CN114927786A - Regeneration method of waste lithium ion battery anode material - Google Patents
Regeneration method of waste lithium ion battery anode material Download PDFInfo
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- CN114927786A CN114927786A CN202210391522.3A CN202210391522A CN114927786A CN 114927786 A CN114927786 A CN 114927786A CN 202210391522 A CN202210391522 A CN 202210391522A CN 114927786 A CN114927786 A CN 114927786A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 239000010405 anode material Substances 0.000 title claims abstract description 34
- 238000011069 regeneration method Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 23
- 230000001172 regenerating effect Effects 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 230000008929 regeneration Effects 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000007774 positive electrode material Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 229910013716 LiNi Inorganic materials 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 239000013589 supplement Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 5
- 238000009853 pyrometallurgy Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- -1 and then recovers Co Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
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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
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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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Abstract
The invention discloses a method for regenerating a waste lithium ion battery anode material, which comprises the following steps: (1) discharging and disassembling the waste lithium ion battery, then soaking the disassembled positive plate in alkali liquor, and filtering to obtain black powder; (2) and washing and drying the black powder, adding a boron source into the dried black powder, grinding, and roasting to complete the regeneration of the waste lithium ion battery anode material. According to the invention, residual lithium on the surface of the waste anode material is fully utilized, lithium supplement operation is not required, F element introduced in the battery circulation process is utilized, the added B element is combined, B and F are ensured to be doped in crystal lattices of the material, cracks in the waste ternary material are healed by the B element, the framework of the material is stabilized by the F element, the transmission of lithium ions is accelerated, the obtained regenerated particles are typical quasi-single crystal particles, the surface is smooth and has no cracks, the size is uniform, the particle size is 3-5 mu m, and the full battery assembled by the regenerated anode material has excellent performance.
Description
Technical Field
The invention belongs to the field of treatment of waste lithium ion batteries, and particularly relates to a method for regenerating a positive electrode material of a waste lithium ion battery.
Background
Lithium ion batteries are widely used due to their excellent properties such as high operating voltage, high energy density, no memory effect, light weight, small size, low self-discharge rate, long cycle life, wide operating temperature range, etc. lithium ion batteries have become an energy storage device widely used in consumer electronics and electric vehicles due to their comprehensive advantages in performance and price. World LIB production reaches 20.5 billion in 2005 and 58.6 billion in 2012. The output of the Chinese lithium ion battery is 41.8 hundred million in 2012, and is increased to 78.4 hundred million in 2016, and along with the rapid increase of the demand of the lithium ion battery, the method has important significance for recycling the waste lithium ion battery.
To date, many recovery techniques have been developed based on pyrometallurgical or hydrometallurgical processes. Enterprises such as SONY, Onto, Accurec and the like have commercialized and developed the pyrometallurgical process. Pyrometallurgical processes are often combined with hydrometallurgical processes to recover valuable metals. For example, the Val Eas process adopted by Umicore first melts waste lithium in a furnace to obtain Co Ni Cu Fe alloy, and then recovers Co, Ni and Cu from the alloy by adopting a hydrometallurgical process. In the pyrometallurgical process, acetylene black, organic electrolyte and binder contained in the waste liquid are often burnt, the energy consumption is high, and harmful gases are discharged. In addition, lithium and aluminum are active metals with strong reducibility, and are easily oxidized in the smelting process and enter smelting slag in the form of oxides. In contrast, the hydrometallurgical process has the advantages of high metal recovery rate, high product purity, low energy consumption, less gas emission and the like, but also has the defects of overlong flow, difficult operation and the like.
Therefore, it is important to develop a short-flow and high-efficiency regeneration method for the positive electrode material of the waste lithium ion battery to solve the technical problem of recovery of the pyrometallurgical or hydrometallurgical process.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background art and provide a regeneration method of waste lithium ion batteries.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a regeneration method of a waste lithium ion battery anode material comprises the following steps:
(1) discharging and disassembling the waste lithium ion battery, then soaking the disassembled positive plate in alkali liquor, and filtering to obtain black powder;
(2) and (2) washing and drying the black powder obtained in the step (1), adding a boron source into the dried black powder, grinding, and roasting to complete the regeneration of the anode material of the waste lithium ion battery.
