rate of electronics has reached the 1/300 of the light velocity in graphene, considerably beyond electronics in general semiconductor
Conduction of velocity.Therefore, appropriately and dexterously by the excellent electric conductivity of graphene and the special chemical property of LiFePO4
Combine, exploitation graphene modified phosphate iron lithium anode composite material is possibly realized.Such as patent document CN102683697B public affairs
A kind of preparation method of graphene-based LiFePO4/C composite materials is opened, to solve existing lithium iron phosphate positive material electric conductivity
The problem of difference, high rate performance is poor.
But the most of graphene coated structures currently reported are all very fine and close, particularly a piece of larger graphene nano
Piece often closely wraps a LiFePO completely4Nano particle leads to lithium ion diffusion hindered, is unfavorable for high rate performance
Raising.And graphene is nanometer materials, reunion causes the covered effect of graphene and material poor, coats loose easily de-
From.
Invention content
In view of the shortcomings that above-mentioned prior art, the present invention provides a kind of foamy graphite alkene-composite ferric lithium phosphate material, special
Sign is that LiFePO4 grows synthesis in the network structure of foamy graphite alkene, formed regular appearance, good fluidity spheric bulb
Foam graphene-composite ferric lithium phosphate material, foamy graphite alkene not exclusively closely coat LiFePO4.Further provide for preparation method,
Using foamy graphite alkene as template and controlling agent, promoted under the conditions of colloid by emulsification and high-speed stirred and control spherical phosphorus
The formation of sour iron lithium obtains spherical foam graphene-composite ferric lithium phosphate material.
In order to reach aforementioned goal of the invention, specific scheme is as follows：
A kind of foamy graphite alkene-composite ferric lithium phosphate material, it is characterized in that network knot of the LiFePO4 in foamy graphite alkene
In structure grow synthesis, formed regular appearance, good fluidity spherical foam graphene-composite ferric lithium phosphate material, foam stone
Black alkene not exclusively closely coats LiFePO4, the mass ratio of the foamy graphite alkene and the LiFePO4 is（1-3）：20.
In above-mentioned foamy graphite alkene-composite ferric lithium phosphate material, it is preferable that the hole diameter of the foamy graphite alkene is
50-500nm。
If in general, LiFePO4（LiFePO4）The particle of material is smaller, and cladding substance is more, and tap density will
It is lower.The particularly LiFePO of irregular shape4Encapsulated nanoparticles, tap density are generally no greater than 1.0g/cm3.Cause
This, with respect to traditional structure, above-mentioned foamy graphite alkene-composite ferric lithium phosphate material, the cable of foamy graphite alkene is through ferric phosphate
Lithium, and with LiFePO4 formed one have regular appearance, good fluidity spherical structure, can realize it is tightly packed, significantly
Improve LiFePO4The tap density and energy density of positive electrode, can prepare high-energy density electrode；And spherical structure table
Face is smooth, specific surface area is low, it is possible to reduce the generation with electrolyte side reaction improves the first charge-discharge effect of lithium ion battery
Rate.Further, the electric conductivity of foamy graphite alkene is fully played, not exclusively close cladding LiFePO4, lithium can be improved
The conducting power of ion.
The present invention also provides the preparation methods of above-mentioned foamy graphite alkene-composite ferric lithium phosphate material, include the following steps：
Step 1：Foamy graphite alkene powder is mixed to form colloidal solution and is displayed more than for 24 hours with polysaccharide, water makes grapheme foam complete
Full colloidization；
Step 2：Source of iron and phosphorus source are added in the colloidal solution obtained to step 1, and adds in ammonia spirit and excessive dioxygen
Water obtains mixed solution, and hydro-thermal reaction 5h-10h, then adds in lithium source at a temperature of being placed in 80 DEG C -100 DEG C, in grapheme foam
LiFePO4 is formed in structure, further adds in emulsifier, by being higher than the rotating speed high-speed stirred of 5000rpm, using foam stone
Black alkene is promoted by emulsification and high-speed stirred under the conditions of colloid as template and controlling agent and controls the shape of spherical LiFePO 4
Into, make foamy graphite alkene network LiFePO4 formed gel micro-ball；
Step 3：The gel micro-ball that step 2 is obtained is freeze-dried, and is subsequently placed in protection gas in 700 DEG C of -800 DEG C of temperature
The lower calcining 4-6h of degree, obtains foamy graphite alkene-composite ferric lithium phosphate material.
