CN110240207A - A kind of method that waste lithium cell recycling prepares tertiary cathode material - Google Patents
A kind of method that waste lithium cell recycling prepares tertiary cathode material Download PDFInfo
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- CN110240207A CN110240207A CN201910520840.3A CN201910520840A CN110240207A CN 110240207 A CN110240207 A CN 110240207A CN 201910520840 A CN201910520840 A CN 201910520840A CN 110240207 A CN110240207 A CN 110240207A
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- cathode material
- waste
- tertiary cathode
- lithium
- lithium cell
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- 239000002699 waste material Substances 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000010406 cathode material Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 238000005554 pickling Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 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 4
- 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 4
- 238000003756 stirring Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 2
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 2
- 240000006365 Vitis vinifera Species 0.000 claims description 2
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 239000007774 positive electrode material Substances 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003978 infusion fluid Substances 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
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 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
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 238000012545 processing Methods 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
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of method that waste lithium cell recycling prepares tertiary cathode material, by the preprocessed isolated waste and old positive electrode material of waste and old lithium ion battery, pickling agent, reducing agent and water is added, it leaches, filtering obtains filtrate, it adds lithium source, nickel source, cobalt source, manganese source and mixed solution is made, presoma material is obtained by mixed solution is spray-dried, then tertiary cathode material is made through two-section calcining；The tertiary cathode material crystallinity of the method for the present invention preparation is high, and stable structure, cycle performance and high rate performance are excellent, and present invention process is simple, strong applicability, excellent product performance are, it can be achieved that the green reclaim of waste and old lithium ion battery utilizes.
Description
Technical field
The present invention relates to a kind of methods that waste lithium cell recycling prepares tertiary cathode material, belong to lithium ion battery recycling
Utilize technical field.
Background technique
Lithium ion battery is high with discharge voltage, specific energy is big, self discharge is small, it is excellent with memory-less effect etc. to have extended cycle life
Point has been widely used in the fields such as 3C electronic equipment, space flight and aviation, medical treatment, and China is just greatly developing new-energy automobile, intelligence in addition
Can power grid, the industries such as renewable energy, lithium ion battery is as good power battery and energy storage material, demand and yield
It further increases., it is expected that arriving the year two thousand twenty, ternary lithium ion battery yield reaches 71.6Gwh.And lithium ion battery is repeatedly recycled
After charge and discharge, active material is inactivated and is scrapped since structure changes, thus, waste and old lithium ion battery enormous amount, it is contemplated that, it arrives
The year two thousand twenty, the learies of China's ternary lithium ion battery are up to 19.2Gwh, and about 300,000 tons.
The release of electrolyte pollutes the environment and endangers the ecosystem in waste and old lithium ion battery, while containing in electrode material
There are the valuable metals such as a large amount of nickel, iron, manganese, cobalt, lithium, and the rapid development of New Energy Industry leads to lithium ion battery raw material mineral products
Resource is increasingly reduced, and constrains the benign development of lithium ion battery industry.For this purpose, recycling waste and old lithium ion battery scientific and efficiently
As current urgent problem to be solved.
Waste and old ternary lithium ion battery recovery method is concentrated mainly on wet processing and two kinds of thermal process, and to recycle it
Based on middle valuable metal element.Wherein, pyrogenic process energy consumption is high, seriously polluted, inferior separating effect, and wet process has mild condition, energy consumption
The advantages that smaller, but wet process technology research is mainly leaching-separation of metal ions recovery process, but each in solution after leaching
The high efficient separation technology difficulty of metal ion is big, and Separation Indexes are poor, for this purpose, there is researcher using chemical precipitation method, sol-gel
Method recycles valuable metal ions from infusion solution and directly prepares positive electrode, but there are the use of precipitating reagent, condition be not easily-controllable
The deficiencies of making, be less reproducible, being not easy large-scale industrial application.Do not have now and recycles system from infusion solution using spray drying process
The report of standby tertiary cathode material.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of waste lithium cell recycling and prepares tertiary cathode material
Method, comprising the following steps:
(1) waste and old lithium ion battery is put into remaining electricity, disassembles isolated waste and old positive electrode；
(2) waste and old positive electrode in step (1) is placed in reactor, pickling agent, reducing agent and Jia Shui, mixed liquor is added
Under agitation, 60~100 DEG C of 1~3h of reaction, after reaction, filtering, filtrate is your liquid rich in valuable metal ions；
(3) lithium source, nickel source, cobalt source, manganese source are added into the filtrate of step (2), and mixed solution, lithium in mixed solution is made
Element, nickel element, cobalt element, manganese element molar ratio be 1:x:y:1-x-y, x > 0, y > 0, x+y < 1, adjust solution ph
It is 2~7, stirs evenly, then by the spray-dried obtained ternary precursor powder of mixed solution；
(4) ternary precursor powder two-section calcining under oxygen atmosphere made from step (3), the first section calcining is 400
~600 DEG C of 4~6h of heat preservation, the second section calcining are in 800~900 DEG C of 10~12h of heat preservation, and tertiary cathode material is made in furnace cooling
Material.
