CN115448335A - Recycling method of waste manganese iron phosphate lithium battery - Google Patents
Recycling method of waste manganese iron phosphate lithium battery Download PDFInfo
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- CN115448335A CN115448335A CN202211319874.4A CN202211319874A CN115448335A CN 115448335 A CN115448335 A CN 115448335A CN 202211319874 A CN202211319874 A CN 202211319874A CN 115448335 A CN115448335 A CN 115448335A
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- manganese
- iron
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 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 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 115
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 104
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 97
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 78
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 claims abstract description 71
- 239000000843 powder Substances 0.000 claims abstract description 52
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 47
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 47
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 41
- 239000011574 phosphorus Substances 0.000 claims abstract description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229910000616 Ferromanganese Inorganic materials 0.000 claims abstract description 38
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002244 precipitate Substances 0.000 claims abstract description 34
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 9
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 186
- 238000001914 filtration Methods 0.000 claims description 72
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- JEBAUTBPSKCVJM-UHFFFAOYSA-N [P].[Mn].[Fe] Chemical compound [P].[Mn].[Fe] JEBAUTBPSKCVJM-UHFFFAOYSA-N 0.000 claims description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 28
- 239000012535 impurity Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 22
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 18
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 18
- 239000012670 alkaline solution Substances 0.000 claims description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- MQMHJMFHCMWGNS-UHFFFAOYSA-N phosphanylidynemanganese Chemical compound [Mn]#P MQMHJMFHCMWGNS-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000005188 flotation Methods 0.000 claims description 3
- -1 iron ions Chemical class 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 21
- 239000005955 Ferric phosphate Substances 0.000 description 19
- 229940032958 ferric phosphate Drugs 0.000 description 19
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 19
- 238000005303 weighing Methods 0.000 description 19
- 238000001035 drying Methods 0.000 description 15
- 238000001514 detection method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 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 6
- 239000007787 solid Substances 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- BNBLBRISEAQIHU-UHFFFAOYSA-N disodium dioxido(dioxo)manganese Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- 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
- C01B25/377—Phosphates of heavy metals of manganese
-
- 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
-
- 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
- C01P2006/80—Compositional purity
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for recycling waste lithium manganese iron phosphate batteries comprises the steps of pretreating waste lithium manganese iron phosphate batteries to obtain positive electrode powder and negative electrode powder; preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution for leaching corresponding lithium and ferromanganese phosphorus to obtain a lithium-rich solution and a ferromanganese phosphorus-rich solution, and realizing the target leaching of the lithium and the ferromanganese phosphorus by utilizing the difference of the leaching pH values of the lithium and the ferromanganese phosphorus in the lithium manganese phosphate; purifying and concentrating the leached lithium-rich solution, adding a sodium carbonate solution to obtain a crude lithium carbonate precipitate, and purifying to obtain high-purity lithium carbonate; using Mn for the leached rich Mn-Fe-P solution 2+ 、Fe 3+ 、Al 3+ 、OH ‑ 、PO 4 3+ The separation and purification of the iron phosphate and the manganese phosphate are realized under different pH environments in different forms. The invention can realize the positive and negative electrode materialsThe full components of the material are recovered, and the obtained products such as high-purity lithium carbonate, iron phosphate, manganese phosphate and the like reduce environmental pollution and resource waste, have high added value, can improve the economic benefit of enterprises, and better meet the actual production requirement.
Description
Technical Field
The invention belongs to the technical field of battery recycling, and particularly relates to a recycling method of waste lithium manganese iron phosphate batteries.
Background
LiFePO4 is one of the most widely applied lithium ion battery anode materials in the current market, and has the advantages of good cycle performance, safety, stability, high cost performance and the like. But the further development of the method is limited by the defects of low use voltage, low conductivity, insufficient rate performance and the like. Fe and Mn are combined, and Mn-doped LiFePO4 is used as a lithium iron manganese phosphate serving as a lithium ion battery anode material, so that various defects of the LiFePO4 can be overcome. Compared with ternary lithium manganese iron phosphate, the lithium manganese iron phosphate has the advantages of high cost performance, high safety and long cycle life; compared with lithium iron phosphate, the lithium iron manganese phosphate has high energy density and good low-temperature performance. After the cost is reduced along with the rapid advance of industrialization, the accelerated substitution of the share of the lithium iron phosphate can be realized. At present, battery enterprises and positive electrode material manufacturers are actively laying out the capacity of lithium iron manganese phosphate, and industry analysts predict that stable mass production can be realized in China at the latest in 2023 years, and the lithium iron manganese phosphate can be applied in a large scale.
With the wide application of the anode material of the lithium iron manganese phosphate battery, how to recycle the waste lithium iron manganese phosphate battery and realize the closed loop of the battery material becomes a hot point for research of enterprises and scientists. The Chinese patent with the publication number of CN108736090A discloses a recycling method of a lithium iron manganese phosphate battery anode material, which comprises the following steps: firstly, dissolving a positive electrode material of a lithium ferromanganese phosphate lithium battery in an oxidizing acid solution, performing oxidation reaction to obtain oxidized acidified slurry, and filtering to obtain a lithium-rich solution and ferromanganese slag, wherein the ferromanganese slag is a mixture of manganese oxide and iron phosphate; removing impurities from the lithium-rich solution to obtain a lithium-rich purified solution, and precipitating the lithium-rich purified solution by sodium carbonate to obtain lithium carbonate; adding sodium hydroxide into the ferromanganese slag for roasting, adding water to dissolve the obtained roasted material to obtain a water-soluble roasted material, and filtering the water-soluble roasted material to obtain a sodium manganate solution and iron phosphate; adding a reducing agent into the sodium manganate solution to carry out oxidation-reduction reaction to obtain manganese dioxide. The technical scheme realizes the recovery of the positive electrode material of the lithium iron manganese phosphate battery, and obtains products of lithium carbonate, iron phosphate and manganese oxide, however, the process needs higher roasting energy consumption, and the products of iron phosphate and manganese oxide are not purified, so the invention aims to develop a method which can realize the recovery of all components of the positive electrode material and the negative electrode material of the lithium iron manganese phosphate battery with low energy consumption, and simultaneously prepare high-purity lithium carbonate, iron phosphate and manganese phosphate, improve the added value of the product, and better meet the actual production requirement.