Wherein, the source of iron, phosphorus source and lithium source are according to Fe：P：Li=4：5：5 molar ratio ingredient.
Preferably, the polysaccharide includes the combination of one or more of glucose, sucrose, starch and cellulose.
Preferably, the source of iron includes the combination of one or more of iron chloride, ferric nitrate and ferric sulfate.
Preferably, phosphorus source includes one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate
Combination.
Preferably, the lithium source includes the combination of one or more of lithium acetate, lithium nitrate, lithium carbonate.
In LiFePO4 forming process, foamy graphite alkene is added in as template and controlling agent, and in emulsifier condition
Lower high-speed stirred promotes the formation of spherical structure, and controls material morphology well.The preparation method can obtain porous logical
Foamy graphite alkene-the composite ferric lithium phosphate material in road, macroporous network structure, and foamy graphite alkene not exclusively closely coats
LiFePO4, while lithium ion conduction ability is improved, and the network conduction of foamy graphite alkene is increased, traditional addition
It is compared with doping, foamy graphite alkene-composite ferric lithium phosphate material which obtains is more uniformly distributed, stable quality.It can be big
Width promotes the electric conductivity and quality stability of current ferric phosphate lithium cell.Improve lithium iron phosphate positive material filling under high magnification
Discharge performance.
Above-mentioned foamy graphite alkene-composite ferric lithium phosphate material is used for lithium ion battery as positive electrode.The lithium ion
Battery includes battery case, pole piece and electrolyte, and the pole piece and electrolyte are sealingly received in the battery case, the pole piece packet
Anode, cathode and the diaphragm between positive electrode and negative electrode are included, the anode is including collector and load on a current collector just
Pole material, the cathode include the negative material of collector and load on a current collector, and the main body of the positive electrode is described
Foamy graphite alkene-composite ferric lithium phosphate material.
It is powerful excellent in promotion lithium battery that one typical application has shown foamy graphite alkene-composite ferric lithium phosphate material
Gesture.Using foamy graphite alkene-composite ferric lithium phosphate material in anode material of lithium battery, specific discharge capacity is under 0.1C multiplying powers
Specific discharge capacity is 135 mAh/g- 154mAh/g under 150 mAh/g-170mAh/g, 5C multiplying power.High-rate discharge ability is excellent
It is different.
A kind of foamy graphite alkene-composite ferric lithium phosphate material provided by the invention and preparation method thereof, with prior art phase
Than, protrude the characteristics of and excellent effect be：
（1）Foamy graphite alkene-composite ferric lithium phosphate material provided by the invention, the cable of foamy graphite alkene is through phosphoric acid
Iron lithium, and with LiFePO4 formed one have regular appearance, good fluidity spherical structure, can realize it is tightly packed, greatly
Improve LiFePO greatly4The tap density and energy density of positive electrode.The defects of breaching traditional directly doping, cladding.
（2）Foamy graphite alkene-composite ferric lithium phosphate material provided by the invention, using foamy graphite alkene as template and control
Preparation is promoted by emulsification and high-speed stirred under the conditions of colloid and controls the formation of spherical LiFePO 4, makes foamy graphite alkene
Network LiFePO4 forms gel micro-ball；Surface with rounded structures is smooth, specific surface area is low, it is possible to reduce with electrolyte side reaction
Occur, improve charge-discharge performance of the lithium iron phosphate positive material under high magnification.
（3）The preparation method of foamy graphite alkene-composite ferric lithium phosphate material provided by the invention, technique is easily-controllable, is easy to criticize
Measure stable preparation.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to following example.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material is present embodiments provided, including following step
Suddenly：
Step 1：Foamy graphite alkene powder is mixed to form colloidal solution and is displayed more than for 24 hours with sucrose, water makes grapheme foam complete
Full colloidization；
Step 2：Iron chloride and phosphoric acid are added in the colloidal solution obtained to step 1, and adds in ammonia spirit and excessive pair
Oxygen water, obtains mixed solution, and hydro-thermal reaction 5h-10h, then adds in lithium acetate at a temperature of being placed in 80 DEG C -100 DEG C, in graphene
LiFePO4 is formed in foaming structure, emulsifier NP-10 is further added in, by the rotating speed high-speed stirred of 8000rpm, makes foam
Graphene network LiFePO4 simultaneously forms gel micro-ball；
Step 3：The gel micro-ball that step 2 is obtained is freeze-dried, and is subsequently placed in argon gas protection gas at 700 DEG C -800
DEG C temperature lower calcination 6h, obtains foamy graphite alkene-composite ferric lithium phosphate material.
