CN109119711A - A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery - Google Patents
A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery Download PDFInfo
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- CN109119711A CN109119711A CN201810776910.7A CN201810776910A CN109119711A CN 109119711 A CN109119711 A CN 109119711A CN 201810776910 A CN201810776910 A CN 201810776910A CN 109119711 A CN109119711 A CN 109119711A
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- cobalt
- lithium
- manganese
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000010941 cobalt Substances 0.000 title claims abstract description 56
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 56
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002253 acid Substances 0.000 title description 50
- 239000010405 anode material Substances 0.000 title description 13
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000008139 complexing agent Substances 0.000 claims abstract description 19
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims abstract description 12
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000006104 solid solution Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims 2
- 239000010406 cathode material Substances 0.000 claims 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- IDSMHEZTLOUMLM-UHFFFAOYSA-N [Li].[O].[Co] Chemical compound [Li].[O].[Co] IDSMHEZTLOUMLM-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- CMYCPTASPDMVFC-UHFFFAOYSA-N n,n,n',n'-tetraaminoethane-1,2-diamine Chemical compound NN(N)CCN(N)N CMYCPTASPDMVFC-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 11
- 229910032387 LiCoO2 Inorganic materials 0.000 description 10
- 238000004064 recycling Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000001133 acceleration Effects 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000011833 salt mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910007499 Li1/3Mn2/3 Inorganic materials 0.000 description 1
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开一种采用废旧钴酸锂电池制备高电压正极材料的方法，将剥离得到的废旧钴酸锂电池正极材料清洗、煅烧，检测其中的钴和锂的含量；按照富锂锰基固溶体的化学计量比取镍盐、钴盐和锰盐，配制成镍盐、钴盐、锰盐的混合盐溶液，再分别配制络合剂溶液Ⅰ、络合剂溶液Ⅱ和沉淀剂溶液；在反应釜中加入络合剂溶液Ⅱ作为底液并加入煅烧后的废旧钴酸锂材料，将镍钴锰混合盐溶液、络合剂溶液Ⅰ、沉淀剂溶液分别流加加入进行沉淀反应，控制pH值、络合剂的浓度、反应温度、反应时间，过滤、清洗并干燥得到复合前驱体，将复合前驱体与锂源混合煅烧之后冷却至室温，获得正极材料；本发明所制备的材料结晶度高，结构稳定性高，高电压充放循环稳定性好。
The invention discloses a method for preparing a high-voltage positive electrode material by using waste and used lithium cobalt oxide batteries. The stripped waste and used and used lithium cobalt oxide battery positive electrode materials are cleaned and calcined, and the content of cobalt and lithium therein is detected; Take nickel salt, cobalt salt and manganese salt in stoichiometric ratio, prepare a mixed salt solution of nickel salt, cobalt salt and manganese salt, and then prepare complexing agent solution I, complexing agent solution II and precipitant solution respectively; Add the complexing agent solution II as the bottom liquid and add the calcined waste lithium cobaltate material, and add the nickel-cobalt-manganese mixed salt solution, the complexing agent solution I, and the precipitating agent solution separately to carry out the precipitation reaction, and control the pH value, The concentration of the complexing agent, the reaction temperature, the reaction time, filtration, cleaning and drying to obtain a composite precursor, the composite precursor is mixed with a lithium source and calcined and then cooled to room temperature to obtain a positive electrode material; the material prepared by the present invention has high crystallinity, High structural stability and good high-voltage charge-discharge cycle stability.
Description
Technical field
The present invention relates to waste and old lithium ion batteries to recycle field, uses waste and old cobalt acid lithium battery more particularly to a kind of
The method for preparing high-voltage anode material.