Disclosure of Invention
The invention aims to provide a recycling method of a waste manganese iron phosphate lithium battery, which aims to solve the technical problems of reducing the energy consumption of all-component recycling of anode and cathode materials of the manganese iron phosphate lithium battery and improving the purity of the recycled components.
In order to solve the technical problems, the specific technical scheme of the recycling method of the waste lithium iron manganese phosphate battery is as follows:
a recycling method of waste ferric manganese phosphate lithium batteries comprises the following steps:
A. pretreatment: respectively obtaining positive electrode powder and negative electrode powder through the steps of discharging, crushing, pyrolysis, winnowing, flotation and the like;
B. preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: hydrogen peroxide, sodium persulfate and sulfuric acid are prepared into lithium leachate, and acid solution with a certain concentration is prepared to be used as manganese iron phosphorus leachate for later use;
C. preparation of high-purity lithium carbonate: adding a lithium leaching solution into the positive electrode powder for leaching, performing primary filtration after leaching to obtain a lithium-rich solution and ferromanganese, iron and phosphorus filter residues, and purifying the lithium-rich solution to remove impurities, concentrating and precipitating, and performing carbonation purification to obtain high-purity lithium carbonate;
D. preparing high-purity iron phosphate: mixing the manganese iron phosphorus filter residue obtained by the first filtration with the manganese iron phosphorus leachate for reaction, performing second filtration after the reaction is finished to obtain a manganese iron phosphorus-rich solution, adding an alkaline solution into the manganese iron phosphorus-rich solution to neutralize and precipitate the iron phosphate in an environment with the pH =1.6-2.0, performing third filtration to obtain crude iron phosphate and a manganese phosphorus-rich solution, adding phosphoric acid into the crude iron phosphate to just dissolve the crude iron phosphate, adding water to dilute the solution, raising the pH value of the solution, separating out and crystallizing the iron phosphate, and performing fourth filtration to obtain high-purity iron phosphate, wherein impurities such as copper and aluminum are left in the solution;
E. preparing high-purity manganese phosphate: adding an alkaline solution into the manganese-phosphorus-rich solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide under the environment of pH =2.0-4.0, performing fifth filtration to separate aluminum hydroxide impurities, adding an alkaline solution into the filtrate obtained by the fifth filtration to precipitate manganese phosphate under the environment of pH =4.0-6.0, performing sixth filtration to obtain crude manganese phosphate, washing the crude manganese phosphate with a phosphoric acid solution to remove impurities, and performing seventh filtration to obtain high-purity manganese phosphate.
And further, drying the negative electrode powder in the step A to directly recycle, and carrying out the next step on the positive electrode powder.
Further, in the lithium leaching solution in the step B, the mass fraction of sulfuric acid is 0.1-10%, the mass fraction of hydrogen peroxide is 1-8%, and the mass fraction of sodium persulfate is 0.1-1%; the manganese iron phosphorus leaching solution is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and the mass fraction of the acid is 5-50%.
Further, in the step C, before adding the lithium leaching solution into the positive electrode powder for leaching, a certain amount of water is added so that the solid-to-liquid ratio is 1 to 5-20; when the lithium leaching solution is added for leaching, pH monitoring is required to be carried out simultaneously, the lithium leaching solution is stopped to be added when the pH reaches 4.0-4.5, the leaching temperature is 50-90 ℃, and the leaching time is 20-120 min; the stirring speed is 250-600 r/min in the leaching process; in the purification and impurity removal process, alkali solution is added to adjust the pH to be 8-10, iron ions and manganese ions in the solution generate hydroxide precipitate, and the hydroxide precipitate is subjected to centrifugal separation.
Further, in the step D, adding the manganese-iron-phosphorus leaching solution into the manganese-iron-phosphorus filter residue obtained by the first filtration, stopping adding the manganese-iron-phosphorus leaching solution when the pH value reaches 0-0.5, wherein the leaching temperature is 75-90 ℃, the leaching time is 30-120 min, the stirring speed in the leaching process is 250-600 r/min, and the alkaline solution added in the process of preparing the crude iron phosphate by neutralization and precipitation can be one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide; in the process of dissolving the rough ferric phosphate by phosphoric acid, the concentration range of the added phosphoric acid is 8-30%, and in the process of preparing the high-purity ferric phosphate by recrystallization of the rough ferric phosphate, water is added for dilution until the pH of the solution is = 1.6-1.8.
Further, in the step E, the alkaline solution added for neutralizing the precipitate may be one or more of ammonia, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, the pH of the phosphoric acid solution for washing the crude manganese phosphate is = 2-4, and the solid-to-liquid ratio is 1-5.
