CN115744851A - Method for recycling and preparing battery-grade iron phosphate - Google Patents
Method for recycling and preparing battery-grade iron phosphate Download PDFInfo
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- CN115744851A CN115744851A CN202211277446.XA CN202211277446A CN115744851A CN 115744851 A CN115744851 A CN 115744851A CN 202211277446 A CN202211277446 A CN 202211277446A CN 115744851 A CN115744851 A CN 115744851A
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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 92
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 52
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012065 filter cake Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 23
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 23
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 238000004537 pulping Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- -1 dihydrate ferric phosphate Chemical class 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 4
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 12
- 239000012535 impurity Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000012216 screening Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
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- 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
Abstract
The invention provides a method for recycling and preparing battery-grade iron phosphate, which comprises the following steps: (1) Mixing the high-iron phosphate content anode waste powder with water and acid, heating, stirring, fully reacting, filtering, and collecting filtrate, wherein the filtrate is leachate; (2) Adding a pH regulator into the leaching solution, regulating the pH to 3.5-4.5, carrying out solid-liquid separation after full reaction, and collecting filtrate, wherein the filtrate is iron-rich filtrate; (3) Adding oxidant into the iron-rich filtrate to obtain Fe 2+ Oxidation to Fe 3+ Forming iron phosphate precipitate, and fully reacting to obtain iron phosphate slurry; (4) Filtering the iron phosphate slurry, collecting a filter cake, pulping the filter cake, and washing with water for multiple times to obtain an iron phosphate filter cake; (5) Adding pure water into the iron phosphate filter cake, pulping, adding phosphoric acid, heating, keeping the temperature, stirring and reacting until the slurry turns white, and continuing to react for a period of time to obtain ferric phosphate dihydrate slurry; (6) And filtering the ferric phosphate dihydrate slurry, collecting a filter cake, washing with water, drying, and calcining to obtain the battery-grade anhydrous ferric phosphate.
Description
Technical Field
The invention belongs to the technical field of new energy battery anode materials, and particularly relates to a method for recycling and preparing battery-grade iron phosphate.
Background
With the development and upgrade of electric vehicles and various electric vehicles, the usage of secondary batteries becomes larger and larger, and if a large amount of waste secondary batteries cannot be safely disposed and utilized, the waste of resources and serious environmental pollution problems can be caused. Therefore, the method has double meanings of economic value and social benefit for effectively recycling and reusing the waste batteries.
The patent CN106684485B proposes a method for recovering and processing waste lithium iron phosphate positive electrode materials by acid leaching, which comprises the steps of after acid leaching the waste lithium iron phosphate positive electrode materials, oxidizing ferrous ions in filtrate into iron ions, adjusting the pH value to 1.5-4, generating iron phosphate precipitate, filtering, and washing to obtain iron phosphate. However, this patent does not remove impurities such as Al and Cu, and the final product is crude iron phosphate containing many impurities. .
Patent CN110422831A proposes a method for recovering iron phosphate from lithium iron phosphate batteries, which comprises the steps of battery crushing, screening, airflow screening, calcining, acid leaching, oxidation, precipitation and the like, and the iron phosphate is separated out, and the screening step is to add an adsorbent to adsorb excessive impurities, so that most of aluminum powder and copper powder in lithium iron phosphate powder can be removed, but the residual problem of Al and Cu still exists, and the quality of the recovered iron phosphate is affected.
The patent CN111646447B provides a method for recovering iron phosphate from iron phosphorus slag after lithium extraction of a lithium iron phosphate battery, and the method comprises the steps of mixing the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery with water, carrying out acid leaching, carrying out liquid-solid separation to obtain leachate containing iron phosphorus ions, carrying out iron addition displacement copper removal and resin aluminum removal to obtain purified liquid, oxidizing, adjusting pH (potential of hydrogen) to obtain iron phosphate precursor precipitate, and carrying out post-treatment to obtain a battery-grade iron phosphate precursor product. According to the method, al and Cu are required to be removed respectively, and ion exchange resin is required to be additionally added to serve as an adsorbent, so that the process flow is complex, and the cost is increased.