Preferably, in the method for regenerating the cathode material of the waste lithium ion battery, the chemical formula of the waste lithium ion battery is LiNi x Co y Mn z O 2 ，0.3≤x<1，0<y≤0.3，0<z is less than or equal to 0.3, the electrolyte of the waste lithium ion battery contains HF, HF in the electrolyte is immersed in the ternary material in the long-cycle process of the lithium ion battery, and F element enters the material as a doping element in the recovery process of the waste lithium battery.
Preferably, in the step (2), the boron source is any one of boron oxide, boron trichloride and boron hydroxide, and the addition amount of the boron source accounts for 0.1-3% of the molar weight of the lithium ion battery anode material body according to the molar percentage.
Preferably, in the step (2), the grinding speed is 200-500rpm, and the grinding time is 10-30 min.
In the above method for regenerating the cathode material of the waste lithium ion battery, preferably, in the step (2), the roasting is performed in an oxygen-rich atmosphere.
Preferably, in the step (2), the roasting is performed in two stages, the first stage roasting temperature is 500-550 ℃, the roasting time is 5-15h, the second stage roasting temperature is 600-850 ℃, and the roasting time is 5-50 h.
Preferably, in the step (1), the discharging refers to soaking the waste lithium ion battery in a sodium chloride solution with a mass concentration of 0.2-15% for 10-72 hours.
In the above method for regenerating the anode material of the waste lithium ion battery, preferably, the alkali solution in the step (1) is one or more of a sodium hydroxide solution, ammonia water and a potassium hydroxide solution, or a mixed solution of a calcium hydroxide solution and a sodium hydroxide solution, ammonia water or a potassium hydroxide solution; the concentration of the alkali liquor is 1-3 mol/L, and the pH value is 12-14.
Preferably, in the step (1), the anode plate is soaked in the alkali liquor for 1-24 hours.
Preferably, in the step (2), the chemical formula of the regenerated waste lithium ion battery is LiNi x Co y Mn z B a F b O 2 Wherein x, y, z, a, b and c are mole numbers, x is more than or equal to 0.3<1，0<y≤0.3，0<z≤0.3，x+y+z＝1，0.001≤a≤0.03，0<b≤0.1。
Compared with the prior art, the invention has the advantages that:
(1) the regeneration method of the waste lithium ion battery anode material is simple, does not need to recover metal elements in the ternary anode material and perform lithium supplement operation, and can be realized by directly adding a boron source into the waste lithium ion anode material and re-sintering.
(2) According to the invention, residual lithium on the surface of the anode material is fully utilized in the regeneration sintering process of the anode material of the waste lithium ion battery, so that lithium supplement operation is not required, the F element introduced in the battery circulation process is utilized, the added B element is combined, the B and F are ensured to be doped in the crystal lattice of the material, the B element enables cracks in the waste ternary material to heal, the F element is doped to stabilize the framework of the material, the transmission of lithium ions is accelerated, the obtained regenerated particles are typical quasi-single crystal particles, the surface is smooth and crack-free, the size is uniform, the particle size is 3-5 mu m, and the full battery assembled by the regenerated anode material has excellent performance.
