WO2022213676A1 - 磷酸铁废料循环再生的方法及其应用 - Google Patents
磷酸铁废料循环再生的方法及其应用 Download PDFInfo
- Publication number
- WO2022213676A1 WO2022213676A1 PCT/CN2021/142510 CN2021142510W WO2022213676A1 WO 2022213676 A1 WO2022213676 A1 WO 2022213676A1 CN 2021142510 W CN2021142510 W CN 2021142510W WO 2022213676 A1 WO2022213676 A1 WO 2022213676A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- iron phosphate
- iron
- phosphate
- recycling
- regenerating
- Prior art date
Links
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 133
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 101
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 5
- 238000011069 regeneration method Methods 0.000 title abstract 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 40
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 54
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 34
- 239000005955 Ferric phosphate Substances 0.000 claims description 32
- 229940032958 ferric phosphate Drugs 0.000 claims description 32
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000004064 recycling Methods 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000000706 filtrate Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- -1 iron ions Chemical class 0.000 claims description 14
- 230000001172 regenerating effect Effects 0.000 claims description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000001000 micrograph Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- 238000012546 transfer Methods 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- 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
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the invention belongs to the technical field of resource recycling, and in particular relates to a method for recycling iron phosphate waste and its application.
- lithium-ion batteries Compared with traditional batteries, lithium-ion batteries have the advantages of high voltage, large specific capacity, long cycle life and good safety performance as energy storage materials. They are widely used in portable electronic equipment, electric vehicles, aerospace and military engineering and other fields. application prospects and huge economic benefits. Lithium iron phosphate batteries are widely used in portable batteries, electric vehicles and other fields due to their environmental friendliness, low price, and long cycle life.
- lithium iron phosphate batteries Since the application of lithium iron phosphate batteries in electric taxis and electric buses since 2010, more and more lithium iron phosphate batteries have been retired. It is difficult to recover the performance of lithium iron phosphate only by simple physical methods. Decommissioned lithium iron phosphate batteries are given priority to extract lithium, and the rest are often discharged as industrial waste, causing a series of environmental pollution problems such as eutrophication of water quality, and a serious waste of phosphorus and iron resources.
- the related art discloses the recycling of lithium iron phosphate positive and negative electrode sheets, and then replenishing lithium to prepare lithium iron phosphate after recovering lithium. With the development of technology, the performance of the recovered lithium iron phosphate material can fully meet the standard of commercial application. It is particularly important to develop a green and environmentally friendly method for recycling and preparing iron phosphate with simple process, low cost and easy control. A true closed-loop industrial chain is of great significance.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a method for recycling and regenerating iron phosphate waste and its application. This process has simple preparation process, high product consistency, low cost, high productivity, low energy consumption, is suitable for large-scale industrial production, and is more environmentally friendly .
- step S4 Repeat steps S1 and S3 for cyclic preparation, wherein the iron phosphate precipitant added to the iron phosphorus solution in step S3 is the iron phosphate dihydrate precipitate left in the previous batch of step S3.
- the iron phosphate waste includes iron phosphate scraps, waste after lithium iron phosphate extraction, iron phosphorus slag after lithium iron phosphate pole piece recovery, or lithium iron phosphate battery dismantling for lithium extraction One or more of the iron-phosphorus slag.
- the acid solution includes one or more of hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
- step S1 the molar ratio of acid radicals in the acid solution to iron ions in the iron phosphate waste is (1.1-1.5):1.
- step S1 the mixing and dissolving process is as follows: stirring while adding the acid solution, the stirring rate is 100-400 r/min, and the stirring time is 3-5 h.
- the lye comprises one or more of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, diammonium hydrogen phosphate, sodium bicarbonate or potassium bicarbonate ;
- the rate of adding lye is 0.1 ⁇ 6L/min.
- step S2 the pH is 0.5-2.5.
- the stirring speed is 200-600 rpm/min
- the heating temperature is 80-100° C.
- the holding reaction time is 2-8 h.
- step S2 the filtered filtrate is added to the remaining iron-phosphorus solution in step S3. Because there is still a small amount of Fe 3+ in the filtrate, direct discharge goes against the original intention of the present invention, and is added to the remaining iron-phosphorus solution in step S3 for the purpose of recycling.
- step S3 the filtered filtrate can be used for dissolving waste iron phosphate in step S1, which can save the usage of acid solution.
