CN109305663A - Battery-grade anhydrous iron phosphate and preparation method thereof - Google Patents
Battery-grade anhydrous iron phosphate and preparation method thereof Download PDFInfo
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- CN109305663A CN109305663A CN201810931479.9A CN201810931479A CN109305663A CN 109305663 A CN109305663 A CN 109305663A CN 201810931479 A CN201810931479 A CN 201810931479A CN 109305663 A CN109305663 A CN 109305663A
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- Prior art keywords
- battery
- iron
- phosphoric acid
- phosphate
- grade anhydrous
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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 23
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 5
- 240000007817 Olea europaea Species 0.000 claims abstract description 4
- 230000000877 morphologic effect Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 238000007689 inspection Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 13
- 235000003891 ferrous sulphate Nutrition 0.000 description 12
- 239000011790 ferrous sulphate Substances 0.000 description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 5
- 235000019838 diammonium phosphate Nutrition 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- 239000005955 Ferric phosphate Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000000618 nitrogen fertilizer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- OXSWKJLAKXNIFG-UHFFFAOYSA-N azane sulfuric acid Chemical compound N.N.N.OS(O)(=O)=O OXSWKJLAKXNIFG-UHFFFAOYSA-N 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical class [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Chemical class 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- -1 iron salt ferrous sulfate Chemical class 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011780 sodium chloride Chemical class 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/242—Preparation from ammonia and sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of battery-grade anhydrous iron phosphate and preparation method thereof, anhydrous phosphoric acid iron powder body is made of the monodisperse olive shape particle of morphological rules, and tap density is up to 1.5-1.6g/cm3；Use the oxidation-precipitation method using air as oxidant, pH adjusting agent solution is added in divalent iron salt and phosphoric acid or phosphatic mixture aqueous solution and controls pH value, it is passed through air, stirring, reaction generates the crystalline state compound containing ammonium root, hydroxyl and the crystallization water, then obtains NH4Fe2 (OH) (PO4) 22H2O powder through separation of solid and liquid, washing, drying；The powder roasts in air atmosphere, decomposes and removes ammonium root, hydroxyl and the crystallization water, obtains battery-grade anhydrous iron phosphate.Battery-grade anhydrous iron phosphate quality of the present invention is high, and simple production process reduces cost and pollution.
Description
Technical field
The present invention relates to battery material preparations, specifically disclose a kind of preparation method of battery-grade anhydrous iron phosphate.
Background technique
It will likely be solar energy, wind energy, tidal power system by the lithium-ion energy storage battery of positive electrode of LiFePO4
The perfect match of system.Therefore, the research of lithium iron phosphate positive material not only has important value in field of lithium ion battery, to the sun
The development and application of the new energy technologies such as energy, wind energy, tide energy also has a very important significance.
At present apparently, LiFePO4 is most possible really large-scale application in power type and accumulation energy type lithium ion battery
Ideal material.Since John professor B.Goodenough in the U.S. in 1997 proposes this material, both at home and abroad to this into
Extensive and in-depth research is gone.People are by mixing conductive materials, crystal grain nanosizing to material progress surface packet conductive carbon, inside
Etc. means improve material electric conductivity；The bulk density of material is improved by the particle shape of optimal control powder, particles size and distribution.
People develop a variety of preparation processes, some have been applied to reality.
The mainstream process of preparing of LiFePO4 haves the shortcomings that common:
First is that reaction process has byproduct salt generation, such as NaNO3, NaCl, Na2SO4, byproduct salt is present in
It reacts in the mother liquor generated, also largely exists in the cleaning solution of phosphoric acid iron product, direct emission will seriously pollute environment, waste liquid
Processing will cause increased costs, and by-product is low-value product again；
Second is that the ferric phosphate generated all contains certain crystallization water, usually two, as FePO42H2O；Product removes
Outside the crystallization water, usually also containing a small amount of absorption water；Since containing the crystallization water and absorption water, the actual constituent of ferric phosphate is not very
It determines reliably, brings certain difficulty for accurate dosing when producing LiFePO4；
In addition, the product containing the crystallization water is in the long-term storage process, it is possible to create the moisture absorption or weathering phenomenon, make product at
Divide and generate variation at any time, has an adverse effect to the stability and homogeneity of product of technique；Therefore, FePO42H2O is uncomfortable
In the raw material for being directly used as production lithium iron phosphate positive material, necessary pretreatment is generally carried out.
