CN105024072B - A kind of method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate - Google Patents
A kind of method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 58
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 47
- 229910000399 iron(III) phosphate Inorganic materials 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000012266 salt solution Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 29
- 150000002505 iron Chemical class 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010828 elution Methods 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 150000003009 phosphonic acids Chemical class 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims 2
- 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
- 230000003750 conditioning effect Effects 0.000 claims 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical group CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- 235000007144 ferric diphosphate Nutrition 0.000 abstract description 2
- 239000011706 ferric diphosphate Substances 0.000 abstract description 2
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 abstract description 2
- 229940036404 ferric pyrophosphate Drugs 0.000 abstract description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 17
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- 239000005955 Ferric phosphate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229940032958 ferric phosphate Drugs 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052493 LiFePO4 Inorganic materials 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- -1 catalysis Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000013313 FeNO test Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- RFGNMWINQUUNKG-UHFFFAOYSA-N iron phosphoric acid Chemical compound [Fe].OP(O)(O)=O RFGNMWINQUUNKG-UHFFFAOYSA-N 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
- C01B25/375—Phosphates of heavy metals of iron
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate, methods described includes：(1) oxidizing agent solution is first added in iron content raffinate, stirred, added extractant and carry out multitple extraction, the organic phase isolated obtains iron salt solutions after inorganic acid elution；(2) using the iron salt solutions of step (1) as source of iron, phosphorus source is added, stirring, pH adjusting agent is added and is reacted, cooled down, then battery level ferric pyrophosphate dusty material is obtained after separation of solid and liquid, washing, drying.The present invention is to prepare ferric orthophosphate using the iron salt solutions for reclaiming to obtain from iron content raffinate as source of iron, not only realizes the regeneration to greatest extent of waste metal iron, while also improve economic benefit and reduce environmental pollution；And whole preparation process is enormously simplify, reduce production cost.
Description
Technical field
The present invention relates to field of lithium ion battery material, and in particular to a kind of method of lithium ion battery ferric orthophosphate,
More particularly to the ferro element reclaimed in a kind of raffinate using iron content is the method that source of iron prepares lithium ion battery ferric orthophosphate
Background technology
Due to ferric orthophosphate (FePO4) there is abundant chemical constitution, in lithium ion battery material, catalysis, glass-ceramic
There is extensive use with fields such as agriculturals.By the development of Market Selection and research and development technology, anode material for lithium-ion batteries phosphorus
Sour iron lithium (LiFePO4) main flow preparation technology phosphoric acid iron process is progressively turned to by ferrous oxalate technique, made from the method
The usual better performances of LiFePO 4 material, suitable for preparing medium-to-high grade lithium battery product.The synthesis technique has the advantage that：The
One, during ferric phosphate synthesizes, by the optimization of synthesis technique, the performance to iron phosphate material can be achieved, such as composition, crystalline substance
The accuracy controlling such as type and pattern, and then obtain high-quality battery-grade iron phosphate and LiFePO 4 material；Second, prepare LiFePO4
During, ferric phosphate and lithium source carbothermic reduction reaction can approximation regard as：FePO4Body skeleton keep constant, Li+Insertion
FePO4Lattice in, be changed into LiFePO4 so as to ferric phosphate, the building-up process is simple and easy to control, and material uniformity is preferable.
The raw material of industrial production ferric phosphate generally includes source of iron, phosphorus source, oxidant and alkali lye, at present source of iron generally use three
Valency molysite or divalent iron salt, the source of iron as disclosed in CN102491302A and CN102555725B are ferrous sulfate (FeSO4), chlorine
Change ferrous iron (FeCl2), ferric nitrate (FeNO3) and iron chloride (FeCl3) etc., divalent iron salt is oxidized to three by adding oxidant
Valency molysite, is the use of non-renewable resources the shortcomings that this method, while the use increase of trivalent iron salt, oxidant and alkali lye
The production cost of ferric phosphate.CN104409732A discloses a kind of preparation side of the LiFePO 4 material using mixing source of iron
Method, it uses a certain proportion of di-iron trioxide and ferric orthophosphate to prepare LiFePO4, reduces cost of material, and prepare
Lithium iron phosphate anode active material is used as maintaining the features such as processing characteristics is good during lithium ion anode material, but it is still deposited
Cost is higher the defects of.
