CN117117166B - Method for repairing ternary positive electrode material by dry method - Google Patents
Method for repairing ternary positive electrode material by dry method Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 101
- 238000005245 sintering Methods 0.000 claims abstract description 88
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000011888 foil Substances 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000002699 waste material Substances 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 5
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 5
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 6
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 claims description 3
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 3
- HAUKUGBTJXWQMF-UHFFFAOYSA-N lithium;propan-2-olate Chemical compound [Li+].CC(C)[O-] HAUKUGBTJXWQMF-UHFFFAOYSA-N 0.000 claims description 3
- 230000008439 repair process Effects 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 28
- 238000001878 scanning electron micrograph Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- 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
- H01M4/52—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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for repairing ternary positive electrode materials by a dry method, which comprises the following steps: a) Carrying out heat treatment on the used waste positive plate to separate powder on the positive plate from foil, and then carrying out ultrasonic vibration screen treatment on the powder to obtain recovered powder; b) Mixing the reclaimed powder with inorganic salt to obtain a mixture; c) Sintering the mixture to obtain a primary sintered material; d) Mixing the primary sintering material with a lithium source, and then performing sintering treatment to obtain a secondary sintering material; e) Crushing, screening and demagnetizing the secondary sintering material to obtain a repaired ternary anode material; wherein the inorganic salt is at least one of Na 2CO3、MgCO3、CaCO3、MgSO4 and CaSO 4. The method is convenient, safe and environment-friendly, and the ternary anode material with excellent performance can be obtained after repair.
Description
Technical Field
The invention relates to the field of material recovery processing, in particular to a method for repairing ternary positive electrode materials by a dry method.
Background
The lithium ion battery is used as a novel energy storage device, is widely applied to various fields because of the advantages of high energy density, no memory effect, excellent cycle performance and the like, and the number of the eliminated lithium ion batteries is increased along with the year-by-year increase of the application scale. The positive electrode material is one of the most important components in the lithium ion battery, and is not deficient in valuable metals such as nickel, cobalt, manganese and the like. In the current large environment with energy shortage, how to efficiently recycle and utilize the anode of the waste lithium ion battery has become an important target of the current research subject.
At present, the research of recycling the waste ternary cathode material mainly utilizes inorganic acid to extract metal cobalt and lithium in the cathode material in a metal salt form to achieve the aim of recycling, and inorganic strong acid is an important reactant in recycling the waste cathode material, but the inorganic acid treatment after the reaction has high requirements on corresponding equipment, and water and soil pollution can be caused to cause high cost for treating waste water and waste gas. In addition, the rare resources of cobalt and lithium greatly increase in price, and if lithium is directly added, the process cost increases.
Disclosure of Invention
In view of this, the present invention provides a method for dry repairing ternary positive electrode materials. The method is convenient, safe and environment-friendly, and the ternary anode material with excellent performance can be obtained after repair.
The invention provides a method for repairing ternary positive electrode materials by a dry method, which comprises the following steps:
a) Carrying out heat treatment on the used waste positive plate to separate powder on the positive plate from foil, and then carrying out ultrasonic vibration screen treatment on the powder to obtain recovered powder;
b) Mixing the reclaimed powder with inorganic salt to obtain a mixture;
c) Sintering the mixture to obtain a primary sintered material;
d) Mixing the primary sintering material with a lithium source, and then performing sintering treatment to obtain a secondary sintering material;
e) Crushing, screening and demagnetizing the secondary sintering material to obtain a repaired ternary anode material;
Wherein,
The inorganic salt is at least one of Na 2CO3、MgCO3、CaCO3、MgSO4 and CaSO 4.
Preferably, in step a), the temperature of the heat treatment is 150 to 300 ℃ and the time is 1 to 10 hours.
Preferably, in the step b), the content of the metal element in the inorganic salt in the mixture is 500-20000 ppm.
Preferably, in step c), the sintering treatment conditions are: the temperature rising rate is less than or equal to 20 ℃/min, the sintering temperature is 600-1000 ℃, and the heat preservation time is 5-20 h.
