CN106169580B - Preparation method of battery-grade iron phosphate/graphene composite material - Google Patents
Preparation method of battery-grade iron phosphate/graphene composite material Download PDFInfo
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- CN106169580B CN106169580B CN201610728831.XA CN201610728831A CN106169580B CN 106169580 B CN106169580 B CN 106169580B CN 201610728831 A CN201610728831 A CN 201610728831A CN 106169580 B CN106169580 B CN 106169580B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 44
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 43
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 6
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000037427 ion transport Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 238000010902 jet-milling Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 15
- 239000005955 Ferric phosphate Substances 0.000 description 10
- 229940032958 ferric phosphate Drugs 0.000 description 10
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- -1 process flow length Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 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 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HEAFLBOWLRRIHV-UHFFFAOYSA-N [Na].[P] Chemical compound [Na].[P] HEAFLBOWLRRIHV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a battery-grade iron phosphate/graphene composite material. The method comprises the following steps: mixing an iron source, graphene and a dispersing agent in a pressurized reaction kettle to prepare slurry a, placing a phosphorus solution b prepared by mixing hydrogen peroxide and a phosphorus source in the pressurized reaction kettle to react with the slurry a, and adding alkali to adjust the pH value to prepare a seed crystal c; preparing an iron source solution d, and mixing hydrogen peroxide and a phosphorus source to prepare a phosphorus solution e; and c and d are uniformly stirred in a pressurized reaction kettle, e is added for reaction, alkali is added for adjusting the pH value to prepare slurry, and spray drying, calcining and jet milling are carried out to prepare the battery-grade iron phosphate/graphene composite material. The preparation method has the advantages of high product yield, high purity, controllable iron-phosphorus ratio and particle size, no wastewater, short process flow, energy conservation, consumption reduction and easy industrialization; and the graphene is used as a template matrix for growing the iron phosphate crystal, so that an ion transport channel is effectively shortened, the conductivity is improved, and the graphene is an excellent precursor battery material for manufacturing the lithium iron phosphate.
Description
Technical field
The invention belongs to lithium ion battery material preparation technical field more particularly to a kind of battery-grade iron phosphate/graphite
The preparation method of alkene composite material.
Background technique
Currently, ferric phosphate lithium cell is with the cycle life of its overlength, fabulous security performance, preferable high-temperature behavior and again
The features such as rate electric discharge, excellent cost performance, it is widely used in energy storage device, electric tool, electric bus, electric car, leisure
The fields such as vehicle, Medical Devices starting, military power supply.The manufacture of lithium iron phosphate positive material generallys use main original both at home and abroad at present
Material (battery level iron oxalate, iron oxide red or ferric phosphate), lithium salts and microcosmic salt mixing carry out solid phase method production, and other methods are for example molten
Glue-gel method, liquid-phase precipitation method, ultrasonic wave and microwave method are the disadvantage is that impurity content is high, wastewater flow rate is big, process flow is long, electrochemical
It is poor etc. to learn performance.Therefore, the quality of LiFePO4 comprehensive performance manufactures used main raw material and manufacturing method with it and has
Much relations.The method for synthesizing ferric phosphate is more: hydro-thermal method the high requirements on the equipment generates a large amount of waste water, process flow length, energy consumption
It is high；Homogeneous precipitation method generates a large amount of waste water, process flow length, impurity content height etc., such as Inst. of Energy, Shandong Prov. Academy
Qin Xianzhong etc. (application number 201610008365.8, notification number 105514431A) uses graphene and inorganic molysite, soda, sodium phosphorus
Salt carries out precipitating synthesis ferric phosphate/graphene composite material, not can avoid and introduces a large amount of sulfate radicals, chlorine root, nitrate anion, sodium ion
Equal objectionable impurities, have the disadvantage that first is that product purity is caused to decline；Second is that need to increase be filtered, washed, discharge of wastewater or place
The techniques such as reason, long flow path, energy consumption are high, industrialization difficulty is big；Third is that carrying out synthesis ferric phosphate using divalent iron salt in case, do not have
Oxidation processes are carried out to ferrous ion, are readily incorporated ferrous ion in product, be easy to causeing product is sub- (II) iron of phosphoric acid and phosphorus
Sour (III) iron mixed system, and ferrous iron is oxidized easily, and is easy also during subsequent manufacture lithium iron phosphate positive material
Original is low to the decline of ferric phosphate lithium cell capacity, high rate performance and cyclicity at simple substance Ferromagnetic Impurities；Fourth is that in manufacture ferric phosphate
Increase ingredient difficulty during lithium anode material, homogeneity of product is unstable etc.；Sol-gel method generated time is long, washing is useless
Big, the dry micropore of water is more, particle is easy contraction etc.；Air oxidation process high temperature, energy consumption is high, and high production cost, granularity are uneven
Deng；Microemulsion method, microwave radiation crystallization method are in laboratory research stage, the industrial equipment of shortcoming and complete sets of Techniques.