- step S3 the mass of the ferric phosphate dihydrate precipitate left behind accounts for 5-40% of the total mass of the generated ferric phosphate dihydrate precipitate.
- step S3 the drying temperature is 110-150° C., and the drying method is flash evaporation or rake drying.
- the invention also provides the application of the method for recycling and regenerating iron phosphate waste in the preparation of lithium iron phosphate batteries.
- the particle size distribution of the iron phosphate precipitate is uniform, the iron phosphate crystallinity is high, and the compactness is good.
- a small amount of precipitation cycle-combination process provided by the present invention is used for the subsequent preparation of iron phosphate by preparing an iron phosphate precipitant, and the iron phosphate prepared each time can be used for the next preparation of iron phosphate.
- the preparation process of this process is simple, Only in the preparation stage of the precipitant, lye is needed, and the use of lye is not involved in subsequent production, which is more environmentally friendly, has high product consistency, low cost, high production capacity and low energy consumption, and is suitable for large-scale industrial production.
- the anhydrous iron phosphate prepared by the present invention has reached the usage standard of iron phosphate for lithium iron phosphate, and has been further optimized in performance.
- the specific capacity of the first charge at 1C reaches 162mAh/g, and the first coulombic efficiency is above 96%, which can be Directly used as a precursor for lithium iron phosphate production.
- Fig. 2 is the scanning electron microscope picture of the iron phosphate prepared for the first time in the embodiment of the present invention 3;
- Fig. 3 is the sectional electron microscope picture of the iron phosphate prepared in the embodiment of the present invention 3;
- Fig. 4 is the scanning electron microscope picture of making lithium iron phosphate with the iron phosphate prepared by Example 3;
- Fig. 5 is the scanning electron microscope image of Langfang Nabo iron phosphate
- Fig. 6 is the scanning electron microscope image of preparing lithium iron phosphate with Langfang Nabo iron phosphate
- Fig. 7 is the scanning electron microscope image of the iron phosphate prepared for the third time in the embodiment of the present invention 3;
- the present embodiment has prepared a kind of iron phosphate, and the concrete process is:
- step S2 in step S1, the iron-phosphorus solution of the A reactor is removed a small amount of impurities through the filtration system, and is transported to the B reactor and the C reactor with a pipeline, and the volume of the iron-phosphorus solution entering the C reactor is 120L, and the iron-phosphorus solution entering the B reactor is 120L.
- the volume of the solution is 30L;
- step S4 add the iron phosphate precipitant of step S3 into the C reaction kettle, heat the C reaction kettle, control the reaction temperature to 88 ° C, and keep the temperature for 6 h to obtain the iron phosphate dihydrate precipitate, filter, and wash the precipitate until the conductivity is 500 ⁇ S Below /cm, press filtration to make iron phosphate dihydrate filter cake, leave 6 kg of iron phosphate dihydrate as the precipitant for the next batch of reactions, the remaining filter cakes are flash dried and kept in a rotary kiln at 500 °C for 10 hours to obtain non-ferrous phosphates. Water ferric phosphate, wherein the filtrate of the C reactor returns to the A reactor to participate in the dissolving of the ferric phosphate waste;
- step (1) repeat step (1) and add the A reactor iron phosphorus solution to the C reactor through filtration, then add the iron phosphate dihydrate left in step S4 in the C reactor, and carry out the ferric phosphate of the next batch.
- Preparation 1 ⁇ 8kg of ferric phosphate dihydrate is reserved after the experiment is completed, and anhydrous ferric phosphate can be cyclically prepared in the C reactor according to the above steps.
- the present embodiment has prepared a kind of iron phosphate, and the concrete process is:
- step S2 in step S1, the iron-phosphorus solution of the A reactor is removed a small amount of impurities through the filtration system, and is transported to the B reactor and the C reactor with a pipeline, and the volume of the iron-phosphorus solution entering the C reactor is 240L, and the iron-phosphorus solution entering the B reactor is 240L.
