CN113904016B - 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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- CN113904016B CN113904016B CN202111181411.1A CN202111181411A CN113904016B CN 113904016 B CN113904016 B CN 113904016B CN 202111181411 A CN202111181411 A CN 202111181411A CN 113904016 B CN113904016 B CN 113904016B
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- ion battery
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- 239000007772 electrode material Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 60
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 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 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- -1 transition metal salt Chemical class 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 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
- 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
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 229910014689 LiMnO Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910032387 LiCoO2 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
- 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 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 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 3
- 239000003513 alkali Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010926 waste battery 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 239000003929 acidic solution 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
- 238000003837 high-temperature calcination Methods 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
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 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
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
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 batteries 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 etching material in the acid solution, filtering and drying the material obtained in the step (2); (4) Mixing and ball milling the material obtained in the step (3) with transition metal salt and lithium salt; (5) And (3) calcining the material obtained in the step (4) in an oxidizing atmosphere to obtain the regenerated monocrystalline electrode material. The method disclosed by the invention has the characteristics of simple process and good repeatability, is suitable for forming a closed-circuit process, does not produce secondary pollution, has the advantages of environmental protection and economic benefit, is simple in process, low in 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 waste positive electrode active materials.
Background
With the rapid development of modern technology, the problems of social energy and environmental ecological pollution are increasingly prominent, and the pollution problem of various waste batteries to the environment and ecology has become the focus of social attention. The lithium ion battery is widely applied to the power battery and the energy storage battery due to the characteristics of high capacity, stable cycle performance, high voltage of a working platform and the like, and the requirements of the power battery and the energy storage battery on battery materials are generally larger than those of a conventional small battery. Therefore, in the future 3-5 years, a large number of lithium ion batteries are scrapped, and the recovery of the lithium ion batteries has high social value.
However, the current technical route for recycling the waste lithium ion batteries in China still has the defect that the main flow mode for treating the electrode active material of the waste lithium ion batteries is acid reduction leaching to obtain leaching liquid containing Li +、Ni2+、Co2+、Mn2+、Al3+ and Fe 3+ plasma, iron and aluminum are precipitated, then the pH value is adjusted to obtain single metal precipitate or nickel-cobalt-manganese precursor respectively, and finally Li 2CO3 is obtained. The method for recovering valuable metals from nickel cobalt lithium manganate batteries and preparing nickel cobalt lithium manganate is disclosed in Chinese patent CN 104538695A, and the method is used for recovering valuable metals from nickel cobalt lithium manganate waste batteries by an acid leaching method, firstly, leaching electrode active materials by inorganic acid to obtain leaching liquid, precipitating iron and aluminum, then adding alkali to control different pH values to obtain precipitates corresponding to single metals, and finally recovering lithium. As another "a method for recovering anode powder of waste lithium ion battery" published in chinese patent CN 201810834647.2, inorganic acid and hydrogen peroxide are used to leach anode material of waste lithium ion battery, then precipitation method is used to purify and remove impurities, and finally extractant is used to extract and separate nickel salt, cobalt salt and manganese salt.
In addition, the organic metal element is dissolved first and then synthesized in the recovery process, so that the recovery process is greatly increased, a large amount of acid or alkali is required to be consumed in the recovery process, and secondary pollution is easy to generate.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for reconstructing a single crystal electrode material from a waste lithium ion battery, which comprises the following steps:
The method for reconstructing the single crystal electrode material from the 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 batteries 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 etching material in the acid solution, filtering and drying the material obtained in the step (2);
(4) Mixing and ball milling the material obtained in the step (3) with transition metal salt and lithium salt;
(5) And (3) calcining the material obtained in the step (4) in an oxidizing atmosphere to obtain the regenerated monocrystalline 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 at least one of LiNiO 2、LiCoO2、LiNixCoyAl1-x-yO2; the Mn-containing material is at least one of LiMnO 2、LiNixCoyMn1-x-yO2; wherein 0< x <1;0< y <1.
Specifically, the alkaline solution in the step (2) is one or more of NaOH, NH 4 OH and KOH solution; the PH value of the alkaline solution is between 10 and 14, the treatment time of the materials in the alkaline solution is between 10 and 60 minutes, and the temperature is between 20 and 50 ℃.
Specifically, the acidic solution in the step (3) is one or more of an inorganic acid solution and an organic acid solution, the soaking time is 5-30h, the temperature is 20-40 ℃, and the solid-liquid ratio is 1:20-1:200g/L.
