CN110661052A - Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder - Google Patents
Production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder Download PDFInfo
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- CN110661052A CN110661052A CN201810747992.2A CN201810747992A CN110661052A CN 110661052 A CN110661052 A CN 110661052A CN 201810747992 A CN201810747992 A CN 201810747992A CN 110661052 A CN110661052 A CN 110661052A
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- manganese
- oxide
- certain amount
- oxalate
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- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 title claims abstract description 25
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 11
- 239000002440 industrial waste Substances 0.000 claims abstract description 6
- 238000011084 recovery Methods 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 20
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 12
- 210000003298 dental enamel Anatomy 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 6
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229920006027 ternary co-polymer Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- 238000012921 fluorescence analysis Methods 0.000 claims description 3
- 239000007770 graphite material Substances 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000004064 recycling Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 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 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0072—Mixed oxides or hydroxides containing 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the technical field of manganese-zinc ferrite powder production, in particular to a production method for preparing manganese-zinc ferrite powder with wide temperature range and low power consumption. The method comprises the following steps: obtaining a battery pole piece; recovering the negative plate; recovering the positive plate; recovering industrial waste residues; producing wide-temperature low-power-consumption manganese-zinc ferrite; and (6) recovering waste liquid. The invention has the advantages that: the recovery rate of the cobalt acid lithium battery is improved, the production cost of the ferrite is reduced, the product performance is improved, considerable economic benefits are brought, energy is saved, emission is reduced, and the cobalt acid lithium battery has a very wide application prospect and economic value.
Description
Technical Field
The invention relates to the technical field of manganese-zinc ferrite powder production, in particular to a production method for preparing manganese-zinc ferrite powder with wide temperature range and low power consumption.
Background
Wide temperature range and low temperatureThe power-consumption manganese-zinc ferrite is used as a high-end product in soft magnetic materials, is widely applied to a DC2DC converter for electric energy conversion of a hybrid electric vehicle, an inverter for an LCD backlight source, an alternating current matcher, a charger and the like, and is required to have lower power loss within the range of 25-125 ℃. Co element is an additive which is often adopted in wide-temperature low-power-consumption ferrite, and a certain amount of Co is added2O3Can make K of material at high temperature1the-T curve becomes flat and the power consumption-temperature curve of the material will also be relatively flat. Meanwhile, the doping of Co can inhibit part of Fe2+When the amount is proper, the resistivity of the material can be improved. According to the analysis of practical production experience, the doping amount of the cobalt oxide is generally 1000-2000 ppm, the price of the cobalt oxide is increased sharply every day along with the increase of the consumption of the cobalt element in new energy, and correspondingly, the cost of the wide-temperature low-power-consumption manganese-zinc ferrite powder is also greatly increased. At present, common lithium ion batteries such as ternary materials or lithium cobaltate batteries contain a large amount of cobalt elements, and if the cobalt elements can be recycled, the production and manufacturing cost of the wide-temperature low-power-consumption manganese-zinc ferrite material can be reduced to a great extent. In addition, a large amount of dust is inevitably generated in the production process of the manganese-zinc ferrite powder, a manufacturer generally recovers the dust by gravity dust removal or a water spraying tower and then performs filter pressing, and filter residue after the filter pressing only can be transferred to a tile manufacturer to be used as a building material at low cost or with money due to poor formula stability and a large amount of impurity ions such as Cl, Na, Si and the like.
On the other hand, with the development of new energy vehicles, after more and more batteries are used for more than 3000 times of circulation, the coulomb efficiency is greatly reduced, so that the batteries cannot be continuously used, a large amount of waste lithium ion batteries are generated, the batteries have potential safety hazards on one hand, and on the other hand, the batteries can seriously pollute the environment. As is well known, the recycling rate of the conventional secondary batteries such as lead-acid batteries is as high as more than 90%, and the cobalt element and the lithium element of the common lithium ion batteries such as lithium cobalt oxide batteries become two types of elements with rapidly increasing prices in recent years, and if the cobalt element and the lithium element are recycled, considerable economic benefits can be brought. However, the lithium ion battery is difficult to recycle due to the problems that the structure of the material itself is damaged after the organic electrolyte is adopted and circulated.
