WO2022166197A1 - Direct repair method for waste lithium-ion battery ternary positive electrode material - Google Patents
Direct repair method for waste lithium-ion battery ternary positive electrode material Download PDFInfo
- Publication number
- WO2022166197A1 WO2022166197A1 PCT/CN2021/117439 CN2021117439W WO2022166197A1 WO 2022166197 A1 WO2022166197 A1 WO 2022166197A1 CN 2021117439 W CN2021117439 W CN 2021117439W WO 2022166197 A1 WO2022166197 A1 WO 2022166197A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- positive electrode
- ternary
- ion battery
- electrode material
- lithium
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- 230000008439 repair process Effects 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 238000003837 high-temperature calcination Methods 0.000 claims description 12
- 239000010406 cathode material Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000009616 inductively coupled plasma Methods 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 238000004611 spectroscopical analysis Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000011403 purification operation Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 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
- 238000012216 screening Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- 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
- 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
Definitions
- the invention belongs to the technical field of solid-phase regeneration of positive electrode materials of waste and used lithium ion batteries, and particularly relates to a direct repair method for ternary positive electrode materials of waste and used lithium ion batteries.
- lithium-ion batteries have outstanding advantages such as high energy density, long cycle life, and environmental friendliness.
- Li-ion batteries also show unlimited potential in electrochemical energy storage and conversion, driving a new revolution in portable electronic devices.
- lithium-ion batteries With the rapid development of electric vehicles, lithium-ion batteries have become the most widely used power battery technology in electric vehicles.
- the service life of ternary lithium-ion batteries is 8 to 10 years. When the life of these batteries expires, if they cannot be used in a cascade, and they are not recycled and reused, millions of tons of waste batteries will be generated, which will inevitably lead to The environment causes serious pollution, and it is also a huge waste of resources.
- the main recycling methods of industrial waste ternary lithium-ion batteries are fire method and wet method.
- the fire method is to recover battery materials by heat treatment.
- the process is relatively simple, but there are problems such as low recovery rate and environmental pollution.
- the wet method realizes the recycling and reuse of battery materials through low-temperature leaching, purification and separation. But the recycling process is complicated. Therefore, it is very necessary to provide a direct repair method for the ternary cathode material of waste lithium ion batteries to solve the above technical problems.
- the present invention provides a direct repair method for the ternary positive electrode material of waste lithium ion batteries.
- a method for directly repairing a ternary positive electrode material of a waste lithium ion battery comprising the following steps:
- Step 1 disassemble the waste lithium-ion battery under the protection of inert gas, and remove the outer casing, the positive and negative terminals, the sealing ring and the cover plate;
- Step 2 Separating the positive and negative electrode sheets, soaking with dimethyl carbonate to remove the electrolyte, and then soaking the positive electrode sheets with an organic solvent at 100°C for 2 to 4 hours, removing the binder, peeling off the positive electrode material, and drying after centrifugation. Dry to obtain waste ternary cathode material;
- step 3 the waste ternary positive electrode material obtained in step 2 is fully washed with organic solvent for 4-8 hours, then washed with ethanol for 1-2 times, and dried after centrifugation to obtain the ternary material to be repaired;
- Step 4 grind the ternary material to be repaired obtained in step 3, and then use 80-mesh, 200-mesh and 400-mesh sieves in sequence to remove impurities to obtain ternary powder to be repaired with uniform particle size;
- Step 5 analyze the composition of the ternary powder to be repaired after the treatment in Step 4, and determine the contents of nickel, cobalt, manganese and lithium elements;
- Step 6 replenish the missing elements of the ternary powder to be repaired in proportion, and after uniform mixing, perform high-temperature calcination treatment under different atmospheric conditions;
- Step 7 After the high-temperature calcination treatment is completed, cool down to room temperature, and take out the black solid for grinding to obtain a repaired ternary positive electrode material.
- the cathode ternary material of the waste lithium-ion battery is the waste NCM523 or NCM622 material that has been cycled about 2000 times.
- organic solvent described in step 2 and step 3 is N-methylpyrrolidone.
- step 4 the time of the grinding treatment is 30min.
- the composition analysis method is as follows: weighing 20-40 mg of the solid substance, fully dissolving it with 1 mL of aqua regia, diluting the volume to 1 L with distilled water, and using inductively coupled plasma spectroscopy (ICP) test to determine. content of each element.
- ICP inductively coupled plasma spectroscopy
- step 6 the lithium salt is supplemented in a ratio of 1.05:1 according to the ratio of the total molar amount of lithium to (nickel, cobalt and manganese).
- the supplemented lithium source comes from one of LiOH or Li 2 CO 3 .
- step 6 the uniform mixing method of the repairing ternary powder and the lithium source is one of ball milling for 4-6 hours or manual grinding for 30-60 minutes.
- the atmospheric condition of high temperature calcination is one of oxygen or air atmosphere.
- the high temperature calcination conditions in step 6 are as follows: the temperature is 500-800° C., and the time is 12-20 h.
- the high-temperature calcination process in step 6 is as follows: the temperature is 500° C. for 4 hours, and then the temperature is raised to 800° C. for 16 hours.
- the present invention has the following beneficial effects: the present invention utilizes the high-temperature solid-phase sintering method to directly repair the ternary positive electrode material, which has the advantages of simplicity and high efficiency, avoids the tedious separation and purification operations in the traditional fire method and wet method recovery process, and improves the material quality. Utilization rate, reducing recycling costs. And the method provided by the invention successfully reduces the Li-Ni mixed arrangement caused by the cycle, and repairs the damaged layered crystal structure. The repaired ternary cathode material has the characteristics of high discharge specific capacity and good cycle performance. In addition, the method provided by the present invention also has the advantages of simplicity, good repeatability, low cost and high yield, and has good potential for large-scale application.