Specifically, the inorganic acid is H 2SO4, HCl or HNO 3; the organic acid is citric acid, oxalic acid or acetic acid; the concentration of the acid is 0.1-0.5mol/L.
Specifically, the step (4) is as follows: firstly 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 measured 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 carbonate and strong oxide of lithium; the specific proportion is that the Li/(Ni+Co+Mn) molar ratio in the added mixture 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 12-24h.
Specifically, the oxygen content is 50-80%.
The invention has the beneficial effects that:
1) The invention innovatively discovers that the non-metering ratio single crystal electrode material with low impurity content can be obtained by adopting dilute acid etching, and the metering ratio regenerated electrode material with good crystallization performance and micro morphology can be successfully prepared by high-temperature calcination of the supplementary salt;
2) The method can be used for treating waste lithium ion batteries of different types, does not need to be recycled respectively, has simple process and good process repeatability, and is particularly suitable for industrial scale-up production unlike the existing method which is mostly only suitable for laboratories.
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, protective atmosphere is not needed, the reaction end point is easy to control, and the like. And the recovery process does not need to consume a large amount of acid or alkali, so that the high-efficiency short-process recovery from the solid phase to the solid phase of the waste battery material can be realized, and the requirements on production equipment and the production cost of the whole recovery process can be greatly reduced.
4) The method is suitable for forming a closed-circuit flow, does not produce secondary pollution, has the advantages of environmental protection and economic benefit, 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 monocrystalline electrode material obtained by etching-salt supplementing calcination can be directly used for preparing packaging battery monomers, and realizes short-flow high-value recovery and regeneration of valuable elements.
Drawings
FIG. 1 is a schematic process flow diagram of the disclosed method;
FIG. 2 (a) is an SEM image of example 8 after etching of spent electrode material;
Fig. 2 (b) is an SEM image of the single crystal electrode material manufactured in example 8.
Detailed Description
The invention will now be described in detail with reference to figures 1-2 and the detailed description. The embodiments shown below do not limit the inventive content described in the claims in any way. The whole contents of the constitution shown in the following examples are not limited to the solution of the invention described in the claims.
Example 1
The method for reconstructing the single crystal electrode material from the 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 LiNiO 2 lithium ion battery 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 10 for 10min at the temperature of 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-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 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 measured result, wherein the molar ratio of Li/(Ni+Co+Mn) in the mixed material is 1.05:1;
(5) And (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 20-80% to calcine for 12 hours at the calcination temperature of 600 ℃ to finally obtain the regenerated monocrystalline electrode material.
Example 2
The method for reconstructing the single crystal electrode material from the 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 LiCoO 2 lithium ion battery to obtain electrode active material powder;
(2) Soaking the electrode active material powder obtained in the step (1) in NH 4 OH solution with the pH value of 12 for 30min at the temperature of 35 ℃, and then 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 15 hours, wherein the solid-to-liquid ratio is 1:100; then filtering and drying;
(4) Measuring the contents of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and 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 (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 50-80% to calcine for 18h at the temperature of 800 ℃ to finally obtain the regenerated monocrystalline electrode material.
Example 3
The method for reconstructing the single crystal electrode material from the 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 LiNi 0.5Co0.2Al0.3O2 lithium ion battery to obtain electrode active material powder;
(2) Soaking the electrode active material powder obtained in the step (1) in KOH solution with the pH value of 14 for 60min at the temperature of 50 ℃, and then filtering and drying;
(3) Soaking and etching the material obtained in the step (2) in 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 contents of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and 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 (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 60% to be calcined for 24 hours, wherein the calcining temperature is 1000 ℃, and finally obtaining the regenerated monocrystalline electrode material.
Example 4
The method for reconstructing the single crystal electrode material from the 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 LiMnO 2 lithium ion battery 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 at the temperature of 30 ℃, and then filtering and drying;
(3) Soaking and etching the material obtained in the step (2) in 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 contents of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and 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 (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 80% to be calcined for 15 hours, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated monocrystalline electrode material.
Example 5
The method for reconstructing the single crystal electrode material from the 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 LiMnO 2 lithium ion battery 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 at the temperature of 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 contents of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and 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 (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 80% to be calcined for 15 hours, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated monocrystalline electrode material.
