CN114249313A - Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder - Google Patents
Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder Download PDFInfo
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- CN114249313A CN114249313A CN202111518616.4A CN202111518616A CN114249313A CN 114249313 A CN114249313 A CN 114249313A CN 202111518616 A CN202111518616 A CN 202111518616A CN 114249313 A CN114249313 A CN 114249313A
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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 128
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 123
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 60
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000000843 powder Substances 0.000 title claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 239000002253 acid Substances 0.000 claims abstract description 27
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 19
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- 238000002386 leaching Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000005955 Ferric phosphate Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 229940032958 ferric phosphate Drugs 0.000 claims description 5
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 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 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 20
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 68
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 63
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000010405 anode material Substances 0.000 description 7
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000003929 acidic solution Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 aluminum ions Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder. Then adding hydrogen peroxide into an acid solution in which waste lithium iron phosphate is dissolved, oxidizing ferrous ions into ferric ions, and then utilizing metal ions in Me+n‑H2O‑PO4 ‑The iron phosphate is selectively precipitated according to different precipitation sequences in the system, and the iron phosphate is purified by using a nitric acid solution, so that the iron phosphate recovered from waste lithium iron phosphate reaches a battery level. The method changes the traditional method for removing impurities by using an extracting agent, and recovers the battery-grade iron phosphate from the scrapped lithium iron phosphate by using simple and easily-obtained acid and alkali, thereby reducing the recovery cost and being suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of waste lithium iron phosphate battery recovery, and particularly relates to a method for recovering battery-grade iron phosphate from waste lithium iron phosphate.
Background
In order to deal with the problem of increasingly nervous energy shortage, new energy automobiles are popularized in various countries, energy storage equipment of the new energy automobiles is mainly lithium iron phosphate batteries, a large number of waste lithium iron phosphate batteries can be generated along with the wide use of the new energy automobiles, and if the new energy automobiles are not properly treated, not only can the ecological environment be seriously damaged, but also the resource waste can be caused. As is well known, the ratio of lithium iron phosphate batteries in the scrapped power batteries is more than half, and since the lithium iron phosphate batteries do not contain metal elements such as manganese, nickel, cobalt and the like, the economic benefit of recycling is much smaller than that of other power batteries, and therefore, research on the aspect is relatively few. However, the waste lithium iron phosphate batteries contain a large amount of iron and phosphorus elements, and if the iron and phosphorus elements can be recovered in the form of iron phosphate, resources can be recycled, and the economic benefit of recovering the waste lithium iron phosphate can be improved, so that the enthusiasm of enterprises on recovering the waste lithium iron phosphate is improved.
At present, the method for recovering iron and phosphorus resources from waste lithium iron phosphate can be divided into a pyrogenic method and a wet method. For pyrogenic recovery, its advantages are short technological process, less investment in apparatus, high energy consumption and low added value of recovered product. The wet recovery method has the advantages of simple process flow, common and easily-obtained raw materials, easily-controlled product performance indexes, high impurity content in the obtained product and high input cost in the impurity removal process. CN113430322A (method for recovering phosphorus and iron in waste lithium iron phosphate battery) placing iron phosphate slag, carbonaceous reducing agent and flux in a mixer for mixing, adding binder during mixing, adding the obtained mixture into an electric furnace for reductionThe original smelting is carried out, the reduction smelting temperature is 1300-1500 ℃, and the ferrophosphorus containing P is obtained2O5Flue gas of steam, slag and other products. The process effectively recovers iron and phosphorus resources from waste lithium iron phosphate, solves the environmental problem caused by stacking of the waste lithium iron phosphate, but the temperature of reduction smelting is overhigh, the energy consumption is overlarge, the obtained product is not a terminal product, and the economic benefit of recovery is not high. CN 112499609A (method for preparing iron phosphate by using waste lithium iron phosphate anode powder lithium extraction slag and application) the process is to separate out iron phosphate precipitate from iron phosphate solution after waste lithium iron phosphate powder is subjected to acid leaching in a heating mode, and then washing and impurity removal are carried out. CN 111333046A (a waste lithium iron phosphate anode material based on hydrochloric acid circulation) when recovering lithium iron phosphate, the process mainly uses an extraction method to recover phosphoric acid, and obtains iron oxide red and a lithium chloride solution through concentration pyrolysis and water leaching. Patents such as CN 113151682A (a leaching method of lithium iron phosphate black powder), CN 110790289 a (a method for producing lithium hydroxide by using waste lithium iron phosphate positive electrode material), CN 109650415 a (a method for extracting lithium carbonate from waste lithium iron phosphate positive electrode powder) mainly aim at leaching waste lithium iron phosphate and recovering lithium resources, but research on recovery of resources such as phosphorus and iron with high economic benefit is less, the price of the current lithium iron phosphate is getting higher day by day, the price of high-quality iron phosphate capable of preparing lithium iron phosphate is also rising, and if iron phosphate can be recovered from waste lithium iron phosphate with low lithium iron cost, the enthusiasm of enterprises on recovery of waste batteries can be certainly improved.
