CN106784817B - Ferric phosphate/graphene composite material preparation method - Google Patents
Ferric phosphate/graphene composite material preparation method Download PDFInfo
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- CN106784817B CN106784817B CN201611236632.3A CN201611236632A CN106784817B CN 106784817 B CN106784817 B CN 106784817B CN 201611236632 A CN201611236632 A CN 201611236632A CN 106784817 B CN106784817 B CN 106784817B
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- iron
- ferric phosphate
- phosphorus
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 153
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 132
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 131
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 131
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 193
- 229910052742 iron Inorganic materials 0.000 claims abstract description 99
- 239000013078 crystal Substances 0.000 claims abstract description 98
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 70
- 239000011574 phosphorus Substances 0.000 claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 230000006698 induction Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract 2
- -1 graphite alkene Chemical class 0.000 claims description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 229910002804 graphite Inorganic materials 0.000 claims description 34
- 239000010439 graphite Substances 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 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 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940085991 phosphate ion Drugs 0.000 claims description 2
- 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 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 25
- 229910000398 iron phosphate Inorganic materials 0.000 abstract description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 106
- 238000000034 method Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 235000013339 cereals Nutrition 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000176 sodium gluconate Substances 0.000 description 4
- 229940005574 sodium gluconate Drugs 0.000 description 4
- 235000012207 sodium gluconate Nutrition 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 3
- CUXQLKLUPGTTKL-UHFFFAOYSA-M microcosmic salt Chemical compound [NH4+].[Na+].OP([O-])([O-])=O CUXQLKLUPGTTKL-UHFFFAOYSA-M 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 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
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IDAGXRIGDWCIET-SDFKWCIISA-L disodium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IDAGXRIGDWCIET-SDFKWCIISA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 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
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004062 sedimentation 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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 invention discloses a kind of preparation methods of ferric phosphate/graphene composite material, comprising the following steps: takes molysite, graphene and dispersant that source of iron solution is made.The first phosphorus solution that phosphorus source is prepared is reacted with the source of iron solution progress first stage, reaction obtains ferric phosphate crystal seed.It takes source of iron, phosphorus source to prepare respectively and obtains the second source of iron solution and the second phosphorus solution.Crystal seed, the second source of iron solution and the second phosphorus source solution and complexing agent are mixed and carry out second stage reaction, iron and P elements in solution are transported to ferric phosphate seed surface, according to form iron phosphate crystal configuration stacked arrangement under the induction of crystal seed, form iron phosphate crystal is grown up in reaction solution.Crystalliferous reaction solution drying will be wrapped, calcining obtains ferric phosphate/graphene composite material.The preparation method of above-mentioned ferric phosphate/graphene composite material, crystal are formed by way of diauxic growth, even particle size, and ferric phosphate obtained/graphene composite material particle size is uniform.
Description
Technical field
The present invention relates to field of lithium ion battery material, particularly, are related to a kind of system of ferric phosphate/graphene composite material
Preparation Method.
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.Quality and its of LiFePO4 comprehensive performance manufacture used main raw material
There are much relations with manufacturing method.The manufacture of lithium iron phosphate positive material generallys use main raw material (LITHIUM BATTERY both at home and abroad at present
Ferrous oxalate, iron oxide red or ferric phosphate), lithium salts and microcosmic salt mixing carry out solid phase method production, other methods such as sol-gel method, liquid
The phase precipitation method, supercritical ultrasonics technology and microwave method.The major defect of these methods has: impurity content is high, wastewater flow rate is big, process flow
Long, especially chemical property is poor etc..Specifically, solid phase method product chemical component uniformity is bad, lot stability is poor；
Hydro-thermal method is at high cost, process flow is long, production wastewater flow rate is big；Homogeneous precipitation method can generate a large amount of waste water, process flow length, impurity
Content is high；Sol-gel method generated time is long, washes dosage is big, product porosity is excessively high, particle is easy contraction etc.；It is empty
Energy consumption is high for gas oxidizing process, high production cost, granularity are uneven；Microemulsion method, microwave radiation crystallization method are still in laboratory research
Stage, the industrial equipment of shortcoming and complete sets of Techniques.
Summary of the invention
The present invention provides a kind of preparation methods of ferric phosphate/graphene composite material, to solve current method preparation
The non-uniform technical problem of ferric phosphate partial size.
The technical solution adopted by the invention is as follows:
A kind of preparation method of ferric phosphate/graphene composite material, comprising the following steps:
Source of iron, graphene and dispersing agent is taken to be dispersed in water obtained first source of iron solution.