Preferably, in step d), the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium ethoxide, lithium methoxide, lithium isopropoxide and lithium butoxide.
Preferably, in step d), the content of Li element in the lithium source is 200-2000 ppm in the obtained mixture after adding the lithium source.
Preferably, in step d), the sintering treatment conditions are: the temperature rising rate is less than or equal to 20 ℃/min, the sintering temperature is 400-900 ℃, and the heat preservation time is 5-20 h.
Preferably, in step c), after the sintering treatment, cooling to room temperature; the cooling rate is less than or equal to 20 ℃/min;
In the step d), after sintering treatment, cooling to room temperature; the cooling rate is less than or equal to 20 ℃/min.
Preferably, in the step a), the screen mesh number of the ultrasonic vibration screen treatment is 325 mesh;
in step b), the mixing is high speed mixing; the rotating speed of the high-speed mixing is 300-700 rpm, and the time is 10-60 min.
Preferably, the positive electrode active material on the waste positive electrode plate is a ternary positive electrode active material;
The ternary positive electrode active material is NCM ternary positive electrode material.
According to the repairing method provided by the invention, the used waste positive plate is subjected to low-temperature heat treatment, so that powder on the positive plate is separated from foil, and then the powder is subjected to ultrasonic vibration sieve treatment, so that recovered powder is obtained; mixing the reclaimed powder with certain inorganic salt in a certain proportion to obtain a mixture; then sintering the mixture to obtain a primary sintered material; mixing the primary sintering material with a certain lithium source in a certain proportion, and performing sintering treatment to obtain a secondary sintering material; and finally, crushing, screening and demagnetizing the secondary sintering material to obtain the repaired ternary anode material. According to the invention, the inorganic salt is added, so that corrosion damage of HF generated by high-temperature decomposition of the binder to the material is reduced, then the lithium source is added for roasting, and further the surface of the material is subjected to structural repair, so that the performance of the repaired ternary positive electrode material is equivalent to that of an unused initial ternary positive electrode material; the method uses specific inorganic salt and lithium source, adds the inorganic salt and the lithium source in a certain proportion, and respectively uses the inorganic salt and the lithium source before primary sintering and secondary sintering, simultaneously controls sintering conditions and the like of the secondary sintering, and ensures that the ternary positive electrode material is effectively repaired and recovered through the cooperation of a series of means, and the performance of the ternary positive electrode material after repair is excellent and is equivalent to the electrochemical performance and the processing performance of the initial ternary positive electrode material which is not used; in addition, the invention is a dry repair method, has simple and convenient process, safety and environmental protection, lower cost and more time development significance in the time of the surge of lithium price.
The test result shows that the discharge capacity of the repaired ternary positive electrode material obtained by the method reaches more than 150mAh/g, and the ternary positive electrode material has excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the material obtained in example 1 and comparative example 1; wherein FIG. 1a is an SEM image of the material obtained in comparative example 1, and FIG. 1b is an SEM image of the material obtained in example 1;
FIG. 2 is an SEM image of the material obtained in example 2 and comparative example 2; wherein, FIG. 2a is an SEM image of the material obtained in comparative example 2, and FIG. 2b is an SEM image of the material obtained in example 2;
FIG. 3 is a graph showing the capacity of assembled batteries of the materials obtained in example 1 and comparative example 1;
Fig. 4 is a graph of capacity of assembled batteries of the materials obtained in example 2 and comparative example 2.
Detailed Description
The invention provides a method for repairing ternary positive electrode materials by a dry method, which comprises the following steps:
a) Carrying out heat treatment on the used waste positive plate to separate powder on the positive plate from foil, and then carrying out ultrasonic vibration screen treatment on the powder to obtain recovered powder;
b) Mixing the reclaimed powder with inorganic salt to obtain a mixture;
c) Sintering the mixture to obtain a primary sintered material;
d) Mixing the primary sintering material with a lithium source, and then performing sintering treatment to obtain a secondary sintering material;
e) Crushing, screening and demagnetizing the secondary sintering material to obtain a repaired ternary anode material;
Wherein,
The inorganic salt is at least one of Na 2CO3、MgCO3、CaCO3、MgSO4 and CaSO 4.