The method for recycling the waste lithium manganese iron phosphate batteries has the following advantages: the invention realizes the target leaching of lithium and manganese iron phosphorus by utilizing the synergistic oxidation of hydrogen peroxide and sodium persulfate and the difference of the leaching pH values of lithium and manganese iron phosphorus in lithium manganese iron phosphate. The separation and purification of the iron phosphate and the manganese phosphate are realized by utilizing different existing forms of Mn2+, fe3+, al3+, OH-and PO43+ in different pH environments. Fe3+ and PO43+ precipitate as ferric phosphate at pH = 1.6-2.0; al3+ precipitates as aluminum hydroxide at pH = 3.0-4.0; mn2+ and PO43+ precipitate as manganese phosphate at pH =4.0 to 6.0. After the rough ferric phosphate is obtained, adding phosphoric acid to enable the rough ferric phosphate to be just dissolved, adding water to dilute the solution, increasing the pH value of the solution, recrystallizing ferric phosphate to obtain high-purity ferric phosphate, and keeping impurities such as copper and aluminum in the solution, wherein a small amount of ferric hydroxide in the rough ferric phosphate is converted into the ferric phosphate. After the rough manganese phosphate is obtained, washing the rough manganese phosphate by using a dilute phosphoric acid solution, so that a small amount of manganese hydroxide in the rough manganese phosphate can be converted into manganese phosphate, and the high-purity manganese phosphate is obtained.
Compared with the traditional recovery process, the method for recycling the waste lithium manganese iron phosphate batteries can realize the full component recovery of the positive and negative electrode materials, avoid the pollution to the environment and the resource waste problem caused by the direct abandonment of the positive and negative electrode materials of the waste lithium manganese iron phosphate batteries, obtain high-purity products such as lithium carbonate, iron phosphate, manganese phosphate and the like, have high added value of the products, can improve the economic benefit of enterprises, and better meet the actual production needs.
Drawings
FIG. 1 is a process diagram of the recycling method of waste lithium iron manganese phosphate batteries according to the present invention;
Detailed Description
In order to better understand the purpose, structure and function of the present invention, the method for recycling waste lithium iron manganese phosphate batteries of the present invention is described in further detail below with reference to the accompanying drawings.
The method for recycling the waste lithium iron manganese phosphate batteries comprises the steps of firstly, pretreating the waste lithium iron manganese phosphate batteries to obtain positive electrode powder and negative electrode powder; preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution for leaching corresponding lithium and ferromanganese phosphorus to obtain a lithium-rich solution and a ferromanganese phosphorus-rich solution, and realizing the target leaching of the lithium and the ferromanganese phosphorus by utilizing the difference of the leaching pH values of the lithium and the ferromanganese phosphorus in the lithium manganese phosphate; purifying and concentrating the leached lithium-rich solution, adding a sodium carbonate solution to obtain a crude lithium carbonate precipitate, and purifying to obtain high-purity lithium carbonate; and (3) separating and purifying the iron phosphate and manganese phosphate by using different existing forms of Mn < 2+ >, fe < 3+ >, al < 3+ >, OH < - > and PO < 43+ > in different pH environments after leaching.
Example 1
As shown in figure 1, the recycling method of the waste lithium iron manganese phosphate battery comprises the following steps:
A. pretreatment: discharging, crushing, pyrolyzing and winnowing the waste lithium iron manganese phosphate battery to obtain black powder mixed with positive and negative electrode materials. Because most of the waste batteries have a small amount of electric quantity, the waste batteries need to be completely discharged before treatment, so that the phenomenon that a large amount of energy is possibly discharged by the small amount of electric quantity in subsequent treatment to cause certain potential safety hazards and other adverse factors is avoided. The crushing treatment is to make the anode and cathode materials and other substances undergo multistage crushing, screening and other operations under mechanical force so as to enrich the electrode materials, so as to facilitate subsequent treatment. Screening the mixed black powder of the positive and negative electrode materials in a flotation mode to obtain negative electrode powder and positive electrode powder, wherein the negative electrode powder is graphite, the negative electrode powder is directly recycled after being dried, and the content of each component of the positive electrode powder measured by a spectrometer is respectively as follows: 3.6 percent of lithium, 20.7 percent of manganese, 9.2 percent of iron and 13.4 percent of phosphorus.
B. Preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: hydrogen peroxide, sodium persulfate and sulfuric acid are prepared into a lithium leaching solution, wherein the mass fraction of the sulfuric acid is 0.1-10%, the mass fraction of the sodium persulfate is 0.1-10%, the mass fraction of the hydrogen peroxide is 1-8%, the mass fraction of the sulfuric acid is 6%, the mass fraction of the sodium persulfate is 0.1%, and the mass fraction of the hydrogen peroxide is 4%; an acid solution with the mass fraction of 5% -50% is prepared to serve as the manganese iron phosphorus leaching solution for later use, wherein the acid solution is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and the acid solution in the embodiment is a sulfuric acid solution with the mass fraction of 10%.
C. Preparation of high-purity lithium carbonate: weighing 100g of the pretreated positive electrode powder, adding a certain amount of water into the positive electrode powder to ensure that the solid-to-liquid ratio is 1-20, adding 500g of water in the embodiment, then adding a lithium leachate to leach, leaching lithium in the positive electrode powder through the synergistic oxidation of hydrogen peroxide and sodium persulfate in the lithium leachate, wherein the pH of the liquid is gradually reduced along with the addition of the lithium leachate due to the fact that the lithium leachate contains sulfuric acid, when the lithium leachate is added into the positive electrode powder to leach, pH monitoring is required to be carried out simultaneously, and the lithium leachate is stopped to be added until the pH is =4.0, wherein the leaching temperature is 50-90 ℃, and the leaching time is 20-120 min; the stirring speed is 250-600 r/min in the leaching process; in this example, the immersion was carried out at 50 ℃ for 60 minutes with a stirring speed of 250r/min. And after leaching, carrying out primary filtration to obtain a lithium-rich solution and ferromanganese phosphorus filter residues, adding 1mol/L sodium hydroxide into the lithium-rich solution, adjusting the pH of the solution to =8.0, generating hydroxide precipitates from iron ions and manganese ions in the lithium-rich solution, carrying out centrifugal separation to obtain a purified lithium-rich solution, carrying out evaporation concentration until crystals begin to precipitate, adding 200mL of 2mol/L sodium carbonate solution, centrifuging to obtain a crude lithium carbonate precipitate, and purifying by a carbonation method to finally obtain the high-purity lithium carbonate. After drying, 17.4g of lithium carbonate product is obtained by weighing, and the recovery rate of lithium is 92%.