And industrially production FePO42H2O generallys use ferrous sulfate (FeSO4) as raw material, and cost is relatively low.But it adopts
With prior art, it is necessary to consume a large amount of oxidants such as hydrogen peroxide (H2O2), sodium hypochlorite (NaClO), sodium chlorate (NaClO3), mistake
Ammonium sulfate ((NH4) 2S2O8) etc., increases cost to a certain extent.
In conclusion preparing lithium iron phosphate positive material using the ferric phosphate containing the crystallization water, there is at high cost, pollution greatly
And in production process accurate dosing difficulty shortcoming.
Summary of the invention
It is an object of the invention to: a kind of battery-grade anhydrous iron phosphate to solve the above problem, quality is high, produces work
Skill is simple, reduces cost and pollution.
The technical solution adopted by the present invention is that such:
Battery-grade anhydrous iron phosphate, anhydrous phosphoric acid iron powder body are made of the monodisperse olive shape particle of morphological rules, jolt ramming
Density is up to 1.5-1.6g/cm3.Specific step is as follows for preparation method:
A, divalent iron salt and phosphoric acid or phosphate mixed aqueous solution are prepared；
B, secure ph adjusts agent solution；
C, by above-mentioned prepared divalent iron salt and phosphoric acid or phosphate mixed aqueous solution, pH adjusting agent solution pump point
Be not successively inputted to stirring reactor in, by air compressor, with certain flow into reactor input air；Pass through
Water bath with thermostatic control controls to adjust the temperature of reaction solution in reactor and is maintained at constant within the scope of 40-98 DEG C；Constant divalent iron salt with
The flow of phosphoric acid or phosphate mixed aqueous solution and air, control to adjust reactor in reaction solution pH value be 0.5-7.5 simultaneously
It keeps constant；Charging is completed, and is continued stirring and is aged and is continually fed into air oxidation, generates crystalline state compound NH4Fe2 (OH)
(PO4)2·2H2O；
D, upper step resulting material is transferred in solid-liquid separator and is separated by solid-liquid separation, be washed with deionized and be separated by solid-liquid separation institute
The solid product obtained, until using BaCl2Solution inspection does not measure the SO42- in washing water, or uses AgNO3Solution inspection does not measure washing
Cl in water-Until；Product after washing is 2~10 hours dry in 80~120 DEG C in an oven, obtains NH4Fe2 (OH)
(PO4) 22H2O powder；
E, by NH4Fe2 (OH) (PO4) 22H2O powder in air atmosphere, 500-700 DEG C is roasted 20~24 hours, point
Solution removes ammonium root, hydroxyl and the crystallization water, obtains with battery-grade anhydrous iron phosphate.
Further, in the divalent iron salt and phosphoric acid or phosphate mixed aqueous solution the concentration of iron be 0.2-2 moles/
It rises, the molar ratio of phosphorus and iron is 0.95-1.05: 1 in the aqueous solution.
Further, the divalent iron salt is frerrous chloride, and the frerrous chloride, which is reacted by hydrochloric acid with metallic iron, to be made.
In conclusion due to the adoption of the above technical scheme, the beneficial effects of the present invention are:
The present invention prepares the battery-grade anhydrous phosphoric acid of high-quality using cheap divalent iron salt ferrous sulfate, frerrous chloride as raw material
Iron only contains ammonium salt in the mother liquor and cleaning solution of generation, can be used as nitrogenous fertilizer and be directly used in agricultural and forestry production, do not pollute the environment, nothing
Need liquid waste processing；
Preparation process is using air as oxidant, can significant save the cost without consuming additional oxidant；
Preparation gained is the anhydrous iron phosphate without containing the crystallization water and absorption water, and crystallinity and reactivity are high, and ingredient is true
It is fixed reliable, stablize save-resistant, is the desirable feedstock for preparing LiFePO4, the stability for being conducive to improve technique is consistent with product
Property；
This preparation method is suitable for the scale, economy, stabilization, reliable production of high-quality battery-grade iron phosphate, has apparent
Advantage, it is very with practical value.