Background technique
Lithium ion battery with its high-energy density, the service life is long, self discharge is small, memory-less effect and it is environmentally protective the advantages that quilt
International community is known as optimal electrochmical power source, is widely used in mobile phone, laptop, electric tool and portable takes the photograph
The electronic products such as camera.Meanwhile lithium ion battery is in the clean energy resource energy storage field of the discontinuity such as wind energy, solar energy and tide energy
It plays an important role.In addition, the electric car being growing, electric bicycle, aerospace, military mobile communication facility
Bigger development space will be brought to lithium ion battery with fields such as equipment.And lithium ion battery passes through multiple cycle charge-discharge
Afterwards, active material is inactivated and is scrapped since structure changes, thus, waste and old lithium ion battery enormous amount.Waste and old lithium ion battery
The release of middle electrolyte pollutes the environment and endangers the ecosystem, while containing a large amount of nickel, iron, manganese, cobalt, lithium in electrode material
Equal valuable metals, and the rapid development of New Energy Industry causes lithium ion battery raw material mineral resources increasingly to reduce, and constrains lithium
The benign development of ion battery industry.It is asked for this purpose, recycling waste and old lithium ion battery scientific and efficiently and becoming urgently to be resolved at present
Topic.
So far, cobalt acid lithium is the irreplaceable anode material for lithium-ion batteries of middle and high end electronic field, and with length
The charge-discharge cycle of time, the cobalt acid lithium battery scrapped are growing day by day.Even to this day, waste and old cobalt acid lithium battery recovery method mainly collects
In in wet processing and two kinds of thermal process, and to recycle wherein based on valuable metal element.Wherein, pyrogenic process energy consumption is high, pollutes
Seriously, inferior separating effect；And although wet process has many advantages, such as that mild condition, energy consumption are smaller, wet processing is unavoidable big
The discharge of the three wastes is measured, a series of problems, such as and process flow is long, and technical requirements are high, and process control difficulties are big.Old and useless battery is just
Active material in the material of pole remains the component and structure for the preceding active material that fails substantially, directly by old and useless battery positive electrode
Techniqueflow and the period of battery recycling will be greatly shortened by simply handling to prepare completely new anode material and recycle.
Currently, many team develop a series of recovery method of science for waste and old cobalt acid lithium.CN 103199319A discloses one kind
The method that cobalt acid lithium is recycled from cobalt acid lithium battery waste positive, CN 102703706B pass through work of the organic solvent to battery
Property substance carry out immersion removing, most binder can be dissolved, directly obtain clean aluminium, copper, nickel foil and diaphragm, and promoted
LiCoO is dissolved into the direct haptoreaction of subsequent acid solution and cobalt acid lithium and using sulfuric acid solution2.However, existing in above method
Following insufficient: 1) the anode material processing after removing is still incorporated into wet-leaching, precipitation process, and process flow is relatively long, technology
Difficulty is larger；2) material that recycling obtains cannot be directly used as active material, and product increment is unobvious.Patent of invention CA
105428747A discloses a kind of method using cobalt acid lithium in lithium hydroxide solution processing recycling old and useless battery, however should
The performance for the repair materials that method obtains is only common cobalt acid lithium material horizontal, is rised in value unobvious.Rich lithium manganese base solid solution is because of it
The characteristics such as inexpensive, less toxic, high-energy density, high voltage and become the very popular series material of research at present.2001
Zhonghua Lu et al. succeeds in developing rich lithium manganese base solid solution for the first time, and the molecular formula of the material can be expressed as xLi2MO3•(1-
x)LiM'O2(M Mn, Ti, Zr etc., or any combination thereof；M' is Mn, Ni or Co, 0≤x≤1), it is considered as laminarization
Close object Li2MnO3(i.e. Li [Li1/3Mn2/3]O2) and LiM'O2Composition.Not only capacity is high for these bicomponent materials rich in manganese, fills
Discharge voltage window is wide, at low cost, environmentally friendly, safety is good, and its capacity is about LiCoO2Twice, receive section
Grind the extensive concern of scholar.Yu L Y et al. high temperature solid-state method, has synthesized 0.65Li [Li at 700 DEG C1/3Mn2/3]O2•
0.35Li[Ni1/3Co1/3Mn1/3]O2, initial capacity is only 97mAh/g(2.5~4.6V, 100mAh/g), the institute after activating for several times
Obtained capacity is 229mAh/g.Existing recovery technology patent document at present is summarized, has no straight about cobalt acid lithium old and useless battery
Connect the document report for preparing high voltage cobalt acid lithium material as anode material for lithium-ion batteries.