Summary of the invention
The present invention overcomes existing technology of preparing insufficient, provides a kind of preparation of battery-grade iron phosphate/graphene composite material
Method, product conductivity height, high income, purity is high, iron phosphorus ratio and the size tunable, process flow obtained using the preparation method
It is short, without waste water, it is energy-saving, be easy to industrialize.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of battery-grade iron phosphate/graphene composite material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of solvent is added, dispersing agent, graphene, source of iron are uniformly mixed to prepare slurry
A, wherein dispersing agent accounts for the 0.1-0.5% of gross mass, and source of iron concentration 0.05-0.2mol/L, graphene account for the 0.1- of gross mass
0.5%；
(2) phosphorus for solvent, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio and phosphorus source being mixed to prepare 0.05-0.2mol/L is molten
Liquid b, which is added in compressive reaction kettle heat up 80-100 DEG C with slurry a, to react, and alkaline matter is added and adjusts pH=2.0-5.5, instead
2-4h is answered, crystal seed c is made；
(3) solvent and source of iron are mixed to prepare to the source of iron solution d of 1.0-4.0mol/L, by solvent, 1.5 times of stoichiometric ratios
20% hydrogen peroxide and phosphorus source are mixed to prepare 1.0-4.0mol/L phosphorus solution e；
(4) crystal seed c and source of iron solution d are sufficiently mixed uniformly in compressive reaction kettle, solution e is added and carries out temperature reaction
To 80-100 DEG C, alkaline matter is added and adjusts pH=2.0-5.5, reacts 2-4h；
(5) then spray drying, 500-600 DEG C of high-temperature calcination 5-7 hours, air-flow crushing can be prepared by LITHIUM BATTERY phosphoric acid
Iron/graphene composite material.
Preferably, the solvent refers to the combination of one or more of pure water, methanol, ethyl alcohol.
Preferably, the source of iron includes one or both of ferric acetyl acetonade, iron oleate, ferric formate, ferrous acetate
Above combination.
Preferably, the dispersing agent include one or both of ethylene glycol, polyvinylpyrrolidone, polyethylene glycol with
On combination.
Preferably, the phosphorus source includes the group of one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid
It closes.
Preferably, the alkaline matter includes the group of one or more of ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate
It closes.
The beneficial effects of the present invention are:
Using graphene as form iron phosphate crystal growth templates matrix, ion transport channel is effectively shortened, improve conductivity；It produces
During the preparation process, there is no the removal of impurities of a large amount of pure waters, filter progress, and product yield and purity greatly improve for product；Pass through crystalline substance
Kind and dispersing agent effectively control partial size 1.5um≤D50≤20.0um, iron phosphorus ratio in 0.96-1.00；It abandons removal of impurities, filtering and gives up
The big process of water process three, process flow are further shortened, and no waste water is energy-saving, are easy to industrialize, are for manufacturing ferric phosphate
The splendid presoma battery material of lithium anode material.
Specific embodiment
Embodiment 1
A kind of preparation method of battery-grade iron phosphate/graphene composite battery material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of ethyl alcohol is added, ferric acetyl acetonade, graphene, ethylene glycol are uniformly mixed into system
Slurry a is obtained, wherein dispersing agent accounts for the 0.1% of gross mass, and concentration of iron 0.05mol/L, graphene account for the 0.1% of gross mass；
(2) the phosphorus solution b that pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.05mol/L with phosphorus source is added
Enter heat up 80 DEG C with slurry a in compressive reaction kettle and react, ammonium hydroxide is added and adjusts pH=2.0, reacts 3h, crystal seed c is made；
(3) ethyl alcohol and ferric acetyl acetonade are mixed to prepare to the ferrous solution d of 1.0mol/L, by pure water, 1.5 times of stoichiometric ratios
20% hydrogen peroxide and ammonium dihydrogen phosphate are mixed to prepare 1.0mol/L phosphorus solution e；
(4) crystal seed c and ferrous solution d are sufficiently mixed uniformly in a kettle, solution e is added and carries out temperature reaction to 80
DEG C, add ammonium hydroxide to adjust pH=2.0, reacts 3h；
(5) then spray drying, 500 DEG C of high-temperature calcinations 6 hours, air-flow crushing can be prepared by battery-grade iron phosphate/graphite
Alkene composite A.