At present, people are more the lifting of its economic benefit and yield to waste metal recovery concern, but to price phase
Processing and recovery concern to relatively low iron is less.The sour molten, extraction of waste metal material process factory major part recovery process use,
The steps such as condensing crystallizing, relatively valuable metal, such as gold, silver, nickel, chromium, manganese are only reclaimed, and iron is led because economic benefit is relatively low
Unmanned recovery is caused, but often contains a large amount of iron ions in the waste liquid after actual treatment；After waste liquid after the extraction still needs processing,
Discharging of waste liquid could be carried out；The scum filtered out simultaneously can only make waste treatment or resell to give scum treatment plant.So this place
Not only reason mode can not obtain resource regeneration to greatest extent, while it can also cause certain environmental pollution and reduce factory
The economic benefit of family.
CN101462704A discloses a kind of production method of ultrafine cell level ferric orthophosphate, its used ferrous salt
Waste residue or industrial acid-washed waste liquid of the solution from titanium white production discharge；The preparation method of wherein ferrous salt solution is：By titanium
In the input water of the production waste particle containing ferrous sulfate of white powder production discharge, heat fully dissolving and take it after precipitation separates
Ferrous salt solution of the clarified solution as production ferric orthophosphate, or the pickle liquor containing ferrous sulfate is added into waste iron filing reaction
Spent acid amount is consumed, takes ferrous salt solution of its clarified solution as production ferric orthophosphate.However, the extraction of the ferrous salt solution compared with
Slightly, the inside still has a large amount of impurity, and active ingredient concentration is relatively low.
Therefore, one kind how is designed effectively to reclaim ferro element from iron content waste liquid and be used to prepare positive phosphorus as source of iron
Sour iron is current urgent problem to be solved.
The content of the invention
To solve the shortcomings of the prior art, it is an object of the invention to provide a kind of lithium ion battery ferric orthophosphate
Method, it is prepared using the iron salt solutions for reclaiming to obtain from iron content raffinate as source of iron, is not only realized
The regeneration to greatest extent of waste metal iron, while also improve economic benefit and reduce environmental pollution；It is and significantly simple
Change whole preparation process, reduce production cost.
To use following technical scheme up to this purpose, the present invention：
The invention provides a kind of method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate, including it is following
Step：
(1) oxidizing agent solution is first added in iron content raffinate, stirred, added extractant and carry out multitple extraction, pH is adjusted
It is 0.5-5 to save agent regulation pH value, and the organic phase isolated obtains iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) as source of iron, phosphorus source is added, stirring, addition pH adjusting agent is reacted, cold
But battery level ferric pyrophosphate dusty material, then after separation of solid and liquid, washing, drying is obtained.
In the step (1) of the present invention, in the recovery of ferro element in carrying out to iron content raffinate, oxidant is first added, so
After add extractant after, can also add a certain amount of pH adjusting agent, and the oxidant and pH adjusting agent are exactly to prepare lithium ion
Raw material required for battery ferric orthophosphate, therefore, in step (2), carrying out the preparation of lithium ion battery ferric orthophosphate
When, without adding oxidant and can reduce the dosage of pH adjusting agent, thus, relative to prior art, the present invention realizes pair
The omission of said components, the preparation of lithium ion battery ferric orthophosphate but can be equally realized, and its effect is suitable.
In the step (1) of the present invention, multitple extraction refers to extraction 3-10 times so that the purity that step (1) obtains molysite reaches
More than 99.9%.
Step (1) the iron content raffinate is the solution containing divalence and/or ferric ion in the present invention.