Summary of the invention
In view of the problems of the existing technology and insufficient, the present invention provides a kind of using the high electricity of waste and old cobalt acid lithium battery preparation
The method for pressing positive electrode, simply and efficiently recycles waste and old cobalt acid lithium battery, and high performance high-voltage anode material is made,
Realize effective recycling of waste and old cobalt acid lithium battery.
A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery, specifically includes the following steps:
(1) the waste and old cobalt acid lithium battery positive electrode cleaning for taking removing to obtain, which is placed in Muffle furnace, calcines, and removes conductive carbon, glues
The impurity such as agent are tied, waste and old cobalt acid lithium dusty material is obtained, detects the content of cobalt and lithium therein；
(2) according to rich lithium manganese base solid solutionStoichiometric ratio,
Weigh corresponding nickel salt, cobalt salt and manganese salt, be configured to nickel salt, cobalt salt, manganese salt mixing salt solution, Ni+Co+ in mixing salt solution
The sum of concentration of Mn is 0.01 ~ 2mol/L, then respectively compound concentration be 1 ~ 14mol/L enveloping agent solution I, concentration be 0.1 ~
The enveloping agent solution II and concentration of 0.5mol/L is the precipitant solution of 0.5 ~ 10mol/L, enveloping agent solution I and enveloping agent solution
Complexing agent is identical in II；
(3) enveloping agent solution II is added in a kettle as bottom liquid and the obtained waste and old cobalt acid lithium material of step (1) calcining is added
The nickel cobalt manganese mixing salt solution, enveloping agent solution I, precipitant solution of step (2) are flowed respectively plus are added in reaction kettle and precipitated by material
Reaction, the reason that wherein nickel cobalt manganese mixed salt solution is calculated according to waste and old cobalt acid lithium material and according to nickel cobalt manganese mixing salt solution
By rich lithium manganese base solid solutionMass ratio is the ratio of 100:0.1 ~ 10
Example is added, and liquid pH value is 9 ~ 11 in the flow acceleration control reaction kettle in reaction process by controlling each solution, control
The concentration of complexing agent processed is 0.1 ~ 0.5mol/L, and reaction temperature is 20 ~ 95 DEG C, reacts 10 ~ 260min, obtains containing precursor material
Slurry, precursor material is filtered, clean, is dried to obtain composite precursor；
(4) composite precursor and lithium source obtained step (3) is by (Ni+Co+Mn) in end product: Li molar ratio be 1:1 ~
The mixing of 1.1 ratio uniforms, is placed in atmosphere furnace 600 ~ 950 DEG C of 2 ~ 20h of calcining under air atmosphere, is cooled to room temperature later, obtains
Positive electrode.
Step (2) x is 0.1 ~ 0.9.
Step (2) nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate.
Step (2) cobalt salt is one or more of cobaltous sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
Step (2) manganese salt is one or more of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate.
Step (2) complexing agent is ammonium hydroxide, triethanolamine, citric acid, oxalic acid, sodium ethylene diamine tetracetate and ammonium hydrogen carbonate
One or more of arbitrary proportion mixing.
Step (2) precipitating reagent is sodium hydroxide, and precipitating reagent is also used as PH value control agent.
Step (3) cleaning is cleans precipitating for several times using 20 ~ 80 DEG C of deionized water, until the pH value of final washing lotion is low
In 10；The drying is dry 6 ~ 60h at 60 ~ 150 DEG C.
Step (4) lithium source is lithium hydroxide or lithium carbonate.
Present invention firstly provides by rich lithium manganese base solid solution
It is introduced into waste and old cobalt acid lithium surface modification, prepares the high voltage cobalt acid lithium base composite positive pole with high voltage stability,
Efficient, the green reclaim that waste and old cobalt acid lithium battery can be achieved are used again；Material crystalline degree prepared by the present invention is high, structural stability
Height, high voltage charge-discharge cycle stability are good；The present invention avoids leaching recycling process, can be by waste and old cobalt acid lithium battery positive electrode
It is converted into high-performance high voltage lithium cobalt oxide anode, to realize the efficient green reparation and increment benefit of waste and old cobalt acid lithium
With method is simple, efficient, and exploitativeness is strong.