- the volume of the solution is 60L;
- step S4 Add the iron phosphate precipitant of step S3 into the C reaction kettle, heat the C reaction kettle, control the reaction temperature to 94 ° C, and keep the temperature for 3 hours to obtain the iron phosphate dihydrate precipitate, filter, and wash the precipitate until the conductivity is 500 ⁇ S Below /cm, press filtration to make iron phosphate dihydrate filter cake, leave 10kg of iron phosphate dihydrate as the precipitant for the next batch reaction, and the remaining filter cakes are rake-dried at 120 °C and kept in a rotary kiln at 650 °C for 5 hours. Anhydrous iron phosphate is obtained, wherein the filtrate of the C reactor returns to the A reactor to participate in the dissolving of the iron phosphate waste;
- step (1) repeat step (1) and add the A reactor iron phosphorus solution to the C reactor through filtration, then add the iron phosphate dihydrate left in step S4 in the C reactor, and carry out the ferric phosphate of the next batch.
- Preparation 2 ⁇ 16kg of ferric phosphate dihydrate is reserved after the experiment is completed, and anhydrous ferric phosphate can be cyclically prepared in the C reactor according to the above steps.
- the present embodiment has prepared a kind of iron phosphate, and the concrete process is:
- step S2 in step S1, the iron-phosphorus solution of the A reactor is removed a small amount of impurities through the filtration system, and is transported to the B reactor and the C reactor with a pipeline, and the volume of the iron-phosphorus solution entering the C reactor is 300L, and the iron-phosphorus solution entering the B reactor is 300L.
- the volume of the solution is 70L;
- the reaction kettle B is heated, and the temperature is set to 92°C after heating up, and the temperature is kept for 5 hours. After filtration, washing, and flash drying at 120°C, a ferric phosphate precipitant is obtained, which is used in step S4, wherein the filtrate of the reaction kettle B is passed into the reaction kettle C. ;
- step S4 add the iron phosphate precipitant of step S3 into the C reaction kettle, heat the C reaction kettle, control the reaction temperature to 90 ° C, and keep the temperature for 5 h to obtain the iron phosphate dihydrate precipitate, filter, and wash the precipitate until the conductivity is 500 ⁇ S Below /cm, press filtration to make iron phosphate dihydrate filter cake, leaving 4kg of iron phosphate dihydrate as the precipitant for the next batch reaction, the remaining filter cakes are flash dried at 120 °C, and kept in a rotary kiln at 550 °C for 10 hours. Anhydrous iron phosphate is obtained, wherein the filtrate of the C reactor returns to the A reactor to participate in the dissolving of the iron phosphate waste;
- step (1) repeat step (1) and add the A reactor iron phosphorus solution to the C reactor through filtration, then add the iron phosphate dihydrate left in step S4 in the C reactor, and carry out the ferric phosphate of the next batch.
- Preparation 2 ⁇ 20kg of ferric phosphate dihydrate is reserved after the experiment is completed, and anhydrous ferric phosphate can be cyclically prepared in the C reactor according to the above steps.
- the present embodiment has prepared a kind of iron phosphate, and the concrete process is:
- step S4 add the iron phosphate precipitant of step S3 into the C reaction kettle, heat the C reaction kettle, control the reaction temperature to 96 ° C, and keep the temperature for 3 hours to obtain the iron phosphate dihydrate precipitate, filter, and wash the precipitate until the conductivity is 500 ⁇ S Below /cm, press filtration to make iron phosphate dihydrate filter cake, leaving 3kg of iron phosphate dihydrate as the precipitant for the next batch reaction, the remaining filter cakes are rake-dried at 120 °C, and kept in a rotary kiln at 600 °C for 5 hours. Anhydrous iron phosphate is obtained, wherein the filtrate of the C reactor returns to the A reactor to participate in the dissolving of the iron phosphate waste;
- step (1) repeat step (1) and add the A reactor iron phosphorus solution to the C reactor through filtration, then add the iron phosphate dihydrate left in step S4 in the C reactor, and carry out the ferric phosphate of the next batch.
- Preparation 1.5-12 kg of ferric phosphate dihydrate is reserved after the experiment is completed, and anhydrous ferric phosphate can be cyclically prepared in the C reactor according to the above steps.
- This comparative example has prepared a kind of iron phosphate, and the specific process is:
- anhydrous iron phosphate and commercially available anhydrous iron phosphate (purchased from Langfang Nabo Chemical Technology Co., Ltd.) prepared for the first time in the above-mentioned embodiment 3 and prepared for the 3rd time to prepare lithium iron phosphate according to the following method: 2800ml of water, weigh 1000g of iron phosphate, add 80g of glucose, add 80g of PEG dispersed in advance, disperse the PEG with 200g of hot water, and finally control the solid-liquid ratio to 35%, disperse it with a high-speed disperser for 30min, and then pour it into a sand mill for fine grinding , control the fine abrasive slurry D50 to 500 ⁇ 550nm.