Example 6
The method for reconstructing the single crystal electrode material from the 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 LiMnO 2 lithium ion battery 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 at the temperature of 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 contents of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and 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 (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 80% to be calcined for 15 hours, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated monocrystalline electrode material.
Example 7
The method for reconstructing the single crystal electrode material from the 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 LiMnO 2 lithium ion battery 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 at the temperature of 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-liquid ratio is 1:70; then filtering and drying;
(4) Measuring the contents of lithium and transition metal elements in the material obtained in the step (3) by using an atomic absorption spectrometry, and 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 (3) placing the material obtained in the step (4) into an oxidizing atmosphere with the oxygen content of 80% to be calcined for 15 hours, wherein the calcining temperature is 700 ℃, and finally obtaining the regenerated monocrystalline electrode material.
Example 8
And (3) immersing the waste LiNi 0.5Co0.2Mn0.3O2 ternary lithium ion battery in a 5% sulfurous acid solution until the discharge termination voltage is 1V, disassembling to obtain a battery cell, and then carrying out integral mechanical crushing and screening to obtain crushed aggregates (battery cell mixture) with the particle size smaller than 0.1 mm. The crushed aggregates are etched by dilute acid, and the specific parameters are as follows: 0.1mol/LH 2SO4, solid-to-liquid ratio of 1:50g/L, time 16h, temperature 35 ℃. Then, the element components of the etched powder are measured, mixed with Li 2CO3、NiCO3、CoCO3、MnCO3 according to the mol ratio Li/(Ni+Co+Mn) =1.05:1, and put into a planetary ball mill for ball milling, and specific parameters are as follows: ball milling time is 2h, and ball milling rotating speed is 400 rpm. After ball milling is completed, the obtained sample is calcined at high temperature under the oxygen atmosphere, and the specific process parameters are as follows: oxygen content 50%, temperature 800 ℃ and time 20h. An SEM image of the resulting reconstituted 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 (7)
1. The method for reconstructing the single crystal electrode material from the 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 batteries 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; the alkaline solution is one or more of NaOH, NH 4 OH and KOH solution; the pH value of the alkaline solution is between 10 and 12, the treatment time of the electrode active material powder in the alkaline solution is 10 to 60 min, and the temperature is 20 to 50 ℃;
(3) Soaking, etching, filtering and drying the material obtained in the step (2) in an acid solution; the acid solution is one or more of an inorganic acid solution and an organic acid solution, the concentration of acid in the acid solution is 0.1-0.5 mol/L, the soaking time is 5-30h, the temperature is 20-40 ℃, and the solid-liquid ratio is 1:20-1:200 g/L;
(4) Firstly measuring the content of lithium and transition metal elements in the material obtained in the step (3), and 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 measured result;
(5) And (3) calcining the material obtained in the step (4) in an oxidizing atmosphere to obtain the regenerated monocrystalline electrode material.
2. The method for reconstructing single-crystal electrode materials from waste lithium ion batteries according to claim 1, wherein the electrode active material in the step (1) is a Mn-free material or a Mn-containing material.
3. The method for reconstructing a single crystal electrode material from a spent lithium ion battery according to claim 2, wherein said Mn-free material is at least one of LiNiO 2、LiCoO2、LiNixCoyAl1-x-yO2; the Mn-containing material is at least one of LiMnO 2、LiNixCoyMn1-x-yO2; wherein 0< x <1;0< y <1.
4. The method for reconstructing a single crystal electrode material from a waste lithium ion battery according to claim 1, wherein the inorganic acid is H 2SO4, HCl or HNO 3; the organic acid is citric acid, oxalic acid or acetic acid.
5. The method for reconstructing single crystal electrode materials from waste lithium ion batteries according to claim 1, wherein the method measured in said step (4) 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 carbonate and strong oxide of lithium; the certain proportion is as follows: the addition was carried out in such a way that the molar ratio of Li/(Ni+Co+Mn) in the mixture after the addition was 1.05:1.
6. The method for reconstructing single crystal electrode materials from waste lithium ion batteries according to any one of claims 1 to 5, wherein said calcining apparatus in step (5) is a tube atmosphere furnace; the oxygen content in the oxidizing atmosphere is 20-80%; the calcination temperature is 600-1000 ℃ and the calcination time is 12-24h.
7. The method for reconstructing a single crystal electrode material from a spent lithium ion battery according to claim 6, wherein the oxygen content is 50-80%.
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