D. Preparing high-purity iron phosphate: adding 500g of water into the manganese-iron-phosphorus filter residue obtained by the first filtration, then adding the manganese-iron-phosphorus leachate, gradually reducing the pH value of the solution with the addition of the manganese-iron-phosphorus leachate, simultaneously monitoring the pH when the manganese-iron-phosphorus leachate is added, stopping adding the manganese-iron-phosphorus leachate when the pH =0, wherein the leaching temperature is 75-90 ℃, the leaching time is 30-120 min, and the stirring speed is 250-600 r/min during the leaching process, in the embodiment, the manganese-iron-phosphorus filter residue is leached at 75 ℃ for 100 min, and the stirring speed is 250r/min. After the reaction is finished, performing secondary filtration to obtain a manganese-iron-phosphorus-rich solution, adding an alkaline solution into the manganese-iron-phosphorus-rich solution to neutralize and precipitate the iron phosphate in an environment with the pH =1.6, wherein the alkaline solution can be one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, the alkaline solution is a 1mol/L sodium hydroxide solution in the embodiment, then performing third filtration to obtain crude iron phosphate and a manganese-phosphorus-rich solution, adding 8-30% by mass of phosphoric acid into the crude iron phosphate to just dissolve the crude iron phosphate, the phosphoric acid is 10% by mass in the embodiment, adding water to raise the pH of the solution to 1.6, separating out crystals of the iron phosphate, performing fourth filtration to obtain high-purity iron phosphate, and impurities such as copper and aluminum remain in the solution. After drying, 23.2g of iron phosphate product was obtained by weighing, with an iron recovery rate of 93%.
E. Preparing high-purity manganese phosphate: adding an alkaline solution to the manganese-phosphorus-rich solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide in an environment with a pH =2.0, wherein the alkaline solution may be one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, in the embodiment, a 1mol/L potassium hydroxide solution, performing a fifth filtration to separate aluminum hydroxide impurities, adding the alkaline solution to the filtrate obtained by the fifth filtration to precipitate manganese phosphate in an environment with a pH =4.0, wherein the alkaline solution may be one or more of ammonia water, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide, in the embodiment, a 1mol/L sodium carbonate solution, performing a sixth filtration to obtain crude manganese phosphate, washing and removing impurities from the crude manganese phosphate with a pH = 2-4 phosphoric acid solution at a liquid-solid ratio of 1-5, 20, and performing a seventh filtration to obtain high-purity manganese phosphate. In this example, the specific phosphoric acid solution with PH =2 has a liquid-solid ratio of 1.
The detection results of the high-purity lithium carbonate components in the embodiment are shown in the following table:
table 1 results of measuring high purity lithium carbonate content in example 1
The detection results of the high-purity iron phosphate components in the present example are as follows:
table 2 results of measuring high purity lithium carbonate content in example 1
The detection results of the high-purity manganese phosphate components in the embodiment are as follows:
table 3 results of measuring high purity manganese phosphate component in example 1
Example 2
The invention discloses a recycling method of waste manganese iron phosphate lithium batteries, which comprises the following steps:
A. pretreatment: the method comprises the following steps of discharging, crushing, pyrolyzing, sorting, floating and the like to obtain anode powder and cathode powder, and the contents of all components of the anode powder are measured by a spectrometer and are respectively as follows: 3.6 percent of lithium, 20.7 percent of manganese, 9.2 percent of iron and 13.4 percent of phosphorus.
B. Preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: hydrogen peroxide, sodium persulfate and sulfuric acid are prepared into a lithium leaching solution, wherein the mass fraction of the sulfuric acid is 10%, the mass fraction of the sodium persulfate is 1.0%, the mass fraction of the hydrogen peroxide is 7%, and a 30% sulfuric acid solution is prepared to serve as a manganese iron phosphorus leaching solution for later use.
C. Preparation of high-purity lithium carbonate: weighing 100g of the pretreated positive electrode powder, adding 1000g of water into the positive electrode powder, then adding the lithium leaching solution for leaching until the pH =4.3, stopping adding the lithium leaching solution, leaching for 20 minutes at 80 ℃, and stirring at 500r/min. And after leaching, performing primary filtration to obtain a lithium-rich solution and manganese iron phosphorus filter residues, adding 2mol/L potassium hydroxide into the lithium-rich solution, adjusting the pH of the solution to =9, performing centrifugal separation to obtain a purified lithium-rich solution, performing evaporation concentration until crystals begin to precipitate, adding 200mL of 2mol/L sodium carbonate solution, performing centrifugation to obtain a crude lithium carbonate precipitate, and purifying by a carbonation method to finally obtain the high-purity lithium carbonate. After drying, 18.0g of lithium carbonate product was obtained by weighing, and the recovery rate of lithium was 94%.
