CN104362340B - High-performance lithium iron phosphate cathode material and preparation method thereof - Google Patents
High-performance lithium iron phosphate cathode material and preparation method thereof Download PDFInfo
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- CN104362340B CN104362340B CN201410478278.XA CN201410478278A CN104362340B CN 104362340 B CN104362340 B CN 104362340B CN 201410478278 A CN201410478278 A CN 201410478278A CN 104362340 B CN104362340 B CN 104362340B
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- iron phosphate
- lithium iron
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000010406 cathode material Substances 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003701 mechanical milling Methods 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010405 anode material Substances 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-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
- 239000002245 particle Substances 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 150000002835 noble gases Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000011164 primary particle Substances 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims 2
- 238000009413 insulation Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910021389 graphene Inorganic materials 0.000 description 10
- 229910052493 LiFePO4 Inorganic materials 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 239000011363 dried mixture Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 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 2
- 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 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- -1 compound lithium iron phosphate Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 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 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 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
- H01M4/58—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
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a high-performance lithium iron phosphate cathode material for a lithium ion battery. During the preparation process, a carbon source used is a product obtained after nitrogen treatment of cigarette filters in ammonia gas. The invention also provides a preparation method of the lithium iron phosphate cathode material. The preparation method comprises the following steps: a product obtained after nitrogen treatment of cigarette filters in ammonia gas is firstly used as a carbon source of the lithium iron phosphate cathode material; then, an iron source, a lithium source, a phosphorus source and the above carbon source successively undergo uniform mixing, ball milling, drying, crushing and roasting so as to prepare the lithium iron phosphate cathode material. The lithium iron phosphate cathode material has outstanding merits as follows: the preparation technology is simple; cost is low; and the material is easy for large-scale production. As the product obtained after nitrogen treatment of waste cigarette filters in ammonia gas is used as the carbon source, resources are saved to realize cyclic utilization of wastes, and the lithium iron phosphate cathode material with high specific capacity and good rate capability also can be obtained. The lithium iron phosphate cathode material has important practical application value.
Description
Technical field
The present invention relates to a kind of high-performance lithium iron phosphate cathode material and preparation method thereof, especially by garbage again
The method that recycles introduces new carbon source, and using a kind of low energy consumption, environmental protection, preparation process is simple, be easy to large-scale production
The one-step technology method for preparing lithium iron phosphate cathode material for lithium ion battery.Belong to new energy materialses field.
Background technology
Global ecology and energy crisis are increasingly serious, the research and development in new type lithium ion battery and associated materials field and should
With enjoying favor, wherein, lithium iron phosphate cathode material for lithium ion battery is because with excellent chemical property, charge and discharge platform
Steadily, voltage is high, energy density is big, good cycle, little self discharge, memory-less effect, operating temperature range width the advantages of and
It is widely used, is the focus for competitively researching and developing both at home and abroad at present.Meanwhile, with the deterioration of ecological environment, the environmental protection of people
Consciousness constantly strengthens, it is well known that the cigarette end of cigarette with filter tip is seen everywhere in street corner, it is estimated that, the whole world produces big per annual meeting
About 5.6 trillion stubs, gross weight is up to 766571 tons.Many countries are all formulating strict regulation, it is desirable to reduce thus band
The pollution for coming and disaster hidden-trouble.The present invention takes the mode of environmental protection that these cigarette ends are carried out with harmless nitridationization and processes, by which
The carbon source being converted in lithium iron phosphate positive material preparation process, had not only economized on resources and has realized recycling waste but also can obtain
Specific capacity is high, the lithium iron phosphate positive material of good rate capability, with important actual application value.
