CN113904016A - Method for reconstructing single crystal electrode material from waste lithium ion battery - Google Patents
Method for reconstructing single crystal electrode material from waste lithium ion battery Download PDFInfo
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- CN113904016A CN113904016A CN202111181411.1A CN202111181411A CN113904016A CN 113904016 A CN113904016 A CN 113904016A CN 202111181411 A CN202111181411 A CN 202111181411A CN 113904016 A CN113904016 A CN 113904016A
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- lithium ion
- single crystal
- reconstructing
- waste lithium
- electrode material
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- 239000007772 electrode material Substances 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 239000013078 crystal Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- -1 transition metal salt Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000012216 screening Methods 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001479 atomic absorption spectroscopy Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 229910002993 LiMnO2 Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 claims description 2
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005530 etching Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 229910012623 LiNi0.5Co0.2 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910013292 LiNiO Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZJRWDIJRKKXMNW-UHFFFAOYSA-N carbonic acid;cobalt Chemical compound [Co].OC(O)=O ZJRWDIJRKKXMNW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Images
Classifications
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for reconstructing a single crystal electrode material from a waste lithium ion battery, which comprises the following steps: (1) carrying out short-circuit discharge, disassembly, crushing, roasting and screening on the waste lithium ion battery to obtain electrode active material powder; (2) treating the electrode active material powder obtained in the step (1) by adopting an alkaline solution, filtering and drying; (3) soaking the material obtained in the step (2) in an acid solution to etch the material, filtering and drying; (4) mixing the material obtained in the step (3) with transition metal salt and lithium salt, and ball-milling; (5) and (4) calcining the material obtained in the step (4) in an oxidizing atmosphere to obtain the regenerated single crystal electrode material. The method disclosed by the invention has the characteristics of simple process and good repeatability, is suitable for forming a closed-loop process, does not generate secondary pollution, gives consideration to environmental protection and economic benefits, has simple process and low production cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, in particular to a method for recovering a waste positive active material.
Background
With the rapid development of modern technology, the pollution problem of social energy and environment ecology becomes more and more prominent, and the pollution problem of various waste batteries to the environment and the ecology becomes the focus of social attention. Lithium ion batteries are widely used in power batteries and energy storage batteries due to their high capacity, stable cycle performance, high platform voltage, and the like, and the demand of power and energy storage batteries on battery materials is generally greater than that of conventional small batteries. Therefore, in the future 3-5 years, a large number of lithium ion batteries are scrapped, and the recycling of the lithium ion batteries has high social value.
However, the current domestic technical route for recycling the waste lithium ion batteries still has defects, and the main way for treating the electrode active materials of the waste lithium ion batteries is to obtain Li-containing materials by acidic reduction leaching+、Ni2+、Co2+、Mn2+、Al3+And Fe3+Precipitating the leachate of plasma to remove iron and aluminum, then adjusting the pH value to respectively obtain precipitates of single metal or nickel-cobalt-manganese precursors, and finally obtaining Li2CO3. Such as "Ni-Co-Mn acid" published in Chinese patent CN 104538695AA method for recovering valuable metals from lithium batteries and preparing nickel cobalt lithium manganate is characterized in that valuable metals in waste nickel cobalt lithium manganate batteries are recovered by an acid leaching method, electrode active materials are leached by inorganic acid to obtain leachate, iron and aluminum are precipitated and removed, then alkali is added to control different pH values to obtain precipitates corresponding to a single metal, and finally lithium is recovered. Also, as "a method for recovering anode powder of a waste lithium ion battery" disclosed in chinese patent CN 201810834647.2, a negative electrode material of a waste lithium ion battery is leached by using inorganic acid and hydrogen peroxide, then purified and decontaminated by using a precipitation method, and finally extracted and separated by using an extractant to obtain nickel salt, cobalt salt and manganese salt.