Most of lithium cobaltate or ternary materials recovered by the traditional method are repeatedly applied to lithium battery production, but the crystal structure of the material is damaged, and a certain amount of impurity components are contained, so that the product performance is seriously fluctuated when the lithium cobaltate or ternary materials are recovered and applied to the production of the lithium battery, and even potential safety hazards appear in the PACK process. Moreover, most manufacturers can produce a large amount of sewage in the process of recovering the lithium battery pole pieces, and the sewage can cause great pollution when being discharged to the environment.
Disclosure of Invention
The invention aims to provide a production method for preparing manganese zinc ferrite powder with wide temperature range and low power consumption by using recovered industrial waste residues and a lithium ion battery, so as to solve the technical problems.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder is characterized by comprising the following steps: the method comprises the following steps:
1. obtaining a battery pole piece: after the recycled waste lithium batteries are completely discharged, mechanically crushing and disassembling are carried out, and a negative plate and a positive plate are selected;
2. and (3) recovering the negative plate: soaking the negative plate obtained in the step 1 in water, then filtering and washing to obtain copper foil, and recovering graphite slurry; adding a certain amount of sulfuric acid into the graphite slurry to control the pH value of the graphite slurry to be 1-3; adding a small amount of ascorbic acid for ultrasonic stripping, aging for 1 day, filtering and washing with deionized water for 3 times, and roasting the filter residue at the high temperature of 600-1000 ℃ for 1 hour to obtain a graphite material with the purity of more than 98% and containing partial conductive graphene; placing the filtrate in an enamel jar for later use;
3. and (3) recovering the positive plate: placing the positive plate obtained in the step 1 in a mixed solution of sulfuric acid and hydrogen peroxide with the concentration of 1-3 mol/L, soaking for more than 2 hours at the temperature of 60-80 ℃, filtering, adding a certain amount of ammonium carbonate into filtrate, and strictly controlling the pH value of the solution to be 4-5.5 by using dilute sulfuric acid; aging for 1 hour, filtering, adding a certain amount of oxalic acid solution into the filtrate, filtering to obtain cobalt oxalate or binary or ternary copolymer of cobalt oxalate, nickel oxalate and manganese oxalate, adding a certain amount of ammonium carbonate into the filtrate, controlling the pH value to be more than 7, and filtering to obtain lithium carbonate; calcining cobalt oxalate or binary or ternary copolymer of cobalt oxalate, nickel oxalate and manganese oxalate and lithium carbonate at the high temperature of 600 ℃ and 450 ℃ respectively to obtain cobalt oxide or binary or ternary oxide of cobalt oxide, nickel oxide and manganese oxide and high-purity lithium carbonate; placing the waste liquid obtained in the whole process in the enamel tank in the step 2 for later use;
4. recovering industrial waste residues: pouring the recovered waste residues into a sulfuric acid solution, and controlling the pH value to be 1-5; after fully reacting at 60 ℃, adding polyacrylamide with the weight of 2 per mill of the solution, and filtering; adding a certain amount of ammonia water into the filtrate at the temperature of 80 ℃, and adjusting the pH value of the solution to be 3-6; adding oxalic acid solution with the concentration of 1-5 mol/L to obtain a precipitate, and fully roasting the precipitate at the high temperature of 700-900 ℃ to obtain a ferrite precursor; placing the waste liquid obtained in the whole process in the enamel tank in the step 2 for later use;
5. production of wide-temperature low-power-consumption manganese-zinc ferrite: measuring the contents of iron, manganese and zinc in the ferrite precursor obtained in the step 4 by adopting a fluorescence analysis method; supplementing a certain amount of ferric oxide, manganese oxide or zinc oxide to ensure that the mol percent of the ferric oxide is 52-53 mol percent, the mol percent of the zinc oxide is 10-11 mol percent, and the balance is the manganese oxide; adding the cobalt oxide obtained in the step 3 into the mixture according to the weight percentage of 0.1-0.2%, and simultaneously adding Nb with the weight percentage of 0.01-0.04%2O50.01 to 0.06% by weight of V2O50.01 to 0.06 weight percent of calcium carbonate; and then, placing the powder in a sand mill, fully sanding, adding a certain amount of polyvinyl alcohol adhesive, and spray drying to obtain the manganese-zinc ferrite powder with excellent electromagnetic performance and low power consumption at wide temperature.