Drawings
FIG. 1 is an SEM photograph of a regenerated positive electrode material in example 1 of the present invention;
FIG. 2 is an SEM image of the positive electrode material of the waste lithium ion battery in example 1 of the invention;
fig. 3 is an electrochemical diagram of a full cell prepared by regenerating positive electrode materials of example 1 and comparative example 1 according to the present invention;
FIG. 4 is an SEM photograph of a regenerated positive electrode material in example 2 of the present invention;
FIG. 5 is an SEM photograph of a regenerated positive electrode material in example 3 of the present invention;
fig. 6 is an SEM image of the regenerated positive electrode material in comparative example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the following specific embodiments.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a regeneration method of a waste lithium ion battery anode material comprises the following steps:
(1) the anode material is LiNi 0.83 Co 0.11 Mn 0.06 O 2 The waste ternary lithium ion battery (the electrolyte of the battery contains HF) is soaked in a sodium chloride solution with the concentration of 0.5% for 36 hours for discharging, and then the battery is disassembled to obtain a positive plate;
(2) placing the positive plate obtained by the disassembly in the step (1) in NaOH and NH with the total molar weight of 3mol/L 3 ·H 2 Soaking in O mixed solution for 12 hr to completely dissolve aluminum foil, controlling pH of the system to 12.5 with liquid alkali, and filtering to obtain black powder (shown in electron microscope picture asAs shown in fig. 2, the particles are broken single crystal particles, have rough surfaces and cracks, and have a particle size of 3-5 μm);
(3) 10g (about 0.1mol) of black powder are weighed out and 0.007g (0000.1mol) of B are then added to the black powder 2 O 3 Grinding for 30min at the rotating speed of 400 rpm;
(4) and (3) calcining the ground black powder in an oxygen-rich atmosphere for two sections: firstly heating to 500 ℃, calcining for 10h, then heating to 820 ℃ and calcining for 16h to obtain the regenerated cathode material LiNi 0.83 Co 0.11 Mn 0.06 B 0.002 F 0.001 O 2 。
The SEM image of the regenerated cathode material of the present embodiment is shown in fig. 1, and it can be seen from fig. 1 that the regenerated ternary cathode material particles are typical quasi-single crystal particles, have smooth and crack-free surfaces, uniform sizes, and particle diameters of 3 to 5 μm.
The regenerated positive electrode material LiNi of the present example was used 0.83 Co 0.11 Mn 0.06 B 0.002 F 0.001 O 2 The full cell is assembled, and the test is carried out at 25 ℃ within the voltage range of 2.75-4.6V, the result is shown in figure 3, the first discharge gram capacity reaches 212.3mAh/g under the 0.1C multiplying power, the first discharge gram capacity reaches 200.6mAh/g under the 1C multiplying power, the cycle is 200 circles under the 1C, the capacity is 178.35mAh/g, and the capacity retention rate reaches 88.9%.
Example 2:
a regeneration method of a waste lithium ion battery anode material comprises the following steps:
(1) the anode material is LiNi 0.88 Co 0.06 Mn 0.06 O 2 The waste ternary lithium ion battery (the electrolyte of the battery contains HF) is placed into a sodium chloride solution with the mass concentration of 0.8% for soaking and discharging for 35 hours, and a positive plate is obtained after disassembly;
(2) placing the positive plate in NaOH and NH with the total molar weight of 3mol/L 3 ·H 2 Soaking in the mixed solution of O for 11h, controlling the pH of the system to be 12.8 by using liquid alkali, and filtering after the aluminum foil is completely dissolved to obtain black powder;
(3) 10g (about 0.1mol) of black powder was weighed and added to the black powder0.014g (0000.2mol) of B 2 O 3 Grinding for 30min at the rotating speed of 400 rpm;
(4) calcining the ground black powder in an oxygen-rich atmosphere for two sections: firstly heating to 520 ℃, calcining for 11h at the temperature, then heating to 830 ℃ and calcining for 17h to obtain the regenerated cathode material LiNi 0.88 Co 0.06 Mn 0.06 B 0.004 F 0.002 O 2 。
An SEM image of the regenerated cathode material obtained in this example is shown in fig. 4, and the particles of the cathode material are typical quasi-single crystal particles, have smooth and crack-free surfaces, are uniform in size, and have a particle size of 3 to 5 μm.