- the compacted density and specific surface area of the lithium iron phosphate powder synthesized by the anhydrous iron phosphate of the embodiment of the present invention are higher than those synthesized by using commercially available iron phosphate, and the electrochemical performance of the present invention is higher. It is also slightly better than commercially available ferric phosphate, indicating that the anhydrous ferric phosphate prepared by the present invention has reached the use standard of ferric phosphate for lithium ferric phosphate, and has further optimization in performance, and can be directly used as a precursor for the production of lithium ferric phosphate.
- the properties of the anhydrous ferric phosphate prepared for the first time and the third cycle are equivalent, indicating that the anhydrous ferric phosphate prepared by the cycle process has stable quality and good process stability.
- Fig. 1 is the process flow diagram of the embodiment of the present invention, as can be seen from the figure, iron phosphate waste is mixed and dissolved with acid solution in A reactor, obtains iron phosphorus solution, and iron phosphorus solution part is passed into B reactor to carry out precipitation reaction
- the iron phosphate precipitant is prepared, the filtered filtrate is returned to the A reactor, the filter residue is washed and added to the C reactor as a precipitant, and the remaining iron and phosphorus solutions are all entered into the C reactor, and the iron phosphorus solution in the C reactor is precipitated in the iron phosphate.
- Ferric phosphate dihydrate precipitation is formed under the action of the agent, the filtered filtrate is returned to the A reactor, and a small amount of filter residue is taken as a precipitant and returned to the C reactor. The remaining filter residues are washed, dried and sintered to obtain anhydrous iron phosphate products.
- Fig. 2 and Fig. 3 are respectively the scanning electron microscope image and the cross-sectional electron microscope image of the iron phosphate prepared for the first time in the embodiment of the present invention 3, as can be seen from the figure, the iron phosphate crystallinity is good, the shape is spherical and uniform in all directions, and the agglomeration Dense, thin sub-structure lamellae, micropores inside the iron phosphate, uniform particle size distribution.
- Figure 4 is a scanning electron microscope image of lithium iron phosphate made from the iron phosphate prepared in Example 3. It can be seen from the figure that the lithium iron phosphate particles are round and regular in shape.
- Fig. 5 is the scanning electron microscope image of Langfang Nabo iron phosphate, as can be seen from the figure, iron phosphate is formed by stacking flaky sub-structure, and its particle morphology is not as regular as the iron phosphate of Example 3, and the particle size distribution is not as good as the implementation Example 3 is uniform.
- Figure 6 is a scanning electron microscope image of the preparation of lithium iron phosphate with Langfang Nabo iron phosphate. From the electron microscope image, the particles are very irregular, and the particles with this morphology will lead to low compaction density of lithium iron phosphate. In addition, the irregularity of the particles will also lead to the non-uniform carbon coating. The non-uniform coating material body is easily eroded by the electrolyte, and the electrical properties are easily deteriorated due to the dissolution of elements during the rate and long cycle.
- Fig. 7 is the scanning electron microscope image of the iron phosphate prepared by the third cycle in Example 3. It can be seen from the electron microscope that the phosphoric acid prepared in the third cycle and the iron phosphate prepared for the first time maintain inheritance in morphology. The process has good stability.
- Fig. 8 is the scanning electron microscope picture of the iron phosphate prepared according to the conventional process in Comparative Example 1, and it is seen from the electron microscope that the iron phosphate prepared by the conventional method is in sheet shape, and the secondary agglomeration is relatively loose.
- the present invention also compares the amount of alkali consumed in Example 3 and Comparative Example 1, as shown in Table 3.
