CN106784817A - The preparation method of ferric phosphate/graphene composite material - Google Patents
The preparation method of ferric phosphate/graphene composite material Download PDFInfo
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- CN106784817A CN106784817A CN201611236632.3A CN201611236632A CN106784817A CN 106784817 A CN106784817 A CN 106784817A CN 201611236632 A CN201611236632 A CN 201611236632A CN 106784817 A CN106784817 A CN 106784817A
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- solution
- source
- 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 158
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 139
- 239000005955 Ferric phosphate Substances 0.000 title claims abstract description 137
- 229940032958 ferric phosphate Drugs 0.000 title claims abstract description 137
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 194
- 229910052742 iron Inorganic materials 0.000 claims abstract description 100
- 239000013078 crystal Substances 0.000 claims abstract description 97
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 71
- 239000011574 phosphorus Substances 0.000 claims abstract description 71
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 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 description 3
- -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 33
- 239000010439 graphite Substances 0.000 claims description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 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
- 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
- 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
- 238000001694 spray drying Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 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
- 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
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- 150000002500 ions Chemical class 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
- 239000000203 mixture Substances 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
- 239000002253 acid Substances 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 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
- 235000011114 ammonium hydroxide Nutrition 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 27
- 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 107
- 238000000034 method Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000006911 nucleation Effects 0.000 description 10
- 238000010899 nucleation Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 239000007788 liquid Substances 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
- 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
- 238000007792 addition Methods 0.000 description 4
- 235000012501 ammonium carbonate Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 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
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 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
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000001556 precipitation Methods 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 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
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 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
- 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 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
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 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
- 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
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method 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 method of ferric phosphate/graphene composite material, comprise the following steps：Take molysite, Graphene and dispersant and source of iron solution is obtained.The first phosphorus solution that phosphorus source is prepared carries out first stage reaction with source of iron solution, and reaction obtains ferric phosphate crystal seed.Take source of iron, phosphorus source and prepare respectively and obtain 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 carries 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, calcining will be wrapped and obtain ferric phosphate/graphene composite material.The preparation method of above-mentioned ferric phosphate/graphene composite material, crystal is formed by way of diauxic growth, even particle size, and obtained ferric phosphate/graphene composite material particle size is homogeneous.
Description
Technical field
The present invention relates to field of lithium ion battery material, especially, it is related to a kind of system of ferric phosphate/graphene composite material
Preparation Method.
Background technology
At present, 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 automobile, leisure
The fields such as car, Medical Devices startup, military power supply.Quality and its of LiFePO4 combination property manufacture used main raw material
There are much relations with manufacture method.The manufacture of lithium iron phosphate positive material, generally uses 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 method such as sol-gel process, 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, technological process
Long, particularly chemical property is poor etc..Specifically, solid phase method product chemical composition uniformity is bad, lot stability is poor；
Hydro-thermal method high cost, technological process are long, production wastewater flow rate is big；Homogeneous precipitation method can produce that a large amount of waste water, technological process are long, impurity
Content is high；Sol-gel process generated time is long, washes consumption big, product porosity is too high, particle easily shrinks etc.；It is empty
Gas oxidizing process energy consumption is big, production cost is high, granularity is uneven；Microemulsion method, microwave crystallization method are still in laboratory research
The industrial equipment of stage, shortcoming and complete sets of Techniques.
The content of the invention
The invention provides a kind of preparation method of ferric phosphate/graphene composite material, to solve prepared by current method
The uneven technical problem of ferric phosphate particle diameter.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of ferric phosphate/graphene composite material, comprises the following steps：
Take source of iron, Graphene and dispersant and the first source of iron solution is obtained in water.
The first phosphorus solution and the first source of iron solution mixed oxidization that phosphorus source is prepared carry out first stage reaction, obtain phosphoric acid
Iron crystal seed composite graphite alkene.
Take source of iron and complexing agent preparation soluble in water obtains the second source of iron solution, separately take phosphorus source preparation soluble in water and 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 carried out into second stage
Reaction, the ferric phosphate that reaction is obtained is crystallized under the induction of the crystal seed of ferric phosphate crystal seed composite graphite alkene, and in ferric phosphate crystal seed
Separated out on composite graphite alkene, obtain ferric phosphate/Graphene presoma.