In addition, in the recovery process, organic metal elements are dissolved firstly and then synthesized, so that the recovery process is greatly increased, a large amount of acid or alkali is consumed in the recovery process, and secondary pollution is easily caused.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for reconstructing a single crystal electrode material from a waste lithium ion battery, which specifically comprises the following steps:
a method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) carrying out short-circuit discharge, disassembly, crushing, roasting and screening on the waste lithium ion battery to obtain electrode active material powder;
(2) treating the electrode active material powder obtained in the step (1) by adopting an alkaline solution, filtering and drying;
(3) soaking the material obtained in the step (2) in an acid solution to etch the material, filtering and drying;
(4) mixing the material obtained in the step (3) with transition metal salt and lithium salt, and ball-milling;
(5) and (4) calcining the material obtained in the step (4) in an oxidizing atmosphere to obtain the regenerated single crystal electrode material.
Specifically, the electrode active material in the step (1) is a Mn-free material or a Mn-containing material.
Specifically, the Mn-free material is LiNiO2、LiCoO2、LiNixCoyAl1-x-yO2At least one of; the Mn-containing material is LiMnO2、LiNixCoyMn1-x-yO2At least one of; wherein, 0<x<1；0<y<1。
Specifically, the alkaline solution in the step (2) is NaOH, NH4OH and KOH solution or a plurality of OH and KOH solutions; the pH value of the alkaline solution is 10-14, the treatment time of the materials in the alkaline solution is 10-60min, and the temperature is 20-50 ℃.
Specifically, the acidic solution in the step (3) is one or more of an inorganic acid solution or an organic acid solution, the soaking time is 5-30h, the temperature is 20-40 ℃, and the solid-to-liquid ratio is 1:20-1:200 g/L.
Specifically, the inorganic acid is H2SO4HCl or HNO3(ii) a The organic acid is citric acid, oxalic acid or acetic acid; the concentration of the acid is 0.1-0.5 mol/L.
Specifically, the step (4) is: measuring the content of lithium and transition metal elements in the material obtained in the step (3), and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain proportion according to a measurement result.
Specifically, the measurement method is atomic absorption spectrometry; the transition metal salt is one or more of hydroxide, carbonate or oxalate of nickel, cobalt or manganese; the lithium salt is one or more of lithium carbonate and strong oxide; the specific proportion is that the Li/(Ni + Co + Mn) molar ratio in the added mixed material is 1.05: 1.
Specifically, the calcining equipment in the step (5) is a tubular atmosphere furnace; the oxygen content in the oxidizing atmosphere is 20-80%; the calcination temperature is 600-1000 ℃, and the calcination time is 12-24 h.
Specifically, the oxygen content is 50-80%.
The invention has the beneficial effects that:
1) the invention innovatively discovers that a non-stoichiometric single crystal electrode material with low impurity content can be obtained by adopting dilute acid etching, and a stoichiometric regeneration electrode material with good crystallization performance and good micro-morphology can be successfully prepared by salt-supplementing high-temperature calcination;
2) the method can also be used for treating different types of waste lithium ion batteries without respectively recovering, has simple process and good process repeatability, is different from the prior method which is mostly only suitable for laboratories, and is particularly suitable for industrial scale-up production.
3) Compared with the existing waste lithium ion battery recovery technology, the method has the advantages that no harmful gas is generated in the treatment process, no protective atmosphere is needed, the reaction end point is easy to control, and the like. And a large amount of acid or alkali is not required to be consumed in the recovery process, so that the high-efficiency short-flow recovery of the waste battery materials from the solid phase to the solid phase can be realized, and the requirements on production equipment and the production cost in the whole recovery process can be greatly lowered.
4) The method is suitable for forming a closed-loop process, does not produce secondary pollution, has environmental protection and economic benefits, has simple process and low production cost, and is suitable for large-scale industrial production.
5) The method can be perfectly compatible with the existing lithium ion battery anode material production line. The single crystal electrode material obtained by etching-salt supplementing calcination can be directly used for preparing a packaged battery monomer, and short-flow high-value recovery and regeneration of valuable elements are realized.
Drawings
FIG. 1 is a schematic process flow diagram of the disclosed method;
FIG. 2(a) is an SEM image of the waste electrode material of example 8 after etching;
FIG. 2(b) is an SEM photograph of a single-crystal electrode material as reproduced in example 8.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings 1-2 and the detailed description thereof. The embodiments shown below do not limit the inventive content described in the claims. The entire contents of the configurations shown in the following embodiments are not limited to those required as solutions of the inventions described in the claims.