The first phosphorus solution that phosphorus source is prepared is reacted with the first source of iron solution mixed oxidization progress first stage, obtains phosphoric acid
Iron crystal seed composite graphite alkene.
It takes source of iron and complexing agent preparation soluble in water to obtain the second source of iron solution, phosphorus source preparation soluble in water is separately taken to obtain the
Two phosphorus source solution.
Ferric phosphate crystal seed composite graphite alkene, the second source of iron solution and the second phosphorus source solution mixed oxidization are subjected to second stage
Reaction, the ferric phosphate reacted crystallize under the induction of the crystal seed of ferric phosphate crystal seed composite graphite alkene, and in ferric phosphate crystal seed
It is precipitated on composite graphite alkene, obtains ferric phosphate/graphene presoma.
Ferric phosphate/graphene presoma separation, dry, calcining are obtained into ferric phosphate/graphene composite material.
Further, the iron concentration of the first source of iron solution is 0.05~0.08mol/L, the phosphate radical of the first phosphorus solution
Ion concentration is 0.025~0.04mol/L, and the molar ratio of iron ion and graphene is 1:0.05~0.1 in the first source of iron solution,
The volume ratio of first source of iron solution and the first phosphorus solution is 1:0.45~0.55.
Further, in the second source of iron solution iron concentration be 1.0~4.0mol/L, complexing agent concentration be 0.05~
0.2mol/L, the phosphorus acid ion concentration of the second phosphorus solution are 1.0~4.0mol/L.
The molar ratio of ferro element and the P elements in the second phosphorus solution is 1:1.05~1.10 in second source of iron solution, by institute
It states ferric phosphate crystal seed composite graphite alkene and the second source of iron solution and 500~1000mL described in 550~1100mL is added according to every 1~5g
In second phosphorus source solution and it is sufficiently mixed.
Further, the first stage reaction operation include:
First phosphorus solution, the first source of iron solution and the first oxidant are mixed, are 0.5~5.0 in 50~70 DEG C, pH value
Under the conditions of, continue to be stirred to react 0.5~2.0 hour.
Second stage reaction operation include:
Ferric phosphate crystal seed composite graphite alkene, the second source of iron solution, the second phosphorus source solution and the second oxidant are uniformly mixed,
Under conditions of 30~60 DEG C, pH value are 4.0~5.0, continue to be stirred to react 3 hours.
Further, the first oxidant is hydrogen peroxide, and hydrogen peroxide is added in equal volume with the water as solvent, the matter of hydrogen peroxide
Measuring percentage solubility is 9~11%.
Second oxidant is oxygen, and oxygen is passed through in reaction solution with 1~2ml/Lmin speed.
Further, first stage reaction adjusts pH value by addition acidic materials, passes through addition in second stage reaction
Alkaline matter adjusts pH value, and acidic materials are selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, acetic acid, and alkaline matter is selected from
One or more of ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate.
Further, dry to be spray-dried, calcining carries out in atmosphere furnace, and calcination temperature is 500~650 DEG C, calcining
Time is 4~10 hours, and preferably the atmosphere in atmosphere furnace is air or oxygen.
Further, source of iron is selected from one or more of frerrous chloride, ferrous nitrate, ferrous acetate, ferrous oxalate.
Further, phosphorus source is selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate.
Further, dispersing agent is selected from one or more of ethylene glycol, acetone, polyethylene glycol, ethyl alcohol, and complexing agent is selected from
One or more of sodium gluconate, gluconic acid.
The invention has the following advantages: the preparation method of above-mentioned ferric phosphate/graphene composite material, in the first stage
In reaction, ferric phosphate crystal seed is made by the first phosphorus solution and source of iron solution oxide and is adsorbed on graphene.It is anti-in second stage
Ying Zhong, source of iron solution and the reaction of the second phosphorus solution, under the induction of crystal seed, the ferric phosphate for reacting generation is crystallized in seed surface is analysed
Out, so that the ferric phosphate crystal seed on graphene gradually grows up to form crystal, ferric phosphate/graphene presoma is obtained.Complexing agent can
To keep the stabilization of iron ion in solution, inhibit the formation of other chemical products.Pass through after ferric phosphate/graphene presoma separation
Dry, calcining obtains ferric phosphate/graphene composite material.The preparation method of above-mentioned ferric phosphate/graphene composite material, crystal are logical
The mode for crossing diauxic growth is formed, even particle size, and ferric phosphate obtained/graphene composite material particle is uniform.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
Below with reference to figure, the present invention is described in further detail.