Ferric phosphate/Graphene presoma is separated, is dried, calcining obtains 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 mol ratio of iron ion and Graphene is 1 in the first source of iron solution:0.05~0.1,
The volume ratio of the 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 is 1.0~4.0mol/L.
The mol ratio of the P elements in the second source of iron solution in ferro element and the second phosphorus solution is 1:1.05~1.10, by institute
State ferric phosphate crystal seed composite graphite alkene and add the second source of iron solution and 500~1000mL described in 550~1100mL according to every 1~5g
In second phosphorus source solution and it is sufficiently mixed.
Further, the operation of first stage reaction includes：
First phosphorus solution, the first source of iron solution and the first oxidant are mixed, is 0.5~5.0 in 50~70 DEG C, pH value
Under the conditions of, continue stirring reaction 0.5~2.0 hour.
The operation of second stage reaction includes：
Ferric phosphate crystal seed composite graphite alkene, the second source of iron solution, the second phosphorus source solution and the second oxidant are well mixed,
Under conditions of 30~60 DEG C, pH value are for 4.0~5.0, continue stirring reaction 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
Amount 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 adding acidic materials, by addition in second stage reaction
Alkaline matter adjusts pH value, and selected from one or more in phosphoric acid, ammonium dihydrogen phosphate, acetic acid, alkaline matter is selected from acidic materials
One or more in ammoniacal liquor, ammonium carbonate, ammonium hydrogen carbonate.
Further, it is spray drying to dry, and calcining is carried out in atmosphere furnace, and calcining heat 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 in frerrous chloride, ferrous nitrate, ferrous acetate, ferrous oxalate.
Further, phosphorus source is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate.
Further, selected from one or more in ethylene glycol, acetone, polyethylene glycol, ethanol, complexing agent is selected from dispersant
One or more in sodium gluconate, gluconic acid.
The invention has the advantages that：The preparation method of above-mentioned ferric phosphate/graphene composite material, in the first stage
In reaction, ferric phosphate crystal seed is obtained 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 second phosphorus solution react, and under the induction of crystal seed, the ferric phosphate for reacting generation crystallizes analysis in seed surface
Go out so that the ferric phosphate crystal seed on Graphene gradually grows up to form crystal, obtain ferric phosphate/Graphene presoma.Complexing agent can
To keep the stabilization of iron ion in solution, suppress the formation of other chemical products.Ferric phosphate/Graphene presoma passes through after separating
Dry, calcining obtains ferric phosphate/graphene composite material.The preparation method of above-mentioned ferric phosphate/graphene composite material, crystal leads to
The mode for crossing diauxic growth is formed, even particle size, and obtained ferric phosphate/graphene composite material particle is homogeneous.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The accompanying drawing for constituting the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate, for explaining the present invention, not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is the transmission electron microscope TEM image of the ferric phosphate crystal seed composite graphite alkene that the preferred embodiment of the present invention 2 is obtained；
Fig. 2 is the form iron phosphate crystal scanning electron microscope sem image on the ferric phosphate/graphene composite material of embodiment 1~4；
Fig. 3 is the form iron phosphate crystal scanning electron microscope sem image on the ferric phosphate/graphene composite material of embodiment 1.
Specific embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing, but the present invention can be defined by the claims
Multitude of different ways with covering is implemented.
Reference picture 1, the preferred embodiments of the present invention provide a kind of preparation method of ferric phosphate/graphene composite material,
Comprise the following steps：
Take source of iron, Graphene and dispersant and the first source of iron solution is obtained in water.
The first phosphorus solution and the first source of iron solution mixed oxidization that phosphorus source is prepared carry out first stage reaction, obtain phosphoric acid
Iron crystal seed composite graphite alkene.