Therefore, the existing method for recycling and preparing the iron phosphate has the problems of incomplete impurity removal, complex recycling process flow and higher cost.
Disclosure of Invention
Therefore, the method for recycling and preparing the battery-grade iron phosphate is good in impurity removal effect, simple in recycling process flow and low in production cost.
The method comprises the following steps: (1) Mixing the high-content iron phosphate anode waste powder with water and acid, heating, stirring, fully reacting, filtering, and collecting filtrate, wherein the filtrate is leachate. (2) And adding a pH regulator into the leachate, regulating the pH to 3.5-4.5, after full reaction, carrying out solid-liquid separation, and collecting filtrate, wherein the filtrate is iron-rich filtrate. (3) Adding oxidant into the iron-rich filtrate to obtain Fe 2+ Oxidation to Fe 3+ To form iron phosphate precipitate, and fully reacting to obtain iron phosphate slurry. (4) And filtering the iron phosphate slurry, collecting a filter cake, pulping the filter cake, washing with water for multiple times, and obtaining the iron phosphate filter cake. (5) Adding pure water into the iron phosphate filter cake, pulping, adding phosphoric acid, heating, keeping the temperature, stirring and reacting until the slurry turns white, and continuing to react for a period of time after the slurry turns white to obtain the ferric phosphate dihydrate slurry. (6) And filtering the dihydrate ferric phosphate slurry, collecting a filter cake, washing with water, drying, and calcining to obtain the battery-grade anhydrous ferric phosphate.
Preferably, in the step (1), the acid used for leaching is a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid and acetic acid, the solid-to-liquid ratio of the mixture of the high-content positive electrode waste powder of iron phosphate and water is 1-2-5, and the amount of the acid is 20-100 wt% of the high-content positive electrode waste powder of iron phosphate.
Preferably, in the step (1), the mixture is heated to 70-100 ℃, and is stirred and reacted for 1-2 hours under the condition of heat preservation.
Preferably, in the step (1), the high content of iron phosphate cathode waste powder is lithium iron phosphate powder, lithium iron manganese phosphate powder or sodium iron phosphate powder.
Preferably, in the step (2), the pH regulator is one of a sodium hydroxide solution, ammonia water and a potassium hydroxide solution.
Preferably, in the step (3), the oxidizing agent is one of hydrogen peroxide, guanidine carbonate, guanidine nitrate and peroxyacetic acid.
Preferably, in the step (3), pH adjustment is not required, and after the reaction is finished, the pH of the solution is 1.8 to 2.5.
Preferably, the battery grade iron phosphate is recovered and prepared from lithium iron phosphate powder, and in the step (4), the iron phosphate slurry is filtered, and in addition to collecting the filter cake, a filtrate is also collected, and the filtrate is a lithium-rich filtrate and is used for extracting lithium.
Preferably, in the step (4), during the multiple water washing of the filter cake, the filtrate for washing the filter cake is collected and mixed with the lithium-rich filtrate for extracting lithium.
Preferably, in the step (5), the pulping solid content of the pure water is 5-20%, the temperature is heated to 85-100 ℃, and the reaction is carried out for 1-2 hours under the condition of heat preservation and stirring.
In the process of recovering the iron phosphate, the pH value is adjusted to 3.5-4.5 for one-step impurity removal, and then the 2-valent iron is oxidized into 3-valent iron without adding a pH regulator, so that the iron phosphate is in the optimal environment with the pH value of 1.8-2.5 after the oxidation is finished. The method can avoid the loss of iron and phosphorus in the impurity removal process, saves the pH regulator, and has simple process flow and lower cost.
Drawings
FIG. 1 is a schematic process flow diagram according to an embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The method for recycling and preparing the battery-grade iron phosphate is suitable for recycling and treating the high-content battery anode waste materials such as the anode materials of lithium iron phosphate, lithium manganese iron phosphate, sodium iron phosphate and the like. The method comprises the following steps: mixing the high-iron-phosphate-content anode waste powder with water and acid, heating, stirring, fully reacting, filtering, and collecting filtrate, wherein the filtrate is leachate.