The regenerated anode material obtained in the embodiment is assembled into a full cell, and the first discharge gram capacity reaches 216.3mAh/g under 0.1C multiplying power and 205.6mAh/g under 1C multiplying power when the voltage is in a range of 2.75-4.6V and the temperature is 25 ℃, and the capacity is 178mAh/g and the capacity retention rate reaches 86.58% after 200 cycles under 1C.
Example 3:
a regeneration method of a waste lithium ion battery anode material comprises the following steps:
(1) the anode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 The waste ternary lithium ion battery (the electrolyte of the battery contains HF) is placed into a sodium chloride solution with the mass concentration of 0.9% to discharge for 34h, and a positive plate is obtained through disassembly;
(2) placing the positive plate in NaOH and NH with the total molar weight of 3mol/L 3 ·H 2 Soaking the mixture in the mixed solution of O for 10h, controlling the pH of the system to be 12.7, and filtering after the aluminum foil is completely dissolved to obtain black powder;
(3) 10g (about 0.1mol) of black powder were weighed out and 0.007g (0000.1mol) of B were added to the black powder 2 O 3 Grinding for 30min at the rotating speed of 400 rpm;
(4) and (3) calcining the ground black powder in an oxygen-rich atmosphere for two sections: firstly heating to 550 ℃ and calcining for 10h, then heating to 840 ℃ and calcining for 16h at the temperature to obtain the regenerated cathode material LiNi 0.8 Co 0.1 Mn 0.1 B 0.002 F 0.003 O 2 。
An SEM image of the regenerated ternary cathode material obtained in this example is shown in fig. 5, and the particles are typical quasi-single crystal particles, have smooth and crack-free surfaces, are uniform in size, and have a particle size of 3 to 5 μm.
The regenerated ternary cathode material obtained in the embodiment is assembled into a full cell, and the full cell is tested at 25 ℃ within the voltage range of 2.75-4.6V, the first discharge gram capacity reaches 208.4.3mAh/g under the 0.1C multiplying power, the first discharge gram capacity reaches 198.3mAh/g under the 1C multiplying power, the capacity is 169.09mAh/g after 200 cycles under the 1C multiplying power, and the capacity retention rate reaches 85.1%.
Comparative example 1
The method for regenerating the anode material of the waste lithium ion battery in the comparative example comprises the following steps:
(1) the positive electrode material is LiNi 0.83 Co 0.11 Mn 0.06 O 2 The waste ternary lithium ion battery (the electrolyte of the battery contains HF) is placed into a sodium chloride solution with the concentration of 0.5% for discharging for 36 hours, and a positive plate is obtained after disassembly;
(2) placing the positive plate in NaOH and NH with the total molar weight of 3mol/L 3 ·H 2 Soaking the mixture in the mixed solution of O for 12h, controlling the pH of the system to be 12.5 by using liquid alkali, and filtering to obtain black powder after the aluminum foil is completely dissolved;
(3) 10g (about 0.1mol) of black powder is weighed and ground for 30min at the rotating speed of 400rpm, and the ground black powder is subjected to two-stage calcination under the oxygen-rich atmosphere: firstly heating to 500 ℃ to calcine for 10h, then heating to 820 ℃ and calcining for 16h to obtain the regenerated cathode material LiNi 0.83 Co 0.11 Mn 0.06 F 0.001 O 2 。
An SEM image of the regenerated cathode material obtained in the comparative example is shown in FIG. 6, and the particles are broken single crystal particles, have rough surfaces and cracks, and have a particle size of 3-5 μm.
The regenerated positive electrode material of the comparative example is assembled into a full cell, and is tested at 25 ℃ within the voltage range of 2.75-4.6V, as shown in figure 3, the first discharge gram capacity is 130.4mAh/g under 0.1C multiplying power, the first discharge gram capacity is 115.3mAh/g under 1C multiplying power, the cycle is 200 circles under 1C, the capacity is 48.43mAh/g, and the capacity retention rate is only 42%.