Take source of iron and complexing agent preparation soluble in water obtains the second source of iron solution, separately take phosphorus source preparation soluble in water and 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 carried out into second stage
Reaction, the ferric phosphate that reaction is obtained is crystallized under the induction of the crystal seed of ferric phosphate crystal seed composite graphite alkene, and in ferric phosphate crystal seed
Separated out on composite graphite alkene, obtain ferric phosphate/Graphene presoma.
Ferric phosphate/Graphene presoma is separated, is dried, calcining obtains ferric phosphate/graphene composite material.
In the presence of dispersant, graphene dispersion is uniform, can be fully contacted with source of iron, while avoiding Graphene in source of iron
Assemble sedimentation in solution, form precipitation.Source of iron is ferrous compound, and ferrous oxidation and the first phosphorus solution react to form ferric phosphate,
Ferric phosphate seed crystal is separated out and adsorbed on graphene sheet layer in mixed solution, and ferric phosphate crystal seed composite graphite is obtained after separation
Alkene.It is less single crystal grain in the stage ferric phosphate, is isolated ferric phosphate aggregation analysis in being reacted as induction second stage
The crystal seed for going 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 of iron ion in solution can be kept, suppresses the formation of other chemical products.Ferric phosphate is in ferric phosphate crystal seed composite graphite
In the absorption of ferric phosphate seed crystal face, deposition and then regularly arranged under the induction of the crystal seed on alkene, new ferric phosphate is eventually formed brilliant
Body shell layer, therefore crystal is able to constantly grow up, and obtains ferric phosphate/Graphene presoma.Ferric phosphate/Graphene presoma can pass through
Filter type is separated, and is dried, is calcined and then forms ferric phosphate/graphene composite material.Above-mentioned ferric phosphate/graphene composite material
Preparation method, crystal formed by way of diauxic growth, even particle size, obtained ferric phosphate/Graphene composite wood
Material particle is homogeneous.The formation of ferric phosphate/graphene composite material presoma includes two stages, and first stage reaction nucleation is formed
Crystal seed, in second stage reaction solution form iron phosphate crystal growth, crystal seed induced crystal growth and assemble form the larger particle of particle,
And its even particle size.First stage reacts and the reaction condition of 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 reacting in the first stage, by the first phosphorus solution and iron
Source solution oxide is obtained ferric phosphate crystal seed and adsorbs on Graphene.In second stage reaction, source of iron solution and the second phosphorus are molten
Liquid is reacted, and under the induction of crystal seed, the ferric phosphate crystallization for reacting generation is separated out so that ferric phosphate crystal seed on Graphene gradually into
Length forms crystal, obtains ferric phosphate/Graphene presoma.Complexing agent can keep the stabilization of iron ion in solution, suppress other
The formation of chemical product.Ferric phosphate/Graphene presoma obtains ferric phosphate/Graphene composite wood after separating by drying, calcining
Material.The preparation method of above-mentioned ferric phosphate/graphene composite material, crystal is formed by way of diauxic growth, and granular size is equal
Even, obtained ferric phosphate/graphene composite material particle is homogeneous.
At the same time, the preparation method product yield of above-mentioned ferric phosphate/graphene composite material is high, purity is high, iron phosphorus ratio
Reach 0.96~1.00, size tunable (1.0um≤D50≤30.0um), technological process is short, wastewater flow rate is few, be easy to industrialization
The advantages of, 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 iron phosphorus than all being reached in terms of electrochemistry capacitance and cycle performance most preferably in the LiFePO 4 material of above range.
Alternatively, 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 mol ratio of iron ion and Graphene is 1 in the first source of iron solution:0.05~0.1, 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 less than this concentration range lower limit, nucleation quantity very little, in production limited to by large-scale application；If being higher than this concentration
Range limit, then nucleation is excessive, crystal growth rate is dramatically increased, and can form many bulky grains, is unfavorable for controlling ferric phosphate
Grain granularity.
Alternatively, 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 is 1.0~4.0mol/L.Ferro element and the second phosphorus are molten in second source of iron solution
The mol ratio of the 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 according to mass ratio 1:550~1100:500~1000 mixing.