Specific embodiment
Battery-grade anhydrous iron phosphate, anhydrous phosphoric acid iron powder body are made of the monodisperse olive shape particle of morphological rules, accumulation
Density is high, and tap density is up to 1.5-1.6g/cm3.
Embodiment 1
Battery-grade anhydrous iron phosphate preparation method,
Prepare ferrous sulfate, phosphoric acid, diammonium hydrogen phosphate mixed aqueous solution, wherein ferrous sulfate concentration be 1.0 mol/Ls,
Phosphoric acid concentration is 0.5 mol/L, diammonium hydrogen phosphate concentration is 0.5 mol/L；
Compound concentration is the ammonia spirit of 4.0 mol/Ls as pH adjusting agent；
Add 1 liter of deionized water in advance in the reaction kettle that volume is 7 liters, it is strong to stir, and be passed through into reacting kettle jacketing
Thermostatted water, controlling water temperature in reaction kettle is 45 DEG C；
By air compressor, using 10 liters/min of flow into reaction kettle input air as oxidant；
By ferrous sulfate, phosphoric acid, diammonium hydrogen phosphate mixed aqueous solution, ammonia spirit is successively inputted to reaction kettle with pump respectively
In, control ferrous sulfate, phosphoric acid, diammonium hydrogen phosphate mixed aqueous solution flow be 20 ml/mins, adjust the stream of ammonia spirit
Amount, the pH value for controlling reaction solution in reaction kettle is 2.30 ± 0.05；By water bath with thermostatic control, reaction solution in reaction kettle is controlled to adjust
Temperature is simultaneously maintained within the scope of 44-46 DEG C；After 2 liters of ferrous sulfate, phosphoric acid, diammonium hydrogen phosphate mixed aqueous solution is added toward reaction kettle
Stop charging；
It is passed through high-temperature constant warm water into reacting kettle jacketing, material in reactor is heated up, controls material in reactor temperature
Within the scope of 94-96 DEG C, to continue stirring ageing 10 hours, while being continually fed into air；
After ageing, the material in reaction kettle is discharged, is separated by solid-liquid separation with centrifuge, with 60 DEG C of deionized water
Washing is separated by solid-liquid separation resulting solid product, until not measuring the SO42- in washing water with BaCl2 inspection；
By the product after washing, condition is 4 hours dry at 120 DEG C in an oven, obtains NH4Fe2 (OH) (PO4) 2
2H2O powder；
NH4Fe2 (OH) (PO4) 22H2O powder is placed in corundum crucible, 500 DEG C of roastings in air atmosphere muffle furnace
It burns 24 hours, decomposes and remove ammonium root, hydroxyl and the crystallization water, obtain that there is the battery-grade anhydrous phosphoric acid of the high-quality of rhombic form
Iron.
The ammonia that Roasting Decomposition generates can use sulfuric acid absorption, generate ammonium sulfate；In mother liquor and cleaning solution after centrifuge separation
Only contain ammonium sulfate；After two batches ammonium sulfate ammonia spirit tune pH value to neutrality, it can be used directly as nitrogenous fertilizer.
Embodiment 2
Battery-grade anhydrous iron phosphate preparation method,
Ferrous sulfate and ammonium dihydrogen phosphate mixed aqueous solution are prepared, wherein ferrous sulfate concentration is 1.5 mol/Ls, phosphoric acid
Dihydro ammonium concentration is 1.5 mol/Ls；
Compound concentration is the urea liquid of 2.5 mol/Ls as pH adjusting agent；
Add 2 liters of deionized waters in advance in the reaction kettle that volume is 7 liters, it is strong to stir, and be passed through into reacting kettle jacketing
Thermostatted water, controlling water temperature in reaction kettle is 90 DEG C.By air compressor, inputted with 10 liters/min of flow into reaction kettle
Air is as oxidant；
Ferrous sulfate and ammonium dihydrogen phosphate mixed aqueous solution, urea liquid are successively inputted in reaction kettle respectively with pump,
The flow for controlling ferrous sulfate and ammonium dihydrogen phosphate mixed aqueous solution is 20 ml/mins, adjusts the flow of urea liquid, is controlled
The pH value of reaction solution is 5.00 ± 0.05 in reaction kettle processed；By water bath with thermostatic control, the temperature of reaction solution in reaction kettle is controlled to adjust
And it is maintained within the scope of 89-91 DEG C；
Stop charging after 2 liters of ferrous sulfate and ammonium dihydrogen phosphate mixed aqueous solution are added toward reaction kettle, continues stirring ageing 8
Hour, while being continually fed into air；In ageing process, it should remain that the temperature of reaction solution within the scope of 89-91 DEG C, and is fitted
When add urea liquid, the pH value for controlling reaction solution in reaction kettle is 5.00 ± 0.05；
After ageing, the material in reaction kettle is discharged, is separated by solid-liquid separation with centrifuge, with 60 DEG C of deionized water
Washing is separated by solid-liquid separation resulting solid product, until not measuring the SO42- in washing water with the inspection of BaCl2 solution；
Product after washing is 4 hours dry under conditions of 105 DEG C in an oven, obtain NH4Fe2 (OH) (PO4)
22H2O powder；
NH4Fe2 (OH) (PO4) 22H2O powder is placed in corundum crucible, 600 DEG C of roastings in air atmosphere muffle furnace
It burns 6 hours, decomposes and remove ammonium root, hydroxyl and the crystallization water, obtain the battery-grade anhydrous iron phosphate with rhombic form.