Further, the production method for preparing the wide-temperature low-power-consumption manganese-zinc ferrite powder further comprises waste liquid recovery, and the method comprises the following specific steps: adding a certain amount of ferric sulfate solution into an enamel tank containing the filtrate obtained in the step 2 and the waste liquid obtained in the steps 3 and 4, and adjusting the pH value to be 5-7 by using ammonia water; after full reaction, the precipitate is filtered to obtain ferric oxalate, and the filtrate is crystallized and dried to obtain ammonium sulfate crystal, ammonium phosphate and sodium chloride.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the waste battery is recycled by adopting a process of mixing a dry method and a wet method, so that the recovery rate of the lithium cobaltate battery is greatly improved, and meanwhile, the waste liquid generated in the wet method process can be treated to obtain a product with economic benefits;
(2) the wide-temperature low-power-consumption manganese zinc ferrite produced by recycling the cobalt oxide in the lithium battery can greatly reduce the production cost of the wide-temperature low-power-consumption manganese zinc ferrite;
(3) the lithium cobaltate or the cobalt oxide of the cobalt-containing binary and ternary material battery contains elements such as manganese, nickel and the like, and the elements are components required by the wide-temperature low-power consumption material, so that the excellent effect can be achieved by slightly adjusting the formula during use, and other trace elements such as lithium, sulfur, aluminum and the like have no great influence on the ferrite;
(4) the copper foil, the conductive graphite containing graphene, lithium carbonate and the like can be indirectly recycled in the process of recycling the battery, and considerable economic benefits can be brought along with the increase of the recycling amount;
(5) the ferrite material is prepared by adopting the recycled industrial waste residues, so that on one hand, considerable economic benefits can be brought, the environmental pollution is avoided, on the other hand, three elements of iron, manganese and zinc can be mixed at an atomic level by adopting an oxalate coprecipitation method, the reaction activity of the material is higher, the later-stage treatment temperature of powder can be reduced, the cost of a magnetic core manufacturer is effectively reduced, and the product performance is improved;
(6) the oxalate coprecipitation method is adopted to prepare the ferrite, so that the steps of material preparation, primary sand grinding, red spraying and the like required by the traditional process can be omitted, and meanwhile, the precursor has better activity, so that the presintering temperature can be reduced, the energy is saved, and the emission is reduced;
(7) the main components of all the waste liquid are ammonium ions, sulfate ions and the like, so that the waste material is intensively treated to reduce the recovery cost;
(8) as the recycled battery is generally subjected to more than 3000 charge-discharge cycles, the graphite interlayer spacing is enlarged by lithium ion intercalation and deintercalation, partial stripping can occur after a certain amount of ascorbic acid and sulfuric acid are added for ultrasonic treatment, and a certain amount of graphene material is formed.
Detailed Description
The invention is further described with reference to specific examples.