Example 1
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiNiO is used2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) soaking the electrode active material powder obtained in the step (1) in a NaOH solution with the pH value of 10 for 10min, wherein the solution temperature is 20 ℃, and then filtering and drying;
(3) soaking and etching the material obtained in the step (2) in an inorganic acid solution with the concentration of 0.1mol/L and the temperature of 20 ℃ for 5 hours, wherein the solid-to-liquid ratio is 1: 20; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3), and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain proportion according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (4) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 20-80% for 12h at 600 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 2
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiCoO2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) adopting NH with the pH value of 12 to the electrode active material powder obtained in the step (1)4Soaking in OH solution at 35 deg.C for 30minThen filtering and drying;
(3) soaking and etching the material obtained in the step (2) in an organic acid solution with the concentration of 0.3mol/L and the temperature of 30 ℃ for 15h, wherein the solid-to-liquid ratio is 1: 100; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain ratio according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (4) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 50-80% for 18h at 800 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 3
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiNi0.5Co0.2Al0.3O2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) soaking the electrode active material powder obtained in the step (1) in a KOH solution with the pH value of 14 for 60min, wherein the solution temperature is 50 ℃, and then filtering and drying;
(3) soaking and etching the material obtained in the step (2) in a sulfuric acid solution with the concentration of 0.5mol/L and the temperature of 40 ℃ for 30 hours, wherein the solid-to-liquid ratio is 1: 200; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain ratio according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (5) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 60% for 24h, wherein the calcining temperature is 1000 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 4
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiMnO2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) soaking the electrode active material powder obtained in the step (1) in NaOH solution with the pH value of 14 for 50min, wherein the solution temperature is 30 ℃, and then filtering and drying;
(3) soaking and etching the material obtained in the step (2) in a hydrochloric acid solution with the concentration of 0.4mol/L and the temperature of 25 ℃ for 25 hours, wherein the solid-to-liquid ratio is 1: 70; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain ratio according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (5) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 80% for 15h, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 5
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiMnO2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) soaking the electrode active material powder obtained in the step (1) in NaOH solution with the pH value of 14 for 50min, wherein the solution temperature is 30 ℃, and then filtering and drying;
(3) soaking and etching the material obtained in the step (2) in a nitric acid solution with the concentration of 0.4mol/L and the temperature of 25 ℃ for 25 hours, wherein the solid-to-liquid ratio is 1: 70; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain ratio according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (5) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 80% for 15h, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 6
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiMnO2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) soaking the electrode active material powder obtained in the step (1) in NaOH solution with the pH value of 14 for 50min, wherein the solution temperature is 30 ℃, and then filtering and drying;
(3) soaking and etching the material obtained in the step (2) in a citric acid solution with the concentration of 0.4mol/L and the temperature of 25 ℃ for 25 hours, wherein the solid-to-liquid ratio is 1: 70; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain ratio according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (5) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 80% for 15h, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 7
A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) waste LiMnO2The lithium ion battery is subjected to short-circuit discharge, disassembly, crushing, roasting and screening to obtain electrode active material powder;
(2) soaking the electrode active material powder obtained in the step (1) in NaOH solution with the pH value of 14 for 50min, wherein the solution temperature is 30 ℃, and then filtering and drying;
(3) soaking and etching the material obtained in the step (2) in a mixed solution of acetic acid and hydrochloric acid with the total concentration of 0.4mol/L and the temperature of 25 ℃ for 25 hours, wherein the solid-to-liquid ratio is 1: 70; then filtering and drying;
(4) measuring the content of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain ratio according to a measurement result, wherein the molar ratio of Li/(Ni + Co + Mn) in the mixed material is 1.05: 1;
(5) and (5) calcining the material obtained in the step (4) in an oxidizing atmosphere with oxygen content of 80% for 15h, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated single crystal electrode material.