Disclosure of Invention
The invention aims to provide a method for preparing iron phosphate from waste iron phosphateA method for economically recovering battery-grade iron phosphate from a lithium anode material is characterized in that waste lithium iron phosphate powder is leached in an acid solution, so that lithium iron phosphate is dissolved in a sulfuric acid solution, and meanwhile, the lithium iron phosphate is separated from active carbon, PVDF, a current collector and the like. Then adding hydrogen peroxide into an acid solution in which waste lithium iron phosphate is dissolved, oxidizing ferrous ions into ferric ions, and then utilizing metal ions in Me+n-H2O-PO4 -The precipitation order in the system is different (Fe)+3 >Al+3>Cu+2≈Fe+2>CO+2>Mn+2 ≈Ni+2 >Li+) Selectively depositing ferric phosphate, but Al can be caused by the local overhigh pH value in the process of dropping alkali liquor+3The metal ions are coprecipitated with the iron phosphate in the form of phosphate, so that the impurities in the iron phosphate are higher. Based on the property that the iron phosphate is insoluble in a nitric acid solution, and the properties that the aluminum phosphate, the calcium phosphate, the magnesium phosphate and the like are soluble in the nitric acid solution, the invention selectively uses the nitric acid solution to purify the iron phosphate, so that the iron phosphate recovered from the waste lithium iron phosphate reaches the battery level. According to the method, the battery-grade iron phosphate is prepared from the scrapped lithium iron phosphate power battery, the method that the traditional recovery method uses an extracting agent for impurity removal is changed, the battery-grade iron phosphate is recovered from the scrapped lithium iron phosphate by using simple and easily-obtained acid and alkali, the recovery cost is reduced, the method is suitable for recovering the battery-grade iron phosphate from the waste lithium iron phosphate positive material in a large-scale industrialized mode, and the recovery rate of the iron phosphate is 90% -95%.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recovering battery-grade iron phosphate from waste lithium iron phosphate comprises the following steps:
(1) dissolving the crushed waste lithium iron phosphate powder in acid, and filtering to obtain an acidic filtrate;
(2) dropwise adding hydrogen peroxide into the acidic solution to oxidize ferrous ions into ferric ions;
(3) transferring the oxidized solution into a reaction kettle, and dripping an alkali solution while heating and simultaneously stirring to separate out iron phosphate;
(4) transferring the obtained iron phosphate into a nitric acid solution for impurity removal, and removing calcium, aluminum and magnesium impurities in the iron phosphate; (5) and filtering the solid-liquid mixture, leaching the filtered iron phosphate solid with deionized water to wash away sodium ions in the iron phosphate solid, and drying to obtain the battery-grade iron phosphate.
Preferably, in the step (1), the waste lithium iron phosphate powder contains 29-34 wt.% of iron, 1-4 wt.% of lithium, 15-18 wt.% of phosphorus, 0.0012-0.0849 wt.% of sodium, 0.0032-0.0249 wt.% of magnesium, 0.0010-0.0089 wt.% of nickel, 0.0075-0.098 wt.% of calcium, 0.0130-0.132 wt.% of aluminum and trace impurities such as cobalt and manganese.