Detailed description of the invention
The attached drawing constituted part of this application is used to provide further understanding of the present invention, schematic reality of the invention
It applies example and its explanation is used to explain the present invention, do not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the transmission electron microscope TEM image for the ferric phosphate crystal seed composite graphite alkene that the preferred embodiment of the present invention 2 obtains；
Fig. 2 is the form iron phosphate crystal scanning electron microscope sem image on ferric phosphate/graphene composite material of Examples 1 to 4；
Fig. 3 is the form iron phosphate crystal scanning electron microscope sem image on ferric phosphate/graphene composite material of embodiment 1.
Specific embodiment
The embodiment of the present invention is described in detail below in conjunction with attached drawing, but the present invention can be defined by the claims
Implement with the multitude of different ways of covering.
Referring to Fig.1, the preferred embodiment of the present invention provides a kind of preparation method of ferric phosphate/graphene composite material,
The following steps are included:
Source of iron, graphene and dispersing agent is taken to be dispersed in water obtained first source of iron solution.
The first phosphorus solution that phosphorus source is prepared is reacted with the first source of iron solution mixed oxidization progress first stage, obtains phosphoric acid
Iron crystal seed composite graphite alkene.
It takes source of iron and complexing agent preparation soluble in water to obtain the second source of iron solution, phosphorus source preparation soluble in water is separately taken to obtain the
Two phosphorus source solution.
Ferric phosphate crystal seed composite graphite alkene, the second source of iron solution and the second phosphorus source solution mixed oxidization are subjected to second stage
Reaction, the ferric phosphate reacted crystallize under the induction of the crystal seed of ferric phosphate crystal seed composite graphite alkene, and in ferric phosphate crystal seed
It is precipitated on composite graphite alkene, obtains ferric phosphate/graphene presoma.
Ferric phosphate/graphene presoma separation, dry, calcining are obtained into ferric phosphate/graphene composite material.
Under the action of dispersing agent, graphene dispersion is uniform, can come into full contact with source of iron, while avoiding graphene in source of iron
Assemble sedimentation in solution, forms precipitating.Source of iron is ferrous compound, and ferrous oxidation reacts to form ferric phosphate with the first phosphorus solution,
Ferric phosphate seed crystal is precipitated and is adsorbed on graphene sheet layer in mixed solution, and ferric phosphate crystal seed composite graphite is obtained after separation
Alkene.Ferric phosphate is lesser single crystal grain at this stage, is isolated as ferric phosphate aggregation analysis in induction second stage reaction
Crystal seed out.In second stage reaction, the second source of iron solution and the second phosphorus source solution mixed oxidization generate ferric phosphate.Complexing agent
The stabilization that can keep iron ion in solution inhibits the formation of other chemical products.Ferric phosphate is in ferric phosphate crystal seed composite graphite
It is regularly arranged in turn in the absorption of ferric phosphate seed crystal face, deposition under the induction of crystal seed on alkene, it is brilliant to eventually form new ferric phosphate
Body shell layer, therefore crystal is constantly grown up, and ferric phosphate/graphene presoma is obtained.Ferric phosphate/graphene presoma can pass through
Filter type separation, dry, calcining and then formation ferric phosphate/graphene composite material.Above-mentioned ferric phosphate/graphene composite material
Preparation method, crystal formed by way of diauxic growth, even particle size, ferric phosphate obtained/graphene composite wood
Expect that particle is uniform.The formation of ferric phosphate/graphene composite material presoma includes two stages, and first stage reaction nucleation is formed
Crystal seed, form iron phosphate crystal growth in second stage reaction solution, crystal seed induced crystal growth are simultaneously assembled and form the biggish particle of particle,
And its even particle size.The reaction condition of first stage reaction and second stage can refer to source of iron, the coprecipitation of phosphorus source
Normal condition.
The preparation method of above-mentioned ferric phosphate/graphene composite material, in the first stage in reaction, by the first phosphorus solution and iron
Source solution oxide is made ferric phosphate crystal seed and is adsorbed on graphene.In second stage reaction, source of iron solution and the second phosphorus are molten
Liquid reaction, under the induction of crystal seed, the ferric phosphate crystallization for reacting generation is precipitated so that ferric phosphate crystal seed on graphene gradually at
Length forms crystal, obtains ferric phosphate/graphene presoma.Complexing agent can keep the stabilization of iron ion in solution, inhibit other
The formation of chemical product.Ferric phosphate/graphene composite wood is obtained by dry, calcining after ferric phosphate/graphene presoma separation
Material.The preparation method of above-mentioned ferric phosphate/graphene composite material, crystal are formed by way of diauxic growth, and granular size is equal
Even, ferric phosphate obtained/graphene composite material particle is uniform.