In the step (1), the acid for leaching is one or a mixture of sulfuric acid, hydrochloric acid, nitric acid and acetic acid, and the solid-to-liquid ratio of the mixture of the high-content ferric phosphate positive electrode waste powder and water is 1: 2-5, wherein the dosage of the acid is 20-100 wt% of the high-content anode waste powder of the ferric phosphate. Heating to 70-100 ℃, preserving heat, stirring and reacting for 1-2 h.
The high-content ferric phosphate positive electrode waste powder is lithium ferric phosphate powder, lithium iron manganese phosphate powder or sodium iron phosphate powder.
And (2) adding a pH regulator into the leachate, regulating the pH to 3.5-4.5, carrying out solid-liquid separation after full reaction, and collecting filtrate, wherein the filtrate is iron-rich filtrate.
The pH regulator is one of sodium hydroxide solution, ammonia water and potassium hydroxide solution. The reaction is stirred for 1 hour at normal temperature.
In the process, impurities such as Al, cu and the like form phosphate and hydroxide precipitates, and the filtrate contains almost no impurities.
Step (3) adding an oxidant into the iron-rich filtrate to obtain Fe 2+ Oxidation to Fe 3+ And forming iron phosphate precipitate, and fully reacting to obtain iron phosphate slurry.
The oxidant is one of hydrogen peroxide, guanidine carbonate, guanidine nitrate and peroxyacetic acid.
In the step (3), pH adjustment is not needed, and after the reaction is finished, the pH of the solution is 1.8-2.5.
And (4) filtering the iron phosphate slurry, collecting a filter cake, pulping the iron phosphate filter cake, washing with water for multiple times, and obtaining the iron phosphate filter cake.
If the battery-grade iron phosphate is recovered from the lithium iron phosphate powder, filtering the iron phosphate slurry in the step (4), collecting a filtrate besides the filter cake, wherein the filtrate is a lithium-rich filtrate and is used for extracting lithium.
And in the process of washing the filter cake for multiple times, if the battery-grade iron phosphate is recovered and prepared from the lithium iron phosphate powder, collecting and washing filtrate of the filter cake, and mixing the filtrate with the lithium-rich filtrate for extracting lithium. The number of washing with water may be 2 to 5.
And (5) adding pure water into the iron phosphate filter cake, pulping, adding phosphoric acid, heating, preserving heat, stirring and reacting until the slurry turns white, and continuing to react for a period of time after the slurry turns white to obtain the ferric phosphate dihydrate slurry.
And (5) adding phosphoric acid to carry out aging reaction to promote the crystal form conversion of the iron phosphate, wherein the iron phosphate in the iron phosphate filter cake obtained in the step (4) is in an amorphous form.
The solid content of the pulping by adding pure water is 5-20%, the heating is carried out to 85-100 ℃, and the reaction is carried out for 1-2 h by heat preservation and stirring.
And (6) filtering the dihydrate ferric phosphate slurry, collecting a filter cake, washing with water, drying, and calcining to obtain the battery-grade anhydrous ferric phosphate. The calcining temperature is 500-700 ℃.
The process flow in the embodiment of the invention is schematically shown in fig. 1.
For a further understanding of the present invention, preferred embodiments of the present invention are described below with reference to the following examples. In this example, the preparation of battery grade iron phosphate recovered from lithium iron phosphate is taken as an example.
Examples
(1) Preparing lithium iron phosphate powder and water into slurry according to a solid-to-liquid ratio of 1; filtering, and collecting filtrate as leachate.
(2) Adding 20% sodium hydroxide solution into the leachate, adjusting the pH value of the solution to 4.0, stirring at normal temperature for reaction for 1 hour, and forming phosphate and hydroxide precipitates from Al and Cu in the solution; and filtering to obtain a solution almost containing no Al and Cu elements, wherein the filtrate is an iron-rich filtrate.