- Fig. 1 is the XRD pattern before and after the repair of NCM523 material in example 1;
- Fig. 2 is the XRD pattern before and after the repair of NCM622 material in example 2;
- Fig. 3 is the Raman spectrum before and after the repair of NCM523 material in example 1;
- Fig. 4 is the Raman spectrum before and after the repair of NCM622 material in example 2;
- Fig. 5 is the scanning electron microscope image after NCM523 material repair in example 1;
- Fig. 6 is the scanning electron microscope picture after NCM622 material repair in example 2;
- Fig. 7 is the discharge curve diagram before and after the repair of NCM523 material in Example 1;
- Fig. 8 is the discharge curve diagram before and after the repair of NCM622 material in Example 2;
- Fig. 9 is the galvanostatic cycle performance diagram before and after the repair of NCM523 material in Example 1;
- Fig. 10 is the galvanostatic cycle performance diagram before and after the repair of NCM622 material in Example 2;
- Example 11 is a graph of the rate performance of the NCM523 repaired in Example 1 and the NCM622 material repaired in Example 2.
- the experimental methods used in the following examples are conventional methods unless otherwise specified.
- the used materials, reagents, methods and instruments, unless otherwise specified, are conventional materials, reagents, methods and instruments in the art, which can be obtained by those skilled in the art through commercial channels.
- the tube furnace is cooled to room temperature, and the black solid is taken out for grinding and screening to obtain the repaired NCM523 positive electrode material.
- Figure 1 is the XRD comparison diagram of the NCM523 material before and after the repair in this example
- Figure 3 is the NCM523 material
- the Raman spectra before and after repair, Figure 1 and Figure 3 show that the layered crystal structure of the repaired NCM523 material has been significantly restored, and the Li-Ni mixing has been significantly improved.
- Figure 5 shows the morphology of the repaired material.
- the tube furnace is cooled to room temperature, and the black solid is taken out for grinding and screening to obtain the repaired NCM622 positive electrode material.
- Figure 2 is the XRD comparison of the NCM622 material before and after the repair in this example
- Figure 4 is the NCM622 material
- the Raman spectra before and after repair, Figures 2 and 4 show that the layered crystal structure of the repaired NCM622 material is significantly restored, and the Li-Ni mixing is significantly improved.
- Figure 6 shows the morphology of the repaired material.
- Figure 8 shows that the first-cycle discharge specific capacity of the lithium-ion battery fabricated with the repaired NCM622 material increases from 96.72 mAh/g to 198.81 mAh/g at a current density of 0.1 C.
- Figure 10 shows that the capacity of the lithium-ion battery made of the repaired NCM622 material remains at 128.58mAh/g after 100 cycles at a current density of 1C. It can be seen from Figure 11 that the repaired NCM622 material exhibits good rate performance.
- Example 1 The only difference between this example and Example 1 is that the method for mixing the lithium source and the material in step 6 is manual grinding for 30-60 minutes, and the rest of the operation steps are the same as those in Example 1.
- Example 2 The only difference between this example and Example 2 is that the method of mixing the lithium source and the material in step 6 is manual grinding for 30-60 minutes, and the rest of the operation steps are the same as those in Example 2.
- step 6 Li 2 CO 3 is supplemented in a ratio of 1.05:1 to the total molar ratio of lithium to nickel, cobalt and manganese, and the rest of the operation steps are the same as those of embodiment 1.
- step 6 Li 2 CO 3 is supplemented in a ratio of 1.05:1 to the total molar ratio of lithium to nickel, cobalt and manganese, and the rest of the operation steps are the same as those of embodiment 2.
Landscapes
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to the technical field of solid-phase regeneration of waste lithium-ion battery positive electrode materials. Disclosed is a direct repair method for a waste lithium-ion battery ternary positive electrode material. The present invention solves the problem of complicated separation and purification operations in the process of recovering lithium-ion battery ternary positive electrode materials by means of conventional dry methods and wet methods. By repairing a ternary positive electrode material directly by using a high-temperature solid-phase sintering method, the present invention has the advantages of simplicity and high efficiency, increases the utilization rate of the material, lowers recovery cost, successfully reduces Li-Ni mixed discharge caused by cycles, and repairs a damaged layered crystal structure, and the repaired ternary positive electrode material has the characteristics of high specific discharge capacity, good cycle performance, etc. In addition, the method provided by the present invention also has the advantages of simplicity, good repeatability, low cost, and high yield, and has good potential for large-scale application.
Description
本申请要求于2021年02月05日提交中国专利局、申请号为202110161218.5、发明名称为“一种废旧锂离子电池三元正极材料的直接修复方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed on February 5, 2021 with the application number of 202110161218.5 and the invention titled "A method for direct repair of ternary cathode materials for waste lithium-ion batteries", the entire contents of which are Incorporated herein by reference.
本发明属于废旧锂离子电池正极材料固相再生技术领域，具体涉及一种废旧锂离子电池三元正极材料的直接修复方法。The invention belongs to the technical field of solid-phase regeneration of positive electrode materials of waste and used lithium ion batteries, and particularly relates to a direct repair method for ternary positive electrode materials of waste and used lithium ion batteries.
锂离子电池作为21世纪电池系统的首选技术，具有能量密度高、循环寿命长、环境友好等突出优势。此外，锂离子电池在电化学储能和转换方面也显示出无限的潜力，推动了便携式电子设备的新革命。随着电动汽车的飞速发展，锂离子电池也成为电动汽车中应用最广泛的动力电池技术。通常三元锂离子电池的使用寿命为8～10年，当这些电池寿命终止时，如不能够梯次利用，又不对其进行回收和再利用，将产生上百万吨的废电池，势必会对环境造成严重的污染，同时也是对资源的巨大浪费。As the preferred technology for battery systems in the 21st century, lithium-ion batteries have outstanding advantages such as high energy density, long cycle life, and environmental friendliness. In addition, Li-ion batteries also show unlimited potential in electrochemical energy storage and conversion, driving a new revolution in portable electronic devices. With the rapid development of electric vehicles, lithium-ion batteries have become the most widely used power battery technology in electric vehicles. Usually, the service life of ternary lithium-ion batteries is 8 to 10 years. When the life of these batteries expires, if they cannot be used in a cascade, and they are not recycled and reused, millions of tons of waste batteries will be generated, which will inevitably lead to The environment causes serious pollution, and it is also a huge waste of resources.