- Example 3 only used lye in the first preparation, and the amount of lye consumed in the first preparation only accounted for about 1/4 of the amount of lye in Comparative Example 1, and the phosphoric acid in Example 3
- the subsequent recycling of iron precipitation will not involve the use of lye, and the alkali consumption of Comparative Example 1 will increase with the increase of the treatment amount of iron phosphorus slag, indicating that the method of the present invention is more environmentally friendly and has a lower cost.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Removal Of Specific Substances (AREA)
- Compounds Of Iron (AREA)
- Fertilizers (AREA)
Abstract
Description
Claims (10)
- 一种磷酸铁废料循环再生的方法,其特征在于,包括以下步骤:S1:将磷酸铁废料和酸液混合溶解,过滤,得到铁磷溶液;S2:取部分所述铁磷溶液,加入碱液调节pH,搅拌并加热保温反应,过滤,得到磷酸铁沉淀剂;S3:将所述磷酸铁沉淀剂洗涤后加入到余下的铁磷溶液中,搅拌并加热保温反应,得到二水磷酸铁沉淀,过滤,洗涤,留下部分二水磷酸铁沉淀作为以后批次反应的沉淀剂,其余二水磷酸铁沉淀经干燥、烧结,制得无水磷酸铁;S4:重复步骤S1和S3进行循环制备,其中,步骤S3中加入到铁磷溶液的磷酸铁沉淀剂是之前批次步骤S3中留下的二水磷酸铁沉淀。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,所述磷酸铁废料包括磷酸铁边角料、磷酸铁锂提锂后的废料、磷酸铁锂极片回收提锂后铁磷渣或磷酸铁锂电池拆解提锂后的铁磷渣中的一种或多种。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S1中,所述酸液包括盐酸、硫酸、硝酸或磷酸中的一种或多种;所述酸液中的酸根与铁离子的摩尔比为(1.1~1.5):1。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S2中,所述过滤后的滤液加入到步骤S3余下的铁磷溶液中;步骤S3中,所述过滤后的滤液可用于步骤S1磷酸铁废料的溶解。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S1中,所述混合溶解的过程为:边加酸液边搅拌,搅拌的速率为100~400r/min,搅拌的时间为3~5h。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S2中,所述碱液包括氨水、氢氧化钠、氢氧化钾、碳酸钠、磷酸氢二铵、碳酸氢钠或碳酸氢钾中的一种或几种。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S2中,所 述pH为0.5~2.5。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S2和骤S3中,所述搅拌的速度为200~600rpm/min,所述加热的温度为80~100℃,所述保温反应的时间为2~8h。
- 根据权利要求1所述的磷酸铁废料循环再生的方法,其特征在于,步骤S3中,留下二水磷酸铁沉淀的质量占生成二水磷酸铁沉淀总质量的5~40%。
- 权利要求1~9任一项所述的磷酸铁废料循环再生的方法在制备磷酸铁锂电池中的应用。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2315158.2A GB2620057A (en) | 2021-04-06 | 2021-12-29 | Iron phosphate waste cyclic regeneration method and application thereof |
ES202390110A ES2950678A2 (es) | 2021-04-06 | 2021-12-29 | Metodo para el reciclaje de desechos de fosfato de hierro y su uso |
MA61721A MA61721A1 (fr) | 2021-04-06 | 2021-12-29 | Procédé de régénération cyclique de déchets de phosphate de fer et application correspondante |
DE112021006151.8T DE112021006151T5 (de) | 2021-04-06 | 2021-12-29 | Verfahren zum recycling von eisenphosphatabfall und anwendung davon |
HU2200267A HUP2200267A2 (hu) | 2021-04-06 | 2021-12-29 | Eljárás vasfoszfát hulladékok újrahasznosítására és annak felhasználása |
MX2023011731A MX2023011731A (es) | 2021-04-06 | 2021-12-29 | Metodo de regeneracion ciclica de residuos de fosfato de hierro y su aplicacion. |
US18/373,966 US20240021903A1 (en) | 2021-04-06 | 2023-09-28 | Method for recycling iron phosphate waste and use thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110365978.8 | 2021-04-06 | ||