Heretofore described oxidant be hydrogen peroxide, sodium hypochlorite, sodium peroxide or sodium perchlorate in any one or
In at least two combination, preferably hydrogen peroxide, sodium peroxide or sodium perchlorate any one or at least two combination, enter
One step is preferably hydrogen peroxide.
The quality of step (1) described oxidant is the 10-300% of iron content raffinate quality in the present invention, such as can be
10%th, 20%, 50%, 80%, 100%, 120%, 150%, 180%, 200%, 220%, 230%, 250%, 270%,
280%th, 300%, preferably 50-200%, more preferably 120%.
Step (1) described extractant is organic phosphoric acid kind of extractants in the present invention.
Heretofore described organic phosphoric acid kind of extractants is for any one in P204, P507, N290 or 5709 or at least
In two kinds of combination, preferably P204, P507 or N290 any one or at least two combination.Chinese entitled the two of P204
(2- ethylhexyls) phosphate, P507 Chinese entitled 2- ethylhexyl phosphoric acids list -2- ethylhexyls, Chinese entitled the two of N290
(2,4,4)-tri-methyl-amyl phosphonic acids, 5709 Chinese entitled isoalkyl phosphonic acids (1- methyl-heptyls) ester.
The mass ratio of step (1) extractant and solution is 1 in the present invention:100-4000, such as can be 1:100、
1:200、1:400、1:500、1:650、1:800、1:1000、1:1200、1:1500、1:1800、1:2000、1:2500、1:
2800、1:3000、1:3200、1:3500、1:4000, preferably 1:500-1000, more preferably 1:650.
The temperature of step (1) described extraction is 10-80 DEG C in the present invention, for example, can be 10 DEG C, 12 DEG C, 15 DEG C, 20 DEG C,
25 DEG C, 30 DEG C, 35 DEG C, 42 DEG C, 45 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 75 DEG C, preferably 80 DEG C, 20-60 DEG C, more preferably
42℃。
The pH value of step (1) described extraction is 0.5-5 in the present invention, for example, can be 0.5,0.8,1,1.2,1.5,2,
2.5th, 2.8,3,3.2,3.5,3.8,4,4.5,5, preferably 1.5-3, more preferably 2.
Step (1) described pH adjusting agent is acid or alkali in the present invention, and the acid is preferably appointing in sulfuric acid, nitric acid or hydrochloric acid
Anticipate a kind of or at least two combinations, the alkali is preferably sodium hydroxide and/or ammoniacal liquor.
The time of step (1) described extraction is 0.5-5h in the present invention, for example, can be 0.5h, 1.2h, 1.5h, 1.8h,
2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, preferably 4.5h, 5h, 1.5-3h, more preferably
2.2h。
The time of step (1) described stirring is 1-10h in the present invention, for example, can be 1h, 1.2h, 1.5h, 1.8h, 2h,
2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h, 4.2h, 4.5h, 5h, 6h, 7h, 8h, 9h, 10h, preferably 2-6h,
More preferably 5h.
Step (1) described inorganic acid is any one in sulfuric acid, nitric acid or hydrochloric acid or at least two group in the present invention
Close.
In the present invention step (2) phosphorus source be phosphoric acid, ammonium dihydrogen phosphate or monoammonium phosphate in any one or extremely
Few two kinds combination.
Step (2) described reaction temperature is 40-90 DEG C in the present invention, for example, can be 40 DEG C, 42 DEG C, 45 DEG C, 50 DEG C, 60
DEG C, 65 DEG C, 70 DEG C, 75 DEG C, more preferably 80 DEG C, preferably 90 DEG C, 60-80 DEG C, 65 DEG C.
Step (2) described pH adjusting agent is sour or alkali in the present invention, any in the acid preferably phosphoric acid or phosphate
It is a kind of or at least two combination, the alkali is preferably sodium hydroxide and/or ammoniacal liquor.
It is 0.5-5 that step (2), which adds pH adjusting agent regulation pH value, in the present invention, for example, can be 0.5,0.8,1,1.2,
1.5th, 2,2.5,2.8,3,3.2,3.5,3.8,4,4.5,5, preferably 1.5-2.5, more preferably 2.