目前，工业上废旧三元锂离子电池的主要回收再利用方法为火法和湿法。火法是通过热处理的方式来回收电池材料，其工艺过程比较简单，但存在回收率低，容易造成环境污染等问题；湿法是通过低温浸出，纯化和分离来实现电池材料的回收再利用，但再利用工艺复杂。因此，提供一种废旧锂离子电池三元正极材料的直接修复方法来解决上述技术问题是十分必要的。At present, the main recycling methods of industrial waste ternary lithium-ion batteries are fire method and wet method. The fire method is to recover battery materials by heat treatment. The process is relatively simple, but there are problems such as low recovery rate and environmental pollution. The wet method realizes the recycling and reuse of battery materials through low-temperature leaching, purification and separation. But the recycling process is complicated. Therefore, it is very necessary to provide a direct repair method for the ternary cathode material of waste lithium ion batteries to solve the above technical problems.
发明内容SUMMARY OF THE INVENTION
本发明为了解决上述技术问题，提供一种废旧锂离子电池三元正极材料的直接修复方法。In order to solve the above-mentioned technical problems, the present invention provides a direct repair method for the ternary positive electrode material of waste lithium ion batteries.
本发明的技术方案：Technical scheme of the present invention:
一种废旧锂离子电池三元正极材料的直接修复方法，该方法包括以下步骤：A method for directly repairing a ternary positive electrode material of a waste lithium ion battery, the method comprising the following steps:
步骤一，将废旧锂离子电池在惰性气体保护下进行拆解，除去外壳、 正负极端子、密封圈及盖板；Step 1, disassemble the waste lithium-ion battery under the protection of inert gas, and remove the outer casing, the positive and negative terminals, the sealing ring and the cover plate;
步骤二，将正负极片分离，使用碳酸二甲酯浸泡去除电解液，然后在100℃条件下，使用有机溶剂浸泡正极片2～4h，去除粘结剂，剥离出正极材料，离心后烘干获得废旧三元正极材料；Step 2: Separating the positive and negative electrode sheets, soaking with dimethyl carbonate to remove the electrolyte, and then soaking the positive electrode sheets with an organic solvent at 100°C for 2 to 4 hours, removing the binder, peeling off the positive electrode material, and drying after centrifugation. Dry to obtain waste ternary cathode material;
步骤三，将步骤二获得的废旧三元正极材料使用有机溶剂充分洗涤4～8h，再使用乙醇洗涤1～2次，离心后烘干获得待修复三元材料；In step 3, the waste ternary positive electrode material obtained in step 2 is fully washed with organic solvent for 4-8 hours, then washed with ethanol for 1-2 times, and dried after centrifugation to obtain the ternary material to be repaired;
步骤四，将步骤三获得的待修复三元材料进行研磨处理，然后依次使用80目、200目和400目的筛子筛分去除杂质，获得粒径均匀的待修复三元粉末；Step 4, grind the ternary material to be repaired obtained in step 3, and then use 80-mesh, 200-mesh and 400-mesh sieves in sequence to remove impurities to obtain ternary powder to be repaired with uniform particle size;
步骤五，将经过步骤四处理后的待修复三元粉末进行成分分析，确定镍、钴、锰和锂元素的含量； Step 5, analyze the composition of the ternary powder to be repaired after the treatment in Step 4, and determine the contents of nickel, cobalt, manganese and lithium elements;
步骤六，按比例补充待修复三元粉末缺失的元素，均匀混合后，在不同气氛条件下进行高温煅烧处理；Step 6, replenish the missing elements of the ternary powder to be repaired in proportion, and after uniform mixing, perform high-temperature calcination treatment under different atmospheric conditions;
步骤七，高温煅烧处理结束后，冷却至室温，取出黑色固体进行研磨，获得修复后的三元正极材料。Step 7: After the high-temperature calcination treatment is completed, cool down to room temperature, and take out the black solid for grinding to obtain a repaired ternary positive electrode material.
进一步地，废旧锂离子电池的正极三元材料为循环2000次左右的废旧NCM523或NCM622材料。Further, the cathode ternary material of the waste lithium-ion battery is the waste NCM523 or NCM622 material that has been cycled about 2000 times.
进一步地，步骤二和步骤三中所述的有机溶剂为N-甲基吡咯烷酮。Further, the organic solvent described in step 2 and step 3 is N-methylpyrrolidone.
进一步地，步骤四中，所述研磨处理的时间为30min。Further, in step 4, the time of the grinding treatment is 30min.
进一步地，步骤五中，所述的成分分析方法为：称量固体物质20～40mg，利用1mL王水将其充分溶解，用蒸馏水定容至1L，利用电感耦合等离子光谱(ICP)测试，确定各元素含量。Further, in step 5, the composition analysis method is as follows: weighing 20-40 mg of the solid substance, fully dissolving it with 1 mL of aqua regia, diluting the volume to 1 L with distilled water, and using inductively coupled plasma spectroscopy (ICP) test to determine. content of each element.
进一步地，步骤六中按照锂与(镍、钴和锰)总摩尔量之和的比为1.05：1的比例补充锂盐。Further, in step 6, the lithium salt is supplemented in a ratio of 1.05:1 according to the ratio of the total molar amount of lithium to (nickel, cobalt and manganese).
进一步地，所述的步骤六中，补充的锂源来自LiOH或Li
2CO
3中的一种。
Further, in the step 6, the supplemented lithium source comes from one of LiOH or Li 2 CO 3 .
进一步地，步骤六中，采用的修复三元粉末与锂源均匀混合方式为球磨处理4～6h或手动研磨30～60min中的一种。Further, in step 6, the uniform mixing method of the repairing ternary powder and the lithium source is one of ball milling for 4-6 hours or manual grinding for 30-60 minutes.