Dismantling mode is mechanical, manual or both integrated processes in step (1).
Pickling agent is that one of acetic acid, oxalic acid, lactic acid, tartaric acid, glycine or a variety of arbitrary proportions are mixed in step (2)
It closes, H in the mixed liquor in reactor+Concentration is 1~5mol/L.
Reducing agent is glucose, grape pip, Victoria C, hydrazine hydrate, the one or more arbitrary proportions of sodium borohydride in step (2)
It mixes, the concentration of reducing agent is 1~3mol/L in the mixed liquor in reactor.
The mass volume ratio g:mL of step (2) positive electrode and water is 1:10~100.
Lithium source is that one or more of lithium hydroxide, lithium carbonate, lithium chloride, lithium acetate or lithium nitrate are appointed in step (3)
The mixing of meaning ratio；Nickel source is the arbitrary proportion mixing of one or more of nickel chloride, nickel acetate or nickel nitrate；Cobalt source is chlorination
The mixing of one or more of cobalt, cobalt acetate or cobalt nitrate arbitrary proportion；Manganese source is one in manganese chloride, manganese acetate or manganese nitrate
Kind or the mixing of several arbitrary proportions.
PH value is reconciled using ammonium hydroxide, sal volatile or ammonium bicarbonate soln in step (3).
The inlet temperature being spray-dried in step (3) is 150~200 DEG C, 200~700mL/h of charging rate.
The intake of oxygen is 8~10mL/min when two-section calcining under oxygen atmosphere in step (4).
Beneficial effects of the present invention: the present invention leaches recycling preparation process primarily directed to waste and old lithium ion battery, can be real
The problems such as now effectively alleviating poor, complicated for operation, precipitating reagent the use of stability in removal process, realization waste and old lithium ion battery
Positive electrode green high-efficient recycles, and the tertiary cathode material crystallinity of the method for the present invention preparation is high, stable structure, cyclicity
Can and high rate performance it is excellent, present invention process is simple, strong applicability, excellent product performance.
Detailed description of the invention
Fig. 1 is the charge-discharge property figure for the battery that the tertiary cathode material that embodiment 1 is prepared is prepared；
Fig. 2 is the tertiary cathode material SEM figure that embodiment 2 is prepared；
Fig. 3 is the cycle performance curve for the battery that the tertiary cathode material that embodiment 3 is prepared is prepared.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1
A kind of method that waste lithium cell recycling prepares tertiary cathode material, the waste lithium cell come from Shenzhen City, Guangdong Province
Certain returned enterprise, predominantly waste and old ternary power lithium battery, specifically comprises the following steps:
(1) waste and old lithium ion battery is put into remaining electricity, then disassembles isolated waste and old positive electrode through machinery；
(2) waste and old positive mix in step (1) is placed in reactor, pickling agent acetic acid, reducing agent glucose is added, and
Afterwards plus water obtains mixed liquor, and the mass volume ratio g:mL of positive electrode and water is 1:20, H in mixed liquor+Concentration is 1mol/L, also
The concentration of former agent is 1mol/L, and under agitation, 80 DEG C of reaction 2h, after reaction, filtering, filtrate is rich in having to mixed liquor
Your liquid of valence metal ion；
(3) lithium hydroxide, nickel chloride, cobalt chloride, manganese chloride are added into the filtrate of step (2), mixed solution is made, mix
Close solution in elemental lithium, nickel element, cobalt element, manganese element molar ratio be 1:0.6:0.2:0.2 so that obtained ternary material
Chemical formula be LiNi0.6Co0.2Mn0.2O2, adjusting mixed solution pH value with the ammonium hydroxide of mass percent concentration 28% is 2, stirring
Uniformly, mixed solution is spray-dried after, the inlet temperature of spray dryer is 170 DEG C, charging rate 500mL/h, system
Obtain ternary precursor powder；
It (4) is two-section calcining under 9mL/min atmosphere in oxygen intake by ternary precursor powder made from step (3),
First section calcining is in 480 DEG C of heat preservation 5h of temperature, and the first section calcining is in 850 DEG C of heat preservation 11h, and tertiary cathode is made in furnace cooling
Material.