Step (2) reaction time is 1-24h in the present invention, for example, can be 1h, 2h, 5h, 10h, 12h, 13h,
15h, 16h, 18h, 20h, 21h, 22h, 23h, 24h, preferably 2-20h, more preferably 10h.
As currently preferred technical scheme, methods described may comprise steps of：
(1) oxidizing agent solution is added in iron content raffinate, the quality of the oxidant is the 10- of iron content raffinate quality
300%, 1-10h is stirred, the reaction temperature for controlling solution is 10-80 DEG C, and pH value is between 0.5-5；Add the multistage extraction of extractant
Take, the mass ratio of extractant and solution is 1 in every grade of extraction tank:100-4000, extraction temperature are 10-80 DEG C, and pH value is in 0.5-5
Between, 0.5-3h is extracted, organic phase is isolated and obtains iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) recovery as source of iron, phosphorus source or phosphate, stirring are added, reaction temperature is
60-80 DEG C, pH adjusting agent is added to pH value between 0.5-5, reaction 1-24h, cooling, then after separation of solid and liquid, washing, drying
Obtain lithium ion battery ferric orthophosphate dusty material.
The second object of the present invention also resides in the lithium ion battery obtained according to method as described in the first aspect of the invention
With ferric orthophosphate dusty material.
The lithium ion battery obtained in the present invention is 10-100nm with the particle diameter of the primary particle of ferric orthophosphate dusty material.
Compared with prior art, the present invention at least has the advantages that：
(1) preparation method of the present invention can realize the regeneration to greatest extent of waste metal iron, and it is obtained
Iron salt solutions purity up to more than 99.9%, effectively increase the utilization rate of ferro element in iron content extract, saved life
Cost is produced, while reduces environmental pollution.
(2) present invention can simplify by using specific way of recycling to iron content raffinate and prepare lithium ion battery use
The whole process of ferric orthophosphate method, and used raw material is saved, production efficiency is improved, and saved production cost.
Embodiment
Technical scheme is further illustrated below by embodiment.
Those skilled in the art it will be clearly understood that the embodiment be only to aid in understand the present invention, be not construed as to this hair
Bright concrete restriction.
Embodiment 1
(1) hydrogen peroxide solution is added in iron content raffinate, the quality of the hydrogen peroxide is iron content raffinate quality
10%, 2h is stirred, the reaction temperature for controlling solution is 20 DEG C, pH value 2；Add organic phosphoric acid kind of extractants P204 and carry out multistage
Extract, the mass ratio of extractant and solution is 1 in every grade of extraction tank:200, extraction temperature is 20 DEG C, pH value 2, extracts 1h, point
Separate out organic phase and obtain iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) recovery as source of iron, phosphoric acid, stirring are added, reaction temperature is 55 DEG C, is added
PH adjusting agent to pH value is 2, reacts 2h, cooling, then lithium ion battery orthophosphoric acid is obtained after separation of solid and liquid, washing, drying
Iron powder material.
Embodiment 2
(1) liquor natrii hypochloritis is added in iron content raffinate, the quality of the sodium hypochlorite is iron content raffinate quality
30%, stir 3h, control solution reaction temperature be 40 DEG C, pH value 1.5；Organic phosphoric acid kind of extractants P507 is added to carry out
Multitple extraction, the mass ratio of extractant and solution is 1 in every grade of extraction tank:400, extraction temperature is 10 DEG C, pH value 1.5, extraction
1.5h is taken, organic phase is isolated and obtains iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) recovery as source of iron, ammonium dihydrogen phosphate, stirring, reaction temperature 65 are added
DEG C, it is 2 to add pH adjusting agent to pH value, reacts 5h, cooling, then lithium ion battery use is obtained after separation of solid and liquid, washing, drying
Ferric orthophosphate dusty material.