At the same time, the preparation method product yield height of above-mentioned ferric phosphate/graphene composite material, purity is high, iron phosphorus ratio
Reach that 0.96~1.00, size tunable (1.0um≤D50≤30.0um), process flow is short, wastewater flow rate is few, is easy to industrialize
The advantages that, it is the splendid presoma battery material for manufacturing lithium iron phosphate positive material.A large amount of technical literatures and synthesis experience
All show that iron phosphorus all reaches best than the LiFePO 4 material in above range in terms of electrochemistry capacitance and cycle performance.
Optionally, the iron concentration of the first source of iron solution is 0.05~0.08mol/L, the phosphate radical of the first phosphorus solution from
Sub- concentration is 0.025~0.04mol/L, and the molar ratio of iron ion and graphene is 1:0.05~0.1 in the first source of iron solution, the
The volume ratio of one source of iron solution and the first phosphorus solution is 1:0.45~0.55.
Under conditions of the iron ion and phosphonium ion, crystal nucleation forms the ferric phosphate single crystal grain of very little, as brilliant
Kind.If being lower than this concentration range lower limit, it is very little to be nucleated quantity, and large-scale application is limited in production；If being higher than this concentration
Range limit is then nucleated excessive, crystal growth rate and dramatically increases, will form many bulky grains, is unfavorable for controlling ferric phosphate
Grain granularity.
Optionally, in the second source of iron solution iron concentration be 1.0~4.0mol/L, complexing agent concentration be 0.05~
0.2mol/L, the phosphate ion concentration of the second phosphorus solution are 1.0~4.0mol/L.Ferro element and the second phosphorus are molten in second source of iron solution
The molar ratio of P elements in liquid is 1:1.05~1.10, ferric phosphate crystal seed composite graphite alkene, the second source of iron solution and the second phosphorus
Source solution is mixed according to mass ratio 1:550~1100:500~1000.
If iron phosphate grains grow slower, low yield lower than this concentration range and quality than lower limit；If it is dense to be higher than this
Than the upper limit, then growth rate is too fast and may have new core or even other chemical precipitates to generate, and is unfavorable for particle for degree and quality
The control of degree.Under this condition, because the condition of pH and temperature limits, nucleation is restricted, the second source of iron solution and the second phosphorus
The reaction of source solution is formed larger and size uniformity crystal grain and is precipitated based on crystal growth.
Optionally, the operation of first stage reaction includes: to mix the first phosphorus solution, the first source of iron solution and the first oxidant
It closes, under conditions of 50~70 DEG C, pH value are 0.5~5.0, continues to be stirred to react 0.5~2.0 hour.
The operation of second stage reaction includes: that ferric phosphate crystal seed composite graphite alkene, the second source of iron solution, the second phosphorus source is molten
Liquid and the second oxidant are uniformly mixed, and under conditions of 30~60 DEG C, pH value are 4.0~5.0, continue to be stirred to react 3 hours.
It reacts in the first stage, by the first phosphorus solution and source of iron solution in 50~70 DEG C, the condition that pH value is 0.5~5.0
Under, it reacts 0.5~2 hour, while oxidant being added into reaction solution.Temperature is excessively high, pH value is too low or reaction time mistake
Long, then ferric phosphate nucleation quantity is excessive and is accompanied by the fast-growth of crystal so that the granularity of ferric phosphate increases, particle diameter distribution not
Uniformly, meaning of the ferric phosphate crystal seed as the presoma of the form iron phosphate crystal of synthesis uniform particle size is lost；Conversely, if temperature mistake
It is low, pH value is excessively high or the reaction time is too short, then ferric phosphate nucleation slowly, crystal seed quantity is very few, it is difficult to separation and be precipitated, ferric phosphate
Production combined coefficient it is also restrained.
It include: by ferric phosphate crystal seed composite graphite alkene, the second source of iron solution and complexing in the operation of second stage reaction
Agent mixes, and the second phosphorus source solution is added, 30~60 DEG C, pH value be 4.0~5.0 under conditions of, react 3 hours, while to anti-
It answers and the second oxidant is added in solution.Temperature be higher than this range, pH value is too low, the reaction time is too long, form iron phosphate crystal was grown
Cause size distribution uneven fastly.And temperature is too low, pH value is excessively high, the reaction time is too short, and one causes ferric phosphate to be nucleated quantity
Few slow, the very few particle of crystal seed quantity is tiny, it is difficult to and separation and precipitation, the production combined coefficient of ferric phosphate is also restrained,
Second is that being likely to form other easy precipitated chemical products such as iron hydroxide (Fe (OH)3)。
Optionally, for the oxidant used in first stage of reaction for hydrogen peroxide, hydrogen peroxide and the water as solvent are isometric
It is added, the mass percent solubility of hydrogen peroxide is 9~11%.The oxidant used in second stage of reaction is oxygen, and oxygen is with 1
~2ml/L min speed is passed through in reaction solution.