According to the repairing method provided by the invention, the used waste positive plate is subjected to low-temperature heat treatment, so that powder on the positive plate is separated from foil, and then the powder is subjected to ultrasonic vibration sieve treatment, so that recovered powder is obtained; mixing the reclaimed powder with certain inorganic salt in a certain proportion to obtain a mixture; then sintering the mixture to obtain a primary sintered material; mixing the primary sintering material with a certain lithium source in a certain proportion, and performing sintering treatment to obtain a secondary sintering material; and finally, crushing, screening and demagnetizing the secondary sintering material to obtain the repaired ternary anode material. The method is convenient, safe and environment-friendly, and the ternary anode material with excellent performance can be obtained after repair.
Regarding step a):
a) And carrying out heat treatment on the used waste positive plate to separate powder on the positive plate from foil, and then carrying out ultrasonic vibration screen treatment on the powder to obtain recovered powder.
In the invention, the used waste positive plate refers to a positive plate of a used lithium ion battery, and the acquisition mode is not particularly limited, and the method is a conventional processing mode in the field, for example, the recovered lithium ion battery is disassembled, so as to obtain the positive plate. The positive plate generally comprises a foil and a positive electrode material compounded on the foil; the positive electrode material generally includes a positive electrode active material, a binder, and the like. Wherein the positive electrode active material is preferably an NCM ternary positive electrode material, i.e., the treatment method of the present invention is more suitable for an NCM ternary positive electrode material, i.e., liNi xCoyMn1-x-yO2, and more preferably at least one of an NCM5 ternary positive electrode material (i.e., x=0.50 to 0.59 in the above formula), an NCM6 ternary positive electrode material (i.e., x=0.60 to 0.69 in the above formula), and an NCM7 ternary positive electrode material (i.e., x=0.70 to 0.79 in the above formula).
In the invention, the heat treatment is low-temperature heat treatment, the heat treatment temperature is particularly preferably 150-300 ℃, and particularly can be 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃,200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ and 300 ℃; if the temperature is too low, the binder PVDF in the positive electrode material cannot be effectively aged and further cannot be failed to effectively separate the material from the foil, if the temperature is too high, the PVDF is decomposed to generate HF, which causes corrosion to the surface of the material and damages the structure of the positive electrode active material. In the present invention, the time of the heat treatment is preferably 1 to 10 hours, and may specifically be 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours.
In the invention, after the heat treatment, the powder on the positive plate is separated from the foil, and then the peeled powder is subjected to ultrasonic vibration screen treatment, so as to obtain recovered powder. In the invention, the screen mesh size of the ultrasonic vibration screen is preferably 325 meshes, namely, 325 mesh powder is obtained.
Regarding step b):
b) And mixing the reclaimed powder with inorganic salt to obtain a mixture.
In the present invention, the inorganic salt is preferably at least one of Na 2CO3、MgCO3、CaCO3、MgSO4 and CaSO 4. The PVDF binder in the ternary pole piece material can be decomposed at high temperature to generate HF, which has corrosion effect on the surface of the material, damages the material structure and reduces the material capacity, but the specific inorganic salt is introduced to preferentially react with HF rapidly to form stable fluoride, so that the HF is prevented from corroding the surface of the material, and the specific inorganic salt can only effectively act, and the problems cannot be solved if other inorganic salts such as CaCl 2 and the like are adopted.