D. Preparing high-purity iron phosphate: adding 250g of water into the manganese iron phosphorus filter residue obtained by the first filtration, then adding the manganese iron phosphorus leachate to ensure that the pH of the solution is =0.3, leaching for 30 minutes at 90 ℃, and stirring at the speed of 500r/min. And after the reaction is finished, carrying out secondary filtration to obtain a manganese-iron-phosphorus-rich solution, adding 1mol/L sodium hydroxide into the manganese-iron-phosphorus-rich solution to precipitate iron phosphate in an environment with the pH =1.8, carrying out tertiary filtration to obtain crude iron phosphate and a manganese-phosphorus-rich solution, adding phosphoric acid with the mass fraction of 20% to just dissolve the crude iron phosphate, adding water to raise the pH of the solution to 1.7, separating out iron phosphate for crystallization, carrying out fourth filtration to obtain high-purity iron phosphate, and keeping impurities such as copper and aluminum in the solution. And drying and weighing to obtain 22.3g of iron phosphate product, wherein the recovery rate of iron is 90%.
E. Preparing high-purity manganese phosphate: adding 1mol/L of sodium carbonate into the manganese-rich phosphorus solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide under the environment of pH =3.5, performing fifth filtration to separate aluminum hydroxide impurities, continuously adding 0.1mol/L of sodium hydroxide into the filtrate obtained by the fifth filtration to precipitate manganese phosphate under the environment of pH =5.0, performing sixth filtration to obtain crude manganese phosphate, washing and removing impurities from the crude manganese phosphate by using a phosphoric acid solution with the pH =3.0 and a liquid-solid ratio of 1, and performing seventh filtration to obtain high-purity manganese phosphate. After drying, 43.3g of manganese phosphate product is obtained by weighing, and the recovery rate of manganese is 97%.
The detection results of the impurities in the high-purity lithium carbonate in the embodiment are shown in the following table:
table 4 results of measuring high purity lithium carbonate content in example 2
The detection results of the high-purity iron phosphate components in the embodiment are as follows:
table 5 results of measuring high purity iron phosphate content in example 2
The detection results of the high-purity manganese phosphate component in the embodiment are as follows:
table 6 results of detecting high purity manganese phosphate component in example 2
Example 3
The invention discloses a recycling method of waste manganese iron phosphate lithium batteries, which comprises the following steps:
A. pretreatment: the method comprises the following steps of discharging, crushing, pyrolyzing, sorting, floating and the like to obtain anode powder and cathode powder, and the contents of all components of the anode powder are measured by a spectrometer and are respectively as follows: 3.6 percent of lithium, 20.7 percent of manganese, 9.2 percent of iron and 13.4 percent of phosphorus.
B. Preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: hydrogen peroxide, sodium persulfate and sulfuric acid are prepared into a lithium leaching solution, wherein the mass fraction of the sulfuric acid is 10%, the mass fraction of the sodium persulfate is 0.5%, the mass fraction of the hydrogen peroxide is 7%, and a 30% sulfuric acid solution is prepared to serve as a manganese iron phosphorus leaching solution for later use.
C. Preparation of high-purity lithium carbonate: weighing 100g of the pretreated cathode powder, adding 1000g of water into the cathode powder, then adding the lithium leaching solution for leaching, stopping adding the lithium leaching solution until the pH is =4.5, leaching for 20 minutes at 80 ℃, and stirring at 500r/min. And after leaching, performing primary filtration to obtain a lithium-rich solution and manganese iron phosphorus filter residues, adding 2mol/L potassium hydroxide into the lithium-rich solution, adjusting the pH of the solution to =10, performing centrifugal separation to obtain a purified lithium-rich solution, performing evaporation concentration until crystals begin to precipitate, adding 200mL of 2mol/L sodium carbonate solution, performing centrifugation to obtain a crude lithium carbonate precipitate, and purifying by a carbonation method to finally obtain the high-purity lithium carbonate. After drying, 18.0g of lithium carbonate product was obtained by weighing, and the recovery rate of lithium was 94%.
D. Preparing high-purity iron phosphate: 250g of water is added into the manganese iron phosphorus filter residue obtained by the first filtration, then the manganese iron phosphorus leachate is added to ensure that the pH of the solution is =0.5, and the solution is leached for 30 minutes at 90 ℃ at a stirring speed of 500r/min. And after the reaction is finished, carrying out secondary filtration to obtain a manganese-iron-phosphorus-rich solution, adding 1mol/L of sodium hydroxide into the manganese-iron-phosphorus-rich solution to precipitate the iron phosphate in an environment with pH =2, carrying out tertiary filtration to obtain crude iron phosphate and a manganese-phosphorus-rich solution, adding phosphoric acid with the mass fraction of 20% to just dissolve the crude iron phosphate, adding water to raise the pH of the solution to 1.8, separating out crystals from the iron phosphate, carrying out tertiary filtration to obtain high-purity iron phosphate, and keeping impurities such as copper and aluminum in the solution. And weighing 22.3g of iron phosphate product after drying, wherein the recovery rate of iron is 90%.
E. Preparing high-purity manganese phosphate: adding 1mol/L of sodium carbonate into the manganese-phosphorus-rich solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide in a pH =4 environment, performing fifth filtration to separate aluminum hydroxide impurities, adding 0.1mol/L of sodium hydroxide into the filtrate obtained by the fifth filtration to precipitate manganese phosphate in a pH =6.0 environment, performing sixth filtration to obtain crude manganese phosphate, washing the crude manganese phosphate with a pH =4.0 phosphoric acid solution at a liquid-solid ratio of 1. After drying, 42.8g of manganese phosphate product is obtained by weighing, and the recovery rate of manganese is 96%.