First stage has Oxidation of Fe using hydrogen peroxide2+Ion generates Fe3+And FePO is formed in turn4Effect, hydrogen peroxide
Additional amount be added in equal volume with the water in the first source of iron solution as solvent.When the amount of hydrogen peroxide is excessive, ferric phosphate nucleation
The excessive and fast-growth with crystal of quantity loses ferric phosphate so that the granularity of ferric phosphate increases, particle diameter distribution is uneven
Meaning of the crystal seed as the presoma of the form iron phosphate crystal of synthesis uniform particle size；Conversely, when the amount of its hydrogen peroxide is very few, then phosphoric acid
Iron is nucleated that quantity is few slow, and the very few particle of crystal seed quantity is tiny, it is difficult to separation and be precipitated, the production combined coefficient of ferric phosphate also by
To limitation.
The oxidant used in second stage of reaction has Oxidation of Fe for oxygen2+For Fe3+And in turn in FePO4Crystal seed
New FePO is generated under catalysis and induction4Crystal shell；If still using hydrogen peroxide, new FePO can be generated in the solution4
Nucleus in turn grow up too quickly by crystal grain, and particle size is difficult to control.And oxygen is passed through with 1~2ml/Lmin speed reacts molten
In liquid.If oxygen intake is too big, cause size distribution uneven one is form iron phosphate crystal growth is too fast, the second is may shape
At other easy precipitated chemical products such as iron hydroxide (Fe (OH)3).If oxidant intake is too small, lead to form iron phosphate crystal
Growth rate is excessively slow, and crystal development is incomplete, it is difficult to which separation and precipitation, the production combined coefficient of ferric phosphate are also restrained.
Optionally, first stage reaction adjusts pH value by addition acidic materials, passes through addition alkali in second stage reaction
Property substance adjust pH value, acidic materials be selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, acetic acid, alkaline matter be selected from ammonia
One or more of water, ammonium carbonate, ammonium hydrogen carbonate.
Optionally, dry for spray drying, calcining carries out in atmosphere furnace, and calcination temperature is 500~650 DEG C, when calcining
Between be 4~10 hours, preferably the atmosphere in atmosphere furnace be air or oxygen.
Optionally, source of iron is selected from one or more of frerrous chloride, ferrous nitrate, ferrous acetate, ferrous oxalate.
Optionally, phosphorus source is selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate.
Optionally, dispersing agent is selected from one or more of ethylene glycol, acetone, polyethylene glycol, ethyl alcohol, and complexing agent is selected from Portugal
One or more of grape sodium saccharate, gluconic acid.
Optionally, phosphorus source is selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid.
Embodiment 1
A kind of preparation method of ferric phosphate/graphene composite battery material, comprising the following steps:
(1) in a kettle, by frerrous chloride (FeCl2·4H2O) 5g, graphene 0.02g, ethylene glycol 20ml mixing, add
Enter the hydrogen peroxide and water of isometric mass concentration 9%, so that overall solution volume is 500mL, iron concentration is made
The first source of iron solution a of 0.05mol/L.
(2) the first phosphorus solution b meter 910mL that 0.025mol/L is made in ammonium dihydrogen phosphate is added in reaction kettle and the first iron
Source solution a carries out 55 DEG C of reactions of heating, adds phosphoric acid to adjust pH=4.0, reacts 1.5h, ferric phosphate crystal seed composite graphite alkene c is made.
(3) the source of iron solution d for configuring frerrous chloride concentration 1.0mol/L counts 2000mL, and complexing agent sodium gluconate, which is added, to be made
Its concentration reaches 0.5mol/L, and the second phosphorus solution e for preparing biphosphate ammonium concentration 1.0mol/L counts 2120mL.
(4) 3g ferric phosphate crystal seed composite graphite alkene c and source of iron solution d are sufficiently mixed uniformly in a kettle, addition the
Oxygen is simultaneously passed through in reaction solution by two phosphorus solution e with 1~2ml/Lmin speed, is carried out temperature reaction to 30 DEG C, is added carbonic acid
Ammonium adjusts pH=5.0, reacts 3h.