(3) Adding hydrogen peroxide (oxidant: guanidine carbonate, guanidine nitrate, peroxyacetic acid, etc.) into the iron-rich filtrate to oxidize ferrous iron into ferric iron and oxidized Fe 3+ PO in solution 4- Forming ferric phosphate precipitate, adjusting the pH of the solution without adding an acidic solution in the process, stirring and reacting for 1h, wherein the pH of the solution is 2.0-2.5 after the reaction is finished, and obtaining the fully reacted ferric phosphateAnd (3) slurry.
(4) Filtering the iron phosphate slurry, and collecting a filter cake and a filtrate, wherein the filtrate is a lithium-rich filtrate and is used for extracting lithium; pulping and washing the filter cake for 2 times, collecting the iron phosphate filter cake and filtrate, and mixing the filtrate in the process with the lithium-rich filtrate for extracting lithium.
(5) Adding pure water into the iron phosphate filter cake for pulping, wherein the solid content of the pulping is 10%, adding phosphoric acid, heating to 95 ℃, keeping the temperature, stirring and reacting until the slurry turns white, continuing stirring and reacting for 1h after the slurry turns white, and obtaining the ferric phosphate dihydrate slurry after the reaction is finished.
(6) Filtering the ferric phosphate dihydrate slurry, washing and drying a filter cake, and calcining at 550 ℃ to obtain the battery-grade anhydrous ferric phosphate.
The index results of the iron phosphate prepared by the method provided by the invention are shown in table 1, and as can be seen from table 1, the iron phosphate prepared by the embodiment of the invention has an Al content of 25ppm and a Cu content of 1ppm, and the specific surface, the median diameter D50, the tap density and the water content of the iron phosphate reach the battery level.
TABLE 1
The method for recycling and preparing the battery-grade iron phosphate has the following advantages: 1. the recovery rate of the ferric phosphate is high. 2. The Al, cu and other impurities are removed effectively, and the prepared iron phosphate material has high purity and narrow particle size distribution. 3. The recovery process flow is simple, the production cost is low, and the environment is friendly.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The method for recycling and preparing battery-grade iron phosphate is characterized by comprising the following steps:
(1) Mixing the high-iron phosphate content anode waste powder with water and acid, heating, stirring, fully reacting, filtering, and collecting filtrate, wherein the filtrate is leachate;
(2) Adding a pH regulator into the leachate, regulating the pH to 3.5-4.5, carrying out solid-liquid separation after full reaction, and collecting filtrate, wherein the filtrate is iron-rich filtrate;
(3) Adding oxidant into the iron-rich filtrate to obtain Fe 2+ Oxidation to Fe 3+ Forming iron phosphate precipitate, and fully reacting to obtain iron phosphate slurry;
(4) Filtering the iron phosphate slurry, collecting a filter cake, pulping the filter cake, and washing with water for multiple times to obtain an iron phosphate filter cake;
(5) Adding pure water into the iron phosphate filter cake, pulping, adding phosphoric acid, heating, keeping the temperature, stirring and reacting until the slurry turns white, and continuing to react for a period of time after the slurry turns white to obtain ferric phosphate dihydrate slurry;
(6) And filtering the dihydrate ferric phosphate slurry, collecting a filter cake, washing with water, drying, and calcining to obtain the battery-grade anhydrous ferric phosphate.
2. The method for recycling and preparing battery-grade ferric phosphate according to claim 1, wherein in the step (1), the acid used for leaching is a mixture of one or more of sulfuric acid, hydrochloric acid, nitric acid and acetic acid, the solid-to-liquid ratio of the ferric phosphate high-content positive electrode waste powder and water is 1.
3. The method for recycling and preparing the battery-grade iron phosphate according to claim 1, characterized in that in the step (1), the mixture is heated to 70-100 ℃ and stirred for reaction for 1-2 h under heat preservation.