The detection results of impurities in the high-purity lithium carbonate in this example are shown in the following table:
table 7 results of measuring high purity lithium carbonate content in example 3
The detection results of the high-purity iron phosphate components in the present example are as follows:
table 8 test results of high purity iron phosphate composition in example 3
The detection results of the high-purity manganese phosphate component in the embodiment are as follows:
table 9 results of measuring high purity manganese phosphate component in example 3
It should be noted that the main differences between examples 2-3 and example 1 are that the PH value changes in lithium leaching, lithium carbonate precipitation and purification, ferromanganese phosphorus leaching, iron phosphate precipitation, ferromanganese phosphate precipitation and corresponding purification operations, and the mass fractions and components of the remaining corresponding lithium leachate and ferromanganese phosphorus leachate and the parameters in the preparation process all meet the ranges in example 1, which are not repeated in examples 2-3,
Comparative example 1
The method for preparing high-purity lithium carbonate, iron phosphate and manganese phosphate from waste lithium iron manganese phosphate batteries in the comparison embodiment comprises the following steps:
A. pretreatment: the method comprises the following steps of discharging, crushing, pyrolyzing, sorting, floating and the like to obtain anode powder and cathode powder, and the contents of all components of the anode powder are measured by a spectrometer and are respectively as follows: 3.6 percent of lithium, 20.7 percent of manganese, 9.2 percent of iron and 13.4 percent of phosphorus.
B. Preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: preparing hydrogen peroxide, sodium persulfate and sulfuric acid into a lithium leaching solution, wherein the mass fraction of the sulfuric acid is 6%, the mass fraction of the sodium persulfate is 1%, and the mass fraction of the hydrogen peroxide is 4%; preparing a sulfuric acid solution with the mass fraction of 10% as a manganese iron phosphorus leaching solution for later use.
C. Preparation of high-purity lithium carbonate: weighing 100g of the pretreated positive electrode powder, adding 500g of water into the positive electrode powder, then adding the lithium leaching solution for leaching until the pH =3.0, stopping adding the lithium leaching solution, leaching for 60 minutes at 50 ℃, and stirring at 250r/min. And after leaching, performing primary filtration to obtain a lithium-rich solution and manganese iron phosphorus filter residues, adding 1mol/L sodium hydroxide into the lithium-rich solution, adjusting the pH of the solution to =9, performing centrifugal separation to obtain a purified lithium-rich solution, performing evaporation concentration until crystals begin to precipitate, adding 200mL of 2mol/L sodium carbonate solution, performing centrifugation to obtain a crude lithium carbonate precipitate, and purifying by a carbonation method to finally obtain the high-purity lithium carbonate. After drying, 18.5g of lithium carbonate product is obtained by weighing, and the recovery rate of lithium is 96.6%.
D. Preparing high-purity iron phosphate: 500g of water is added into the filter residue obtained by the first filtration, and then manganese iron phosphorus leachate is added to ensure that the pH of the solution is =1, and the solution is leached for 100 minutes at 75 ℃, and the stirring speed is 250r/min. And after the reaction is finished, carrying out secondary filtration to obtain a solution containing manganese, iron and phosphorus, adding 1mol/L of sodium hydroxide into the filtrate to precipitate the iron phosphate in an environment with pH =1.8, carrying out tertiary filtration to obtain crude iron phosphate and a manganese and phosphorus-rich solution, adding phosphoric acid with the mass fraction of 10% to just dissolve the crude iron phosphate, adding water to raise the pH of the solution to 1.7, separating out the iron phosphate to crystallize, carrying out tertiary filtration to obtain high-purity iron phosphate, and keeping impurities such as copper and aluminum in the solution. After drying, 11.6g of iron phosphate product was obtained by weighing, and the recovery rate of iron was 46.8%.
E. Preparing high-purity manganese phosphate: adding 1mol/L of potassium hydroxide into the manganese-phosphorus-rich solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide in an environment with pH =3.0, performing fifth filtration to separate aluminum hydroxide impurities, adding 1mol/L of sodium carbonate into the filtrate obtained by the fifth filtration to precipitate manganese phosphate in an environment with pH =4, performing sixth filtration to obtain crude manganese phosphate, washing and removing impurities from the crude manganese phosphate by using a phosphoric acid solution with pH =2.0 and a liquid-solid ratio of 1. And drying, and weighing to obtain 28g of manganese phosphate product, wherein the recovery rate of manganese is 64%.
TABLE 10 results of measuring high purity lithium carbonate component in comparative example 1
The detection results of the high-purity iron phosphate components in the present example are as follows:
table 11 results of measuring high purity iron phosphate content in comparative example 1
The detection results of the high-purity manganese phosphate components in the embodiment are as follows:
TABLE 12 results of determination of high purity manganese phosphate component in comparative example 1
Comparative example 2
The method for preparing high-purity lithium carbonate, iron phosphate and manganese phosphate from waste lithium iron manganese phosphate batteries in the comparison embodiment comprises the following steps:
A. pretreatment: the method comprises the following steps of discharging, crushing, pyrolyzing, sorting, floating and the like to obtain anode powder and cathode powder, and the contents of all components of the anode powder are measured by a spectrometer and are respectively as follows: 3.6 percent of lithium, 20.7 percent of manganese, 9.2 percent of iron and 13.4 percent of phosphorus.
B. Preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: preparing hydrogen peroxide, sodium persulfate and sulfuric acid into a lithium leaching solution, wherein the mass fraction of the sulfuric acid is 6%, the mass fraction of the sodium persulfate is 1%, and the mass fraction of the hydrogen peroxide is 4%; preparing a sulfuric acid solution with the mass fraction of 10% as a manganese iron phosphorus leaching solution for later use.