(5) then spray drying, the high-temperature calcination 6 hours of 550 DEG C of atmosphere furnace can be prepared by ferric phosphate/graphene composite wood
Material.
Embodiment 2
A kind of preparation method of ferric phosphate/graphene composite material, comprising the following steps:
(1) in a kettle, by 10g ferrous nitrate (Fe (NO3)2·6H2O), 0.04g graphene and 40mL acetone are mixed
It closes, the first source of iron solution a that concentration is 0.08mol/L is made in the hydrogen peroxide and water that add isometric mass concentration 10%.
(2) the total 800mL of the first phosphorus solution b for 0.04mol/L being made in diammonium hydrogen phosphate is added molten with source of iron in reaction kettle
Liquid a carries out 70 DEG C of reactions of heating, adds acetic acid to adjust pH=3.0, reacts 0.5h, ferric phosphate crystal seed composite graphite alkene c is made.
(3) the source of iron solution d for preparing ferrous nitrate concentration 2.0mol/L counts 1500mL, and complexing agent sodium gluconate, which is added, to be made
Its concentration reaches 0.1mol/L, and the second phosphorus solution e for preparing diammonium hydrogen phosphate concentration 2.0mol/L counts 1600mL.
(4) 2.5g ferric phosphate crystal seed composite graphite alkene c and source of iron solution d are sufficiently mixed uniformly in a kettle, are added
Second phosphorus solution e carries out temperature reaction to 35 DEG C, and ammonium hydroxide is added to adjust pH=4.5, reacts 3h.
(5) then spray drying, the high-temperature calcination 10 hours of 500 DEG C of atmosphere furnace can be prepared by ferric phosphate/graphene composite wood
Material.
Embodiment 3
A kind of preparation method of ferric phosphate/graphene composite material, comprising the following steps:
(1) in a kettle, 15g ferrous acetate, 0.09g graphene, 100mL polyethylene glycol are mixed, adds and waits bodies
The hydrogen peroxide and water of long-pending mass concentration 11%, the first source of iron solution a that concentration 0.06mol/L is made count 1430mL.
(2) by phosphoric acid be made 0.03mol/L the first phosphorus solution b meter 2700mL be added reaction kettle in source of iron solution a into
98 DEG C of reactions of row heating, add ammonium hydrogen carbonate to adjust pH=2.5, react 0.5h, ferric phosphate crystal seed composite graphite alkene c is made.
(3) the second source of iron solution total 3000mL of d for preparing ferrous acetate concentration 3.0mol/L, is added complexing agent gluconic acid
Its concentration is set to reach 0.15mol/L, the second phosphorus solution e for preparing phosphoric acid concentration 3.0mol/L counts 3200mL.
(4) ferric phosphate crystal seed composite graphite alkene c and source of iron solution d are sufficiently mixed uniformly in a kettle, are added second
Phosphorus solution e carries out temperature reaction to 50 DEG C, and ammonium hydrogen carbonate is added to adjust pH=4.5, reacts 3h.
(5) then spray drying, the high-temperature calcination 6 hours of 550 DEG C of atmosphere furnace can be prepared by ferric phosphate/graphene composite wood
Material.
Embodiment 4
A kind of preparation method of ferric phosphate/graphene composite material, comprising the following steps:
(1) in a kettle, by 25g ferrous acetate, 5g frerrous chloride (FeCl2·4H2O) admixed graphite alkene 0.23g, third
Ketone 120mL and ethylene glycol 130mL mixing, adds the hydrogen peroxide and water of isometric mass concentration 10%, and concentration is made
The first source of iron solution a of 0.08mol/L amounts to 2430mL.
(2) by the first phosphorus solution b meter 4860mL that 0.04mol/L is made in ammonium dihydrogen phosphate and phosphoric acid be added in reaction kettle with
Source of iron solution a carries out 70 DEG C of reactions of heating, adds ammonium hydroxide and ammonium carbonate to adjust pH=2.0, reacts 3h, it is compound that ferric phosphate crystal seed is made
Graphene c.
(3) ferrous acetate is prepared, the second source of iron solution d of frerrous chloride concentration 4.0mol/L counts 4000mL, addition complexing
Agent gluconic acid and sodium gluconate make its concentration reach 0.2mol/L, prepare ammonium dihydrogen phosphate and phosphoric acid concentration 4.0mol/L
Second phosphorus solution e counts 4400mL.