Detailed description of the invention
Fig. 1 is 1 process flow chart of the embodiment of the present invention；
Fig. 2 is SEM pair of the composite precursor that the cobalt acid lithium that 1 step of the embodiment of the present invention (1) removing obtains and step (3) obtain
Than figure (cobalt acid lithium that figure a is removed, the composite precursor that figure b step (3) obtains)；
Fig. 3 is the XRD diagram of positive electrode prepared by the embodiment of the present invention 1；
Fig. 4 is the TEM figure of positive electrode prepared by the embodiment of the present invention 2；
Fig. 5 is positive electrode 1C cycle performance curve prepared by the embodiment of the present invention 2；
Fig. 6 is that the SEM comparison diagram of cobalt acid lithium and positive electrode that 3 step of the embodiment of the present invention (1) removing obtains (schemes a to remove
The cobalt acid lithium arrived, the positive electrode that figure b is obtained).
Specific embodiment
The present invention is described in further details with attached drawing combined with specific embodiments below.
Embodiment 1
A method of high-voltage anode material being prepared using waste and old cobalt acid lithium battery, as shown in Figure 1, specifically including following step
It is rapid:
(1) waste and old cobalt acid lithium battery is placed in the metabisulfite solution of 2mol/L and discharges remaining electricity, discharge time for 24 hours, isolates just
Pole piece, and placing it in mass percent concentration is to be stirred to react 12h, washing filtering filter residue is useless in 6% sodium hydroxide solution
Old positive electrode；By obtained filter residue in atmosphere furnace under air atmosphere, 600 DEG C of calcining 2h obtain waste and old LiCoO2Powder material
Material detects the percentage composition (Co, Li) of wherein cobalt and lithium；
(2) according to rich lithium manganese base solid solutionStoichiometric ratio,
Weigh nickel sulfate, cobaltous sulfate and manganese sulfate, be configured to nickel salt, cobalt salt, manganese salt mixing salt solution, Ni+Co+ in mixing salt solution
The sum of concentration of Mn be 0.01mol/L, then respectively compound concentration be 1mol/L citric acid solution, 0.1mol/L citric acid solution and
The sodium hydroxide solution of 5mol/L；
(3) in a kettle be added 1L 0.1mol/L citric acid solution as bottom liquid and be added step (1) calcining obtain give up
Old cobalt acid lithium material 100g, by the nickel cobalt manganese mixing salt solution of step (2), citric acid solution, the sodium hydroxide solution of 1mol/L
Precipitation reaction in reaction kettle is added in stream respectively, and nickel cobalt manganese mixing salt solution charging rate is 10mL/min, and wherein nickel cobalt manganese is mixed
Close the rich lithium manganese base solid solution that salting liquid is obtained according to waste and old cobalt acid lithium dusty material quality and nickel cobalt manganese salt-mixture theoretical calculationMass ratio be 100:0.1 ratio be added, pass through control
The citric acid solution of 1mol/L processed, sodium hydroxide solution flow acceleration by pH value control in reaction process be 9 ± 0.1, control
The concentration of complexing agent citric acid is 0.1mol/L, and reaction temperature is 20 DEG C, reacts 10min, obtains the slurry containing precursor material,
Precursor material is filtered, for several times using 20 DEG C of deionized water cleaning precipitatings, until final ph is lower than 10, it is dry at 60 DEG C
60h obtains composite precursor；
(4) composite precursor for obtaining step (3) carries out the content analysis of Ni, Co, Mn and Li, and according to molar ratio (Ni+Co
+ Mn): the ratio of Li=1:1 adds lithium hydroxide, is uniformly mixed and is placed in air atmosphere in 950 DEG C of calcining 2h, cools down later
To room temperature, positive electrode is obtained, analysis is the results show that surrounding phase in the composite materialMass percent be 0.1%, main phase LiCoO2Quality percentage
Than being 99.9%.