C. Preparation of high-purity lithium carbonate: weighing 100g of the pretreated cathode powder, adding 500g of water into the cathode powder, then adding the lithium leaching solution for leaching, stopping adding the lithium leaching solution until the pH is =5.0, leaching for 60 minutes at 50 ℃, and stirring at 250r/min. And after leaching, carrying out primary filtration to obtain a lithium-rich solution and manganese iron phosphorus filter residues, adding 1mol/L sodium hydroxide into the lithium-rich solution, adjusting the pH of the solution to =9, carrying out centrifugal separation to obtain a purified lithium-rich solution, carrying out evaporation concentration until crystals begin to precipitate, adding 200mL of 2mol/L sodium carbonate solution, carrying out centrifugation to obtain a crude lithium carbonate precipitate, and purifying by a carbonation method to finally obtain the high-purity lithium carbonate. After drying, 9.5g of lithium carbonate product was obtained by weighing, and the recovery rate of lithium was 49.7%.
D. Preparing high-purity iron phosphate: 500g of water is added to the filter residue obtained by the first filtration, and then manganese iron phosphorus leachate is added to ensure that the pH of the solution is =0.5, and the solution is leached for 100 minutes at 75 ℃ with the stirring speed of 250r/min. And after the reaction is finished, carrying out secondary filtration to obtain a manganese iron phosphorus-rich solution, adding 1mol/L of sodium hydroxide into the filtrate to precipitate the iron phosphate in an environment with pH =1.5, carrying out tertiary filtration to obtain crude iron phosphate and a manganese phosphorus-rich solution, adding phosphoric acid with the mass fraction of 10% to just dissolve the crude iron phosphate, adding water to raise the pH of the solution to 1.8, separating out the iron phosphate to crystallize, carrying out tertiary filtration to obtain high-purity iron phosphate, and keeping impurities such as copper and aluminum in the solution. After drying, 13.9g of iron phosphate product is obtained by weighing, and the recovery rate of iron is 56%.
E. Preparing high-purity manganese phosphate: adding 1mol/L of potassium hydroxide into the manganese-phosphorus-rich solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide under the condition of pH =3.0, performing fifth filtration to separate aluminum hydroxide impurities, adding 1mol/L of sodium carbonate into the filtrate obtained by the fifth filtration to precipitate manganese phosphate under the condition of pH =3.6, performing sixth filtration to obtain crude manganese phosphate, washing the crude manganese phosphate with a phosphoric acid solution with the pH =2.0 and the liquid-solid ratio of 1 to remove impurities, and performing seventh filtration to obtain high-purity manganese phosphate. After drying, 0.7g of manganese phosphate product is obtained by weighing, and the recovery rate of manganese is 1.6%.
Table 13 comparative example 2 for the results of measuring the content of high-purity lithium carbonate
The detection results of the high-purity iron phosphate components in the present example are as follows:
table 14 results of measuring high purity iron phosphate content in comparative example 2
The detection results of the high-purity manganese phosphate components in the embodiment are as follows:
TABLE 15 results of determination of high purity manganese phosphate component in comparative example 2
As can be seen from the comparative example 1, when the positive electrode powder is subjected to lithium leaching under the condition of PH =3 in the step C, the PH value is relatively low, so that part of manganese is leached while lithium is leached, manganese loss is caused, and the subsequent manganese recovery rate is affected; in addition, when the ferromanganese, iron and phosphorus are leached in the step D under the condition that the pH =1, the pH value is relatively high, the leaching rate of iron is influenced, and the iron cannot be leached completely, so that the recovery rate of the iron is influenced; in addition, in step C of comparative example 2, when the positive electrode powder is subjected to lithium leaching under the condition of PH =5, the PH is relatively high, so that lithium in the positive electrode powder cannot be leached, and the rejection rate of the positive electrode powder is greatly reduced, in step D, ferric phosphate is precipitated under the condition of PH =1.5, and the relatively low PH cannot completely precipitate ferric phosphate, so that the final recovery rate of iron is greatly reduced.
The invention mainly utilizes the synergistic oxidation of hydrogen peroxide and sodium persulfate and the difference of leaching pH values of lithium and ferromanganese phosphorus in lithium manganese iron phosphate to realize the targeted leaching of the lithium and the ferromanganese phosphorus. The separation and purification of the iron phosphate and the manganese phosphate are realized by utilizing different existing forms of Mn2+, fe3+, al3+, OH-and PO43+ in different pH environments. Fe3+ and PO43+ precipitate as ferric phosphate at pH = 1.6-2.0; al3+ precipitates as aluminum hydroxide at pH = 3.0-4.0; mn2+ and PO43+ precipitate as manganese phosphate at pH =4.0 to 6.0. After the rough ferric phosphate is obtained, adding phosphoric acid to enable the rough ferric phosphate to be just dissolved, adding water to dilute the solution, increasing the pH value of the solution, recrystallizing ferric phosphate to obtain high-purity ferric phosphate, and keeping impurities such as copper and aluminum in the solution, wherein a small amount of ferric hydroxide in the rough ferric phosphate is converted into the ferric phosphate. After the rough manganese phosphate is obtained, washing the rough manganese phosphate by using a dilute phosphoric acid solution, so that a small amount of manganese hydroxide in the rough manganese phosphate can be converted into manganese phosphate, and the high-purity manganese phosphate is obtained.