(4) 15g ferric phosphate crystal seed composite graphite alkene c and the second source of iron solution d are sufficiently mixed uniformly in a kettle, are added
Enter the second phosphorus solution e and carry out temperature reaction to 60 DEG C, adds ammonium hydroxide and ammonium carbonate to adjust pH=4.0, react 3h.
(5) then spray drying, the high-temperature calcination 5 hours of 600 DEG C of atmosphere furnace can be prepared by ferric phosphate/graphene composite wood
Material.
It is the ferric phosphate/graphene composite material chemical component synthesized by Examples 1 to 4 listed by table 1.Iron phosphorus ratio is all
Between 0.96~1.Impurity content reaches the content standard of LITHIUM BATTERY industrial application substantially within 10ppm.Wherein impurity
Element is mainly due to impurities introducing in the reaction raw material such as molysite, microcosmic salt.Change phase of the granularity also with reaction condition
Alternation should be showed.
1 ferric phosphate of table/graphene composite material index
As can be seen from the above embodiments, the present invention can stablize and efficiently control the granularity of form iron phosphate crystal, and
Form iron phosphate crystal is compound with graphene, is conducive to the conductivity for promoting positive electrode；The present invention is using oxygen as oxidant, Bu Huiyin
Enter foreign ion, obtained ferric phosphate impurity content is low, chemical composition stability.The technique and item that method provided by the invention is related to
Part is less toxic, environmentally friendly, easy to operate, is conducive to the industrial production of ferric phosphate.
The ferric phosphate crystal seed composite graphite alkene of Example 2 is scanned electron microscope analysis, as a result as shown in Figure 2.Scheme medium and small
Stain is ferric phosphate crystal seed.Image shows the size of ferric phosphate crystal seed in 5~10nm, quite a few crystal seed is attached to graphene
Surface (picture right dark color sheet region).Ferric phosphate was all microcosmic salt and molysite in the past in bigger concentration (> 0.3mol/
L synthesis) and at higher temperature is reacted, the particle of obtained phosphoric acid iron monocrystal is generally in 500nm or more；And phosphoric acid of the invention
Iron/graphene composite material preparation method is received by the way that synthesis of the low concentration solution under 50~70 DEG C of cryogenic conditions is minimum
Rice form iron phosphate crystal.
Examples 1 to 4 is respectively the phosphoric acid in second stage reaction process under different iron ion solubility and P elements concentration
Iron/graphene composite material preparation method.In the first stage in reaction process, ferric phosphate crystal seed composite graphite in each embodiment
The granular size of the ferric phosphate crystal seed of alkene differs smaller, the particle of the form iron phosphate crystal of final ferric phosphate/graphene composite material
Size is mainly determined by second stage reaction process.The form iron phosphate crystal of Example 1~4 is (by ferric phosphate composite graphite alkene point
It is dispersed in the aqueous solution of ethylene glycol, ultrasonic wave is layered ten minutes, stands and then take bottom white depositions) it is scanned Electronic Speculum point
Analysis, scanning result respectively correspond (1) in Fig. 2, (2) in Fig. 2, (4) in (3) and Fig. 2 in Fig. 2.Above-mentioned SEM figure
As showing that the second source of iron solution and the second phosphorus source solution concentration are higher, reaction temperature is higher, then particle size is bigger.In above-mentioned member
The solution concentration of element is 1mol/L, and when temperature is 30 DEG C, the size of form iron phosphate crystal particle only has 2~5um；And 2mol/L's is molten
The iron phosphate grains average-size of solution preparation of the liquid at 35 DEG C then reaches 10~15um；For 3mol/L solution at 50 DEG C and
Granular size of the 4mol/L solution reaction at 70 DEG C respectively reaches 20 and 30um.From figure it is found that ferric phosphate/graphite of the invention
The form iron phosphate crystal particle size that the preparation method of alkene composite material can be more accurately controlled, and ferric phosphate partial size is uniform
Property is good.
Ferric phosphate/graphene composite material of Example 1 is scanned electron microscope analysis, and scanning result respectively corresponds Fig. 3.