进一步地，所述的步骤六中，高温煅烧的气氛条件为氧气或空气氛围中的一种。Further, in the step 6, the atmospheric condition of high temperature calcination is one of oxygen or air atmosphere.
进一步地，步骤六中高温煅烧条件为：温度500～800℃，时间12～20h。Further, the high temperature calcination conditions in step 6 are as follows: the temperature is 500-800° C., and the time is 12-20 h.
进一步地，步骤六中高温煅烧过程为：温度为500℃保温4h，然后升温至800℃保温16h。Further, the high-temperature calcination process in step 6 is as follows: the temperature is 500° C. for 4 hours, and then the temperature is raised to 800° C. for 16 hours.
本发明具有以下有益效果：本发明利用高温固相烧结法直接修复三元正极材料具有简单高效的优点，避免了传统火法和湿法回收过程中的繁琐分离和提纯的操作，提高了材料的利用率，降低了回收成本。并且本发明提供的方法成功减少了由于循环造成的Li-Ni混排，并修复了受损的层状晶体结构，修复后的三元正极材料具有放电比容量高，循环性能好等特点。此外，本发明提供的方法还具有简单易行，重复性好，成本低，产量高等优点，具有良好的大规模应用潜能。The present invention has the following beneficial effects: the present invention utilizes the high-temperature solid-phase sintering method to directly repair the ternary positive electrode material, which has the advantages of simplicity and high efficiency, avoids the tedious separation and purification operations in the traditional fire method and wet method recovery process, and improves the material quality. Utilization rate, reducing recycling costs. And the method provided by the invention successfully reduces the Li-Ni mixed arrangement caused by the cycle, and repairs the damaged layered crystal structure. The repaired ternary cathode material has the characteristics of high discharge specific capacity and good cycle performance. In addition, the method provided by the present invention also has the advantages of simplicity, good repeatability, low cost and high yield, and has good potential for large-scale application.
说明书附图Instruction drawings
图1为实例1中NCM523材料修复前后的XRD图；Fig. 1 is the XRD pattern before and after the repair of NCM523 material in example 1;
图2为实例2中NCM622材料修复前后的XRD图；Fig. 2 is the XRD pattern before and after the repair of NCM622 material in example 2;
图3为实例1中NCM523材料修复前后的拉曼谱图；Fig. 3 is the Raman spectrum before and after the repair of NCM523 material in example 1;
图4为实例2中NCM622材料修复前后的拉曼谱图；Fig. 4 is the Raman spectrum before and after the repair of NCM622 material in example 2;
图5为实例1中NCM523材料修复后的扫描电镜图；Fig. 5 is the scanning electron microscope image after NCM523 material repair in example 1;
图6为实例2中NCM622材料修复后的扫描电镜图；Fig. 6 is the scanning electron microscope picture after NCM622 material repair in example 2;
图7为实例1中NCM523材料修复前后的放电曲线图；Fig. 7 is the discharge curve diagram before and after the repair of NCM523 material in Example 1;
图8为实例2中NCM622材料修复前后的放电曲线图；Fig. 8 is the discharge curve diagram before and after the repair of NCM622 material in Example 2;
图9为实例1中NCM523材料修复前后的恒电流循环性能图；Fig. 9 is the galvanostatic cycle performance diagram before and after the repair of NCM523 material in Example 1;
图10为实例2中NCM622材料修复前后的恒电流循环性能图；Fig. 10 is the galvanostatic cycle performance diagram before and after the repair of NCM622 material in Example 2;
图11为实施例1修复的NCM523和实施例2修复后的NCM622材料的倍率性能图。11 is a graph of the rate performance of the NCM523 repaired in Example 1 and the NCM622 material repaired in Example 2.
下述实施例中所使用的实验方法如无特殊说明均为常规方法。所用材料、试剂、方法和仪器，未经特殊说明，均为本领域常规材料、试剂、方法和仪器，本领域技术人员均可通过商业渠道获得。The experimental methods used in the following examples are conventional methods unless otherwise specified. The used materials, reagents, methods and instruments, unless otherwise specified, are conventional materials, reagents, methods and instruments in the art, which can be obtained by those skilled in the art through commercial channels.
实施例1：修复废旧NCM523材料锂离子电池Example 1: Repairing used NCM523 lithium-ion battery
一、将废旧NCM523电池在惰性气体保护下进行拆解，除去外壳、正负极端子、密封圈及盖板；1. Disassemble the waste NCM523 battery under the protection of inert gas, and remove the outer casing, positive and negative terminals, sealing ring and cover plate;
二、将正负极片分离，用DMC浸泡去除电解液；在100℃的温度下用N-甲基吡咯烷酮浸泡正极片2～4h，除去粘结剂，剥离出正极材料，离心后烘干获得废旧NCM523正极材料；2. Separate the positive and negative electrode sheets, soak them with DMC to remove the electrolyte; soak the positive electrode sheets with N-methylpyrrolidone at a temperature of 100 ° C for 2 to 4 hours, remove the binder, peel off the positive electrode material, and dry after centrifugation to obtain Waste NCM523 cathode material;
三、将步骤二中获得的废旧NCM523正极材料用有N-甲基吡咯烷酮充分洗涤5h，再用乙醇洗涤2次，离心后烘干获得待修复的NCM523材料；3. Fully washing the waste NCM523 cathode material obtained in step 2 with N-methylpyrrolidone for 5 hours, then washing with ethanol twice, and drying after centrifugation to obtain the NCM523 material to be repaired;
四、将待修复的NCM523材料研磨30min，依次用80目、200目和400目的筛子筛分去除杂质，获得粒径均匀的待修复三元粉末；4. Grind the NCM523 material to be repaired for 30 minutes, then sieve with 80-mesh, 200-mesh and 400-mesh sieves to remove impurities to obtain ternary powder with uniform particle size to be repaired;
五、将废旧NCM523材料溶解到王水中进行成分分析，确定镍(Ni)、钴(Co)、锰(Mn)、锂(Li)元素的含量；5. Dissolve the waste NCM523 material into aqua regia for composition analysis to determine the content of nickel (Ni), cobalt (Co), manganese (Mn), and lithium (Li) elements;
六、按照锂与(镍、钴和锰)总摩尔量之和的比为1.05：1的比例补充LiOH，球磨6h混合后氧气气氛进行高温煅烧，反应条件是温度为500℃保温4h，升温至800℃保温16h；6. Supplement LiOH at a ratio of 1.05:1 to the sum of the total molar amounts of lithium and (nickel, cobalt, and manganese), and then perform high-temperature calcination in an oxygen atmosphere after ball milling for 6 hours. 800℃ for 16h;
七、反应完毕后，将管式炉冷却至室温，取出黑色固体进行研磨筛分，即得到修复后的NCM523正极材料。7. After the reaction is completed, the tube furnace is cooled to room temperature, and the black solid is taken out for grinding and screening to obtain the repaired NCM523 positive electrode material.