CN202110365978.8A CN113044824B (zh) | 2021-04-06 | 2021-04-06 | 磷酸铁废料循环再生的方法及其应用 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US18/373,966 Continuation US20240021903A1 (en) | 2021-04-06 | 2023-09-28 | Method for recycling iron phosphate waste and use thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022213676A1 true WO2022213676A1 (zh) | 2022-10-13 |
Family
ID=76517451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2021/142510 WO2022213676A1 (zh) | 2021-04-06 | 2021-12-29 | 磷酸铁废料循环再生的方法及其应用 |
Country Status (9)
Country | Link |
---|---|
US (1) | US20240021903A1 (zh) |
CN (1) | CN113044824B (zh) |
DE (1) | DE112021006151T5 (zh) |
ES (1) | ES2950678A2 (zh) |
GB (1) | GB2620057A (zh) |
HU (1) | HUP2200267A2 (zh) |
MA (1) | MA61721A1 (zh) |
MX (1) | MX2023011731A (zh) |
WO (1) | WO2022213676A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115650192A (zh) * | 2022-11-02 | 2023-01-31 | 四川顺应动力电池材料有限公司 | 一种红土镍矿高铁渣制备高纯磷酸铁的方法 |
CN115676790A (zh) * | 2022-10-28 | 2023-02-03 | 贵州川恒化工股份有限公司 | 一种高振实球形电池级磷酸铁的制备方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113044824B (zh) * | 2021-04-06 | 2023-04-11 | 广东邦普循环科技有限公司 | 磷酸铁废料循环再生的方法及其应用 |
CN113428848A (zh) * | 2021-07-19 | 2021-09-24 | 四川大学 | 一种电池级磷酸铁的循环制备工艺 |
CN116675197A (zh) * | 2022-02-23 | 2023-09-01 | 中国科学院过程工程研究所 | 一种从废磷酸铁锂正极粉提锂后铁磷渣制备磷酸铁的方法 |
CN114852983A (zh) * | 2022-04-14 | 2022-08-05 | 湖北大学 | 一种从回收废旧锂电池的副产物磷铁废渣中提取电池级磷酸铁的方法 |
CN114524572B (zh) * | 2022-04-24 | 2022-07-12 | 深圳永清水务有限责任公司 | 一种磷酸铁生产所产生的废水综合处理方法 |
CN115367722B (zh) * | 2022-08-03 | 2023-10-27 | 宜都兴发化工有限公司 | 磷铁矿制备磷酸铁的方法 |
CN115490219B (zh) * | 2022-09-02 | 2024-03-12 | 广东邦普循环科技有限公司 | 磷酸铁及其合成工艺、***以及应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106684485A (zh) * | 2016-12-19 | 2017-05-17 | 天齐锂业股份有限公司 | 酸浸法回收处理废旧磷酸铁锂正极材料的方法 |
CN110683528A (zh) * | 2019-10-17 | 2020-01-14 | 湖南雅城新材料有限公司 | 一种磷酸铁废料的再生方法 |
CN112357899A (zh) * | 2020-11-23 | 2021-02-12 | 湖南金源新材料股份有限公司 | 一种废旧磷酸铁锂电池的综合回收利用方法 |
CN112499609A (zh) * | 2020-12-03 | 2021-03-16 | 广东邦普循环科技有限公司 | 利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法和应用 |
CN113044824A (zh) * | 2021-04-06 | 2021-06-29 | 广东邦普循环科技有限公司 | 磷酸铁废料循环再生的方法及其应用 |
-
2021
- 2021-04-06 CN CN202110365978.8A patent/CN113044824B/zh active Active
- 2021-12-29 WO PCT/CN2021/142510 patent/WO2022213676A1/zh active Application Filing
- 2021-12-29 MA MA61721A patent/MA61721A1/fr unknown
- 2021-12-29 ES ES202390110A patent/ES2950678A2/es active Pending
- 2021-12-29 HU HU2200267A patent/HUP2200267A2/hu unknown
- 2021-12-29 GB GB2315158.2A patent/GB2620057A/en active Pending
- 2021-12-29 DE DE112021006151.8T patent/DE112021006151T5/de active Pending
- 2021-12-29 MX MX2023011731A patent/MX2023011731A/es unknown
-
2023
- 2023-09-28 US US18/373,966 patent/US20240021903A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106684485A (zh) * | 2016-12-19 | 2017-05-17 | 天齐锂业股份有限公司 | 酸浸法回收处理废旧磷酸铁锂正极材料的方法 |