Embodiment 2
A kind of preparation method of battery-grade iron phosphate/graphene composite material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of methanol is added, iron oleate, graphene, polyvinylpyrrolidone are uniformly mixed
It closes and slurry a is made, wherein dispersing agent accounts for the 0.2% of gross mass, and concentration of iron 0.1mol/L, graphene account for the 0.15% of gross mass；
(2) the phosphorus solution b that pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.1mol/L with phosphorus source is added
Enter heat up 80 DEG C with slurry a in compressive reaction kettle and react, ammonium carbonate is added and adjusts pH=3.0, reacts 3h, crystal seed c is made；
(3) methanol and iron oleate are mixed to prepare to the ferrous solution d of 2.0mol/L, by pure water, 1.5 times of stoichiometric ratios 20%
Hydrogen peroxide and diammonium hydrogen phosphate are mixed to prepare 2.0mol/L phosphorus solution e；
(4) crystal seed c and ferrous solution d are sufficiently mixed uniformly in a kettle, solution e is added and carries out temperature reaction to 80
DEG C, add ammonium hydroxide to adjust pH=3.0, reacts 3h；
(5) then spray drying, 550 DEG C of high-temperature calcinations 6 hours, air-flow crushing can be prepared by battery-grade iron phosphate/graphite
Alkene composite material B.
Embodiment 3
A kind of preparation method of battery-grade iron phosphate/graphene composite material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of methanol is added, ferric formate, graphene, polyethylene glycol are uniformly mixed to prepare
Slurry a, wherein dispersing agent accounts for the 0.25% of gross mass, and concentration of iron 0.15mol/L, graphene account for the 0.35% of gross mass；
(2) the phosphorus solution b that pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.15mol/L with phosphorus source is added
Enter heat up 80 DEG C with slurry a in compressive reaction kettle and react, ammonium hydrogen carbonate is added and adjusts pH=4.0, reacts 3h, crystal seed is made
c；
(3) methanol and ferric formate are mixed to prepare to the ferrous solution d of 3.0mol/L, by pure water, 1.5 times of stoichiometric ratios 20%
Hydrogen peroxide and phosphoric acid are mixed to prepare 3.0mol/L phosphorus solution e；
(4) crystal seed c and ferrous solution d are sufficiently mixed uniformly in a kettle, solution e is added and carries out temperature reaction to 80
DEG C, add ammonium hydroxide to adjust pH=4.0, reacts 3h；
(5) then spray drying, 550 DEG C of high-temperature calcinations 6 hours, air-flow crushing can be prepared by battery-grade iron phosphate/graphite
Alkene composite material C.
Embodiment 4
A kind of preparation method of battery-grade iron phosphate/graphene composite material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of ethyl alcohol is added, by ferrous acetate, graphene, polyvinylpyrrolidone and second
Glycol is uniformly mixed to prepare slurry a, and wherein dispersing agent accounts for the 0.5% of gross mass, and concentration of iron 0.2mol/L, graphene account for gross mass
0.5%；
(2) the phosphorus solution b that pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.2mol/L with phosphorus source is added
Enter heat up 80 DEG C with slurry a in compressive reaction kettle and react, ammonium hydroxide is added and ammonium carbonate adjusts pH=4.0, reacts 3h, is made
Crystal seed c；
(3) ethyl alcohol and ferrous acetate are mixed to prepare to the ferrous solution d of 4.0mol/L, by pure water, 1.5 times of stoichiometric ratios
20% hydrogen peroxide and phosphoric acid, ammonium dihydrogen phosphate are mixed to prepare 4.0mol/L phosphorus solution e；
(4) crystal seed c and ferrous solution d are sufficiently mixed uniformly in a kettle, solution e is added and carries out temperature reaction to 80
DEG C, ammonium hydroxide is added and ammonium carbonate adjusts pH=4.0, reacts 3h；
(5) then spray drying, 600 DEG C of high-temperature calcinations 6 hours, air-flow crushing can be prepared by battery-grade iron phosphate/graphite
Alkene composite material D.