Preferably, the acid in the step (1) is one of sulfuric acid, nitric acid, citric acid and glacial acetic acid, and the volume ratio of the acid to the deionized water in preparing the acid solution is 1: 50-10: 50, the weight ratio of the waste material to the acid is 1: 3-1: 30, the dissolving temperature is 15-60 ℃, and the stirring speed is 100-800 rmp. The invention does not adopt hydrochloric acid, and mainly has the defect that when hydrochloric acid is adopted, a certain amount of ferric hydroxide colloid exists when alkali liquor is dripped to precipitate ferric phosphate, so that the electrochemical performance of the ferric hydroxide colloid is influenced.
Preferably, the concentration of the hydrogen peroxide in the step (2) is 10-30%, the dropping speed of the hydrogen peroxide is 0.05-0.8 ml/min, and the stirring speed is 100-800 rmp.
Preferably, the temperature of an oil bath pot of the heating reaction kettle in the step (3) is 40-130 ℃, the alkali is one of sodium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, the concentration of the alkali is 0.1-2 mol/L, the dropping speed of the alkali liquor is 0.1-2 ml/min, and the precipitation pH value of the ferric phosphate is 1-2.0. The pH value of the precipitated iron phosphate is controlled within the range of 1-2.5, so that a large amount of precipitation of aluminum ions can be avoided, when the pH value exceeds 2.0, a large amount of aluminum and other metal impurity ions can be precipitated together with the iron phosphate, and if a large amount of aluminum and the iron phosphate are co-precipitated, aluminum removal through subsequent operation is difficult. According to the invention, an oil bath heating method is adopted when the iron phosphate is precipitated by alkali, and the oil bath heating is favorable for inhibiting the generation of the iron hydroxide, so that more iron exists in the form of the iron phosphate, and the purity of the prepared iron phosphate is higher.
Preferably, the concentration of the nitric acid solution subjected to impurity removal in the step (4) is 2-20%, and the solid-to-liquid ratio is 1: 2-1: 20, soaking the iron phosphate containing impurities in a nitric acid solution for 0.5-12 h in the impurity removal process.
The invention has the beneficial effects that: the method is characterized in that battery-grade iron phosphate is recovered from a scrapped lithium iron phosphate power battery, the conventional idea of recovering battery-grade lithium carbonate from waste lithium iron phosphate is changed, the iron-phosphorus ratio in the iron phosphate, the yield of the iron phosphate, the contents of nickel, cobalt, manganese, zinc, copper and other impurity elements in the iron phosphate and the contents of calcium, magnesium, aluminum and other impurity elements which are easy to precipitate simultaneously with ferric iron in the iron phosphate are removed by soaking the iron phosphate in a nitric acid solution through the concentration of an alkali solution, the dropping speed of the alkali solution, the reaction temperature of the precipitated iron phosphate and the pH value during precipitation. By the method, battery-grade iron phosphate with higher economic value can be obtained, and the recovery cost can be reduced.
Drawings
FIG. 1 is a process flow diagram for recovering battery grade iron phosphate from waste lithium iron phosphate;
fig. 2 is an XRD analysis pattern of battery grade iron phosphate obtained by recycling waste lithium iron phosphate positive electrode material according to the present invention;
FIG. 3 is a graph of the particle size distribution of the recovered battery grade iron phosphate of the present invention;
fig. 4 is a charge-discharge performance curve diagram obtained by assembling lithium iron phosphate into a button cell by using the obtained battery-grade iron phosphate.
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
A method for economically recycling battery-grade iron phosphate from waste lithium iron phosphate positive electrode materials comprises the following steps:
1) placing the waste lithium iron phosphate anode material in sulfuric acid solution (98% H)2SO4And deionized water in a volume ratio of 1: 10) and (3) carrying out medium acid leaching for 3 hours, wherein the stirring speed during acid leaching is 200rmp, the leaching rate of iron is 97%, and the leaching rate of phosphorus is 96.7%. Filtering to obtain iron phosphate solution
2) And (3) dropwise adding hydrogen peroxide into the obtained iron phosphate acidic solution, and adding a stirrer into the iron phosphate solution during dropwise adding. The concentration of the hydrogen peroxide is 20 percent, the dropping speed of the hydrogen peroxide is 0.12ml/min, and the stirring speed is 300 rmp. Fe+299.2% of the iron is oxidized into Fe+3。
3) And (3) transferring the oxidized iron phosphate solution into a reaction kettle, placing the reaction kettle into an oil bath, and dropwise adding a sodium hydroxide solution into the oxidized iron phosphate solution in the step (2). The temperature of the oil bath kettle is 80 ℃, the alkali liquor is sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.25mol/L, the dropping speed of the sodium hydroxide solution is 0.55ml/min, the stirring speed is 800rmp, and the pH of the reaction end point is = 1.8.