At present, in large-scale production, the synthetic technology of lithium ion battery anode material lithium iron phosphate generally adopts high temperature solid-state
Reaction method, its outstanding advantages are that equipment is simple and convenient to operate, is easy to industrialized production.But the high temperature solid phase synthesis of routine exist
Shortcomings are there is also when preparing LiFePO4, secondary clacining is such as generally carried out, be increased energy consumption.Such as, Chinese invention patent
" preparation method of active compound lithium iron phosphate of lithium ion secondary battery anode " (Application No. 200710154685.5), its phosphoric acid
The preparation method of ferrum lithium is to mix source of iron, phosphorus source, lithium source and carbon source additive, by the mixture for obtaining 300～600
First sintering is carried out at DEG C, sintering time is 3～12h.The product of first sintering is carried out into ball milling and is dried, then carried out
Sinter for second, sintering temperature is 700～900 DEG C, and sintering time is 5～20h, obtains LiFePO4.Wherein, the method is also wrapped
Include before first sintering or after first sintering, under oxidizing atmosphere, by the mixture in 60～250 DEG C of temperature
Degree is lower to be heated.LiFePO4 is prepared using the method needs three calcination process, and has the temperature of two-step sintering process higher, burns
The knot time is longer, not only increased energy consumption but also has made process complications.Additionally, the carbon source that adopted is most for glucose, sucrose, even
There are CNT, Graphene etc., not only complex process but also increased cost.Such as, Chinese invention patent " a kind of LiFePO4/
The preparation method of graphene nanocomposite material " (Application No. 201210246985.7), is carbon source by solvent with Graphene
Thermal response prepares lithium iron phosphate positive material.Chinese invention patent " the preparation side of lithium iron phosphate/graphene nano composite material
Method " (Application No. 201210039290.1), Graphene or graphene oxide is scattered in aqueous solution, in inert gas shielding
The lower lithium salts added as ferric lithium phosphate precursor is simultaneously flowed back, and then obtains graphene oxide or Graphene in high annealing
The LiFePO 4 material of cladding.Above-mentioned carbon source adopts Graphene, not only complicated process of preparation but also relatively costly.
The content of the invention
High-temperature solid phase reaction method prepares problems present in LiFePO4 process at present：(1) majority needs low temperature pre-
Burning, high temperature sintering twice sintering process, sintering temperature often 600～900 DEG C of even more high temperature, calcination time mostly be 20～
60h, secondary wet process ball milling is needed, energy consumption increases in causing production process, and cost is improved.(2) the carbon source majority for being adopted is for Portugal
Grape sugar, sucrose, nanotube, Graphene etc., not only complex process but also increased cost.The present invention is primarily directed to above-mentioned existing
Problem, there is provided a kind of method for being recycled by garbage again introduces new carbon source, and using a kind of step firing process,
Low energy consumption, environmental protection, preparation process is simple, the one-step technology for being easy to large-scale production are just preparing lithium ion battery LiFePO4
The method of pole material.
The above-mentioned technical problem of the present invention is carried out by the following technical programs：A kind of high-performance acid ferrum lithium positive pole
Material and preparation method thereof, the carbon source adopted during lithium iron phosphate positive material is prepared are by discarded cigarette filter
Product in ammonia after nitrogen treatment, its preparation method are comprised the following steps：First by discarded cigarette filter in ammonia
Nitrogen treatment be used as lithium iron phosphate positive material carbon source, then by source of iron, lithium source, phosphorus source and the mixing of above-mentioned carbon source, ball milling, do
Dry, crushing, roasting are obtained above-mentioned lithium iron phosphate positive material.Concrete preparation process includes：
(1) prepared by carbon source：The discarded cigarette filter for coming will be collected to enter between 800～950 DEG C in ammonia atmosphere
Row 1.5～3h of nitrogen treatment, programming rate are maintained at 2～8 DEG C/min, obtain the nitrogenous carbon materials with sub-hole and microcellular structure
Material is used as carbon source.
(2) by lithium source, source of iron, phosphorus source and carbon source ball milling 2～12 hours, continue ball milling 2～8 in then proceeding to Ultrafine Grinding little
When, titanium oxide sol is added in mechanical milling process, the colloidal sol is formed by butyl titanate or titanium tetraisopropylate hydrolysis, its
In, the molar content of titanium is the 0.5～5% of lithium iron phosphate positive material, is then entered ball milling product using microwave drying process
Row is fully dried.
In the lithium source, source of iron, phosphorus source, lithium, ferrum, the mol ratio of phosphorus are (1～1.03): 1: 1, carbon source is just accounting for LiFePO4
The 1～25% of pole material gross mass, preferred content are 3～20%, and the content being more highly preferred to is 5～15%.
Ball-milling medium used is zirconia ball, and solvent is deionized water, or deionized water and dehydrated alcohol, polyethylene
The mixture of at least one of alcohol, ethylene glycol, n-butyl alcohol, isobutanol, acetone, hexamethylene.