If less than this concentration range and quality than lower limit, iron phosphate grains growth is relatively slow, low yield；If dense higher than this
Than the upper limit, then growth rate is too fast and may have new core or even other chemical precipitates to produce, and is unfavorable for particle for degree and quality
The control of degree.Under this condition, because the condition limitation of pH and temperature, nucleation is restricted, the second source of iron solution and the second phosphorus
Based on crystal growth, formation is larger and the crystal grain of size uniformity is separated out for the reaction of source solution.
Alternatively, the operation of first stage reaction includes：First phosphorus solution, the first source of iron solution and the first oxidant are mixed
Close, under conditions of 50~70 DEG C, pH value are for 0.5~5.0, continue stirring reaction 0.5~2.0 hour.
The operation of second stage reaction includes：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 well mixed, under conditions of 30~60 DEG C, pH value are for 4.0~5.0, continue stirring reaction 3 hours.
React in the first stage, by the first phosphorus solution and source of iron solution in the condition that 50~70 DEG C, pH value are 0.5~5.0
Under, react 0.5~2 hour, while to adding oxidant in reaction solution.Temperature is too high, pH value is too low or the reaction time is long,
Then ferric phosphate nucleation quantity is excessive and fast-growth with crystal so that the granularity increase of ferric phosphate, particle diameter distribution are uneven
It is even, lose meaning of the ferric phosphate crystal seed as the presoma of the form iron phosphate crystal of synthesis uniform particle size；If conversely, temperature it is too low,
PH value is too high or the reaction time is too short, then ferric phosphate nucleation is slow, and crystal seed quantity is very few, it is difficult to separates and separates out, ferric phosphate
Production combined coefficient is also restrained.
Include in the operation of second stage reaction：By ferric phosphate crystal seed composite graphite alkene, the second source of iron solution and complexing
Agent is mixed, and adds the second phosphorus source solution, under conditions of 30~60 DEG C, pH value are for 4.0~5.0, is reacted 3 hours, while to anti-
Answer and add the second oxidant in solution.Temperature is too low higher than this scope, pH value, the reaction time is oversize, and form iron phosphate crystal grew
Cause size distribution uneven soon.And temperature is too low, pH value is too high, the reaction time is too short, and one causes ferric phosphate nucleation quantity
Few slow, the very few particle of crystal seed quantity is tiny, it is difficult to separates and separates out, the production combined coefficient of ferric phosphate is also restrained, its
Two is to be likely to form other easy precipitated chemical products such as iron hydroxide (Fe (OH)3)。
Alternatively, the oxidant for being used in first stage of reaction is hydrogen peroxide, and hydrogen peroxide is isometric with water as solvent
Add, 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/Lmin speed is passed through in reaction solution.
First stage has Oxidation of Fe using hydrogen peroxide2+Ion generates Fe3+And and then formation FePO4Effect, hydrogen peroxide
Addition and the first source of iron solution in added in equal volume as the water of solvent.When the amount of hydrogen peroxide is excessive, ferric phosphate nucleation
Quantity is excessive and fast-growth with crystal so that the granularity increase of ferric phosphate, particle diameter distribution are uneven, lose ferric phosphate
Crystal seed as synthesis uniform particle size form iron phosphate crystal presoma meaning；Conversely, when the amount of its hydrogen peroxide is very few, then phosphoric acid
Iron nucleation quantity is slow less, and the very few particle of crystal seed quantity is tiny, it is difficult to separates and separates out, the production combined coefficient of ferric phosphate is also received
To limitation.
The oxidant used in second stage of reaction is oxygen, with Oxidation of Fe2+It is Fe3+And and then in FePO4Crystal seed
Catalysis and the new FePO of the lower generation of induction4Crystal shell；If still using hydrogen peroxide, new FePO can be in the solution produced4
Nucleus and then crystal grain is grown up too quickly, particle size is difficult to control to.And it is molten that oxygen is passed through reaction with 1~2ml/Lmin speed
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
Into other easy precipitated chemical products such as iron hydroxide (Fe (OH)3).If oxidant intake is too small, cause form iron phosphate crystal
Growth rate is excessively slow, and crystal development is incomplete, it is difficult to separates and separates out, the production combined coefficient of ferric phosphate is also restrained.