Tertiary cathode material LiNi made from the present embodiment0.6Co0.2Mn0.2O2The charge and discharge for the first time for the battery being prepared
Electrical property is said as shown in Figure 1, from fig. 1, it can be seen that charge-discharge performance of the tertiary cathode material made from this method at 0.1C is excellent
Bright this method strong applicability.
Embodiment 2
A kind of method that waste lithium cell recycling prepares tertiary cathode material, waste lithium cell sample come from Yunnan Province Kunming
City's returned enterprise, sample are mainly waste mobile phone lithium battery, are specifically comprised the following steps:
(1) waste and old lithium ion battery is first put into remaining electricity, then manually disassembles isolated waste and old positive electrode；
(2) waste and old positive mix in step (1) is placed in reactor, pickling agent glycine, reducing agent Victoria C is added, and
Afterwards plus water obtains mixed liquor, and the mass volume ratio g:mL of positive electrode and water is 1:100, H in mixed liquor+Concentration is 5mol/L,
The concentration of reducing agent is 3mol/L, and under agitation, 100 DEG C of reaction 1h, after reaction, filtering, filtrate is richness to mixed liquor
Your liquid containing valuable metal ions；
(3) lithium hydroxide, nickel acetate, cobalt acetate, manganese acetate are added into the filtrate of step (2), mixed solution is made, mix
Close solution in elemental lithium, nickel element, cobalt element, manganese element molar ratio be 1:0.5:0.2:0.3 so that obtained ternary material
Chemical formula be LiNi0.5Co0.2Mn0.3O2, it is 3 that the sal volatile for being 0.5mol/L with concentration, which adjusts mixed solution pH value, is stirred
Mix uniformly, after mixed solution is spray-dried, the inlet temperature of spray dryer is 200 DEG C, charging rate 200mL/h,
Ternary precursor powder is made；
It (4) is two-section calcining under 10mL/min atmosphere in oxygen intake by ternary precursor powder made from step (3),
First section calcining is in 600 DEG C of heat preservation 4h of temperature, and the first section calcining is in 900 DEG C of heat preservation 10h, and tertiary cathode is made in furnace cooling
Material.
Tertiary cathode material LiNi made from the present embodiment0.5Co0.2Mn0.3O2SEM as shown in Fig. 2, as can be seen from Figure 2, should
Ternary lithium ion anode material made from method is spherical in shape, and structural behaviour is excellent.
Embodiment 3
A kind of method that waste lithium cell recycling prepares tertiary cathode material, waste lithium cell sample come from ChangSha, Hunan Province
City's returned enterprise, sample are mainly that waste and old ternary power is obtained with lithium battery, are specifically comprised the following steps:
(1) waste and old lithium ion battery is first put into remaining electricity, then obtains waste and old positive electrode through mechanical and manual joint dismantling；
(2) waste and old positive mix in step (1) is placed in reactor, pickling agent tartaric acid, reducing agent hydrazine hydrate is added,
Then plus water obtains mixed liquor, and the mass volume ratio g:mL of positive electrode and water is 1:10, H in mixed liquor+Concentration is 2mol/L,
The concentration of reducing agent be 2mol/L, mixed liquor under agitation, 60 DEG C of reaction 3h, after reaction, filtering, filtrate for rich in
Your liquid of valuable metal ions；
(3) lithium acetate, lithium chloride, nickel nitrate, nickel chloride, cobalt nitrate, cobalt acetate, chlorine are added into the filtrate of step (2)
Change manganese, mixed solution is made in manganese nitrate, the molar ratio of lithium acetate and lithium chloride is 1:1, and the molar ratio of nickel nitrate and nickel chloride is
The molar ratio of 1:1, cobalt nitrate and cobalt acetate is 1:1, and the molar ratio of manganese chloride and manganese nitrate is 1:1, elemental lithium in mixed solution,
Nickel element, cobalt element, manganese element molar ratio be 1:1/3:1/3:1/3 so that the chemical formula of obtained ternary material is
LiNi1/3Co1/3Mn1/3O2, it is 7 that the ammonium bicarbonate soln for being 1mol/L with concentration, which adjusts mixed solution pH value, it stirs evenly, after
Mixed solution is spray-dried, the inlet temperature of spray dryer is 150 DEG C, charging rate 700mL/h, before ternary is made
Drive body powder；
It (4) is two-section calcining under 8mL/min atmosphere in oxygen intake by ternary precursor powder made from step (3),
First section calcining is in 400 DEG C of heat preservation 6h of temperature, and the first section calcining is in 800 DEG C of heat preservation 12h, and tertiary cathode is made in furnace cooling
Material.