Embodiment 3
(1) sodium peroxide solution is added in iron content raffinate, the quality of the sodium peroxide is iron content raffinate quality
100%, stir 5h, control solution reaction temperature be 70 DEG C, pH value 3；Organic phosphoric acid kind of extractants N290 is added to carry out
Multitple extraction, the mass ratio of extractant and solution is 1 in every grade of extraction tank:800, extraction temperature is 70 DEG C, pH value 1.5, extraction
2.5h is taken, organic phase is isolated and obtains iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) recovery as source of iron, ammonium dihydrogen phosphate, stirring, reaction temperature 72 are added
DEG C, it is 2 to add pH adjusting agent to pH value, reacts 8h, cooling, then lithium ion battery use is obtained after separation of solid and liquid, washing, drying
Ferric orthophosphate dusty material.
Embodiment 4
(1) sodium perchlorate solution is added in iron content raffinate, the quality of the sodium perchlorate is iron content raffinate quality
200%, stir 8h, control solution reaction temperature be 75 DEG C, pH value 4；Organic phosphoric acid kind of extractants 5709 is added to carry out
Multitple extraction, the mass ratio of extractant and solution is 1 in every grade of extraction tank:2000, extraction temperature is 80 DEG C, pH value 2, extraction
2.5h, isolate organic phase and obtain iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) recovery as source of iron, monoammonium phosphate, stirring, reaction temperature 60 are added
DEG C, it is 2 to add pH adjusting agent to pH value, reacts 11h, cooling, then obtain lithium ion battery after separation of solid and liquid, washing, drying
With ferric orthophosphate dusty material.
Embodiment 5
(1) sodium peroxide solution is added in iron content raffinate, the quality of the sodium peroxide is iron content raffinate quality
300%, stir 10h, control solution reaction temperature be 60 DEG C, pH value 5；Add organic phosphoric acid kind of extractants and carry out multistage
Extract, the mass ratio of extractant and solution is 1 in every grade of extraction tank:4000, extraction temperature is 80 DEG C, pH value 1.5, extraction
3h, isolate organic phase and obtain iron salt solutions after inorganic acid elution；
(2) using the iron salt solutions of step (1) recovery as source of iron, phosphoric acid, stirring are added, reaction temperature is 80 DEG C, is added
PH adjusting agent to pH value is 2, reacts 24h, cooling, then lithium ion battery orthophosphoric acid is obtained after separation of solid and liquid, washing, drying
Iron powder material.
Following comparative example 1 is that the system of lithium ion battery ferric orthophosphate dusty material is directly carried out using ferrous salt solution
Preparation Method, comparative example 2 and 3 are that the method for using other recovery ferro elements carries out lithium ion battery orthophosphoric acid to provide source of iron
The preparation method of iron lithium powder material.
Comparative example 1
(1) ferrous salt solution is added in catalytic reaction kettle, after adjusting pH, hydrogen peroxide is added, brings it about exothermic reaction,
It is 55 DEG C to control its temperature, pH=2；
(2) dissolving phosphoric acid salt and add it in catalytic reaction kettle and strong stirring, add soda ash or ammonia adjustment pH value,
It is 55 DEG C to control its temperature, pH=2, obtains ferric phosphate sizing agent；Again lithium-ion electric is obtained after separation of solid and liquid, washing, drying
Pond ferric orthophosphate dusty material.
Comparative example 2
(1) by the input water of the production waste particle containing ferrous sulfate of titanium white production discharge, fully dissolving is heated
Ferrous salt solution of its clarified solution as production ferric orthophosphate is taken after sedimentation separation；
(2) ferrous salt solution is added in catalytic reaction kettle, after adjusting pH, hydrogen peroxide is added, brings it about exothermic reaction,
It is 55 DEG C to control its temperature, pH=2；
(3) dissolving phosphoric acid salt and add it in catalytic reaction kettle and strong stirring, add soda ash or ammonia adjustment pH value,
It is 55 DEG C to control its temperature, pH=2, obtains ferric phosphate sizing agent；Again lithium-ion electric is obtained after separation of solid and liquid, washing, drying
Pond ferric orthophosphate dusty material.