The electron microscope of Fig. 3 illustrates that graphene and ferric phosphate form uniformly mixed composite material.Apparent granule-morphology belongs in figure
Form iron phosphate crystal, the substance of sheet or fold is graphene in Electronic Speculum；Graphene dispersion between iron phosphate grains or
It is coated on particle periphery.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (5)
1. a kind of preparation method of ferric phosphate/graphene composite material, which comprises the following steps:
Source of iron, graphene and dispersing agent is taken to be dispersed in water obtained first source of iron solution；
The first phosphorus solution that phosphorus source is prepared is reacted with the first source of iron solution mixed oxidization progress first stage, obtains phosphoric acid
Iron crystal seed composite graphite alkene；
It takes source of iron and complexing agent preparation soluble in water to obtain the second source of iron solution, phosphorus source preparation soluble in water is separately taken to obtain the second phosphorus
Source solution；
The ferric phosphate crystal seed composite graphite alkene, the second source of iron solution and the second phosphorus source solution mixed oxidization are carried out second
Elementary reaction, the ferric phosphate reacted crystallize under the induction of the crystal seed of the ferric phosphate crystal seed composite graphite alkene, and in institute
It states and is precipitated on ferric phosphate crystal seed composite graphite alkene, obtain ferric phosphate/graphene presoma；
Ferric phosphate/graphene presoma separation, dry, calcining are obtained into ferric phosphate/graphene composite material；
The iron concentration of the first source of iron solution is 0.05~0.08mol/L, the phosphate anion of first phosphorus solution
Concentration is 0.025~0.04mol/L, in the first source of iron solution the molar ratio of iron ion and the graphene be 1:0.05~
0.1, the volume ratio of the first source of iron solution and first phosphorus solution is 1:0.45~0.55；
The operation of the first stage reaction includes: by first phosphorus solution, the first source of iron solution and the first oxidant
Mixing continues to be stirred to react 0.5~2.0 hour under conditions of 50~70 DEG C, pH value are 0.5~5.0；
Iron concentration is 1.0~4.0mol/L in the second source of iron solution, and the complexing agent concentration is 0.05~0.2mol/
L, the phosphate ion concentration of second phosphorus solution are 1.0~4.0mol/L, ferro element and described the in the second source of iron solution
The molar ratio of P elements in two phosphorus solutions is 1:1.05~1.10, by the ferric phosphate crystal seed composite graphite alkene according to every 1~
5g is added in the second phosphorus source solution described in the second source of iron solution described in 550~1100mL and 500~1000mL and is sufficiently mixed；
The size of the crystal seed is in 5~10nm；
The operation of second stage reaction includes: by the ferric phosphate crystal seed composite graphite alkene, the second source of iron solution, the
Two phosphorus source solution and the second oxidant are uniformly mixed, and under conditions of 30~60 DEG C, pH value are 4.0~5.0, continue to be stirred to react
3 hours；
The source of iron is ferrous compound, is selected from one of frerrous chloride, ferrous nitrate, ferrous acetate, ferrous oxalate or several
Kind；
First oxidant is hydrogen peroxide, and the hydrogen peroxide is added in equal volume with the water as solvent, the matter of the hydrogen peroxide
Measuring percentage solubility is 9~11%；
Second oxidant is oxygen, and the oxygen is passed through in reaction solution with 1~2ml/Lmin speed.
2. the preparation method of ferric phosphate/graphene composite material according to claim 1, which is characterized in that described first
Elementary reaction adjusts pH value by addition acidic materials, passes through addition alkaline matter in the second stage reaction and adjusts pH value,
The acidic materials are selected from one or more of phosphoric acid, ammonium dihydrogen phosphate, acetic acid, and the alkaline matter is selected from ammonium hydroxide, carbonic acid
One or more of ammonium, ammonium hydrogen carbonate.
3. the preparation method of ferric phosphate/graphene composite material according to claim 1, which is characterized in that the drying
For spray drying, calcining carries out in atmosphere furnace, and calcination temperature is 500~650 DEG C, and calcination time is 4~10 hours, the gas
Atmosphere in atmosphere furnace is air or oxygen.
4. the preparation method of ferric phosphate/graphene composite material described in any one of claim 1 to 3, feature exist
In phosphorus source is selected from one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate.
5. the preparation method of ferric phosphate/graphene composite material described in any one of claim 1 to 3, feature exist
In the dispersing agent is selected from one or more of ethylene glycol, acetone, polyethylene glycol, ethyl alcohol, and the complexing agent is selected from glucose
One or more of sour sodium, gluconic acid.
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| CN107706380B (en) * | 2017-09-27 | 2020-06-12 | 郴州博太超细石墨股份有限公司 | Method for preparing lithium vanadium phosphate/graphene composite cathode material on metal base |
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| CN113851618B (en) * | 2021-08-10 | 2023-06-23 | 桂林理工大学 | Method for preparing high-performance ferric phosphate/graphene composite anode material by utilizing hydrochloric acid leaching solution of iron vitriol slag and application of high-performance ferric phosphate/graphene composite anode material |
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