Wherein, the source of iron, phosphorus source and lithium source are according to Fe：P：Li=4：5：5 molar ratio ingredient.
Foamy graphite alkene, sucrose, LiFePO4 are according to Theoretical Mass 1:0.1:20 dispensings.
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to test, foamy graphite alkene is to spherical junctions
The coverage rate of the LiFePO4 of structure be 21%, a diameter of 4.2 μm -4.9 μm of spherical structure.
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to be made as the positive electrode of lithium ion battery
Button-shaped lithium ion battery, the lithium ion battery lithium ion battery under 0.1C multiplying powers specific discharge capacity be 158 mAh/g, 5C times
Specific discharge capacity is 117 mAh/g under rate.
Embodiment 2
A kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material is present embodiments provided, including following step
Suddenly：
Step 1：Foamy graphite alkene powder is mixed to form colloidal solution and is displayed more than for 24 hours with starch, water makes grapheme foam complete
Full colloidization；
Step 2：Ferric nitrate and ammonium dihydrogen phosphate are added in the colloidal solution obtained to step 1, and add in ammonia spirit and
Excessive hydrogen peroxide, obtains mixed solution, and hydro-thermal reaction 10h, then adds in lithium carbonate at a temperature of being placed in 80 DEG C -100 DEG C, in graphite
LiFePO4 is formed in alkene foaming structure, emulsifier NP-7 is further added in, by the rotating speed high-speed stirred of 12000rpm, makes bubble
Foam graphene network LiFePO4 simultaneously forms gel micro-ball；
Step 3：The gel micro-ball that step 2 is obtained is freeze-dried, and is subsequently placed in nitrogen protection gas at 700 DEG C -800
DEG C temperature lower calcination 4h, obtains foamy graphite alkene-composite ferric lithium phosphate material.
Wherein, the source of iron, phosphorus source and lithium source are according to Fe：P：Li=4：5：5 molar ratio ingredient.
Foamy graphite alkene, starch, LiFePO4 are according to Theoretical Mass 2:0.1:20 dispensings.
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to test, a diameter of the 3.9 of spherical structure
μm-4.5μm。
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to be made as the positive electrode of lithium ion battery
Button-shaped lithium ion battery, the lithium ion battery lithium ion battery under 0.1C multiplying powers specific discharge capacity be 162 mAh/g, 5C times
Specific discharge capacity is 122mAh/g under rate.
Embodiment 3
A kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material is present embodiments provided, including following step
Suddenly：
Step 1：Foamy graphite alkene powder and cellulose, water, which are mixed to form colloidal solution and are displayed more than for 24 hours, makes grapheme foam
Complete colloidization；
Step 2：Ferric sulfate and phosphoric acid are added in the colloidal solution obtained to step 1, and adds in ammonia spirit and excessive pair
Oxygen water, obtains mixed solution, and hydro-thermal reaction 8h, then adds in lithium source at a temperature of being placed in 80 DEG C -100 DEG C, in grapheme foam knot
LiFePO4 is formed in structure, emulsifier polyoxyethylene oleic acid ester is further added in, by the rotating speed high-speed stirred of 6000rpm, makes
Foamy graphite alkene network LiFePO4 simultaneously forms gel micro-ball；
Step 3：The gel micro-ball that step 2 is obtained is freeze-dried, and is subsequently placed in nitrogen protection gas at 700 DEG C -800
DEG C temperature lower calcination 5h, obtains foamy graphite alkene-composite ferric lithium phosphate material.
Wherein, the source of iron, phosphorus source and lithium source are according to Fe：P：Li=4：5：5 molar ratio ingredient.
Foamy graphite alkene, cellulose, LiFePO4 are according to Theoretical Mass 3:0.1:20 dispensings.
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to test, spherical structure foamy graphite alkene-
Composite ferric lithium phosphate material has porous channel structure, and LiFePO4 is embedded in the hole of foamy graphite alkene, spherical structure
A diameter of 4.5 μm -5.2 μm.
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to be made as the positive electrode of lithium ion battery
Button-shaped lithium ion battery, the lithium ion battery lithium ion battery under 0.1C multiplying powers specific discharge capacity be 167 mAh/g, 5C times
Specific discharge capacity is 130 mAh/g under rate.