Tertiary cathode material LiNi made from the present embodiment1/3Co1/3Mn1/3O2The cycle performance for the battery being prepared is such as
Shown in Fig. 3, as can be seen from Figure 3, positive electrode is regenerated under 1C multiplying power, first circle specific discharge capacity reaches 171.21mAh/g, circulation 50
Enclosing capacity retention ratio is about 98.17%, and ternary lithium anode material cycle performance made from this method is excellent.
Claims (10)
1. a kind of method that waste lithium cell recycling prepares tertiary cathode material, which comprises the following steps:
(1) waste and old lithium ion battery is put into remaining electricity, disassembles isolated waste and old positive electrode；
(2) in the waste and old positive electrode of step (1) be added pickling agent, reducing agent, water, mixed liquor under agitation, 60~
100 DEG C of 1~3h of reaction, after reaction, filtering；
(3) lithium source, nickel source, cobalt source, manganese source are added into the filtrate of step (2), and mixed solution is made, elemental lithium in mixed solution,
Nickel element, cobalt element, manganese element molar ratio be 1:x:y:1-x-y, x > 0, y > 0, x+y < 1, adjust solution ph be 2~
7, it stirs evenly, then by the spray-dried obtained ternary precursor powder of mixed solution；
(4) ternary precursor powder two-section calcining under oxygen atmosphere made from step (3), the first section calcining is 400~600
DEG C heat preservation 4~6h, the second section calcining is in 800~900 DEG C of 10~12h of heat preservation, and tertiary cathode material is made in furnace cooling.
2. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(2) pickling agent is that one of acetic acid, oxalic acid, lactic acid, tartaric acid, glycine or a variety of arbitrary proportions mix in.
3. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(2) H in mixed liquor+Concentration is 1~5mol/L.
4. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(2) reducing agent is that one of glucose, grape pip, Victoria C, hydrazine hydrate, sodium borohydride or a variety of arbitrary proportions mix in.
5. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(2) concentration of reducing agent is 1~3mol/L in mixed liquor.
6. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(2) the mass volume ratio g:mL of positive electrode and water is 1:10~100.
7. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(3) lithium source is the arbitrary proportion mixing of one or more of lithium hydroxide, lithium carbonate, lithium chloride, lithium acetate or lithium nitrate in；Nickel
Source is the arbitrary proportion mixing of one or more of nickel chloride, nickel acetate or nickel nitrate；Cobalt source is cobalt chloride, cobalt acetate or nitric acid
The mixing of one or more of cobalt arbitrary proportion；Manganese source is any ratio of one or more of manganese chloride, manganese acetate or manganese nitrate
Example mixing.
8. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(3) pH value is reconciled using ammonium hydroxide, sal volatile or ammonium bicarbonate soln in.
9. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(3) inlet temperature being spray-dried in is 150~200 DEG C, and charging rate is 200~700mL/h.
10. the method that waste lithium cell recycling prepares tertiary cathode material according to claim 1, which is characterized in that step
(4) intake of oxygen is 8~10mL/min in.
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| CN113328161B (en) * | 2021-05-14 | 2022-06-03 | 昆明理工大学 | Method for preparing monocrystal-like ternary cathode material by regenerating waste lithium ion battery cathode material |
| CN113328161A (en) * | 2021-05-14 | 2021-08-31 | 昆明理工大学 | Method for preparing monocrystal-like ternary cathode material by regenerating waste lithium ion battery cathode material |
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