Example 8
Waste LiNi0.5Co0.2Mn0.3O2And (3) soaking the ternary lithium ion battery in 5% sulfurous acid solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, and then performing mechanical force integral crushing and screening to obtain crushed materials (battery cell mixture) with the particle size of less than 0.1 mm. The obtained crushed aggregates are etched by dilute acid, and the specific parameters are as follows: 0.1mol/LH2SO4The solid-liquid ratio is 1:50g/L, the time is 16h, and the temperature is 35 ℃. The elemental composition of the etched powder was then measured as the molar ratio Li/(Ni + Co + Mn) 1.05:1 to Li2CO3、NiCO3、CoCO3、MnCO3Mixing and putting into a planetary ball mill for ball milling, wherein the specific parameters are as follows: the ball milling time is 2h, and the ball milling rotating speed is 400 r/m. After the ball milling is finished, the obtained sample is subjected to aerobic atmosphere high-temperature calcination, and the specific technological parameters are as follows: oxygen content is 50%, temperature is 800 ℃, and time is 20 h. The SEM image of the reconstructed single crystal electrode material is shown in FIG. 2.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for reconstructing a single crystal electrode material from a waste lithium ion battery is characterized by comprising the following steps:
(1) carrying out short-circuit discharge, disassembly, crushing, roasting and screening on the waste lithium ion battery to obtain electrode active material powder;
(2) treating the electrode active material powder obtained in the step (1) by adopting an alkaline solution, filtering and drying;
(3) soaking the material obtained in the step (2) in an acid solution to etch the material, filtering and drying;
(4) mixing the material obtained in the step (3) with transition metal salt and lithium salt, and ball-milling;
(5) and (4) calcining the material obtained in the step (4) in an oxidizing atmosphere to obtain the regenerated single crystal electrode material.
2. The method for reconstructing single crystal electrode material from waste lithium ion batteries according to claim 1, wherein the electrode active material in the step (1) is Mn-free material or Mn-containing material.
3. The method for reconstructing single crystal electrode material from waste lithium ion batteries as claimed in claim 2, wherein the Mn-free material is LiNiO2、LiCoO2、LiNixCoyAl1-x-yO2At least one of; the Mn-containing material is LiMnO2、LiNixCoyMn1-x-yO2At least one of; wherein, 0<x<1；0<y<1。
4. The method for reconstructing single crystal electrode material from waste lithium ion batteries according to claim 1, wherein the alkaline solution in the step (2) is NaOH or NH4OH and KOH solution or a plurality of OH and KOH solutions; the pH value of the alkaline solution is between 10 and 14The treatment time of the materials in the alkaline solution is 10-60min, and the temperature is 20-50 ℃.
5. The method for reconstructing the single crystal electrode material from the waste lithium ion battery as claimed in claim 1, wherein the acidic solution in the step (3) is one or more of an inorganic acid solution or an organic acid solution, the soaking time is 5-30h, the temperature is 20-40 ℃, and the solid-to-liquid ratio is 1:20-1:200 g/L.
6. The method for reconstructing single crystal electrode material from waste lithium ion batteries as claimed in claim 5, wherein the inorganic acid is H2SO4HCl or HNO3(ii) a The organic acid is citric acid, oxalic acid or acetic acid; the concentration of the acid is 0.1-0.5 mol/L.
7. The method for reconstructing the single crystal electrode material from the waste lithium ion battery as claimed in claim 1, wherein the step (4) is: measuring the content of lithium and transition metal elements in the material obtained in the step (3), and then fully ball-milling and mixing the material obtained in the step (3) with transition metal salt and lithium salt according to a certain proportion according to a measurement result.
8. The method for reconstructing single crystal electrode material from waste lithium ion batteries according to claim 7, wherein the measuring method is atomic absorption spectrometry; the transition metal salt is one or more of hydroxide, carbonate or oxalate of nickel, cobalt or manganese; the lithium salt is one or more of lithium carbonate and strong oxide; the specific proportion is that the Li/(Ni + Co + Mn) molar ratio in the added mixed material is 1.05: 1.
9. The method for reconstructing the single crystal electrode material from the waste lithium ion battery as claimed in any one of claims 1 to 8, wherein the calcining device in the step (5) is a tubular atmosphere furnace; the oxygen content in the oxidizing atmosphere is 20-80%; the calcination temperature is 600-1000 ℃, and the calcination time is 12-24 h.
10. The method for reconstructing single crystal electrode material from waste lithium ion batteries as claimed in claim 9, wherein the oxygen content is 50-80%.
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