CN110683528A (zh) * | 2019-10-17 | 2020-01-14 | 湖南雅城新材料有限公司 | 一种磷酸铁废料的再生方法 |
CN112357899A (zh) * | 2020-11-23 | 2021-02-12 | 湖南金源新材料股份有限公司 | 一种废旧磷酸铁锂电池的综合回收利用方法 |
CN112499609A (zh) * | 2020-12-03 | 2021-03-16 | 广东邦普循环科技有限公司 | 利用废磷酸铁锂正极粉提锂渣制备磷酸铁的方法和应用 |
CN113044824A (zh) * | 2021-04-06 | 2021-06-29 | 广东邦普循环科技有限公司 | 磷酸铁废料循环再生的方法及其应用 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115676790A (zh) * | 2022-10-28 | 2023-02-03 | 贵州川恒化工股份有限公司 | 一种高振实球形电池级磷酸铁的制备方法 |
CN115676790B (zh) * | 2022-10-28 | 2024-04-02 | 贵州川恒化工股份有限公司 | 一种高振实球形电池级磷酸铁的制备方法 |
CN115650192A (zh) * | 2022-11-02 | 2023-01-31 | 四川顺应动力电池材料有限公司 | 一种红土镍矿高铁渣制备高纯磷酸铁的方法 |
Also Published As
Publication number | Publication date |
---|---|
ES2950678A2 (es) | 2023-10-11 |
CN113044824B (zh) | 2023-04-11 |
DE112021006151T5 (de) | 2023-09-28 |
GB202315158D0 (en) | 2023-11-15 |
GB2620057A (en) | 2023-12-27 |
MX2023011731A (es) | 2023-12-15 |
CN113044824A (zh) | 2021-06-29 |
MA61721A1 (fr) | 2024-01-31 |
US20240021903A1 (en) | 2024-01-18 |
HUP2200267A2 (hu) | 2023-01-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022213676A1 (zh) | 磷酸铁废料循环再生的方法及其应用 | |
CN111370800B (zh) | 一种废旧磷酸铁锂正极材料的回收方法 | |
CN112624076B (zh) | 一种磷酸铁的制备方法及其应用 | |
CN113061723B (zh) | 一种从废旧磷酸铁锂电池中回收锂并制备磷酸铁的方法 | |
CN102891345B (zh) | 从磷酸亚铁锂废料中回收氯化锂的方法 | |
CN102903985A (zh) | 从磷酸亚铁锂废料中回收碳酸锂的方法 | |
CN112993242B (zh) | 镍钴锰正极材料和废旧镍钴锰正极材料的回收方法 | |
CN109119711B (zh) | 一种采用废旧钴酸锂电池制备高电压正极材料的方法 | |
CN102910607B (zh) | 磷酸亚铁锂正极材料综合回收利用方法 | |
CN110482511A (zh) | 一种废旧磷酸铁锂电池正极材料的回收方法 | |
CN115432681B (zh) | 一种废旧磷酸铁锂电池正极材料再生工艺 | |
WO2023142672A1 (zh) | 高纯磷酸铁的制备方法及其应用 | |
WO2023024593A1 (zh) | 镍钴锰酸锂和磷酸铁锂混合废料的回收方法 | |
CN103094571B (zh) | 锂电池用正磷酸铁的制备方法及该方法制备的正磷酸铁 | |
WO2023142677A1 (zh) | 掺杂型磷酸铁及其制备方法和应用 | |
CN110342483A (zh) | 一种利用磷酸锂废料制备电池级磷酸铁的方法 | |
WO2023155544A1 (zh) | 一种聚阴离子型正极材料的制备方法 | |
CN102881960B (zh) | 从磷酸亚铁锂废料中回收氢氧化锂的方法 | |
CN112266020A (zh) | 钠化钒液制备五氧化二钒正极材料的方法 | |
CN112310499B (zh) | 一种废旧磷酸铁锂材料的回收方法、及得到的回收液 | |
CN111137869A (zh) | 磷酸铁锂的制备方法 | |
CN102897803B (zh) | 液相法制备磷酸亚铁锂方法中产生母液的回收利用方法 | |
Fu et al. | A facile route for the efficient leaching, recovery, and regeneration of lithium and iron from waste lithium iron phosphate cathode materials | |
CN115784188A (zh) | 回收制备电池级磷酸铁的方法 | |
CN114865129A (zh) | 一种湿法回收退役磷酸铁锂电池粉提锂制备碳酸锂的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21935892 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 112021006151 Country of ref document: DE |
|
ENP | Entry into the national phase |
Ref document number: 202315158 Country of ref document: GB Kind code of ref document: A Free format text: PCT FILING DATE = 20211229 |
|
WWE | Wipo information: entry into national phase |
Ref document number: MX/A/2023/011731 Country of ref document: MX |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21935892 Country of ref document: EP Kind code of ref document: A1 |