The ammonia that Roasting Decomposition generates can use sulfuric acid absorption, generate ammonium sulfate；In mother liquor and cleaning solution after centrifuge separation
Only contain ammonium sulfate；After two batches ammonium sulfate ammonia spirit tune pH value to neutrality, it can be used directly as nitrogenous fertilizer.
Claims (4)
1. battery-grade anhydrous iron phosphate, it is characterised in that: anhydrous phosphoric acid iron powder body by morphological rules monodisperse olive shape particle
Composition, tap density are up to 1.5-1.6g/cm3.
2. a kind of preparation method of battery-grade anhydrous iron phosphate as described in claim 1, it is characterised in that:
Specific step is as follows:
A, divalent iron salt and phosphoric acid or phosphate mixed aqueous solution are prepared；
B, secure ph adjusts agent solution；
C, above-mentioned prepared divalent iron salt and phosphoric acid or phosphate mixed aqueous solution, pH adjusting agent solution pump are connected respectively
It is continuous to be input in the reactor that band stirs, by air compressor, with certain flow into reactor input air；Pass through constant temperature
Water-bath controls to adjust the temperature of reaction solution in reactor and is maintained at constant within the scope of 40-98 DEG C；Constant divalent iron salt and phosphoric acid
Or the flow of phosphate mixed aqueous solution and air, the pH value for controlling to adjust reaction solution in reactor are 0.5-7.5 and keep
It is constant；Charging is completed, and is continued stirring and is aged and is continually fed into air oxidation, generates crystalline state compound NH4Fe2 (OH) (PO4)
2·2H2O；
D, upper step resulting material is transferred in solid-liquid separator and is separated by solid-liquid separation, it is resulting that separation of solid and liquid is washed with deionized
Solid product, until using BaCl2Solution inspection does not measure the SO42- in washing water, or uses AgNO3Solution inspection does not measure in washing water
Cl-Until；Product after washing is 2~10 hours dry in 80~120 DEG C in an oven, obtains NH4Fe2 (OH) (PO4) 2
2H2O powder；
E, by NH4Fe2 (OH) (PO4) 22H2O powder in air atmosphere, 500-700 DEG C is roasted 20~24 hours, and decomposition removes
Ammonium root, hydroxyl and the crystallization water are removed, is obtained with battery-grade anhydrous iron phosphate.