Embodiment 4
A kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material is present embodiments provided, including following step
Suddenly：
Step 1：Foamy graphite alkene powder and glucose, water, which are mixed to form colloidal solution and are displayed more than for 24 hours, makes grapheme foam
Complete colloidization；
Step 2：Iron chloride and ammonium phosphate are added in the colloidal solution obtained to step 1, and adds in ammonia spirit and excess
Hydrogen peroxide obtains mixed solution, and hydro-thermal reaction 5h, then adds in lithium acetate at a temperature of being placed in 80 DEG C -100 DEG C, is steeped in graphene
LiFePO4 is formed in foam structure, further adds in emulsifier, by being higher than the rotating speed high-speed stirred of 5000rpm, makes foam stone
Black alkene network LiFePO4 simultaneously forms gel micro-ball；
Step 3：The gel micro-ball that step 2 is obtained is freeze-dried, and is subsequently placed in protection gas in 700 DEG C of -800 DEG C of temperature
The lower calcining 6h of degree, obtains foamy graphite alkene-composite ferric lithium phosphate material.
Wherein, the source of iron, phosphorus source and lithium source are according to Fe：P：Li=4：5：5 molar ratio ingredient.
Foamy graphite alkene, glucose, LiFePO4 are according to Theoretical Mass 2:0.1:20 dispensings.
The present embodiment is made foamy graphite alkene-composite ferric lithium phosphate material to test, a diameter of the 4.7 of spherical structure
μm-5.5μm。
Using foamy graphite alkene-composite ferric lithium phosphate material in anode material of lithium battery, discharge ratio under 0.1C multiplying powers
Capacity is 150 mAh/g-170mAh/g, and specific discharge capacity is 135 mAh/g- 154mAh/g under 5C multiplying powers.High-multiplying power discharge
It can be excellent.
Claims (7)
1. a kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material, it is characterized in that LiFePO4 is in foamy graphite alkene
Network structure in grow synthesis, formed regular appearance, good fluidity spherical foam graphene-LiFePO4 composite wood
Material, the mass ratio of the foamy graphite alkene and the LiFePO4 are（1-3）：20；
Preparation method includes the following steps：
Step 1：Foamy graphite alkene powder and polysaccharide, water, which are mixed to form colloidal solution and are displayed more than for 24 hours, makes the complete glue of grapheme foam
State；
Step 2：Source of iron and phosphorus source are added in the colloidal solution obtained to step 1, and adds in ammonia spirit and excessive hydrogen peroxide, is obtained
To mixed solution, hydro-thermal reaction 5h-10h, then adds in lithium source at a temperature of being placed in 80 DEG C -100 DEG C, in grapheme foam structure
LiFePO4 is formed, further adds in emulsifier, by being higher than the rotating speed high-speed stirred of 5000rpm, is made using foamy graphite alkene
For template and controlling agent, promoted under the conditions of colloid by emulsification and high-speed stirred and control the formation of spherical LiFePO 4, made
Foamy graphite alkene network LiFePO4 forms gel micro-ball；
Step 3：The gel micro-ball that step 2 is obtained is freeze-dried, and is subsequently placed in protection gas at a temperature of 700 DEG C -800 DEG C
4-6h is calcined, obtains foamy graphite alkene-composite ferric lithium phosphate material.
2. a kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material according to claim 1, it is characterised in that：
The hole diameter of the foamy graphite alkene is 50-500nm.
3. a kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material according to claim 1, it is characterised in that：
The source of iron, phosphorus source and lithium source are according to Fe：P：Li=4：5：5 molar ratio ingredient.
4. a kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material according to claim 1, it is characterised in that：
The polysaccharide includes the combination of one or more of glucose, sucrose, starch and cellulose.
5. a kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material according to claim 1, it is characterised in that：
The source of iron includes the combination of one or more of iron chloride, ferric nitrate and ferric sulfate.
6. a kind of preparation method of foamy graphite alkene-composite ferric lithium phosphate material according to claim 1, it is characterised in that：
Phosphorus source includes the combination of one or more of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate.
A kind of 7. preparation method of foamy graphite alkene-composite ferric lithium phosphate material according to claim 1, it is characterised in that institute
State the combination that lithium source includes one or more of lithium acetate, lithium nitrate, lithium carbonate.
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| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN103840156A (en) * | 2014-03-03 | 2014-06-04 | 东南大学 | Preparation method for phosphate-graphene foam anode material |
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| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
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