Comparative example 3
(1) pickle liquor containing ferrous sulfate is added into waste iron filing reaction and consumes spent acid amount, take its clarified solution conduct
Produce the ferrous salt solution of ferric orthophosphate；
(2) ferrous salt solution is added in catalytic reaction kettle, after adjusting pH, hydrogen peroxide is added, brings it about exothermic reaction,
It is 55 DEG C to control its temperature, pH=2；
(3) dissolving phosphoric acid salt and add it in catalytic reaction kettle and strong stirring, add soda ash or ammonia adjustment pH value,
It is 55 DEG C to control its temperature, pH=2, obtains ferric phosphate sizing agent；Again lithium-ion electric is obtained after separation of solid and liquid, washing, drying
Pond ferric orthophosphate dusty material.
Lithium ion battery obtained by embodiment 1-5 and comparative example 1-3 is enterprising in performance with ferric orthophosphate dusty material
Row compares, and comparative result is as shown in table 1.
Table 1
Be can be seen that from the data in upper table relative to comparative example 1-3, using the present invention the lithium that is prepared of method from
Sub- battery ferric orthophosphate dusty material has convenient ferrophosphorus ratio, while its specific surface area and tap density are larger, and sulphur
Acid group impurity content is less；Accordingly, with respect to the molysite in other sources, the ferric orthophosphate powder prepared using the method for the present invention
Material purity height and function admirable.Meanwhile the present invention is by using the molysite for coming from iron content raffinate, also achieve lithium from
Omission in the preparation process of sub- battery ferric orthophosphate to preparations such as oxidants uses, and but can still keep ferric orthophosphate powder material
The superperformance of material, therefore, it has important application value.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (33)
- A kind of 1. method that lithium ion battery ferric orthophosphate is prepared using iron content raffinate, it is characterised in that including following step Suddenly：(1) oxidizing agent solution is added in iron content raffinate, the quality of the oxidant is the 10- of iron content raffinate quality 300%, 1-10h is stirred, the reaction temperature for controlling solution is 10-80 DEG C, and pH adjusting agent adjusts pH value between 0.5-5；Add Extractant multitple extraction, the mass ratio of extractant and solution is 1 in every grade of extraction tank:100-4000, extraction temperature 10-80 DEG C, pH adjusting agent adjusts pH value between 0.5-5, extracts 0.5-3h, isolates organic phase and obtain molysite after inorganic acid elution Solution；(2) using the iron salt solutions of step (1) recovery as source of iron, phosphorus source, stirring are added, reaction temperature is 60-80 DEG C, adds pH Conditioning agent between 0.5-5, reacts 1-24h, cooling, then obtain lithium ion battery after separation of solid and liquid, washing, drying to pH value With ferric orthophosphate dusty material.
- 2. according to the method for claim 1, it is characterised in that step (1) the iron content raffinate be containing divalence and/or The solution of ferric ion.
- 3. according to the method for claim 1, it is characterised in that the oxidant is hydrogen peroxide, sodium hypochlorite, sodium peroxide In sodium perchlorate any one or at least two combination.
- 4. according to the method for claim 3, it is characterised in that the oxidant is hydrogen peroxide, sodium peroxide or perchloric acid In sodium any one or at least two combination.
- 5. according to the method for claim 4, it is characterised in that the oxidant is hydrogen peroxide.
- 6. according to the method for claim 1, it is characterised in that the quality of the oxidant is iron content raffinate quality 50-200%.
- 7. according to the method for claim 6, it is characterised in that the quality of the oxidant is iron content raffinate quality 120%.
- 8. according to the method for claim 1, it is characterised in that the extractant is di-(2-ethylhexyl)phosphoric acid ester P204,2- ethylhexyl phosphoric acid list -2- ethylhexyls P507, two (2,4,4)-tri-methyl-amyl phosphonic acids N290 or isoalkyl phosphonic acids In (1- methyl-heptyls) ester 5709 any one or at least two combination.