Alternatively, first stage reaction adjusts pH value by adding acidic materials, by adding alkali in second stage reaction
Property material regulation pH value, acidic materials be selected from phosphoric acid, ammonium dihydrogen phosphate, acetic acid in one or more, alkaline matter be selected from ammonia
One or more in water, ammonium carbonate, ammonium hydrogen carbonate.
Alternatively, it is spray drying to dry, and calcining is carried out in atmosphere furnace, and calcining heat is 500~650 DEG C, during calcining
Between be 4~10 hours, preferably the atmosphere in atmosphere furnace be air or oxygen.
Alternatively, source of iron is selected from one or more in frerrous chloride, ferrous nitrate, ferrous acetate, ferrous oxalate.
Alternatively, phosphorus source is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate.
Alternatively, selected from one or more in ethylene glycol, acetone, polyethylene glycol, ethanol, complexing agent is selected from Portugal to dispersant
One or more in grape sodium saccharate, gluconic acid.
Alternatively, phosphorus source is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid.
Embodiment 1
A kind of preparation method of ferric phosphate/Graphene composite battery material, comprises the following steps：
(1) in a kettle., by frerrous chloride (FeCl2·4H2O) 5g, Graphene 0.02g, ethylene glycol 20ml mixing, plus
Enter the hydrogen peroxide and water of isometric mass concentration 9% so that overall solution volume is 500mL, iron concentration is obtained
The first source of iron solution a of 0.05mol/L.
(2) by ammonium dihydrogen phosphate be obtained 0.025mol/L the first phosphorus solution b meter 910mL add reactor in the first iron
Source solution a carries out the 55 DEG C of reactions that heat up, and phosphorate acid adjustment pH=4.0, reacts 1.5h, and ferric phosphate crystal seed composite graphite alkene c is obtained.
(3) the source of iron solution d meter 2000mL of configuration frerrous chloride concentration 1.0mol/L, add complexing agent sodium gluconate to make
Its concentration reaches 0.5mol/L, prepares the second phosphorus solution e meters 2120mL of biphosphate ammonium concentration 1.0mol/L.
(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
Simultaneously with 1~2ml/Lmin speed be passed through in reaction solution oxygen by two phosphorus solution e, carries out temperature reaction to 30 DEG C, plus 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, comprises the following steps：
(1) in a kettle., by 10g ferrous nitrates (Fe (NO3)2·6H2O), 0.04g Graphenes and 40mL acetone are mixed
Close, the hydrogen peroxide and water for adding isometric mass concentration 10% are obtained the first source of iron solution a that concentration is 0.08mol/L.
(2) will be molten with source of iron in the common 800mL additions reactors of the first phosphorus solution b of the prepared 0.04mol/L of diammonium hydrogen phosphate
Liquid a carries out the 70 DEG C of reactions that heat up, plus acetic acid adjustment pH=3.0, reacts 0.5h, and ferric phosphate crystal seed composite graphite alkene c is obtained.
(3) the source of iron solution d meter 1500mL of ferrous nitrate concentration 2.0mol/L are prepared, adds complexing agent sodium gluconate to make
Its concentration reaches 0.1mol/L, prepares the second phosphorus solution e meters 1600mL of diammonium hydrogen phosphate concentration 2.0mol/L.
(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 ammonification water adjustment 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, comprises the following steps：
(1) in a kettle., 15g ferrous acetates, 0.09g Graphenes, 100mL polyethylene glycol are mixed, the body such as adds
The hydrogen peroxide and water of long-pending mass concentration 11%, are obtained the first source of iron solution a meters 1430mL of concentration 0.06mol/L.
(2) phosphoric acid is obtained during the first phosphorus solution b of 0.03mol/L meters 2700mL adds reactor to enter with source of iron solution a
Row heats up 98 DEG C and reacts, plus ammonium hydrogen carbonate adjustment pH=2.5, reacts 0.5h, and ferric phosphate crystal seed composite graphite alkene c is obtained.