In the invention, the content of metal elements in the inorganic salt in the mixture is preferably 500-20000 ppm, namely, the mass ratio of the mass of the metal elements in the inorganic salt to the mass of the mixture obtained after mixing is 500-20000 ppm, and particularly 500ppm、1000ppm、2000ppm、3000ppm、4000ppm、5000ppm、6000ppm、7000ppm、8000ppm、9000ppm、10000ppm、11000ppm、12000ppm、13000ppm、14000ppm、15000ppm、16000ppm、17000ppm、18000ppm、19000ppm、20000ppm; the invention can effectively ensure the performance of the material under the condition that the content of the inorganic salt is too small, HF can not be adsorbed and reacted in time, thereby the surface of the material can be corroded by HF, the performance of the material can be reduced, and the residual inactive substances and impurities in the material can be increased and the performance of the material can be influenced if the content of the inorganic salt is too large.
In the present invention, when the reclaimed powder and the inorganic salt are mixed, the mixing is preferably performed at a high speed, and specifically, the mixing can be performed by a high-speed mixer. The rotation speed of the high-speed mixing is preferably 300 to 700rpm, and specifically 300rpm, 400rpm, 500rpm, 600rpm, 700rpm may be used. The mixing time is preferably 10-60 min, and specifically can be 10min, 20min, 30min, 40min, 50min, and 60min. After mixing treatment, the evenly mixed mixture is obtained.
Regarding step c):
c) And sintering the mixture to obtain a primary sintered material.
In the invention, the mixture is put into a sagger and then sintered. Among them, the pot loading amount is preferably 2 to 6 kg/pot, specifically, 2 kg/pot, 3 kg/pot, 4 kg/pot, 5 kg/pot, 6 kg/pot. The dimensions of the interior of the sagger are preferably 330mm long by 330mm wide by 120mm high.
In the present invention, the conditions of the sintering treatment are preferably: the temperature rising rate is less than or equal to 20 ℃/min, the sintering temperature is 600-1000 ℃, and the heat preservation time is 5-20 h. Wherein the heating rate can be 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min. The sintering temperature can be specifically 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃ and 1000 ℃. The heat preservation time can be specifically 5h, 6h, 8h, 10h, 12h, 14h, 16h, 18h and 20h. In the invention, after sintering, the temperature is preferably reduced; the temperature is preferably reduced to room temperature; the cooling rate is preferably less than or equal to 20 ℃/min, and can be specifically 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min and 20 ℃/min. After the sintering treatment, a primary sintering material is obtained.
Regarding step d):
d) And mixing the primary sintering material with a lithium source, and then performing sintering treatment to obtain a secondary sintering material.
In the present invention, after the primary sintered material obtained by sintering in step c) is mixed with the lithium source, the primary sintered material is preferably crushed. After crushing, it is mixed with a lithium source.
In the present invention, the lithium source is preferably at least one of lithium carbonate, lithium hydroxide, lithium ethoxide, lithium methoxide, lithium isopropoxide and lithium butoxide, more preferably lithium carbonate and/or lithium hydroxide. The PVDF binder in the ternary pole piece material can be decomposed at high temperature to generate HF, which has corrosion effect on the surface of the material, damages the material structure and reduces the material capacity, the specific inorganic salt is introduced, the fluoride which is stable when the fluoride is reacted with HF rapidly preferentially, the HF is prevented from corroding the surface of the material, but a small amount of HF can react with the surface of the material, li on the surface of the material is hooked out, liF is generated by the reaction, and the material capacity is slightly reduced. Moreover, the present invention achieves a good effect only with the above specific lithium source, but cannot achieve the above effect with other lithium sources such as lithium metal, lithium aluminum alloy, etc.
In the invention, the content of Li element in the mixture obtained after adding the lithium source is preferably 200-2000 ppm, namely the mass ratio of Li in the lithium source to the mass of the mixture obtained after adding the lithium source is 200-2000 ppm, and particularly 200ppm、300ppm、400ppm、500ppm、600ppm、700ppm、800ppm、900ppm、1000ppm、1100ppm、1200ppm、1300ppm、1400ppm、1500ppm、1600ppm、1700ppm、1800ppm、1900ppm、2000ppm. the invention can achieve the best effect under the dosage range, if the lithium is too small, the repair of the surface structure of the material is incomplete, the material performance can not be restored to the level of a normal ternary positive electrode material, and if the lithium is too large, the residual alkali on the surface of the material is too much, and the processability and the high-temperature storage performance of the material are deteriorated.