It is to be understood that the present invention has been described with reference to certain embodiments, and that various changes in the features and embodiments, or equivalent substitutions may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (8)
1. A recycling method of waste manganese phosphate iron lithium batteries is characterized by comprising the following steps: firstly, pretreating a waste lithium iron manganese phosphate battery to obtain positive electrode powder and negative electrode powder; preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution for leaching corresponding lithium and ferromanganese phosphorus to obtain a lithium-rich solution and a ferromanganese phosphorus-rich solution, and realizing the target leaching of the lithium and the ferromanganese phosphorus by utilizing the difference of the leaching pH values of the lithium and the ferromanganese phosphorus in the lithium manganese phosphate; purifying and concentrating the leached lithium-rich solution, adding a sodium carbonate solution to obtain a crude lithium carbonate precipitate, and purifying to obtain high-purity lithium carbonate; using Mn for the leached rich Mn-Fe-P solution 2+ 、Fe 3+ 、Al 3+ 、OH - 、PO 4 3+ Different forms exist under different pH environmentsAnd the separation and purification of iron phosphate and manganese phosphate are realized.
2. The recycling method of the waste lithium iron manganese phosphate batteries according to claim 1, comprising the following steps:
A. pretreatment: obtaining positive electrode powder and negative electrode powder through the steps of discharging, crushing, pyrolysis, air separation and flotation;
B. preparing a lithium leaching solution and a ferromanganese phosphorus leaching solution: preparing hydrogen peroxide, sodium persulfate and sulfuric acid into a lithium leachate, and preparing an acid solution as a ferromanganese phosphorus leachate for later use;
C. preparation of high-purity lithium carbonate: adding a lithium leaching solution into the positive electrode powder for leaching, performing primary filtration after leaching to obtain a lithium-rich solution and ferromanganese, iron and phosphorus filter residues, and purifying the lithium-rich solution to remove impurities, concentrate and precipitate, and performing carbon separation and purification to obtain high-purity lithium carbonate;
D. preparing high-purity iron phosphate: mixing the manganese iron phosphorus filter residue obtained by the first filtration with a manganese iron phosphorus leaching solution for reaction, performing second filtration after the reaction is completed to obtain a manganese iron phosphorus-rich solution, adding an alkaline solution into the manganese iron phosphorus-rich solution to neutralize and precipitate iron phosphate in an environment with the pH =1.6-2.0, performing third filtration to obtain crude iron phosphate and a manganese phosphorus-rich solution, adding phosphoric acid into the crude iron phosphate to just dissolve the crude iron phosphate, adding water to dilute the solution, raising the pH of the solution to separate out iron phosphate for crystallization, and performing fourth filtration to obtain high-purity iron phosphate;
E. preparing high-purity manganese phosphate: adding an alkaline solution into the manganese-phosphorus-rich solution obtained by the third filtration to neutralize and precipitate aluminum hydroxide under the environment of pH =2.0-4.0, performing fifth filtration to separate aluminum hydroxide impurities, adding an alkaline solution into the filtrate obtained by the fifth filtration to neutralize and precipitate manganese phosphate under the environment of pH =4.0-6.0, performing sixth filtration to obtain crude manganese phosphate, washing the crude manganese phosphate with a phosphoric acid solution to remove impurities, and performing seventh filtration to obtain high-purity manganese phosphate.
3. The recycling method of the waste lithium iron manganese phosphate batteries according to claim 2, wherein in the lithium leach solution obtained in the step B, the mass fraction of sulfuric acid is 0.1-10%, the mass fraction of hydrogen peroxide is 1-8%, and the mass fraction of sodium persulfate is 0.1-1%; the acid solution in the manganese iron phosphorus leaching solution is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and the mass fraction of the acid is 5-50%.
4. The recycling method of waste lithium iron manganese phosphate batteries according to claim 3, wherein in said step C, before adding lithium leachate to the positive electrode powder for leaching, a certain amount of water is added to make the solid-to-liquid ratio 1-20; when the lithium leaching solution is added for leaching, pH monitoring is required to be carried out simultaneously, the lithium leaching solution is stopped to be added when the pH reaches 4.0-4.5, the leaching temperature is 50-90 ℃, and the leaching time is 20-120 min; the stirring speed is 250-600 r/min in the leaching process; in the purification and impurity removal process, alkali solution is added to adjust the pH to be 8-10, iron ions and manganese ions in the solution generate hydroxide precipitate, and the hydroxide precipitate is subjected to centrifugal separation.
5. The method for recycling waste lithium iron manganese phosphate batteries according to claim 4, wherein in step D, the manganese iron phosphorus leachate is added to the manganese iron phosphorus filter residue obtained by the first filtration, the manganese iron phosphorus leachate is stopped when the pH reaches 0-0.5, the leaching temperature is 75-90 ℃, the leaching time is 30-120 min, the stirring speed is 250-600 r/min during the leaching process, the concentration of the added phosphoric acid is 8-30% during the dissolution of the crude iron phosphate, and the water is added to dilute the solution until the pH = 1.6-1.8 during the recrystallization of the crude iron phosphate to prepare the high-purity iron phosphate.
6. The recycling method of the waste manganese iron phosphate lithium battery as claimed in claim 5, wherein in the step E, the phosphoric acid solution for washing the crude manganese phosphate has a pH = 2-4, and the solid-to-liquid ratio is 1.
7. The method as claimed in claim 6, wherein in the steps D and E, the alkaline solution added for neutralizing the precipitate can be one or more of ammonia, sodium carbonate, sodium bicarbonate, sodium hydroxide and potassium hydroxide.
8. The method for recycling waste lithium iron manganese phosphate batteries according to claim 7, wherein in step a, the negative electrode powder is dried and directly recycled.
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