(3) the second source of iron solution common 3000mL of d of ferrous acetate concentration 3.0mol/L are prepared, complexing agent gluconic acid is added
Its concentration is reached 0.15mol/L, prepare the second phosphorus solution e meters 3200mL of phosphoric acid concentration 3.0mol/L.
(4) ferric phosphate crystal seed composite graphite alkene c and source of iron solution d are sufficiently mixed uniformly in a kettle., add second
Phosphorus solution e carries out temperature reaction to 50 DEG C, plus ammonium hydrogen carbonate adjustment 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, comprises the following steps：
(1) in a kettle., by 25g ferrous acetates, 5g frerrous chlorides (FeCl2·4H2O) admixed graphite alkene 0.23g, third
Ketone 120mL and ethylene glycol 130mL mixes, and adds the hydrogen peroxide and water of isometric mass concentration 10%, and concentration is obtained
The first source of iron solution a of 0.08mol/L amounts to 2430mL.
(2) by ammonium dihydrogen phosphate and phosphoric acid be obtained the first phosphorus solution b of 0.04mol/L meters 4860mL add in reactor with
Source of iron solution a carries out the 70 DEG C of reactions that heat up, ammonification water and ammonium carbonate adjustment pH=2.0, reacts 3h, ferric phosphate crystal seed is obtained and is combined
Graphene c.
(3) the second source of iron solution d meter 4000mL of ferrous acetate, frerrous chloride concentration 4.0mol/L are prepared, complexing is added
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., plus
Entering the second phosphorus solution e carries out temperature reaction to 60 DEG C, ammonification water and ammonium carbonate adjustment pH=4.0, reacts 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 chemical composition of the ferric phosphate/graphene composite material synthesized by embodiment 1~4 listed by table 1.Iron phosphorus ratio is all
Between 0.96~1.Impurity content is basic within 10ppm, reaches the content standard of LITHIUM BATTERY commercial Application.Wherein impurity is first
Element is introduced mainly due to impurities in the reaction raw material such as molysite, microcosmic salt.Granularity is corresponding also with the change of reaction condition
Show alternation.
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 combined with Graphene, is conducive to being lifted the electrical conductivity of positive electrode；The present invention with oxygen as oxidant, Bu Huiyin
Enter foreign ion, the ferric phosphate impurity content for obtaining is low, chemical composition stability.Technique and bar that the method that the present invention is provided is related to
It is part low toxicity, environmental protection, simple to operate, be conducive to the industrial production of ferric phosphate.
The ferric phosphate crystal seed composite graphite alkene of Example 2 is scanned electronic microscope photos, as a result as shown in Figure 2.Figure is medium and small
Stain is ferric phosphate crystal seed.In 5~10nm, quite a few crystal seed is attached to Graphene to the size of image display ferric phosphate crystal seed
Surface (picture right dark color sheet region).Ferric phosphate be all in the past microcosmic salt and molysite than larger concentration (>0.3mol/
L) and at temperature higher it is synthesized, the particle of the phosphoric acid iron monocrystal for obtaining is general in more than 500nm；And phosphoric acid of the invention
Synthesis of the preparation method of iron/graphene composite material by low concentration solution under 50~70 DEG C of cryogenic conditions is minimum to be received
Rice form iron phosphate crystal.
Phosphoric acid in the respectively second stage course of reaction of embodiment 1~4 under different iron ion solubility and P elements concentration
The preparation method of iron/graphene composite material.In the first stage in course of reaction, 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 course of reaction.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 difference corresponding diagram 2 (1), Fig. 2 (2), Fig. 2 (3) and Fig. 2 (4).Above-mentioned SEM image show the second source of iron solution and
Second phosphorus source solution concentration is higher, and reaction temperature is higher, then particle size is bigger.It is 1mol/ in the solution concentration of above-mentioned element
L, when temperature is 30 DEG C, the size of form iron phosphate crystal particle only has 2~5um；And solution system of the solution of 2mol/L at 35 DEG C
Standby iron phosphate grains average-size then reaches 10~15um；For 3mol/L solution in 50 DEG C and 4mol/L solution reactions 70
DEG C when granular size respectively reach 20 and 30um.Knowable to figure, the preparation side of ferric phosphate/graphene composite material of the invention
The form iron phosphate crystal particle size that method can more be accurately controlled, and the homogeneity of ferric phosphate particle diameter is good.