In the present invention, when the primary sintered material and the lithium source are mixed, the mixing is preferably performed at a high speed, and specifically, the mixing can be performed by using a high-speed mixer. The rotation speed of the high-speed mixing is preferably 300 to 700rpm, and specifically 300rpm, 400rpm, 500rpm, 600rpm, 700rpm may be used. The mixing time is preferably 10-60 min, and specifically can be 10min, 20min, 30min, 40min, 50min, and 60min. After mixing treatment, the evenly mixed mixture is obtained.
In the invention, the mixture is put into a sagger and then sintered. Among them, the pot loading amount is preferably 2 to 6 kg/pot, specifically, 2 kg/pot, 3 kg/pot, 4 kg/pot, 5 kg/pot, 6 kg/pot. The dimensions of the interior of the sagger are preferably 330mm long by 330mm wide by 120mm high.
In the present invention, the conditions of the sintering treatment are preferably: the temperature rising rate is less than or equal to 20 ℃/min, the sintering temperature is 400-900 ℃, and the heat preservation time is 5-20 h. Wherein the heating rate can be 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min. The sintering temperature can be specifically 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃ and 900 ℃. The heat preservation time can be specifically 5h, 6h, 8h, 10h, 12h, 14h, 16h, 18h and 20h. In the invention, after sintering, the temperature is preferably reduced; the temperature is preferably reduced to room temperature; the cooling rate is preferably less than or equal to 20 ℃/min, and can be specifically 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min and 20 ℃/min. And obtaining the secondary sintering material after the sintering treatment.
Regarding step e):
e) And crushing, screening and demagnetizing the secondary sintering material to obtain the repaired ternary anode material.
In the present invention, the manner of the crushing is not particularly limited, and is a conventional operation in the art. The sieving is preferably to screen out 325 mesh powder. The manner of the demagnetization is not particularly limited, and is a conventional operation in the art. After the treatment, a large amount of ternary anode materials are repaired.
According to the repairing method provided by the invention, the used waste positive plate is subjected to low-temperature heat treatment, so that powder on the positive plate is separated from foil, and then the powder is subjected to ultrasonic vibration sieve treatment, so that recovered powder is obtained; mixing the reclaimed powder with certain inorganic salt in a certain proportion to obtain a mixture; then sintering the mixture to obtain a primary sintered material; mixing the primary sintering material with a certain lithium source in a certain proportion, and performing sintering treatment to obtain a secondary sintering material; and finally, crushing, screening and demagnetizing the secondary sintering material to obtain the repaired ternary anode material. According to the invention, the inorganic salt is added, so that corrosion damage of HF generated by high-temperature decomposition of the binder to the material is reduced, then the lithium source is added for roasting, and further the surface of the material is subjected to structural repair, so that the performance of the repaired ternary positive electrode material is equivalent to that of an unused initial ternary positive electrode material; the method uses specific inorganic salt and lithium source, adds the inorganic salt and the lithium source in a certain proportion, and respectively uses the inorganic salt and the lithium source before primary sintering and secondary sintering, simultaneously controls sintering conditions and the like of the secondary sintering, and ensures that the ternary positive electrode material is effectively repaired and recovered through the cooperation of a series of means, and the performance of the ternary positive electrode material after repair is excellent and is equivalent to the electrochemical performance and the processing performance of the initial ternary positive electrode material which is not used; in addition, the invention is a dry repair method, has simple and convenient process, safety and environmental protection, lower cost and more time development significance in the time of the surge of lithium price.
The test result shows that the discharge capacity of the repaired ternary positive electrode material obtained by the method reaches more than 150mAh/g, and the ternary positive electrode material has excellent electrochemical performance.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
A) And (3) sintering the recovered NCM6 positive plate at a low temperature of 250 ℃ for 3 hours, and separating powder from the foil. The peeled powder was passed through an ultrasonic vibration sieve (mesh 325) to obtain reclaimed powder.