The lithium source be lithium carbonate, lithium fluoride, Lithium hydrate, lithium dihydrogen phosphate, lithium acetate and lithium nitrate in one kind or
The two or more mixture of person, preferred lithium source is lithium carbonate, Lithium hydrate, lithium dihydrogen phosphate and lithium acetate, preferred lithium
Source is lithium carbonate or lithium dihydrogen phosphate, or the mixture of lithium carbonate and lithium dihydrogen phosphate；Source of iron is Ferrox., nitric acid
One or more kinds of mixture in ferrum, iron sesquioxide and hydrated ferric oxide., preferred source of iron are Ferrox., acetic acid
Ferrous and hydrated ferric oxide., preferred source of iron is Ferrox.；Phosphorus source be lithium dihydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, five
Aoxidize the one or more kinds of mixture in two phosphorus and phosphoric acid, preferred phosphorus source is lithium dihydrogen phosphate or phosphoric acid, more excellent
The phosphorus source of choosing is lithium dihydrogen phosphate.
(3) dried product in above-mentioned steps (2) is sintered between 600～780 DEG C, it is preferred to sinter
Temperature range is 650～780 DEG C, and preferred sintering range is 700～750 DEG C, the temperature retention time at maximum temperature
For 4～24h, preferred temperature retention time is 5～18h, and preferred temperature retention time is 8～15h.
Further, whole sintering and temperature-fall period are carried out in noble gases or weakly reducing atmosphere, described inertia
Gas or weakly reducing atmosphere are high-purity argon gas, high pure nitrogen, with the addition of high pure nitrogen or height that volume fraction is 1～5% hydrogen
At least one in pure argon gaseous mixture.
It is the homogeneous black powder of good fluidity and color, pH value according to lithium iron phosphate positive material prepared by above-mentioned steps
Less than 10.5, its tap density is more than 1.0g/cm3, primary particle particle diameter between 100～200nm, its particle size distribution D50
Between 1.0～3.0 μm.Prepared lithium iron phosphate positive material is assembled into after battery, 0.1C electric discharge gram volume highests can
Up to 157mAh/g, 10C electric discharge gram volumes reach as high as 112mAh/g.
Advantages of the present invention and good effect are：
(1) used as carbon source, both economized on resources the product using discarded cigarette filter in ammonia after nitrogen treatment realization
Recycling waste can obtain that specific capacity is high again, (0.1C discharges gram volume for lithium iron phosphate positive material of good rate capability
Up to 157mAh/g, 10C discharges gram volume up to 112mAh/g), with important actual application value；
(2) the carbon source wide material sources for adopting, addition is few can to obtain height ratio capacity, powerful iron phosphate lithium positive pole material
Material, while so that LiFePO4 preparation cost is greatly reduced, it is easy to large-scale promotion；
(3) in preparation process in the way of titanium oxide sol doping titanium elements in situ, improve iron phosphate lithium positive pole material
The removal lithium embedded reversibility of material and cyclical stability；
(4) spherical lithium iron phosphate anode material that crystallinity is good, be evenly distributed, letter can be prepared by using a step sintering process
Change preparation technology, reduce energy consumption；
(5) material of the raw material without ammonium dihydrogen phosphate etc. easily to environment, reduces to the unfavorable of environment
Affect.
Specific embodiment：
Embodiment 1
It is prepared by carbon source：The discarded cigarette filter for coming will be collected in ammonia atmosphere in 800 DEG C of nitrogen treatment 3h, heated up
Speed is maintained at 8 DEG C/min, obtains the nitrogenous material with carbon element with sub-hole and microcellular structure as carbon source.
Lithium dihydrogen phosphate, lithium acetate and Ferrox. are matched somebody with somebody for 1: 1: 1 proportioning weighing according to the mol ratio of lithium, ferrum, phosphorus
Material, while the above-mentioned carbon source that weight/mass percentage composition is lithium iron phosphate positive material 1% is added, with deionized water as solvent ball milling
2h, then the ball milling 8h in Ultrafine Grinding, adds titanium oxide sol in mechanical milling process, wherein, the molar content of titanium is phosphoric acid
The 5% of ferrum lithium anode material, the mixture after ball milling is fully dried using microwave drying process.Finally will be dried
Mixture is incubated 24h in 600 DEG C in the high-purity argon gas that volume fraction is 5% hydrogen, and then the natural cooling in the stove, that is, be obtained
The good lithium iron phosphate positive material of crystallinity.After assembling them into battery, 0.1C discharges gram volume for 151mAh/g, and 10C is put
Electric gram volume reaches as high as 105mAh/g.