4) And (3) putting the iron phosphate pumped and filtered out from the step (3) into a nitric acid solution to remove impurities, wherein the concentration of the nitric acid is 8%, and the solid-to-liquid ratio is 1: 10, the time for removing the impurities is 3 hours. And then, carrying out suction filtration to obtain iron phosphate, washing the iron phosphate by using deionized water, and finally drying to obtain battery-grade iron phosphate, wherein the recovery rate of the battery-grade iron phosphate is 95%, and the iron-phosphorus ratio is 1.0136.
Mass fraction of each impurity element in the iron phosphate obtained by recovery
Example 2
A method for economically recycling battery-grade iron phosphate from waste lithium iron phosphate positive electrode materials comprises the following steps:
1) placing the waste lithium iron phosphate anode material in sulfuric acid solution (98% H)2SO4And deionized water in a volume ratio of 1: 15) the acid leaching is carried out for 5 hours, the stirring speed during the acid leaching is 400rmp, and the leaching rate of iron is96.78 percent and the leaching rate of phosphorus is 97.98 percent. Filtering to obtain iron phosphate solution
2) And (3) dropwise adding hydrogen peroxide into the obtained iron phosphate acidic solution, and adding a stirrer into the iron phosphate solution during dropwise adding. The concentration of the hydrogen peroxide is 30 percent, the dropping speed of the hydrogen peroxide is 0.30ml/min, and the stirring speed is 300 rmp. Fe+299.8% of the iron is oxidized into Fe+3。
3) And (3) transferring the oxidized iron phosphate solution into a reaction kettle, placing the reaction kettle into an oil bath, and dropwise adding a sodium hydroxide solution into the oxidized iron phosphate solution in the step (2). The temperature of the oil bath kettle is 100 ℃, the alkali liquor is sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.15mol/L, the dropping speed of the sodium hydroxide solution is 0.55ml/min, the stirring speed is 600rmp, and the pH of the reaction end point is = 2.
4) And (3) removing impurities from the iron phosphate which is filtered out in the step (3) in a nitric acid solution, wherein the concentration of the nitric acid is 15%, and the solid-to-liquid ratio is 1: 10, the time for removing the impurities is 2 hours. And then, carrying out suction filtration to obtain iron phosphate, washing the iron phosphate by using deionized water, and finally drying to obtain battery-grade iron phosphate, wherein the recovery rate of the battery-grade iron phosphate is 94.7%, and the iron-phosphorus ratio is 0.99.
The mass fraction (%)% of each impurity element in the obtained iron phosphate was recovered
Example 3
A method for economically recycling battery-grade iron phosphate from waste lithium iron phosphate positive electrode materials comprises the following steps:
1) placing the waste lithium iron phosphate anode material in sulfuric acid solution (98% H)2SO4And deionized water in a volume ratio of 1: 20) and (3) performing medium acid leaching for 5 hours, wherein the stirring speed during acid leaching is 400rmp, the leaching rate of iron is 97.78%, and the leaching rate of phosphorus is 98.53%. Filtering to obtain iron phosphate solution
2) And (3) dropwise adding hydrogen peroxide into the obtained iron phosphate acidic solution, and adding a stirrer into the iron phosphate solution during dropwise adding. The concentration of hydrogen peroxide is 30Percent, the dropping speed of the hydrogen peroxide is 1.2ml/min, and the stirring speed is 300 rmp. Fe+299.5% of the iron is oxidized into Fe+3。
3) And (3) transferring the oxidized iron phosphate solution into a reaction kettle, placing the reaction kettle into an oil bath, and dropwise adding a sodium hydroxide solution into the oxidized iron phosphate solution in the step (2). The temperature of the oil bath pot is 100 ℃, the alkali liquor is sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.15mol/L, the dropping speed of the sodium hydroxide solution is 0.55ml/min, the stirring speed is 400rmp, and the pH of the reaction end point is = 2.