B) 4000ppm of Na 2CO3 is added into the obtained recovered powder, and the mixture is put into a high-speed mixer to be mixed for 60 minutes at 600rpm, so as to obtain a mixture.
C) 5kg of the mixture was weighed and put into a sagger (the loading amount is 5 kg/sagger, the sagger size is as described above), then sintering treatment was performed, the temperature was raised to 850 ℃ at a rate of 10 ℃/min, and the temperature was kept for 8 hours for sintering, and then the temperature was lowered to room temperature at a rate of 10 ℃/min, to obtain a primary sintered material.
D) After crushing the primary sintering material, adding 400ppm of lithium carbonate, putting into a high-speed mixer for mixing, and mixing at 600rpm for 30min to obtain a mixture. Then 5kg of the mixture is weighed and put into a sagger (the loading amount is 5 kg/sagger), sintering treatment is carried out, the temperature is raised to 780 ℃ at the speed of 10 ℃/min, the heat is preserved and sintered for 5 hours, and then the temperature is lowered to the room temperature at the speed of 10 ℃/min, so as to obtain the secondary sintered material.
E) Crushing, sieving (325 mesh) and demagnetizing the secondary sintering material to obtain the repaired ternary anode material.
Comparative example 1
The procedure is as in example 1, except that Na 2CO3 is not added (i.e., step b) is not performed and that no lithium source is added in step d).
Example 2
A) And (3) sintering the recovered NCM7 positive plate at a low temperature of 250 ℃ for 3 hours, and separating powder from the foil. The peeled powder was passed through an ultrasonic vibration sieve (mesh 325) to obtain reclaimed powder.
B) 3000ppm of Na 2CO3 is added into the obtained recovered powder, and the mixture is put into a high-speed mixer to be mixed for 30 minutes at 600rpm, so as to obtain a mixture.
C) 5kg of the mixture was weighed and put into a sagger (the loading amount is 5 kg/sagger, the sagger size is as described above), then sintering treatment was performed, the temperature was raised to 840 ℃ at a rate of 10 ℃/min, and the temperature was kept for sintering for 8 hours, and then the temperature was lowered to room temperature at a rate of 10 ℃/min, to obtain a primary sintered material.
D) After crushing the primary sintering material, adding 400ppm of lithium carbonate, putting into a high-speed mixer for mixing, and mixing at 600rpm for 30min to obtain a mixture. Then 5kg of the mixture is weighed and put into a sagger (the loading amount is 5 kg/sagger), sintering treatment is carried out, the temperature is raised to 750 ℃ at the speed of 10 ℃/min, the sintering is carried out for 5 hours, and then the temperature is lowered to the room temperature at the speed of 10 ℃/min, so as to obtain the secondary sintering material.
E) Crushing, sieving (325 mesh) and demagnetizing the secondary sintering material to obtain the repaired ternary anode material.
Comparative example 2
The procedure is as in example 2, except that Na 2CO3 is not added (i.e., step b) is not performed and that no lithium source is added in step d).
Example 3: product testing
1. SEM characterization
SEM characterization was performed on the materials obtained in example 1 and comparative example 1, respectively, and the results are shown in fig. 1, where fig. 1 is an SEM image of the materials obtained in example 1 and comparative example 1, and fig. 1a is an SEM image of the materials obtained in comparative example 1, and fig. 1b is an SEM image of the materials obtained in example 1. It can be seen that the morphology of the material obtained in example 1 is not significantly changed compared with comparative example 1, but the binder and carbon black on the surface are reacted thoroughly, and no foreign matter remains.
SEM characterization was performed on the materials obtained in example 2 and comparative example 2, respectively, and the results are shown in fig. 2, wherein fig. 2a is an SEM image of the material obtained in example 2 and comparative example 2, and fig. 2b is an SEM image of the material obtained in example 2. It can be seen that the morphology of the material obtained in example 2 was not significantly changed compared with comparative example 2, but the binder and carbon black and the like on the surface had reacted thoroughly, and the foreign matter residue was reduced.