Example 1:
the production method for preparing the wide-temperature low-power-consumption manganese-zinc ferrite powder comprises the following steps of:
1. obtaining a battery pole piece: after the recycled waste lithium batteries are completely discharged, mechanically crushing and disassembling are carried out, and a negative plate and a positive plate are selected;
2. and (3) recovering the negative plate: soaking the negative plate obtained in the step 1 in water, then filtering and washing to obtain copper foil, and recovering graphite slurry; adding a certain amount of sulfuric acid into the graphite slurry to control the pH value of the graphite slurry to be 1-3; adding a small amount of ascorbic acid for ultrasonic stripping, aging for 1 day, filtering and washing with deionized water for 3 times, and roasting the filter residue at 800 ℃ for 1 hour to obtain a graphite material with the purity of more than 98% and containing partially conductive graphene; placing the filtrate in an enamel jar for later use;
3. and (3) recovering the positive plate: placing the positive plate obtained in the step 1 in a mixed solution of sulfuric acid and hydrogen peroxide with the concentration of 2mol/L, soaking for more than 2 hours at the temperature of 80 ℃, filtering, adding a certain amount of ammonium carbonate into filtrate, and strictly controlling the pH value of the solution to be 4-5.5 by using dilute sulfuric acid; aging for 1 hour, filtering, adding a certain amount of oxalic acid solution into the filtrate, filtering to obtain cobalt oxalate or binary or ternary copolymer of cobalt oxalate, nickel oxalate and manganese oxalate, adding a certain amount of ammonium carbonate into the filtrate, controlling the pH value to be more than 7, and filtering to obtain lithium carbonate; calcining cobalt oxalate or binary or ternary copolymer of cobalt oxalate, nickel oxalate and manganese oxalate and lithium carbonate at the high temperature of 600 ℃ and 450 ℃ respectively to obtain cobalt oxide or binary or ternary oxide of cobalt oxide, nickel oxide and manganese oxide and high-purity lithium carbonate; placing the waste liquid obtained in the whole process in the enamel tank in the step 2 for later use;
4. recovering industrial waste residues: pouring the recovered waste residues into a sulfuric acid solution, and controlling the pH value to be 1-3; after fully reacting at 60 ℃, adding polyacrylamide with the weight of 2 per mill of the solution, and filtering; adding a certain amount of ammonia water into the filtrate at the temperature of 80 ℃, and adjusting the pH value of the solution to be 3-6; adding oxalic acid solution with the concentration of 3mol/L to obtain precipitate, and fully roasting the precipitate at the high temperature of 800 ℃ to obtain a ferrite precursor; placing the waste liquid obtained in the whole process in the enamel tank in the step 2 for later use;
5. production of wide-temperature low-power-consumption manganese-zinc ferrite: measuring the contents of iron, manganese and zinc in the ferrite precursor obtained in the step 4 by adopting a fluorescence analysis method; supplementing a certain amount of ferric oxide, manganese oxide or zinc oxide to ensure that the mol percent of the ferric oxide is 52.5mol percent, the mol percent of the zinc oxide is 10.2mol percent, and the balance is the manganese oxide; adding the cobalt oxide obtained in the step 3 into the mixture according to the weight percentage of 0.1 percent, and simultaneously adding Nb with the weight percentage of 0.04 percent2O50.06% by weight of V2O50.06 percent by weight of calcium carbonate; and then, placing the powder in a sand mill, fully sanding, adding a certain amount of polyvinyl alcohol adhesive, and spray drying to obtain the manganese-zinc ferrite powder with excellent electromagnetic performance and low power consumption at wide temperature.
6. And (3) waste liquid recovery: adding a certain amount of ferric sulfate solution into an enamel tank containing the filtrate obtained in the step 2 and the waste liquid obtained in the steps 3 and 4, and adjusting the pH value to be 5-7 by using ammonia water; after full reaction, the precipitate is filtered to obtain ferric oxalate, and the filtrate is crystallized and dried to obtain ammonium sulfate crystal, ammonium phosphate and sodium chloride.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. A production method for preparing wide-temperature low-power-consumption manganese-zinc ferrite powder is characterized by comprising the following steps: the method comprises the following steps:
(1) obtaining a battery pole piece: after the recycled waste lithium batteries are completely discharged, mechanically crushing and disassembling are carried out, and a negative plate and a positive plate are selected;