对修复前后的NCM523正极材料进行表征并比较，结果由图1、3、5、7、9和11所示：图1为本实例所修复的NCM523材料前后的XRD对比图，图3为NCM523材料修复前后的拉曼谱图，图1和图3表明修复后的NCM523材料层状晶体结构已明显恢复，Li-Ni混排有明显改善。图5显示出修复后的材料的形貌，结合图7可知修复后的NCM523材料制得的锂离子电池在0.1C电流密度下的首圈放电比容量从126.704mAh/g提升到170.964mAh/g，由图9可知修复后的NCM523材料制得的锂离子电池在1C电流密度下循环100圈的容量保持在144.99mAh/g。由图11可知修复后的NCM523材料表现出了良好的倍率性能。The NCM523 cathode materials before and after the repair were characterized and compared, and the results are shown in Figures 1, 3, 5, 7, 9 and 11: Figure 1 is the XRD comparison diagram of the NCM523 material before and after the repair in this example, and Figure 3 is the NCM523 material The Raman spectra before and after repair, Figure 1 and Figure 3 show that the layered crystal structure of the repaired NCM523 material has been significantly restored, and the Li-Ni mixing has been significantly improved. Figure 5 shows the morphology of the repaired material. Combined with Figure 7, it can be seen that the first cycle discharge specific capacity of the lithium-ion battery made of the repaired NCM523 material increases from 126.704mAh/g to 170.964mAh/g at a current density of 0.1C. , it can be seen from Figure 9 that the capacity of the lithium-ion battery made of the repaired NCM523 material remains at 144.99mAh/g under 1C current density for 100 cycles. It can be seen from Figure 11 that the repaired NCM523 material exhibits good rate performance.
实施例2：修复废旧NCM622材料锂离子电池Example 2: Repairing waste NCM622 material lithium-ion battery
一、将废旧NCM622电池在惰性气体保护下进行拆解，除去外壳、正负极端子、密封圈及盖板；1. Disassemble the waste NCM622 battery under the protection of inert gas, and remove the outer casing, positive and negative terminals, sealing ring and cover plate;
二、将正负极片分离，用DMC浸泡去除电解液；在100℃的温度下用N-甲基吡咯烷酮浸泡正极片2～4h，除去粘结剂，剥离出正极材料，离心后烘干获得废旧NCM622正极材料；2. Separate the positive and negative electrode sheets, soak them with DMC to remove the electrolyte; soak the positive electrode sheets with N-methylpyrrolidone at a temperature of 100°C for 2 to 4 hours, remove the binder, peel off the positive electrode material, and dry after centrifugation to obtain Waste NCM622 cathode material;
三、将步骤二中获得的废旧NCM622正极材料用有机溶剂充分洗涤5h，再用乙醇洗涤2次，离心后烘干获得待修复的NCM622材料；3. Fully washing the waste NCM622 cathode material obtained in step 2 with an organic solvent for 5 hours, then washing with ethanol twice, and drying after centrifugation to obtain the NCM622 material to be repaired;
四、将待修复的NCM622材料研磨30min，依次用80目、200目和400目的筛子筛分去除杂质，获得粒径均匀的待修复三元粉末；4. Grind the NCM622 material to be repaired for 30 minutes, then sieve with 80-mesh, 200-mesh and 400-mesh sieves to remove impurities to obtain ternary powder to be repaired with uniform particle size;
五、将废旧NCM622材料溶解到王水中进行成分分析，确定镍(Ni)、钴(Co)、锰(Mn)、锂(Li)元素的含量；5. Dissolve the waste NCM622 material into aqua regia for composition analysis to determine the content of nickel (Ni), cobalt (Co), manganese (Mn) and lithium (Li) elements;
六、按照锂与(镍、钴和锰)总摩尔量之和的比为1.05：1的比例补充LiOH，球磨6h混合后氧气气氛进行高温煅烧，反应条件是温度为500℃保温4h，升温至800℃保温16h；6. Supplement LiOH at a ratio of 1.05:1 to the sum of the total molar amounts of lithium and (nickel, cobalt, and manganese), and then perform high-temperature calcination in an oxygen atmosphere after ball milling for 6 hours. 800℃ for 16h;
七、反应完毕后，将管式炉冷却至室温，取出黑色固体进行研磨筛分，即得到修复后的NCM622正极材料。7. After the reaction is completed, the tube furnace is cooled to room temperature, and the black solid is taken out for grinding and screening to obtain the repaired NCM622 positive electrode material.