4. The method for recycling battery-grade iron phosphate according to claim 1, wherein in the step (1), the high-content positive electrode iron phosphate waste powder is lithium iron phosphate powder, lithium iron manganese phosphate powder or sodium iron phosphate powder.
5. The method for recycling battery-grade iron phosphate according to claim 1, wherein in the step (2), the pH regulator is one of sodium hydroxide solution, ammonia water and potassium hydroxide solution.
6. The method for recycling battery grade iron phosphate according to claim 1, wherein in the step (3), the oxidant is one of hydrogen peroxide, guanidine carbonate, guanidine nitrate and peroxyacetic acid.
7. The method for recycling and preparing battery-grade iron phosphate according to claim 1, wherein in the step (3), pH adjustment is not needed, and after the reaction is finished, the pH of the solution is 1.8-2.5.
8. The method for recycling battery-grade iron phosphate according to claim 1, wherein the battery-grade iron phosphate is recycled from iron phosphate lithium powder, and in the step (4), the iron phosphate slurry is filtered, and in addition to collecting the filter cake, a filtrate is collected, and the filtrate is a lithium-rich filtrate for lithium extraction.
9. The method for recycling battery-grade iron phosphate according to claim 8, wherein in the step (4), during multiple water washes of the filter cake, the filtrate for washing the filter cake is collected and mixed with the lithium-rich filtrate for lithium extraction.
10. The method for recycling and preparing the battery-grade iron phosphate according to claim 1, wherein in the step (5), the pulping solid content of the pure water is 5-20%, the temperature is increased to 85-100 ℃, and the reaction is carried out for 1-2 hours under the condition of heat preservation and stirring.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211277446.XA CN115744851A (en) | 2022-10-19 | 2022-10-19 | Method for recycling and preparing battery-grade iron phosphate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211277446.XA CN115744851A (en) | 2022-10-19 | 2022-10-19 | Method for recycling and preparing battery-grade iron phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116864851A (en) * | 2023-09-05 | 2023-10-10 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044735A (en) * | 2016-05-31 | 2016-10-26 | 百川化工(如皋)有限公司 | Synthesizing method for low-cost battery-grade iron phosphate |
| CN107720715A (en) * | 2017-09-28 | 2018-02-23 | 湖南华菱节能环保科技有限公司 | A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material |
| CN112624077A (en) * | 2020-12-15 | 2021-04-09 | 广东邦普循环科技有限公司 | Battery-grade iron phosphate and preparation method and application thereof |
| CN113735087A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Method for recycling anode materials of waste lithium iron phosphate batteries |
| CN114349030A (en) * | 2021-12-23 | 2022-04-15 | 湖北锂宝新材料科技发展有限公司 | Comprehensive wet recycling method of waste lithium iron phosphate positive plates |
| WO2022116692A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate from lithium extraction slag of waste lithium iron phosphate positive electrode powder and application |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044735A (en) * | 2016-05-31 | 2016-10-26 | 百川化工(如皋)有限公司 | Synthesizing method for low-cost battery-grade iron phosphate |
| CN107720715A (en) * | 2017-09-28 | 2018-02-23 | 湖南华菱节能环保科技有限公司 | A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material |
| WO2022116692A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Method for preparing iron phosphate from lithium extraction slag of waste lithium iron phosphate positive electrode powder and application |
| CN112624077A (en) * | 2020-12-15 | 2021-04-09 | 广东邦普循环科技有限公司 | Battery-grade iron phosphate and preparation method and application thereof |
| CN113735087A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Method for recycling anode materials of waste lithium iron phosphate batteries |
| CN114349030A (en) * | 2021-12-23 | 2022-04-15 | 湖北锂宝新材料科技发展有限公司 | Comprehensive wet recycling method of waste lithium iron phosphate positive plates |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116864851A (en) * | 2023-09-05 | 2023-10-10 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
| CN116864851B (en) * | 2023-09-05 | 2023-11-21 | 赣州市力道新能源有限公司 | Process for deeply removing phosphorus from retired battery recovery feed liquid |
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