Claims (10)
1. A method for regenerating a waste lithium ion battery anode material is characterized by comprising the following steps:
(1) discharging and disassembling the waste lithium ion battery, then soaking the disassembled positive plate in alkali liquor, and filtering to obtain black powder;
(2) and (2) washing and drying the black powder obtained in the step (1), adding a boron source into the dried black powder, grinding, and roasting to complete the regeneration of the anode material of the waste lithium ion battery.
2. The method for regenerating the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein the chemical formula of the positive electrode material of the waste lithium ion battery is LiNi x Co y Mn z O 2 ，0.3≤x<1，0<y≤0.3，0<z is less than or equal to 0.3, and the electrolyte of the waste lithium ion battery contains HF.
3. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (2), the boron source is any one of boron oxide, boron trichloride and boron hydroxide.
4. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (2), the rotation speed of the grinding is 200-500rpm, and the grinding time is 10-30 min.
5. The method for regenerating the positive electrode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (2), the calcination is performed in an oxygen-rich atmosphere.
6. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (2), the roasting is performed in two stages, the temperature of the first stage roasting is 500-550 ℃, the roasting time is 5-15h, the temperature of the second stage roasting is 600-850 ℃, and the roasting time is 5-50 h.
7. The method for regenerating the anode material of the waste lithium ion battery according to claim 1, wherein in the step (1), the discharging is to immerse the waste lithium ion battery in a sodium chloride solution with a mass concentration of 0.2-15% for 10-72 h.
8. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (1), the alkali solution is one or more of a sodium hydroxide solution, an ammonia water solution and a potassium hydroxide solution, or a mixed solution of a calcium hydroxide solution and a sodium hydroxide solution, an ammonia water solution or a potassium hydroxide solution; the concentration of the alkali liquor is 1-3 mol/L, and the pH value is 12-14.
9. The method for regenerating the anode material of the waste lithium ion battery as claimed in claim 1, wherein in the step (1), the anode plate is soaked in the alkali liquor for 1-24 h.
10. The method for regenerating the anode material of the waste lithium ion battery as claimed in any one of claims 1 to 9, wherein in the step (2), the chemical formula of the regenerated anode material of the lithium ion battery is LiNi x Co y Mn z B a F b O 2 Wherein x, y, z, a, b and c are mole numbers, x is more than or equal to 0.3<1，0<y≤0.3，0<z≤0.3，x+y+z＝1，0.001≤a≤0.03，0<b≤0.1。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109904446A (en) * | 2019-02-26 | 2019-06-18 | 广东邦普循环科技有限公司 | A kind of regeneration positive electrode and preparation method thereof and the lithium ion battery comprising the regeneration positive electrode |
| CN112110432A (en) * | 2020-08-28 | 2020-12-22 | 深圳供电局有限公司 | Recovery and regeneration method of lithium iron phosphate anode material of lithium ion battery |
| CN113860321A (en) * | 2021-08-23 | 2021-12-31 | 中南大学 | Preparation method of regenerated precursor material of waste lithium cobaltate battery |
| CN113880100A (en) * | 2021-08-23 | 2022-01-04 | 中南大学 | Preparation method of lithium nickel cobalt oxide battery regenerated ternary cathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109904446A (en) * | 2019-02-26 | 2019-06-18 | 广东邦普循环科技有限公司 | A kind of regeneration positive electrode and preparation method thereof and the lithium ion battery comprising the regeneration positive electrode |
| CN112110432A (en) * | 2020-08-28 | 2020-12-22 | 深圳供电局有限公司 | Recovery and regeneration method of lithium iron phosphate anode material of lithium ion battery |
| CN113860321A (en) * | 2021-08-23 | 2021-12-31 | 中南大学 | Preparation method of regenerated precursor material of waste lithium cobaltate battery |
| CN113880100A (en) * | 2021-08-23 | 2022-01-04 | 中南大学 | Preparation method of lithium nickel cobalt oxide battery regenerated ternary cathode material |
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