对修复前后的NCM622正极材料进行表征并比较，结果由图2、4、6、8、10和11所示：图2为本实例所修复的NCM622材料前后的XRD对比图，图4为NCM622材料修复前后的拉曼谱图，图2和图4表明修复后的NCM622材料层状晶体结构明显恢复，Li-Ni混排有明显改善。图6显示出修复后的材料的形貌。图8展示了用修复后的NCM622材料制得的锂离子电池在0.1C电流密度下的首圈放电比容量从96.72mAh/g提升到198.81mAh/g。图10为修复后的NCM622材料制得的锂离子电池在1C电流密度下循环100圈的容量保持在128.58mAh/g。由图11可知修复后的NCM622材料表现出了良好的倍率性能。The NCM622 cathode materials before and after the repair are characterized and compared, and the results are shown in Figures 2, 4, 6, 8, 10 and 11: Figure 2 is the XRD comparison of the NCM622 material before and after the repair in this example, and Figure 4 is the NCM622 material The Raman spectra before and after repair, Figures 2 and 4 show that the layered crystal structure of the repaired NCM622 material is significantly restored, and the Li-Ni mixing is significantly improved. Figure 6 shows the morphology of the repaired material. Figure 8 shows that the first-cycle discharge specific capacity of the lithium-ion battery fabricated with the repaired NCM622 material increases from 96.72 mAh/g to 198.81 mAh/g at a current density of 0.1 C. Figure 10 shows that the capacity of the lithium-ion battery made of the repaired NCM622 material remains at 128.58mAh/g after 100 cycles at a current density of 1C. It can be seen from Figure 11 that the repaired NCM622 material exhibits good rate performance.
实施例3：Example 3:
本实施例与实施例1区别仅在于：步骤六中所述将锂源与材料进行混合的方法为手动研磨30～60min，其余操作步骤与实施例1相同。The only difference between this example and Example 1 is that the method for mixing the lithium source and the material in step 6 is manual grinding for 30-60 minutes, and the rest of the operation steps are the same as those in Example 1.
实施例4：Example 4:
本实施例与实施例2区别仅在于：步骤六中所述将锂源与材料进行混合的方法为手动研磨30～60min，其余操作步骤与实施例2相同。The only difference between this example and Example 2 is that the method of mixing the lithium source and the material in step 6 is manual grinding for 30-60 minutes, and the rest of the operation steps are the same as those in Example 2.
实施例5：Example 5:
本实施例与实施例1区别仅在于：步骤六中煅烧的气氛为空气，其余操作步骤与实施例1相同。The difference between this embodiment and embodiment 1 is only that the atmosphere for calcination in step 6 is air, and the remaining operation steps are the same as those of embodiment 1.
实施例6：Example 6:
本实施例与实施例2区别仅在于：步骤六中煅烧的气氛为空气，其余操作步骤与实施例2相同。The difference between this embodiment and embodiment 2 is only that the atmosphere for calcination in step 6 is air, and the remaining operation steps are the same as those of embodiment 2.
实施例7：Example 7:
本实施例与实施例1区别仅在于：步骤六中按照锂与镍、钴和锰的总摩尔量的比为1.05：1的比例补充Li
2CO
3，其余操作步骤与实施例1相同。
The only difference between this embodiment and embodiment 1 is that in step 6, Li 2 CO 3 is supplemented in a ratio of 1.05:1 to the total molar ratio of lithium to nickel, cobalt and manganese, and the rest of the operation steps are the same as those of embodiment 1.
实施例8：Example 8:
本实施例与实施例2区别仅在于：步骤六中按照锂与镍、钴和锰的总摩尔量的比为1.05：1的比例补充Li
2CO
3，其余操作步骤与实施例2相同。
The only difference between this embodiment and embodiment 2 is that in step 6, Li 2 CO 3 is supplemented in a ratio of 1.05:1 to the total molar ratio of lithium to nickel, cobalt and manganese, and the rest of the operation steps are the same as those of embodiment 2.
最后，还需要注意的是，以上列举的仅是本发明的若干个具体实施例。显然，本发明不限于以上实施例，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。Finally, it should also be noted that the above enumeration is only a few specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments, and many modifications are possible. All deformations that those of ordinary skill in the art can directly derive or associate from the disclosure of the present invention shall be considered as the protection scope of the present invention.
Claims (11)
- 一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，该方法包括以下步骤：A method for directly repairing a ternary positive electrode material of a waste lithium ion battery, characterized in that the method comprises the following steps:步骤一，将废旧锂离子电池在惰性气体保护下进行拆解，除去外壳、正负极端子、密封圈及盖板；Step 1, disassemble the waste lithium-ion battery under the protection of inert gas, and remove the outer casing, positive and negative terminals, sealing ring and cover plate;步骤二，将正负极片分离，使用碳酸二甲酯浸泡去除电解液；然后在100℃条件下使用有机溶剂浸泡正极片2～4h，去除粘结剂，剥离出正极材料，离心后烘干获得废旧三元正极材料；Step 2: Separating the positive and negative electrode sheets, soaking with dimethyl carbonate to remove the electrolyte; then soaking the positive electrode sheets with an organic solvent at 100°C for 2 to 4 hours, removing the binder, peeling off the positive electrode material, and drying after centrifugation Obtain waste ternary cathode materials;步骤三，将步骤二获得的废旧三元正极材料使用有机溶剂充分洗涤4～8h，再使用乙醇洗涤1～2次，离心后烘干获得待修复三元材料；In step 3, the waste ternary positive electrode material obtained in step 2 is fully washed with organic solvent for 4-8 hours, then washed with ethanol for 1-2 times, and dried after centrifugation to obtain the ternary material to be repaired;步骤四，将步骤三获得的待修复三元材料进行研磨处理，然后依次使用80目、200目和400目的筛子筛分去除杂质，获得粒径均匀的待修复三元粉末；Step 4, grind the ternary material to be repaired obtained in step 3, and then use 80-mesh, 200-mesh and 400-mesh sieves in sequence to remove impurities to obtain ternary powder to be repaired with uniform particle size;步骤五，将经过步骤四处理后的待修复三元粉末进行成分分析，确定镍、钴、锰和锂元素的含量；Step 5, analyze the composition of the ternary powder to be repaired after the treatment in Step 4, and determine the contents of nickel, cobalt, manganese and lithium elements;步骤六，按比例补充待修复三元粉末缺失的元素，均匀混合后，在不同气氛条件下进行高温煅烧处理；Step 6, replenish the missing elements of the ternary powder to be repaired in proportion, and after uniform mixing, perform high-temperature calcination treatment under different atmospheric conditions;步骤七，高温煅烧处理结束后，冷却至室温，取出黑色固体后进行研磨，获得修复后的三元正极材料。Step 7, after the high-temperature calcination treatment is completed, cool to room temperature, take out the black solid, and grind it to obtain a repaired ternary positive electrode material.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的废旧锂离子电池的正极三元材料为循环2000次以上的NCM523或NCM622材料。