Embodiment 2
It is prepared by carbon source：The discarded cigarette filter for coming will be collected to be carried out at nitridation between 950 DEG C in ammonia atmosphere
Reason 1.5h, programming rate are maintained at 2 DEG C/min, obtain the nitrogenous material with carbon element with sub-hole and microcellular structure as carbon source.
By lithium dihydrogen phosphate, lithium acetate, lithium carbonate, Ferrox. and hydrated ferric oxide. according to the mol ratio of lithium, ferrum, phosphorus it is
1.03: 1: 1 proportioning weighs dispensing, while the above-mentioned carbon source that weight/mass percentage composition is lithium iron phosphate positive material 15% is added,
With the mixture of deionized water and dehydrated alcohol as solvent ball milling 12h, then the ball milling 2h in Ultrafine Grinding, adds in mechanical milling process
Enter titanium oxide sol, wherein, the molar content of titanium is the 0.5% of lithium iron phosphate positive material, and the mixture after ball milling is adopted
Fully it is dried with microwave drying process.Finally 4h, Ran Hou will be incubated in 780 DEG C in dried mixture high pure nitrogen
Natural cooling in stove, that is, be obtained the good lithium iron phosphate positive material of crystallinity.After assembling them into battery, 0.1C electric discharges gram are held
Measure as 155mAh/g, 10C electric discharge gram volumes reach as high as 110mAh/g.
Embodiment 3
It is prepared by carbon source：The discarded cigarette filter for coming will be collected in ammonia atmosphere in 900 DEG C of nitrogen treatment 2h, heated up
Speed is maintained at 5 DEG C/min, obtains the nitrogenous material with carbon element with sub-hole and microcellular structure as carbon source.
Lithium dihydrogen phosphate, lithium carbonate and Ferrox. are matched somebody with somebody for 1: 1: 1 proportioning weighing according to the mol ratio of lithium, ferrum, phosphorus
Material, while weight/mass percentage composition is added for the above-mentioned carbon source of lithium iron phosphate positive material 10%, with deionized water and n-butyl alcohol
Mixture is solvent ball milling 6h, and then the ball milling 4h in Ultrafine Grinding, adds titanium oxide sol in mechanical milling process, wherein, titanium
Molar content for lithium iron phosphate positive material 3%, the mixture after ball milling is fully done using microwave drying process
It is dry.Dried mixture is incubated into 10h in 700 DEG C in high-purity argon gas finally, then the natural cooling in the stove, that is, knot is obtained
The good lithium iron phosphate positive material of crystalline substance.After assembling them into battery, 0.1C discharges gram volume for 157mAh/g, 10C electric discharges
Gram volume reaches as high as 112mAh/g.
Embodiment 4
It is prepared by carbon source：The discarded cigarette filter for coming will be collected in ammonia atmosphere in 880 DEG C of nitrogen treatment 2.5h, risen
Warm speed is maintained at 6 DEG C/min, obtains the nitrogenous material with carbon element with sub-hole and microcellular structure as carbon source.
Lithium dihydrogen phosphate, lithium carbonate and Ferrox. are weighed for 1.01: 1: 1 proportioning according to the mol ratio of lithium, ferrum, phosphorus
Dispensing, while the above-mentioned carbon source that weight/mass percentage composition is lithium iron phosphate positive material 7% is added, with deionized water and polyvinyl alcohol
Mixture be solvent ball milling 8h, then the ball milling 6h in Ultrafine Grinding, adds titanium oxide sol in mechanical milling process, wherein,
The molar content of titanium is the 4% of lithium iron phosphate positive material, and the mixture after ball milling is carried out fully using microwave drying process
It is dried.Dried mixture is incubated into 8h in 730 DEG C in high-purity argon gas finally, then the natural cooling in the stove, that is, be obtained
The good lithium iron phosphate positive material of crystallinity.After assembling them into battery, 0.1C discharges gram volume for 153mAh/g, and 10C is put
Electric gram volume reaches as high as 109mAh/g.