2. Electrochemical performance test
Assembling the battery:
9.0g of positive electrode active material, 0.5g of acetylene black (SP) conductive agent and 0.5gPVDF (HSV-900) binder are weighed, fully mixed, added with N-methyl-pyrrolidone (NMP) solvent until the solid content is 70%, dispersed, homogenized uniformly and then pulled on an aluminum foil with the thickness of 16 mu m to prepare the positive electrode plate. The positive electrode plate, the metal lithium plate negative electrode plate, the ceramic diaphragm (thickness 16 μm) and LiPF 6 electrolyte (concentration 1mol/L, solvent is mixed solvent of ethyl carbonate EC: dimethyl carbonate DMC: diethyl carbonate EMC volume ratio=1:1:1) are assembled into a battery in an anaerobic glove box, a standard half-battery configuration is adopted, and a battery shell adopts a (CR 2032) button battery.
The materials obtained in comparative examples 1 to 2 and examples 1 to 2 were each subjected to the above-described battery assembly process as a positive electrode active material.
Ii. Testing of batteries:
The battery was subjected to charge and discharge tests at a current density of 0.2C at a voltage of 4.3 to 3.0V, and as a result, see fig. 3 to 4, respectively, fig. 3 is a graph of capacity of the battery assembled from the materials obtained in example 1 and comparative example 1, and fig. 4 is a graph of capacity of the battery assembled from the materials obtained in example 2 and comparative example 2.
As can be seen from FIG. 3, the discharge capacity of comparative example 1 is brought into 90.88mAh/g, while the discharge capacity of example 1 can reach 154.70mAh/g, the gram capacity is improved by 63.82mAh/g, and the improvement rate reaches 70%.
As can be seen from FIG. 4, the discharge capacity of comparative example 2 is up to 106.30mAh/g, while the discharge capacity of example 2 can be up to 164.01mAh/g, the gram capacity is improved by 57.71mAh/g, and the improvement rate is up to 54%.
The test results of fig. 3-4 prove that the comparative example is directly sintered without adding inorganic salt and lithium source, which causes corrosion of HF on the surface of the material, structural deterioration and low discharge capacity, and the material structure can be effectively repaired after the treatment by the method of the embodiment, so that the discharge capacity of the material is obviously increased.
Example 4
The procedure is as in example 1, except that the inorganic salt Na 2CO3 is replaced with MgCO 3 and the lithium source lithium carbonate is replaced with lithium hydroxide.
Example 5
The procedure is as in example 1, except that the inorganic salt Na 2CO3 is replaced by CaSO 4.
Comparative example 3
The procedure is as in example 1, except that the amount of Na 2CO3 in step b) is increased to 30000ppm and the amount of lithium carbonate in step d) is decreased to 100ppm.
Example 6: product testing
The electrochemical properties of examples 4 to 5 and comparative example 3 were tested according to the test method in example 3, and the results are shown in table 1.