The method for directly repairing a ternary positive electrode material of a waste lithium ion battery according to claim 1, wherein the positive ternary material of the waste lithium ion battery is NCM523 or NCM622 which has been cycled more than 2000 times.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，步骤二和步骤三中所述的有机溶剂为N-甲基吡咯烷酮。The method for directly repairing a ternary positive electrode material of a waste lithium ion battery according to claim 1, wherein the organic solvent described in the second step and the third step is N-methylpyrrolidone.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的成分分析方法为电感耦合等离子光谱法。The method for directly repairing a ternary positive electrode material of a waste lithium-ion battery according to claim 1, wherein the composition analysis method is inductively coupled plasma spectroscopy.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤六中按照锂与镍、钴和锰总摩尔量之和 的比为1.05：1的比例补充锂盐。The direct repair method of a kind of spent lithium-ion battery ternary positive electrode material according to claim 1, is characterized in that, in the described step 6, according to the ratio of the sum of total molar amounts of lithium and nickel, cobalt and manganese is 1.05: A ratio of 1 supplements lithium salts.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤六中，补充的锂源来自LiOH或Li 2CO 3中的一种。 The method for directly repairing a ternary positive electrode material of a spent lithium-ion battery according to claim 1, wherein in the step 6, the supplemented lithium source comes from one of LiOH or Li 2 CO 3 .
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤四中，所述研磨处理的时间为30min。The method for directly repairing a ternary positive electrode material of a waste lithium-ion battery according to claim 1, wherein in the step 4, the grinding treatment time is 30 minutes.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤六中采用的修复三元粉末与锂源均匀混合方式为球磨处理4～6h或手动研磨30～60min中的一种。The method for directly repairing a ternary positive electrode material of a waste lithium ion battery according to claim 1, wherein the uniform mixing method of the repairing ternary powder and the lithium source used in the step 6 is ball milling for 4-6 hours Or one of the manual grinding 30 ~ 60min.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤六中，高温煅烧的气氛条件为氧气或空气氛围中的一种。The method for directly repairing a ternary positive electrode material of a waste lithium-ion battery according to claim 1, wherein in the step 6, the atmospheric condition for high temperature calcination is one of oxygen or air atmosphere.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤六中高温煅烧条件为：温度500～800℃，时间12～20h。The method for directly repairing a ternary positive electrode material of a waste lithium ion battery according to claim 1, wherein the high temperature calcination conditions in the step 6 are: temperature 500-800°C, time 12-20h.
- 根据权利要求1所述的一种废旧锂离子电池三元正极材料的直接修复方法，其特征在于，所述的步骤六中高温煅烧过程为：温度为500℃保温4h，然后升温至800℃保温16h。The method for directly repairing a ternary positive electrode material of a waste lithium ion battery according to claim 1, wherein the high temperature calcination process in the step 6 is: the temperature is 500°C for 4 hours, and then the temperature is raised to 800°C for heat preservation 16h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110161218.5A CN112939096A (en) | 2021-02-05 | 2021-02-05 | Direct repairing method for ternary cathode material of waste lithium ion battery |
| CN202110161218.5 | 2021-02-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022166197A1 true WO2022166197A1 (en) | 2022-08-11 |
Family
ID=76242540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/117439 WO2022166197A1 (en) | 2021-02-05 | 2021-09-09 | Direct repair method for waste lithium-ion battery ternary positive electrode material |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN112939096A (en) |
| WO (1) | WO2022166197A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432699A (en) * | 2022-10-21 | 2022-12-06 | 湖南宸宇富基新能源科技有限公司 | Waste negative electrode base regenerated graphite material and preparation and application thereof |
| CN115724474A (en) * | 2022-11-16 | 2023-03-03 | 清华大学深圳国际研究生院 | Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material |
| CN117619859A (en) * | 2023-11-28 | 2024-03-01 | 吉奥环朋科技(扬州)有限公司 | Recycling recovery method of waste lithium ion power battery |
| CN117673537A (en) * | 2024-01-31 | 2024-03-08 | 江苏维锂新能源材料有限公司 | Environment-friendly repair and regeneration process for lithium iron phosphate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939096A (en) * | 2021-02-05 | 2021-06-11 | 哈尔滨工业大学 | Direct repairing method for ternary cathode material of waste lithium ion battery |
| CN113636605A (en) * | 2021-07-07 | 2021-11-12 | 华中科技大学 | Physical repair method for completely-failed ternary positive electrode material under low-cost air condition |
| CN114204013B (en) * | 2021-12-15 | 2024-03-22 | 中南大学 | Direct repair method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
| CN115432741A (en) * | 2022-09-23 | 2022-12-06 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method for recycling waste lithium battery positive plate and battery |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706477A (en) * | 2017-08-31 | 2018-02-16 | 长沙佳纳锂业科技有限公司 | A kind of waste and old ternary anode material for lithium-ion batteries solid phase regeneration method |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
| CN112939096A (en) * | 2021-02-05 | 2021-06-11 | 哈尔滨工业大学 | Direct repairing method for ternary cathode material of waste lithium ion battery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103915661B (en) * | 2013-01-09 | 2016-12-28 | 中国科学院过程工程研究所 | A kind of direct recovery the method repairing anode material for lithium-ion batteries |
| CN111977704A (en) * | 2020-07-27 | 2020-11-24 | 昆明理工大学 | Rapid regeneration method of waste ternary lithium ion battery anode material |
-
2021
- 2021-02-05 CN CN202110161218.5A patent/CN112939096A/en active Pending