4) And (3) removing impurities from the iron phosphate which is filtered out in the step (3) in a nitric acid solution, wherein the concentration of the nitric acid is 15%, and the solid-to-liquid ratio is 1: 10, the time for removing the impurities is 1 hour. And then, carrying out suction filtration to obtain iron phosphate, washing the iron phosphate by using deionized water, and finally drying to obtain battery-grade iron phosphate, wherein the recovery rate of the battery-grade iron phosphate is 95.8%, and the iron-phosphorus ratio is 1.01.
Mass fraction of each impurity element in the iron phosphate obtained by recovery
Fig. 3 is the test data of the laser particle size analyzer, and it can be seen from the figure that the D50 of the iron phosphate obtained by the process is 5.06um, D90 is 12um, and the particle size range given in the national standard (HG/T4701-2014) is 2-6um, so that the particle size of the iron phosphate recovered by the invention reaches the national standard. Fig. 4 shows that the first charge specific capacity of the lithium iron phosphate prepared by recovering the obtained iron phosphate is 166mAh/g, the first discharge specific capacity is 147mAh/g, and the first charge-discharge efficiency is 88.55%, so that the iron phosphate obtained by the method has better electrochemical performance.
Comparative example 1
A method for economically recycling battery-grade iron phosphate from waste lithium iron phosphate positive electrode materials comprises the following steps:
1) and placing the waste lithium iron phosphate anode material in a diluted hydrochloric acid solution for acid leaching for 3 hours, wherein the stirring speed during acid leaching is 200rmp, the leaching rate of iron is 99.8 percent, and the leaching rate of phosphorus is 99.7 percent. Filtering to obtain iron phosphate solution;
2) and (3) dropwise adding hydrogen peroxide into the obtained iron phosphate acidic solution, and adding a stirrer into the iron phosphate solution during dropwise adding. The concentration of the hydrogen peroxide is 20 percent, the dropping speed of the hydrogen peroxide is 0.12ml/min, and the stirring speed is 300 rmp. Fe+299.8% of the iron is oxidized into Fe+3。
3) And (3) transferring the oxidized iron phosphate solution into a reaction kettle, placing the reaction kettle into an oil bath, and dropwise adding a sodium hydroxide solution into the oxidized iron phosphate solution in the step (2). The temperature of the oil bath kettle is 80 ℃, the alkali liquor is sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.25mol/L, the dropping speed of the sodium hydroxide solution is 0.55ml/min, the stirring speed is 800rmp, and the pH of the reaction end point is = 1.8.
4) And (3) putting the iron phosphate pumped and filtered out from the step (3) into a nitric acid solution to remove impurities, wherein the concentration of the nitric acid is 8%, and the solid-to-liquid ratio is 1: 10, the time for removing the impurities is 3 hours. And then, performing suction filtration to obtain iron phosphate, washing the iron phosphate by using deionized water, and finally drying the iron phosphate to obtain battery-grade iron phosphate, wherein the recovery rate of the battery-grade iron phosphate is 30% (because most of the iron phosphate precipitated in the step 3 is ferric hydroxide, and the ferric hydroxide is dissolved away when impurities are removed), and the iron-phosphorus ratio is 1.0136.