Embodiment 5
A kind of preparation method of battery-grade iron phosphate/graphene composite battery material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of methanol is added, ferric acetyl acetonade and ferric formate, graphene, ethylene glycol is equal
Even to be mixed to prepare slurry a, wherein dispersing agent accounts for the 0.3% of gross mass, and concentration of iron 0.15mol/L, graphene account for gross mass
0.2%；
(2) the phosphorus solution b that pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.15mol/L with phosphorus source is added
Enter heat up 100 DEG C with slurry a in compressive reaction kettle and react, ammonium hydroxide is added and adjusts pH=3.5, reacts 2h, crystal seed c is made；
(3) methanol and ferric acetyl acetonade, ferric formate are mixed to prepare to the ferrous solution d of 3.5mol/L, by pure water, 1.5 times of changes
It learns metering and is mixed to prepare 3.5mol/L phosphorus solution e than 20% hydrogen peroxide and ammonium dihydrogen phosphate；
(4) crystal seed c and ferrous solution d are sufficiently mixed uniformly in a kettle, solution e is added and carries out temperature reaction to 100
DEG C, add ammonium hydroxide to adjust pH=3.5, reacts 2h；
(5) then spray drying, 550 DEG C of high-temperature calcinations 7 hours, air-flow crushing can be prepared by battery-grade iron phosphate/graphite
Alkene composite material E.
Embodiment 6
A kind of preparation method of battery-grade iron phosphate/graphene composite battery material, comprising the following steps:
(1) in compressive reaction kettle, a certain amount of pure water is added, ferrous acetate, graphene, polyvinylpyrrolidone is uniform
It is mixed to prepare slurry a, wherein dispersing agent accounts for the 0.4% of gross mass, and concentration of iron 0.2mol/L, graphene account for the 0.4% of gross mass；
(2) the phosphorus solution b that pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.2mol/L with phosphorus source is added
Enter heat up 90 DEG C with slurry a in compressive reaction kettle and react, ammonium hydroxide is added and adjusts pH=2.5, reacts 5h, crystal seed c is made；
(3) pure water and ferrous acetate are mixed to prepare to the ferrous solution d of 2.0mol/L, by pure water, 1.5 times of stoichiometric ratios
20% hydrogen peroxide and ammonium dihydrogen phosphate are mixed to prepare 2.0mol/L phosphorus solution e；
(4) crystal seed c and ferrous solution d are sufficiently mixed uniformly in a kettle, solution e is added and carries out temperature reaction to 90
DEG C, add ammonium hydroxide to adjust pH=2.5, reacts 5h；
(5) then spray drying, 600 DEG C of high-temperature calcinations 5 hours, air-flow crushing can be prepared by battery-grade iron phosphate/graphite
Alkene composite material F.
Comparative example
(1) in a kettle, a certain amount of pure water is added, inorganic molysite ferrous sulfate (is also possible to ferric nitrate or chlorination
Iron), polyvinylpyrrolidone be uniformly mixed to prepare solution a, wherein dispersing agent accounts for the 0.2% of gross mass, concentration of iron 1mol/L；
(2) pure water, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio and ammonium dihydrogen phosphate are mixed to prepare 1.0mol/L phosphorus solution
b；
(3) a and b are sufficiently mixed uniformly in a kettle, carry out temperature reaction to 90 DEG C, ammonium hydroxide is added to adjust pH=2.5,
5h is reacted, a large amount of pure waters of filter cake are removed part foreign ion by filtrated stock；
(4) then the high-temperature calcination 10 hours of 600 DEG C of filter cake, air-flow crushing can be prepared by battery-grade iron phosphate material G.
The battery-grade iron phosphate material index that the above method is prepared see the table below one.