- 9. according to the method for claim 8, it is characterised in that the extractant is any in P204, P507 or N290 It is a kind of or at least two combination.
- 10. according to the method for claim 1, it is characterised in that the mass ratio of the extractant and solution is 1:500- 1000。
- 11. according to the method for claim 10, it is characterised in that the mass ratio of the extractant and solution is 1:650.
- 12. according to the method for claim 1, it is characterised in that the temperature of step (1) described extraction is 20-60 DEG C.
- 13. according to the method for claim 12, it is characterised in that the temperature of step (1) described extraction is 42 DEG C.
- 14. according to the method for claim 1, it is characterised in that step (1) add extractant multitple extraction when pH value be 0.5-4。
- 15. according to the method for claim 14, it is characterised in that step (1) adds pH value during extractant multitple extraction For 1.5-3.
- 16. according to the method for claim 15, it is characterised in that step (1) adds pH value during extractant multitple extraction For 2.
- 17. according to the method for claim 1, it is characterised in that step (1) described pH adjusting agent is acid or alkali.
- 18. according to the method for claim 17, it is characterised in that the acid is any one in sulfuric acid, nitric acid or hydrochloric acid Kind or at least two combination.
- 19. according to the method for claim 17, it is characterised in that the alkali is sodium hydroxide and/or ammoniacal liquor.
- 20. according to the method for claim 1, it is characterised in that the time of the extraction is 1.5-3h.
- 21. according to the method for claim 1, it is characterised in that the time of the extraction is 2.2h.
- 22. according to the method for claim 1, it is characterised in that the time of step (1) described stirring is 2-6h.
- 23. according to the method for claim 22, it is characterised in that the time of step (1) described stirring is 5h.
- 24. according to the method for claim 1, it is characterised in that step (1) described inorganic acid is sulfuric acid, nitric acid or hydrochloric acid In any one or at least two combination.
- 25. according to the method for claim 1, it is characterised in that step (2) phosphorus source be phosphoric acid, ammonium dihydrogen phosphate or In monoammonium phosphate any one or at least two combination.
- 26. according to the method for claim 1, it is characterised in that step (2) described reaction temperature is 65 DEG C.
- 27. according to the method for claim 1, it is characterised in that step (2) described pH adjusting agent is acid or alkali.
- 28. according to the method for claim 27, it is characterised in that the acid is phosphoric acid.
- 29. according to the method for claim 27, it is characterised in that the alkali is sodium hydroxide and/or ammoniacal liquor.
- 30. according to the method for claim 1, it is characterised in that it is 1.5- that pH adjusting agent regulation pH value is added in step (2) 2.5。
- 31. according to the method for claim 1, it is characterised in that it is 2 that pH adjusting agent regulation pH value is added in step (2).
- 32. according to the method for claim 1, it is characterised in that step (2) reaction time is 2-20h.
- 33. according to the method for claim 32, it is characterised in that step (2) reaction time is 10h.
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| CN108306019B (en) * | 2018-01-29 | 2020-03-27 | 蒋央芳 | Preparation method of carbon-doped lithium iron phosphate |
| CN108821255B (en) * | 2018-07-11 | 2020-12-15 | 方嘉城 | Preparation method of iron phosphate |
| CN109110741B (en) * | 2018-11-08 | 2021-10-12 | 中钢天源股份有限公司 | Method for recycling mother liquor step by step in preparation process of iron phosphate manganese |
| CN112289992B (en) * | 2020-10-20 | 2022-04-12 | 合肥国轩高科动力能源有限公司 | Method for preparing lithium iron phosphate from steel pickling waste liquid and application |
| CN112174106A (en) * | 2020-11-03 | 2021-01-05 | 张响 | Battery-grade iron phosphate and preparation method thereof |
| CN115231538B (en) * | 2022-07-06 | 2023-09-26 | 曲靖市德方纳米科技有限公司 | Preparation method and application of ferrophosphorus source |
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