Claims (4)
1. a kind of preparation method of high-performance lithium iron phosphate cathode material, it is characterised in that by discarded cigarette filter in ammonia
Product in gas after nitrogen treatment is used as the carbon source of lithium iron phosphate positive material, then by source of iron, lithium source, phosphorus source and above-mentioned carbon source
Mixing, ball milling, drying, crushing, roasting are obtained lithium iron phosphate positive material；
Specifically, the method comprising the steps of：
(1) prepared by carbon source：The discarded cigarette filter for coming will be collected carries out nitrogen between 800～950 DEG C in ammonia atmosphere
Change and process 1.5～3h, programming rate is maintained at 2～8 DEG C/min, obtain the nitrogenous material with carbon element with sub-hole and microcellular structure and make
For carbon source；
(2) by lithium source, source of iron, phosphorus source and carbon source ball milling 2～12 hours, in then proceeding to Ultrafine Grinding, continue ball milling 2～8 hours,
Titanium oxide sol is added in mechanical milling process, the colloidal sol is formed by butyl titanate or titanium tetraisopropylate hydrolysis, wherein, titanium
Molar content for lithium iron phosphate positive material 0.5～5%, then ball milling product is carried out fully using microwave drying process
It is dried；
In the lithium source, source of iron, phosphorus source, lithium, ferrum, the mol ratio of phosphorus are (1～1.03): 1: 1, carbon source accounts for iron phosphate lithium positive pole material
The 1～25% of material gross mass；
The lithium source is the one kind or two in lithium carbonate, lithium fluoride, Lithium hydrate, lithium dihydrogen phosphate, lithium acetate and lithium nitrate
Plant the mixture of the above；Source of iron be Ferrox., ferric nitrate, iron sesquioxide and hydrated ferric oxide. in one or two kinds of more than
Mixture；Phosphorus source is the one kind or two in lithium dihydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, phosphorus pentoxide and phosphoric acid
Plant the mixture of the above；
(3) dried product in step (2) is sintered between 600～780 DEG C, the insulation at maximum temperature
Time is 4～24h.
2. the preparation method of high-performance lithium iron phosphate cathode material according to claim 1, it is characterised in that step (2)
Ball-milling medium used is zirconia ball, and solvent is deionized water, or deionized water and dehydrated alcohol, polyvinyl alcohol, second two
The mixture of at least one of alcohol, n-butyl alcohol, isobutanol, acetone, hexamethylene.
3. the preparation method of high-performance lithium iron phosphate cathode material according to claim 1, it is characterised in that step (3)
In whole sintering and temperature-fall period carry out in noble gases or weakly reducing atmosphere, described noble gases or weakly reducing atmosphere
For high-purity argon gas, high pure nitrogen, with the addition of in the high pure nitrogen or high-purity argon gas gaseous mixture that volume fraction is 1～5% hydrogen
It is at least one.
4. the lithium iron phosphate positive material that prepared by method according to claim 1, it is characterised in that prepared iron phosphate
Lithium anode material is the homogeneous black powder of good fluidity and color, and, less than 10.5, its tap density is more than 1.0g/ for pH value
cm3, between 100～200nm, its particle size distribution D50 is between 1.0～3.0 μm for primary particle particle diameter；By prepared phosphoric acid
After ferrum lithium anode material is assembled into battery, 0.1C electric discharge gram volumes reach as high as 157mAh/g, and 10C electric discharge gram volumes are reached as high as
112mAh/g。
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| CN107634205A (en) * | 2017-09-12 | 2018-01-26 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of lithium iron phosphate positive material |
| CN107720722A (en) * | 2017-10-27 | 2018-02-23 | 西安理工大学 | A kind of nitrogenous multi-stage porous Carbon Materials and its preparation method and application |
| CN107946082A (en) * | 2017-10-27 | 2018-04-20 | 西安理工大学 | A kind of preparation method and its usage of cigarette filter/graphene composite material |
| CN108511751B (en) * | 2018-04-11 | 2021-02-02 | 中科锂电新能源有限公司 | Modified lithium iron phosphate, preparation method thereof and lithium ion battery |
| CN114014294B (en) * | 2021-12-08 | 2023-08-22 | 高点(深圳)科技有限公司 | Method for preparing lithium iron phosphate by using pyrite and lithium iron phosphate material |
| CN115535986A (en) * | 2022-10-09 | 2022-12-30 | 山东精工电子科技股份有限公司 | Method for preparing ferric phosphate and high-compaction lithium iron phosphate cathode material by in-situ co-precipitation |
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