Ferric phosphate/the graphene composite material of Example 1 is scanned electronic microscope photos, scanning result difference corresponding diagram 3.
The electron microscope explanation Graphene and ferric phosphate of Fig. 3 form well mixed composite.Obvious granule-morphology belongs in figure
Form iron phosphate crystal, the material of sheet or fold is Graphene in Electronic Speculum；Graphene dispersion between iron phosphate grains or
It is coated on particle periphery.
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of ferric phosphate/graphene composite material, it is characterised in that comprise the following steps：
Take source of iron, Graphene and dispersant and the first source of iron solution is obtained in water；
The first phosphorus solution that phosphorus source is prepared is carried out into first stage reaction with the first source of iron solution mixed oxidization, phosphoric acid is obtained
Iron crystal seed composite graphite alkene；
Take source of iron and complexing agent preparation soluble in water obtains the second source of iron solution, separately take phosphorus source preparation soluble in water and 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 that reaction is obtained is crystallized under the induction of the crystal seed of the ferric phosphate crystal seed composite graphite alkene, and in institute
State and separated out on ferric phosphate crystal seed composite graphite alkene, obtain ferric phosphate/Graphene presoma；
Ferric phosphate/Graphene presoma is separated, is dried, calcining obtains ferric phosphate/graphene composite material.
2. the preparation method of ferric phosphate/graphene composite material according to claim 1, it is characterised in that described first
The iron concentration of source of iron solution is 0.05~0.08mol/L, the phosphorus acid ion concentration of first phosphorus solution for 0.025~
0.04mol/L, the mol ratio of iron ion and the Graphene is 1 in the first source of iron solution:0.05~0.1, described first
Source of iron solution is 1 with the volume ratio of first phosphorus solution:0.45~0.55.
3. the preparation method of ferric phosphate/graphene composite material according to claim 2, it is characterised in that described second
Iron concentration is 1.0~4.0mol/L in source of iron solution, and the complexing agent concentration is 0.05~0.2mol/L, second phosphorus
The phosphate ion concentration of solution is 1.0~4.0mol/L；
The mol ratio of the P elements in the second source of iron solution in ferro element and second phosphorus solution is 1:1.05~1.10,
By the ferric phosphate crystal seed composite graphite alkene according to every 1~5g add the second source of iron solution and 500 described in 550~1100mL~
In second phosphorus source solution described in 1000mL and it is sufficiently mixed.
4. the preparation method of ferric phosphate/graphene composite material according to claim 1, it is characterised in that described first
The operation of elementary reaction includes：
By first phosphorus solution, the first source of iron solution and the first oxidant mix, 50~70 DEG C, pH value be 0.5~
Under conditions of 5.0, continue stirring reaction 0.5~2.0 hour；
The operation of the second stage reaction includes：
The ferric phosphate crystal seed composite graphite alkene, the second source of iron solution, the second phosphorus source solution and the second oxidant are mixed
Uniformly, under conditions of 30~60 DEG C, pH value are for 4.0~5.0, stirring reaction is continued 3 hours.
5. the preparation method of ferric phosphate/graphene composite material according to claim 4, it is characterised in that described first
Oxidant is hydrogen peroxide, and the hydrogen peroxide is added in equal volume with the water as solvent, the mass percent solubility of the hydrogen peroxide
It is 9~11%.
Second oxidant is oxygen, and the oxygen is passed through in reaction solution with 1~2ml/Lmin speed.
6. the preparation method of ferric phosphate/graphene composite material according to claim 5, it is characterised in that described first
Elementary reaction adjusts pH value by adding acidic materials, and pH value is adjusted by adding alkaline matter in the second stage reaction,
The acidic materials are selected from ammoniacal liquor, carbonic acid selected from one or more in phosphoric acid, ammonium dihydrogen phosphate, acetic acid, the alkaline matter
One or more in ammonium, ammonium hydrogen carbonate.