Table 1: electrochemical Properties
| Positive electrode active material | Discharge capacity, mAh/g |
| Example 1 | 154.70 |
| Example 2 | 164.01 |
| Example 4 | 151.90 |
| Example 5 | 150.40 |
| Comparative example 1 | 90.88 |
| Comparative example 2 | 106.30 |
| Comparative example 3 | 141.10 |
As can be seen from the test results in Table 1, the discharge capacity of the materials obtained in examples 1-2,4-5 of the present invention reaches more than 150mAh/g, and excellent electrochemical performance is exhibited. Compared with the example 1, the discharge capacity of the comparative examples 1-2 is obviously reduced, and the direct sintering without adding inorganic salt and lithium source proves that HF corrodes the surface of the material, the structure is deteriorated, and the discharge capacity is very low. The discharge capacity of comparative example 3 is also significantly reduced compared to example 1, and it is demonstrated that the material performance is reduced if the amount of the inorganic salt and the lithium source is too low or too high, and the discharge capacity of the material can be effectively improved by controlling the amount of the inorganic salt and the lithium source to be certain amounts.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (5)
1. The method for repairing the ternary positive electrode material by the dry method is characterized by comprising the following steps of:
a) Carrying out heat treatment on the used waste positive plate to separate powder on the positive plate from foil, and then carrying out ultrasonic vibration screen treatment on the powder to obtain recovered powder;
The temperature of the heat treatment is 150-300 ℃ and the time is 1-10 h,
B) Mixing the reclaimed powder with inorganic salt to obtain a mixture; the content of metal elements in the inorganic salt in the mixture is 1000-5000 ppm,
C) Sintering the mixture to obtain a primary sintered material; in the step c), the sintering treatment conditions are as follows: the temperature rising rate is less than or equal to 20 ℃/min, the sintering temperature is 840-900 ℃, and the heat preservation time is 5-20 h;
d) Mixing the primary sintering material with a lithium source, and then performing sintering treatment to obtain a secondary sintering material; the content of Li element in the lithium source is 200-500 ppm in the mixture obtained after the lithium source is added,
In the step d), the sintering treatment conditions are as follows: the temperature rising rate is less than or equal to 20 ℃/min, the sintering temperature is 750-800 ℃, and the heat preservation time is 5-20 h;
e) Crushing, screening and demagnetizing the secondary sintering material to obtain a repaired ternary anode material;
Wherein,
The inorganic salt is at least one of Na 2CO3、MgCO3、CaCO3、MgSO4 and CaSO 4.
2. The method of claim 1, wherein in step d) the lithium source is at least one of lithium carbonate, lithium hydroxide, lithium ethoxide, lithium methoxide, lithium isopropoxide, and lithium butoxide.
3. The method according to claim 1, wherein in step c), after the sintering treatment, the temperature is lowered to room temperature; the cooling rate is less than or equal to 20 ℃/min;
In the step d), after sintering treatment, cooling to room temperature; the cooling rate is less than or equal to 20 ℃/min.
4. The method according to claim 1, wherein in step a), the screen mesh number of the ultrasonic vibration screen treatment is 325 mesh;
in step b), the mixing is high speed mixing; the rotating speed of the high-speed mixing is 300-700 rpm, and the time is 10-60 min.
5. The method of claim 1, wherein the positive electrode active material on the spent positive electrode sheet is a ternary positive electrode active material;
The ternary positive electrode active material is NCM ternary positive electrode material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110085937A (en) * | 2018-01-26 | 2019-08-02 | 天津理工大学 | A kind of LiFePO4The benefit lithium Regeneration and Repair method of waste material |
| CN112225191A (en) * | 2020-10-09 | 2021-01-15 | 武汉瑞科美新能源有限责任公司 | Method for degrading PVDF in positive electrode of waste lithium iron phosphate battery |
| CN112824327A (en) * | 2019-11-20 | 2021-05-21 | 上海交通大学 | Recovery method of ternary electrode material |
| WO2022055272A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지에너지솔루션 | Method for recovering cathode material |
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| CN106450554A (en) * | 2016-11-10 | 2017-02-22 | 上海交通大学 | Process for peeling positive active material from waste power lithium-ion batteries |
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| CN110010993B (en) * | 2019-05-17 | 2021-03-09 | 清华大学 | A method for in-situ adsorption of fluoride in waste lithium batteries using high-speed iron slag |
| CN110233305A (en) * | 2019-06-28 | 2019-09-13 | 武汉大学 | A kind of fused salt regeneration activating method of waste and old lithium ion battery tertiary cathode material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112824327A (en) * | 2019-11-20 | 2021-05-21 | 上海交通大学 | Recovery method of ternary electrode material |
| WO2022055272A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지에너지솔루션 | Method for recovering cathode material |
| CN112225191A (en) * | 2020-10-09 | 2021-01-15 | 武汉瑞科美新能源有限责任公司 | Method for degrading PVDF in positive electrode of waste lithium iron phosphate battery |
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