Fig. 2 is the composite precursor that the cobalt acid lithium that step (1) removing obtains in the embodiment of the present invention 1 and step (3) obtain
SEM comparison diagram (cobalt acid lithium removed of figure a, figure b step (3) obtain it is compound after presoma), pass through as we know from the figure
The available composite precursor being evenly coated of step (3)；Fig. 3 is the XRD diagram of the positive electrode finally obtained, can be with from figure
Material hasStructure, the more waste and old cobalt acid lithium material of the crystallinity of positive electrode are remarkably reinforced, and crystal structure obtains
Effectively repair；The progress constant current in 3.0 ~ 4.5V voltage window of button cell prepared by anode is done using the positive electrode to fill
Discharge test, discharge capacity is 191mAh/g for the first time at 0.1C, as shown in figure 5, specific discharge capacity is maintained at 186mAh/ under 1C
G, capacity retention ratio is 87.6% after recycling 100 times.
Embodiment 2
A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery, specifically includes the following steps:
(1) waste and old cobalt acid lithium battery is placed in the metabisulfite solution of 2mol/L and discharges remaining electricity, discharge time for 24 hours, isolates just
Pole piece, and placing it in mass percent concentration is to be stirred to react 12h, washing filtering filter residue is useless in 6% sodium hydroxide solution
Old positive electrode；By obtained filter residue in atmosphere furnace under air atmosphere, 600 DEG C of calcining 2h obtain waste and old LiCoO2Powder material
Material detects the percentage composition (Co, Li) of wherein cobalt and lithium；
(2) according to rich lithium manganese base solid solutionStoichiometric ratio,
Weigh nickel chloride, cobalt chloride and manganese chloride, be configured to nickel salt, cobalt salt, manganese salt mixing salt solution, Ni+Co+ in mixing salt solution
The sum of concentration of Mn is 1mol/L, then compound concentration is three ethyl alcohol of the triethanolamine aqueous solution of 5mol/L, 0.3mol/L respectively
The precipitating reagent sodium hydroxide solution of amine aqueous solution and 0.5mol/L；
(3) the triethanolamine aqueous solution of the 0.3mol/L of 10L is added in a kettle as bottom liquid and step (1) is added calcines
The waste and old cobalt acid lithium material 5000g arrived, by the nickel cobalt manganese mixing salt solution of step (2), triethanolamine aqueous solution, the hydrogen of 5mol/L
Sodium hydroxide solution flows respectively plus is added precipitation reaction in reaction kettle, and nickel cobalt manganese mixing salt solution charging rate is 20mL/min,
The rich lithium that middle nickel cobalt manganese mixing salt solution is obtained according to waste and old cobalt acid lithium dusty material quality and nickel cobalt manganese salt-mixture theoretical calculation
Manganese based solid solutionMass ratio be 100:5 ratio be added,
Being controlled pH value in reaction process by the flow acceleration of the triethanolamine aqueous solution of control 5mol/L, sodium hydroxide solution is 10
± 0.1, the concentration of control complexing agent triethanolamine is 0.3mol/L, and reaction temperature is 60 DEG C, 115min is reacted, before being contained
The slurry for driving material, precursor material is filtered, for several times using 50 DEG C of deionized water cleaning precipitatings, until final ph is lower than 10,
Dry 50h obtains composite precursor at 80 DEG C；
(4) composite precursor for obtaining step (3) carries out the content analysis of Ni, Co, Mn and Li, and according to molar ratio (Ni+Co
+ Mn): the ratio of Li=1:1.08 adds lithium hydroxide, is uniformly mixed and is placed in air atmosphere in 850 DEG C of calcining 10h, later
It is cooled to room temperature, obtains positive electrode, analysis is the results show that surrounding phase in the composite materialMass percent be 5%, main phase LiCoO2Mass percent
It is 95%.
Fig. 4 is the transmission electron microscopy result (TEM) for the positive electrode that the present embodiment obtains, can be obviously from TEM data
To matrix LiCoO2Surface is coated with uniform rich lithium manganese base solid solution phase；Discharge capacity is composite material for the first time at 0.1C
189mAh/g, Fig. 5 show specific discharge capacity under 1C and are maintained at 182mAh/g, and recycling 100 capacity retention ratios is 94.5%.