3. a kind of preparation method of battery-grade anhydrous iron phosphate according to claim 2, it is characterised in that: the ferrous iron
The concentration of iron is 0.2-2 mol/L in salt and phosphoric acid or phosphate mixed aqueous solution, and the molar ratio of phosphorus and iron is in the aqueous solution
0.95-1.05∶1。
4. a kind of preparation method of battery-grade anhydrous iron phosphate according to claim 2, it is characterised in that: the ferrous iron
Salt is frerrous chloride, and the frerrous chloride, which is reacted by hydrochloric acid with metallic iron, to be made.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002420A (en) * | 2019-05-07 | 2019-07-12 | 江西赣锋锂业股份有限公司 | A method of anhydrous iron phosphate is prepared using steel plant's pickle liquor |
| CN112265974A (en) * | 2020-10-27 | 2021-01-26 | 安徽同心新材料科技有限公司 | Preparation method and application of amorphous iron phosphate |
| CN113336212A (en) * | 2021-07-08 | 2021-09-03 | 河南佰利新能源材料有限公司 | Method for preparing iron phosphate by recycling mother liquor |
| CN115259124A (en) * | 2021-04-29 | 2022-11-01 | 四川大学 | Preparation method and application of battery-grade iron phosphate precursor |
| CN115571864A (en) * | 2022-09-05 | 2023-01-06 | 六盘水师范学院 | Method for preparing battery-grade iron phosphate by using high-iron type fly ash as raw material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244813A (en) * | 2007-02-15 | 2008-08-20 | 比亚迪股份有限公司 | Alkali type iron ammonium phosphate and production method, production method of iron phosphate and production method of ferrous lithium phosphate |
| CN102491302A (en) * | 2011-12-15 | 2012-06-13 | 湖北万润新能源科技发展有限公司 | Battery-grade anhydrous iron phosphate and preparation method thereof |
| US20120237425A1 (en) * | 2009-09-09 | 2012-09-20 | Takahisa Nishio | Ferric phosphate hydrate particles and process for producing the same, olivine type lithium iron phosphate particles and process for producing the same, and non-aqueous electrolyte secondary battery |
| CN102694169A (en) * | 2012-03-07 | 2012-09-26 | 湖北万润新能源科技发展有限公司 | FePO4/high polymer cracked carbon composite material and preparation method thereof, and NH4Fe2(OH)(PO4)2.2H2O/high polymer composite material and preparation method thereof |
| JP2014065641A (en) * | 2012-09-27 | 2014-04-17 | Murata Mfg Co Ltd | Method for manufacturing iron phosphate, lithium iron phosphate, electrode active material, and secondary battery |
| CN103825024A (en) * | 2014-02-24 | 2014-05-28 | 宁波工程学院 | Battery-grade ferric phosphate and preparation method |
-
2018
- 2018-08-15 CN CN201810931479.9A patent/CN109305663A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101244813A (en) * | 2007-02-15 | 2008-08-20 | 比亚迪股份有限公司 | Alkali type iron ammonium phosphate and production method, production method of iron phosphate and production method of ferrous lithium phosphate |
| US20120237425A1 (en) * | 2009-09-09 | 2012-09-20 | Takahisa Nishio | Ferric phosphate hydrate particles and process for producing the same, olivine type lithium iron phosphate particles and process for producing the same, and non-aqueous electrolyte secondary battery |
| CN102491302A (en) * | 2011-12-15 | 2012-06-13 | 湖北万润新能源科技发展有限公司 | Battery-grade anhydrous iron phosphate and preparation method thereof |
| CN102694169A (en) * | 2012-03-07 | 2012-09-26 | 湖北万润新能源科技发展有限公司 | FePO4/high polymer cracked carbon composite material and preparation method thereof, and NH4Fe2(OH)(PO4)2.2H2O/high polymer composite material and preparation method thereof |
| JP2014065641A (en) * | 2012-09-27 | 2014-04-17 | Murata Mfg Co Ltd | Method for manufacturing iron phosphate, lithium iron phosphate, electrode active material, and secondary battery |
| CN103825024A (en) * | 2014-02-24 | 2014-05-28 | 宁波工程学院 | Battery-grade ferric phosphate and preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002420A (en) * | 2019-05-07 | 2019-07-12 | 江西赣锋锂业股份有限公司 | A method of anhydrous iron phosphate is prepared using steel plant's pickle liquor |
| CN112265974A (en) * | 2020-10-27 | 2021-01-26 | 安徽同心新材料科技有限公司 | Preparation method and application of amorphous iron phosphate |
| CN115259124A (en) * | 2021-04-29 | 2022-11-01 | 四川大学 | Preparation method and application of battery-grade iron phosphate precursor |
| CN113336212A (en) * | 2021-07-08 | 2021-09-03 | 河南佰利新能源材料有限公司 | Method for preparing iron phosphate by recycling mother liquor |
| CN115571864A (en) * | 2022-09-05 | 2023-01-06 | 六盘水师范学院 | Method for preparing battery-grade iron phosphate by using high-iron type fly ash as raw material |
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