7. the preparation method of ferric phosphate/graphene composite material according to claim 1, it is characterised in that the drying
It is spray drying, calcining is carried out in atmosphere furnace, calcining heat is 500~650 DEG C, calcination time is 4~10 hours, preferably institute
It is air or oxygen to state the atmosphere in atmosphere furnace.
8. the preparation method of the ferric phosphate/graphene composite material according to any one of claim 1~7, its feature exists
In the source of iron is selected from one or more in frerrous chloride, ferrous nitrate, ferrous acetate, ferrous oxalate.
9. the preparation method of the ferric phosphate/graphene composite material according to any one of claim 1~7, its feature exists
In phosphorus source is selected from one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, sodium dihydrogen phosphate.
10. the preparation method of the ferric phosphate/graphene composite material according to any one of claim 1~7, its feature exists
In the dispersant is selected from glucose selected from one or more in ethylene glycol, acetone, polyethylene glycol, ethanol, the complexing agent
One or more in sour sodium, gluconic acid.
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| CN107522187A (en) * | 2017-07-18 | 2017-12-29 | 江西悦安超细金属有限公司 | A kind of ferric phosphate and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976302A (en) * | 2012-12-10 | 2013-03-20 | 秦皇岛科维克科技有限公司 | Rare-earth-doped iron phosphate material and preparation method thereof |
| CN103872313A (en) * | 2014-03-10 | 2014-06-18 | 电子科技大学 | Lithium ion cell anode material LiMn2-2xM(II)xSixO4 and preparation method thereof |
| CN103956457A (en) * | 2014-04-22 | 2014-07-30 | 苏州创科微电子材料有限公司 | Fluorocarbon-doped ferroferric oxide used as lithium battery anode material and preparation method thereof |
| CN106169580A (en) * | 2016-08-25 | 2016-11-30 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of battery-grade iron phosphate/graphene composite material |
-
2016
- 2016-12-28 CN CN201611236632.3A patent/CN106784817B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976302A (en) * | 2012-12-10 | 2013-03-20 | 秦皇岛科维克科技有限公司 | Rare-earth-doped iron phosphate material and preparation method thereof |
| CN103872313A (en) * | 2014-03-10 | 2014-06-18 | 电子科技大学 | Lithium ion cell anode material LiMn2-2xM(II)xSixO4 and preparation method thereof |
| CN103956457A (en) * | 2014-04-22 | 2014-07-30 | 苏州创科微电子材料有限公司 | Fluorocarbon-doped ferroferric oxide used as lithium battery anode material and preparation method thereof |
| CN106169580A (en) * | 2016-08-25 | 2016-11-30 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of battery-grade iron phosphate/graphene composite material |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107522187A (en) * | 2017-07-18 | 2017-12-29 | 江西悦安超细金属有限公司 | A kind of ferric phosphate and preparation method thereof |
| CN107706379A (en) * | 2017-09-27 | 2018-02-16 | 郴州博太超细石墨股份有限公司 | A kind of preparation method of phosphoric acid vanadium lithium/graphene/carbon composite positive pole |
| CN107706380A (en) * | 2017-09-27 | 2018-02-16 | 郴州博太超细石墨股份有限公司 | A kind of method that phosphoric acid vanadium lithium/grapheme composite positive electrode material is prepared in Metal Substrate |
| 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 |
| CN108565455A (en) * | 2018-05-30 | 2018-09-21 | 北京石油化工学院 | A kind of method that non-nitrogen containing complexing agent auxiliary prepares spherical nickel cobalt manganese ternary precursor |
| CN112408351A (en) * | 2020-11-23 | 2021-02-26 | 中钢集团南京新材料研究院有限公司 | Preparation method of high-compaction iron phosphate and lithium iron phosphate |
| CN113851618A (en) * | 2021-08-10 | 2021-12-28 | 桂林理工大学 | Method for preparing high-performance iron phosphate/graphene composite negative electrode material by using iron vitriol slag hydrochloric acid leaching solution and application |
| 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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