Mass fraction of each impurity element in the iron phosphate obtained by recovery
Comparative example 2
A method for economically recycling battery-grade iron phosphate from waste lithium iron phosphate positive electrode materials comprises the following steps:
1) placing the waste lithium iron phosphate anode material in sulfuric acid solution (98% H)2SO4And deionized water in a volume ratio of 1: 10) and (3) carrying out medium acid leaching for 3 hours, wherein the stirring speed during acid leaching is 200rmp, the leaching rate of iron is 96 percent, and the leaching rate of phosphorus is 95.7 percent. Filtering to obtain iron phosphate solution
2) Adding hydrogen peroxide into the obtained iron-phosphorus acidic solutionDuring the dropping process, a stirring bar is added into the iron phosphate solution to be stirred. The concentration of the hydrogen peroxide is 20 percent, the dropping speed of the hydrogen peroxide is 0.12ml/min, and the stirring speed is 300 rmp. Fe+299.6% of the iron is oxidized into Fe+3。
3) And (3) transferring the oxidized iron phosphate solution into a reaction kettle, and dropwise adding a sodium hydroxide solution into the oxidized iron phosphate solution in the step (2). The temperature of the oil bath kettle is 80 ℃, the alkali liquor is sodium hydroxide solution, the concentration of the sodium hydroxide solution is 0.25mol/L, the dropping speed of the sodium hydroxide solution is 0.55ml/min, the stirring speed is 800rmp, and the pH of the reaction end point is = 1.8.
4) And (3) putting the iron phosphate pumped and filtered out from the step (3) into a nitric acid solution to remove impurities, wherein the concentration of the nitric acid is 8%, and the solid-to-liquid ratio is 1: 10, the time for removing the impurities is 3 hours. And then, carrying out suction filtration to obtain iron phosphate, washing the iron phosphate by using deionized water, and finally drying to obtain battery-grade iron phosphate, wherein the recovery rate of the battery-grade iron phosphate is 75%, the iron-phosphorus ratio is 1.3136, and the obtained iron phosphate product is not white but brown. The color of battery grade iron phosphate given in the national standard (HG/T4701-.
Mass fraction of each impurity element in the iron phosphate obtained by recovery
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the inventive concept of the present invention, and these are all within the scope of the present invention.
Claims (5)
1. A method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing waste lithium iron phosphate powder with an acid solution, leaching under the condition of stirring and heating, and filtering to obtain a filtrate, PVDF and carbon powder solids;
(2) dropwise adding hydrogen peroxide into the filtrate obtained in the step (1), and stirring to oxidize ferrous iron into ferric iron;
(3) dropwise adding an alkali solution into the liquid obtained in the step (2), stirring, and adjusting the pH value to enable the iron phosphate to precipitate;
(4) and (4) putting the ferric phosphate precipitated in the step (3) into a nitric acid solution for removing impurities, and removing calcium, aluminum and magnesium impurity ions in the ferric phosphate solution.
2. The method of claim 1, wherein: the waste lithium iron phosphate powder in the step (1) contains 29-34 wt% of iron, 1-4 wt% of lithium, 15-18 wt% of phosphorus, 0.0012-0.0849 wt% of sodium, 0.0032-0.0249 wt% of magnesium, 0.0010-0.0089 wt% of nickel, 0.0075-0.098 wt% of calcium, 0.0130-0.132 wt% of aluminum and trace impurities of cobalt and manganese; the acid in the step (1) is one of sulfuric acid, nitric acid, citric acid and glacial acetic acid, and when an acid solution is prepared, the volume ratio of the acid to the deionized water is 1: 50-10: 50, the weight ratio of the waste material to the acid solution is 1: 3-1: 30, the acid leaching temperature is 15-60 ℃, and the stirring speed is 100-800 rmp.
3. The method of claim 1, wherein: in the step (2), the concentration of hydrogen peroxide is 10-30 wt%, the dropping speed of hydrogen peroxide is 0.05-0.8 ml/min, the stirring speed is 100-800 rmp, and the molar ratio of iron to hydrogen peroxide is 2: 1-2: 5.
4. the method of claim 1, wherein: and (3) stirring in a heating reaction kettle at the temperature of 40-130 ℃, the concentration of the alkali solution is 0.1-2 mol/L, the drop acceleration of the alkali solution is 0.1-L/min, and the final pH value of the precipitated iron phosphate is 1-2.5.
5. The method of claim 1, wherein: in the step (4), the concentration of the nitric acid solution is 2-20 wt%, and the solid-to-liquid ratio is 1: 2-1: 20, soaking the iron phosphate containing impurities in a nitric acid solution for 0.5-12 h in the impurity removal process.
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