- 2021-09-09 WO PCT/CN2021/117439 patent/WO2022166197A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107706477A (en) * | 2017-08-31 | 2018-02-16 | 长沙佳纳锂业科技有限公司 | A kind of waste and old ternary anode material for lithium-ion batteries solid phase regeneration method |
| CN112054265A (en) * | 2020-09-30 | 2020-12-08 | 合肥国轩高科动力能源有限公司 | Method for recycling and reusing anode material of waste ternary lithium ion battery |
| CN112939096A (en) * | 2021-02-05 | 2021-06-11 | 哈尔滨工业大学 | Direct repairing method for ternary cathode material of waste lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| MENG XIANGQI, HAO JIE, CAO HONGBIN, LIN XIAO, NING PENGGE, ZHENG XIAOHONG, CHANG JUNJUN, ZHANG XIHUA, WANG BAO, SUN ZHI: "Recycling of LiNi1/3Co1/3Mn1/3O2 cathode materials from spent lithium-ion batteries using mechanochemical activation and solid-state sintering", WASTE MANAGEMENT., ELSEVIER, NEW YORK, NY., US, vol. 84, 1 February 2019 (2019-02-01), US , pages 54 - 63, XP055956891, ISSN: 0956-053X, DOI: 10.1016/j.wasman.2018.11.034 * |
| ZHANG XIAOXIAO, XUE QING, LI LI, FAN ERSHA, WU FENG, CHEN RENJIE: "Sustainable Recycling and Regeneration of Cathode Scraps from Industrial Production of Lithium-Ion Batteries", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, vol. 4, no. 12, 5 December 2016 (2016-12-05), American Chemical Society, US, pages 7041 - 7049, XP055847676, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.6b01948 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115432699A (en) * | 2022-10-21 | 2022-12-06 | 湖南宸宇富基新能源科技有限公司 | Waste negative electrode base regenerated graphite material and preparation and application thereof |
| CN115432699B (en) * | 2022-10-21 | 2023-07-11 | 湖南宸宇富基新能源科技有限公司 | Waste negative electrode-based regenerated graphite material and preparation and application thereof |
| CN115724474A (en) * | 2022-11-16 | 2023-03-03 | 清华大学深圳国际研究生院 | Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material |
| CN115724474B (en) * | 2022-11-16 | 2023-12-08 | 清华大学深圳国际研究生院 | Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material |
| CN117619859A (en) * | 2023-11-28 | 2024-03-01 | 吉奥环朋科技(扬州)有限公司 | Recycling recovery method of waste lithium ion power battery |
| CN117619859B (en) * | 2023-11-28 | 2024-05-24 | 吉奥环朋科技(扬州)有限公司 | Recycling recovery method of waste lithium ion power battery |
| CN117673537A (en) * | 2024-01-31 | 2024-03-08 | 江苏维锂新能源材料有限公司 | Environment-friendly repair and regeneration process for lithium iron phosphate |
| CN117673537B (en) * | 2024-01-31 | 2024-04-16 | 江苏维锂新能源材料有限公司 | Environment-friendly repair and regeneration process for lithium iron phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112939096A (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022166197A1 (en) | Direct repair method for waste lithium-ion battery ternary positive electrode material | |
| CN105428745B (en) | A kind of innoxious comprehensive reutilization method of applying waste lithium ionic power battery | |
| CN108808150B (en) | Method for comprehensively recycling waste ternary electrode material | |
| CN112142029B (en) | Method for repairing and regenerating anode material of waste lithium iron phosphate battery | |
| AU2021103805A4 (en) | Method for degrading poly(vinylidene fluoride) (pvdf) in cathode of waste lithium iron phosphate battery | |
| CN112510281B (en) | Method for recovering all components of waste lithium ion battery | |
| CN110808430A (en) | Separation and purification method of lithium ion battery anode material and obtained lithium ion battery anode material | |
| CN114204151A (en) | Method for repairing and modifying waste lithium ion battery positive electrode active material | |
| CN108172926A (en) | A kind of waste lithium ion cell anode material repair methods | |
| CN111009699A (en) | Method for recycling lithium manganate waste battery | |
| CN111326814A (en) | Method for repairing anode material of waste ternary battery by ultrasonic hydrothermal method | |
| CN111320157A (en) | Method for repairing lithium iron phosphate material based on hydrothermal reaction | |
| CN112886084B (en) | Method for repairing layered oxide positive electrode material of sodium ion battery | |
| CN112670603B (en) | Method for cooperatively repairing and regenerating failure ternary material by using physical method and multielement medium | |
| US20230335817A1 (en) | Method for recycling lithium battery cathode material | |
| CN117096486A (en) | Repairing and regenerating method for waste lithium ion battery anode material | |
| CN116169391A (en) | Regeneration method of layered anode material of integrated waste lithium ion battery | |
| WO2020118716A1 (en) | Method for ultrasonic hydrothermal repair of waste ternary battery cathode material | |
| CN113488714B (en) | Method for repairing failed lithium ion battery positive electrode material, regenerated positive electrode material and application | |
| CN115724474B (en) | Repairing method of failed layered positive electrode material, positive electrode material and application of positive electrode material | |
| CN116093482B (en) | Recycling method and application of waste lithium ion battery anode material | |
| CN116779850A (en) | Waste lithium ion battery regenerated graphite negative electrode based on organic acid pyrolysis gas phase reduction and regeneration method thereof | |
| CN117954725A (en) | High-value regeneration method for graphite cathode material of waste lithium ion battery | |
| CN113860282A (en) | LiFePO4Regeneration and repair method of waste material | |
| CN117096484A (en) | Regeneration method of waste lithium ion battery anode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21924195 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21924195 Country of ref document: EP Kind code of ref document: A1 |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 21924195 Country of ref document: EP Kind code of ref document: A1 |