Embodiment 3
A method of high-voltage anode material is prepared using waste and old cobalt acid lithium battery, specifically includes the following steps:
(1) waste and old cobalt acid lithium battery is placed in the metabisulfite solution of 2mol/L and discharges remaining electricity, discharge time for 24 hours, isolates just
Pole piece, and placing it in mass percent concentration is to be stirred to react 12h, washing filtering filter residue is useless in 6% sodium hydroxide solution
Old positive electrode；By obtained filter residue in atmosphere furnace under air atmosphere, 600 DEG C of calcining 2h obtain waste and old LiCoO2Powder material
Material detects the percentage composition (Co, Li) of wherein cobalt and lithium；
(2) according to rich lithium manganese base solid solutionStoichiometric ratio,
Weigh nickel nitrate, cobalt nitrate and manganese nitrate, be configured to nickel salt, cobalt salt, manganese salt mixing salt solution, Ni+Co+ in mixing salt solution
The sum of concentration of Mn is 2mol/L, then respectively compound concentration be the ammonia spirit of 14mol/L, 0.5mol/L ammonia spirit and
The precipitating reagent sodium hydroxide solution of 10mol/L；
(3) in a kettle be added 10L 0.5mol/L ammonia spirit as bottom liquid and be added step (1) calcine obtain it is waste and old
Cobalt acid lithium material 5000g, by the nickel cobalt manganese mixing salt solution of step (2), the ammonia spirit of 14mol/L, sodium hydroxide solution point
Precipitation reaction in reaction kettle Liu plus not be added, nickel cobalt manganese mixing salt solution charging rate is 10mL/min, and wherein nickel cobalt manganese salt is mixed
Close the rich lithium manganese base solid solution that solution is obtained according to waste and old cobalt acid lithium dusty material quality and nickel cobalt manganese salt-mixture theoretical calculationMass ratio be 100:10 ratio be added, pass through control
The ammonia spirit of 14mol/L, sodium hydroxide solution flow acceleration by pH value control in reaction process be 11 ± 0.1, control network
Mixture ammonia (NH3) concentration be 0.5mol/L, reaction temperature be 95 DEG C, react 260min, obtain the slurry containing precursor material,
Precursor material is filtered, for several times using 80 DEG C of deionized water cleaning precipitatings, until final ph is lower than 10, it is dry at 150 DEG C
6h obtains composite precursor；
(4) composite precursor for obtaining step (3) carries out the content analysis of Ni, Co, Mn and Li, and according to molar ratio (Ni+Co
+ Mn): the ratio of Li=1:1.1 adds lithium carbonate, is uniformly mixed and is placed in air atmosphere in 600 DEG C of calcining 20h, cools down later
To room temperature, positive electrode is obtained, analysis is the results show that surrounding phase in the composite materialMass ratio be 10%, main phase LiCoO2Mass percent be
90%。
Fig. 6 is SEM comparison diagram (the figure a stripping of cobalt acid lithium and positive electrode that 3 step of the embodiment of the present invention (1) removing obtains
From obtained cobalt acid lithium, positive electrode that figure b step (3) obtains), from SEM figure as can be seen that cobalt acid lithium that removing obtains and
Positive electrode is that modify the pattern of front and back be monodisperse particles pattern, without independent between the composite material granular obtained after cladding
Short grained appearance shows that cladding source is all distributed in LiCoO2Particle surface forms uniform clad；Using the anode
Material makees button cell prepared by anode and carries out constant current charge-discharge loop test, composite wood in 3.0 ~ 4.5V voltage window
Expect that the discharge capacity for the first time at 0.1C is 195mAh/g, specific discharge capacity is maintained at 188mAh/g under 1C, recycles 100 capacity
Conservation rate is 89.9%.
The following table 1 show the waste and old LiCoO of step (1) recycling2The material conduct that material and embodiment 1,2,3 respectively obtain
Anode prepares lithium ion button shape cell and carries out constant current charge-discharge loop test in 3.0 ~ 4.5V voltage window, as we know from the figure
The chemical property for the positive electrode that embodiment 1,2,3 is prepared has been obtained compared to waste and old LiCoO2Material is obviously improved.
It should be noted that illustrate the present invention rather than limit it for above embodiment, and ability
Field technique personnel can be designed various alternate embodiments, affiliated skill in the case where without departing from scope of the following claims
The technical staff in art field it will be clearly understood that any improvement in the present invention, equivalence replacement to component selected by the present invention and
Increase, selection of concrete mode of helper component etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (9)
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