One battery-grade iron phosphate of table/graphene composite material index
As can be seen from the above table, using battery-grade iron phosphate/graphene composite material made from method provided by the invention
Fe/P and granularity are controllable, and impurity content is low, and quality stability is good；And comparative example is using conventional liquid phase precipitating synthetic method preparation electricity
Pond grade ferric phosphate, various metals and nonmetallic objectionable impurities content are very high, especially high-content magnetic impurity Zn, Co, Ni, Cr
And sulfate radical, the capacity and cycle performance of ferric phosphate lithium cell are substantially reduced, and a large amount of containing sulfate radicals, microcosmic salt waste water need
Ability standard discharge after progress depth wastewater treatment, the product dehydrate time is long, and energy consumption is high, and process flow is long.In short, the present invention adopts
Use organic source of iron, phosphorus source as main material, hydrogen peroxide is as oxidant, by graphene as form iron phosphate crystal growing substrate,
Particle size growth is controlled using crystal seed and dispersing agent, washing, filtering and wastewater treatment process has been abolished, has greatly optimized technique stream
Journey, it is energy-saving, it is environmentally protective, it is easy to industrialize.
Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made should all be fallen into the protection scope that claims of the present invention determines.
Claims (6)
1. a kind of preparation method of battery-grade iron phosphate/graphene composite material, the preparation method the following steps are included:
(1) in compressive reaction kettle, a certain amount of solvent is added, dispersing agent, graphene, source of iron are uniformly mixed to prepare slurry a,
Middle dispersing agent accounts for the 0.1-0.5% of gross mass, and source of iron concentration 0.05-0.2mol/L, graphene account for the 0.1-0.5% of gross mass；
(2) the phosphorus solution b that solvent, 1.5 times of 20% hydrogen peroxide of stoichiometric ratio are mixed to prepare 0.05-0.2mol/L with phosphorus source is added
Enter heat up 80-100 DEG C with slurry a in compressive reaction kettle and react, alkaline matter is added and adjusts pH=2.0-5.5, reacts 2-
Crystal seed c is made in 4h；
(3) solvent and source of iron are mixed to prepare to the source of iron solution d of 1.0-4.0mol/L, by solvent, 1.5 times of stoichiometric ratios 20%
Hydrogen peroxide and phosphorus source are mixed to prepare 1.0-4.0mol/L phosphorus solution e；
(4) crystal seed c and source of iron solution d are sufficiently mixed uniformly in compressive reaction kettle, solution e is added and carries out temperature reaction extremely
80-100 DEG C, alkaline matter is added and adjusts pH=2.0-5.5, reacts 2-4h；
(5) then spray drying, 500-600 DEG C of high-temperature calcination 5-7 hours, air-flow crushing can be prepared by battery-grade iron phosphate/stone
Black alkene composite material；
Source of iron in the step (1) (3) (4) includes one of ferric acetyl acetonade, iron oleate, ferric formate, ferrous acetate
Or two or more combination.
2. a kind of preparation method of battery-grade iron phosphate/graphene composite material according to claim 1, feature exist
In: 0.2-1.5 MPa of compressive reaction kettle pressure limit in the step (1) (2) (4).
3. a kind of preparation method of battery-grade iron phosphate/graphene composite material according to claim 1, feature exist
In: the solvent in the step (1) (2) (3) refers to the combination of one or more of pure water, methanol, ethyl alcohol.
4. a kind of preparation method of battery-grade iron phosphate/graphene composite material according to claim 1, feature exist
In: the dispersing agent in the step (1) include one or both of ethylene glycol, polyvinylpyrrolidone, polyethylene glycol with
On combination.
5. a kind of preparation method of battery-grade iron phosphate/graphene composite material according to claim 1, feature exist
In: the phosphorus source in the step (2) (3) includes one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid
Combination.
6. a kind of preparation method of battery-grade iron phosphate/graphene composite material according to claim 1, feature exist
In: the alkaline matter in the step (2) (4) includes the group of one or more of ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate
It closes.
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| CN109336227A (en) * | 2018-09-03 | 2019-02-15 | 同济大学 | Graphene-coated amorphous iron phosphate electrode material and preparation method thereof |
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| CN113851618B (en) * | 2021-08-10 | 2023-06-23 | 桂林理工大学 | Method and application of high-performance ferric phosphate/graphene composite negative electrode material prepared by using iron slag hydrochloric acid leaching solution |
| CN116409766A (en) * | 2021-12-30 | 2023-07-11 | 中国科学院过程工程研究所 | A method for flexibly regulating the iron-phosphorus ratio of iron phosphate |
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