(2) and (3) recovering the negative plate: soaking the negative plate obtained in the step (1) in water, then filtering and washing to obtain copper foil, and recovering graphite slurry; adding a certain amount of sulfuric acid into the graphite slurry to control the pH value of the graphite slurry to be 1-3; adding a small amount of ascorbic acid for ultrasonic stripping, aging for 1 day, filtering and washing with deionized water for 3 times, and roasting the filter residue at the high temperature of 600-1000 ℃ for 1 hour to obtain a graphite material with the purity of more than 98% and containing partial conductive graphene; placing the filtrate in an enamel jar for later use;
(3) and (3) recovering the positive plate: placing the positive plate obtained in the step (1) in a mixed solution of sulfuric acid and hydrogen peroxide with the concentration of 1-3 mol/L, soaking for more than 2 hours at the temperature of 60-80 ℃, filtering, adding a certain amount of ammonium carbonate into filtrate, and strictly controlling the pH value of the solution to be 4-5.5 by using dilute sulfuric acid; aging for 1 hour, filtering, adding a certain amount of oxalic acid solution into the filtrate, filtering to obtain cobalt oxalate or binary or ternary copolymer of cobalt oxalate, nickel oxalate and manganese oxalate, adding a certain amount of ammonium carbonate into the filtrate, controlling the pH value to be more than 7, and filtering to obtain lithium carbonate; calcining cobalt oxalate or binary or ternary copolymer of cobalt oxalate, nickel oxalate and manganese oxalate and lithium carbonate at the high temperature of 600 ℃ and 450 ℃ respectively to obtain cobalt oxide or binary or ternary oxide of cobalt oxide, nickel oxide and manganese oxide and high-purity lithium carbonate; waste liquid obtained in the whole process is placed in the enamel tank in the step (2) for standby;
(4) recovering industrial waste residues: pouring the recovered waste residues into a sulfuric acid solution, and controlling the pH value to be 1-5; after fully reacting at 60 ℃, adding polyacrylamide with the weight of 2 per mill of the solution, and filtering; adding a certain amount of ammonia water into the filtrate at the temperature of 80 ℃, and adjusting the pH value of the solution to be 3-6; adding oxalic acid solution with the concentration of 1-5 mol/L to obtain a precipitate, and fully roasting the precipitate at the high temperature of 700-900 ℃ to obtain a ferrite precursor; waste liquid obtained in the whole process is placed in the enamel tank in the step (2) for standby;
(5) production of wide-temperature low-power-consumption manganese-zinc ferrite: measuring the contents of iron, manganese and zinc in the ferrite precursor obtained in the step (4) by adopting a fluorescence analysis method; supplementing a certain amount of ferric oxide, manganese oxide or zinc oxide to ensure that the mol percent of the ferric oxide is 52-53 mol percent, the mol percent of the zinc oxide is 10-11 mol percent, and the balance is the manganese oxide; adding the cobalt oxide obtained in the step (3) into the mixture according to the weight percentage of 0.1-0.2%, and adding Nb with the weight percentage of 0.01-0.04%2O50.01 to 0.06% by weight of V2O50.01 to 0.06 weight percent of calcium carbonate; and then, placing the powder in a sand mill, fully sanding, adding a certain amount of polyvinyl alcohol adhesive, and spray drying to obtain the manganese-zinc ferrite powder with excellent electromagnetic performance and low power consumption at wide temperature.
2. The production method for preparing the wide-temperature low-power-consumption manganese-zinc ferrite powder according to claim 1, characterized in that: the method also comprises waste liquid recovery, and comprises the following specific steps: adding a certain amount of ferric sulfate solution into an enamel tank containing the filtrate obtained in the step (2) and the waste liquid obtained in the steps (3) and (4), and adjusting the pH value to 5-7 by using ammonia water; after full reaction, the precipitate is filtered to obtain ferric oxalate, and the filtrate is crystallized and dried to obtain ammonium sulfate crystal, ammonium phosphate and sodium chloride.
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| CN112250062A (en) * | 2020-10-16 | 2021-01-22 | 武汉轻工大学 | Reduced graphene oxide and preparation method thereof |
| CN115745592A (en) * | 2022-11-17 | 2023-03-07 | 海宁联丰磁业股份有限公司 | Broadband high-Tc high-permeability manganese-zinc ferrite material and preparation method thereof |
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| CN112250062A (en) * | 2020-10-16 | 2021-01-22 | 武汉轻工大学 | Reduced graphene oxide and preparation method thereof |
| CN115745592A (en) * | 2022-11-17 | 2023-03-07 | 海宁联丰磁业股份有限公司 | Broadband high-Tc high-permeability manganese-zinc ferrite material and preparation method thereof |
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